Dabir S.

Viswanath
Tushar K. Ghosh
Veera M. Boddu

Emerging Energetic
Materials: Synthesis,
Physicochemical, and
Detonation Properties
Emerging Energetic Materials: Synthesis,
Physicochemical, and Detonation Properties
Dabir S. Viswanath Tushar K. Ghosh
•

Veera M. Boddu

Emerging Energetic
Materials: Synthesis,
Physicochemical,
and Detonation Properties

123
Dabir S. Viswanath Veera M. Boddu
Nuclear Science and Engineering Institute Environmental Processes Branch
University of Missouri US Army Engineer Research and
Columbia, MO Development Center
USA Champaign, IL
USA
and
and
Nuclear Engineering Teaching Laboratory
Cockrell School of Engineering Plant Polymer Research Unit, National
Austin, TX Center for Agricultural Utilization
USA Research
Agricultural Research Service, US
Tushar K. Ghosh Department of Agriculture
Nuclear Science and Engineering Institute Peoria, IL
University of Missouri USA
Columbia, MO
USA

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Preface

This monograph summarizes science and technology of select new generation

high-energy and insensitive explosives. There is an enormous amount of infor-
mation being generated and published in the open literature on different areas
pertaining to civilian and military uses of these materials. The objectives of this
monograph are to provide the professionals with comprehensive information on
synthesis, physicochemical, and detonation properties of the explosives. Potential
technologies applicable for treatment of contaminated waste streams from manu-
facturing facilities and environmental matrices are also included. This book pro-
vides the reader an insight into the theoretical and empirical models and
experimental techniques currently being developed in the field of energetic mate-
rials. The material in this book should assist researchers involved in both sensitive
and insensitive energetic materials, a program of the United States Department of
Defense.
Physicochemical Measurements on Insensitive Munitions Compounds for
Environmental Applications—Understanding the environmental impact of ener-
getic materials is critical for their acceptance for use in weapons systems. Predicting
their environmental distribution, biotransformation, and determining potential
treatment processes assist both decision-makers and scientists in the development
process. Combustion of explosives involves complex physicochemical changes and
reaction mechanisms. Therefore, there is a need to have knowledge of accurate and
good quality data on properties such as solubility, toxicity, enthalpies of formation
and combustion, thermal properties, and a host of other properties. We have tried to
put together as many properties available in the published literature. Since extensive
testing to design high-energy insensitive munitions and formulations are expensive,
this monograph should help researchers who use multiphysics modeling programs
to achieve high-energy materials and formulations. Thermophysical properties
collected in this monograph should be useful in 2-D numerical codes that will
simulate slow and fast cook-off, and codes that simulate detonation properties.
This monograph has 11 chapters, and each chapter is devoted to one particular
compound with the exception of Chap. 1. Chapter 1 deals with the measurements
and estimations of several physical properties important to the characterization,

v
vi Preface

screening, and utilization of energetic materials. It outlines different experimental

methods of measurement of physical properties, and their limitations.
The remaining ten chapters are devoted to a set of new emerging energetic
materials. Each chapter considers one energetic compound and enumerates the
synthesis methods, structure, physical and chemical properties, decomposition and
destruction, detonation characteristics, toxicity, explosive formulations, and
detection of that compound. The compounds considered in this monograph are as
follows: hexanitrohexaazaisowurtzitane (HNIW, CL-20), 1,1-diamino-2,2-dinitro
ethylene (DADE, FOX-7), 2,4-dinitroanisole (DNAN), 5-nitro-2,4-dihydro-3H-1,2,
4-triazole-3-one (NTO), 1,3,3-trinitroazetidine (TNAZ), triacetone triperoxide
(TATP), 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), 1-azido-2-nitro-2-azapropane
(ANAP), N-methyl-4-nitroaniline (MNA), and hexanitrostilbene (HNS). These com-
pounds represent a cross section of sensitive high energetic materials such as TATP and
insensitive energetic compounds that are used in different applications.
We have tried to present the current literature on these compounds, and bring
together material scattered in different publications. The material presented in this
monograph should supplement material found in several other books such as The
Chemistry of Explosives by J. Akhavan, Propellants and Explosives by N. Kubota,
Organic Chemistry of Explosives by J.P. Agrawal and R. Hodgson, High Energy
Materials by J.P. Agrawal, Advanced Processing Technologies for Next-Generation
Materials by T.M. Klapotke, Liquid Explosives by J. Liu, and others.
With great appreciation, we take this opportunity to thank the editors at Springer.
The authors are thankful to the publishers for agreeing to our repeated requests to
postpone submission of the manuscript. Special thanks are extended to Ms. Cynthia
Feenstra for her coordination and patience in extending the deadline for submitting
the manuscript. We also thank our family members for their support for realization
of this book.

Columbia, MO, USA Dabir S. Viswanath

Columbia, MO, USA Tushar K. Ghosh
Peoria, IL, USA Veera M. Boddu
Contents

1 Properties of Insensitive Energetic Materials and Their

Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Experimental Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Melting Point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3.1 Thiele Tube . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3.2 Thomas–Hoover Uni-Melt Device . . . . . . . . . . . . . . . . . 4
1.3.3 Mel-Temp Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.4 DSC/DTA Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.5 Boiling Point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.6 Critical Temperature, Volume, and Temperature. . . . . . . . . . . . . 8
1.7 Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.8 Detonation Velocity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.9 Detonation Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.10 Volatility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.11 Vapor Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.11.1 Knudsen Effusion Method . . . . . . . . . . . . . . . . . . . . . . . 14
1.11.2 Thermogravimetry Method for Vapor Pressure
Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.11.3 Comparative Method . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.11.4 Vapor Pressure by Gas Chromatography Head Space
Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.12 Strength, Performance, and Brisance of Explosives . . . . . . . . . . 20
1.12.1 Strength Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.12.2 Performance Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.12.3 Brisance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.13 Critical Diameter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
1.14 Chemical Decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.15 Deflagration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

vii
viii Contents

1.16 Detonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.17 Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.17.1 Shock Wave Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
1.17.2 Mechanical Impulses . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
1.17.3 Friction Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
1.17.4 ABL Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1.17.5 BAM Friction Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1.18 Electrostatic Discharge (ESD) Test . . . . . . . . . . . . . . . . . . . . . . . 38
1.18.1 Gap Tests-Shock Wave . . . . . . . . . . . . . . . . . . . . . . . . . 38
1.18.2 Thermal Sensitivity Test . . . . . . . . . . . . . . . . . . . . . . . . 39
1.19 Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20) . . . . . . . . . . . . . . . . 59
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
2.2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
2.2.1 Characterization of Polymorphs of CL-20 . . . . . . . . . . . 64
2.2.2 Diffraction Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.3 Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2.4 Physical and Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.4.1 Vapor Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.4.2 Heat Capacity and Entropy Data . . . . . . . . . . . . . . . . . . 73
2.5 Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.6 Decomposition and Destruction . . . . . . . . . . . . . . . . . . . . . . . . . 74
2.7 Hydrolysis of Hexanitrohexaazaisowurtzitane . . . . . . . . . . . . . . . 76
2.8 Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
2.9 Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.10 Formulations and Detonation Characteristics . . . . . . . . . . . . . . . 82
2.11 CL-20 Based Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
2.12 Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
2.13 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene) . . . . . . . . . . . . . . . . . . . . . 101
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
3.3 Crystallization/Recrystallization . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.4 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
3.4.1 Polymorphic Forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
3.4.2 Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
3.5 Thermophysical Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
3.5.1 Solubility of FOX-7 . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
3.6 Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
3.7 Decomposition and Destruction . . . . . . . . . . . . . . . . . . . . . . . . . 123
Contents ix

3.8 Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124

3.9 Detonation Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
3.10 Cylinder Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
3.11 FOX-7 Formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
3.12 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
4 2,4 Dinitroanisole (DNAN) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
4.2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
4.3 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
4.3.1 Spectral Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
4.4 Physical and Chemical Properties . . . . . . . . . . . . . . . . . . . . . . . . 147
4.4.1 Solubility in Various Media . . . . . . . . . . . . . . . . . . . . . 147
4.4.2 Vapor Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
4.5 Detonation Characteristics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
4.6 Decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
4.7 Biodegradation/Biotransformations . . . . . . . . . . . . . . . . . . . . . . . 152
4.8 Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
4.9 Formulation Using DNAN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO) . . . . . . . . . . . . 163
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
5.2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
5.3 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
5.4 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
5.4.1 Heat Capacity and Entropy . . . . . . . . . . . . . . . . . . . . . . 168
5.4.2 Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
5.4.3 Vapor Pressure of NTO . . . . . . . . . . . . . . . . . . . . . . . . . 174
5.5 Decomposition and Destruction . . . . . . . . . . . . . . . . . . . . . . . . . 175
5.5.1 Laser Induced Decomposition . . . . . . . . . . . . . . . . . . . . 178
5.6 Nitration Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
5.7 Decomposition Kinetic Rates . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
5.8 Photocatalytic Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
5.9 Biodegradation of NTO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
5.10 Spectroscopic Analysis of NTO . . . . . . . . . . . . . . . . . . . . . . . . . 182
5.11 Detonation Characteristics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
5.11.1 Vacuum Stability Test . . . . . . . . . . . . . . . . . . . . . . . . . . 183
5.11.2 Impact Sensitiveness . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
5.11.3 Friction Sensitivity Tests . . . . . . . . . . . . . . . . . . . . . . . . 185
5.11.4 Electrostatic Discharge Sensitivity . . . . . . . . . . . . . . . . . 185
5.11.5 Thermal Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
5.11.6 Shock Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
x Contents

5.12 Detonation Velocity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186

5.13 Detonation Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
5.14 Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
5.15 Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
5.16 Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
5.17 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
6 Hexanitrostilbene (HNS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
6.2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
6.2.1 UK Laboratory HNS Process. . . . . . . . . . . . . . . . . . . . . 216
6.2.2 Kompolthy Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
6.3 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
6.4 Polymorphism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
6.5 Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
6.6 Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
7 N-Methy-4-Nitroaniline (MNA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
7.2 Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
7.3 Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
7.4 Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
7.5 Spectrum. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
8 1-Azido-2-Nitro-2-Azapropane (ANAP) . . . . . . . . . . . . . . . . . . . . . . . 243
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
8.2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB) . . . . . . . . . . . . . . . 247
9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
9.2 Synthesis and Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
9.3 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
9.4 Crystal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
9.5 Physical and Thermodynamic Properties. . . . . . . . . . . . . . . . . . . 254
9.6 Thermodynamic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
9.7 Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
9.8 Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
9.9 TATB Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
9.10 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
Contents xi

10 Triacetone Triperoxide (TATP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273

10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
10.2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
10.3 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
10.4 Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
10.5 Properties of TATP. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
10.6 TATP Decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
10.7 Formulations and Detonation Characteristics . . . . . . . . . . . . . . . 280
10.8 Destruction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
11 1,3,3-Trinitroazetidine (TNAZ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
11.2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
11.3 Phase Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
11.4 Thermodynamic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
11.5 Thermal Decomposition/Dissociation . . . . . . . . . . . . . . . . . . . . . 298
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
Appendix 1: Unit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
Appendix 2: Munitions and Dual-Use Items . . . . . . . . . . . . . . . . . . . . . . . 329
Appendix 3: Chemical Weapons Convention (CWC) . . . . . . . . . . . . . . . . 337
Appendix 4: Chemical Weapons Convention Bulletin . . . . . . . . . . . . . . . 349
Appendix 5: CAS RN Reportable Chemicals . . . . . . . . . . . . . . . . . . . . . . 359
Appendix 6: Material Safety Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
Chapter 1
Properties of Insensitive Energetic
Materials and Their Measurement

Abstract The development of insensitive energetic materials with stability, high

performance, reliability, safety, and low toxicity requires measurement and pre-
diction of thermophysical and thermochemical properties. The measurement and
estimation of properties such as the enthalpy of formation, density, detonation
velocity, detonation pressure and sensitivity are used to screen potential energetic
candidates. Experimental data are also needed to test prediction methods and
molecular models. This chapter outlines experimental methods to measure some of
the important properties. Different methods of determining a property and the
theory associated have been outlined.

1.1 Introduction

There are a number of chemical and physical properties that are important to
energetic materials [EM] for their characterization and comparison with each other,
and a set of different properties particularly important to insensitive energetic
materials [IEM]. Energetic materials by definition are high energy materials that
detonate on shock, pressure, heat, and/or combustion. EM falls into three cate-
gories: propellants, explosives and pyrotechnics. A particular chemical may fall into
one or the other category or more than one category. Explosives are further clas-
sified as primary and secondary explosives based on their susceptibility to initiation.
Primary explosives are highly susceptible to detonation whereas secondary
explosives are used as main charges. Secondary explosives can be further divided
into two categories: melt-cast and plastic-bonded.
The design of future IEM and EM materials requires a sound knowledge of the
chemistry and properties of the existing materials, since most of the new materials
will be developed using the template of the existing materials. For instance, as the
name itself suggests, energetic materials possess very high energy, and this can be
made available if the material has a high enthalpy of formation. The use of existing
IEM and EM materials to design and build weapons systems also requires a sound
knowledge of several properties to achieve better performance, reduced

© US Government (outside the USA) 2018 1

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7_1
2 1 Properties of Insensitive Energetic Materials …

vulnerability during transportation, reduced environmental impact in its manufac-

ture and disposal, better shelf life, and their loading and packing into weapons
delivery systems. It is therefore of interest to know the important physical and
chemical properties of energetic materials, their experimental determination and
prediction.
The main user of most of the explosives in the U.S. is the Department of Defense
(DoD), which has developed standards and protocols for the measurement of var-
ious properties of explosives to qualify for their use by all departments and agencies
under the DoD. These standards are given in “Department of Defense Test method
Standard: Safety and Performance Tests for the Qualification of Explosives (High
Explosives, Propellants, and Pyrotechnics), MIL-STD-1751A, 11 December 2001,
Superseding MIL-STD-1751 (USAF), 20 August 1982 [1]. These qualifying
properties and test procedures are also given in the implementing document for
NATO STANAG 4170, “Principles and Methodology for the Qualification of
Explosive Materials for Military Use,” which has associated with it NATO Allied
Ordnance Publication #7 (AOP-7), “Manual of Tests for the Qualification of
Explosive Materials for Military Use” [2]. Certain test methods also implement
NATO STANAGsAs. The test methods are arranged in groups according to the
qualification data category. The numbering protocols for the groups are given in
Table 1.1.
It may be noted that test groups under 1050, 1080, and 1110 are deleted from the
current version.

Table 1.1 Numerical index Test group Qualification data category

of test methods
(MIL-STD-1751A) 1010 Impact sensitivity
1020 Friction sensitivity
1030 Electrostatic discharge sensitivity
1040 Explosive shock sensitivity
1060 Stability (Constant Temperature)
1070 Stability (Variable Temperature)
1090 Critical diameter
1100 Detonation velocity
1120 Flash point
1130 Detonability of fuel-air explosives
1140 Minimum pressure for vapor ignition
1150 Ignition sensitivity
1.2 Experimental Methods 3

1.2 Experimental Methods

The definition of some of these properties and their experimental determination are
discussed in the following sections. The properties of interest are:
• Melting point (ASTM E794)
• Boiling point (ASTM D7169–11)
• Critical Properties
• Density (ASTM A572/A572 M–13a)
• Dipole moment (ASTM D3132-84(1996))
• Enthalpy of vaporization (ASTM E2071–00(2010))
• Enthalpy of formation ASTM D4612–08, ASTM D4809–13
• Solubility (ASTM E1148–02(2008), ASTM D1696-95(2011), ASTM D1110–
84(2013), ASTM D7553–10
• Detonation velocity ASTM D2541–93(2001), ASTM D2541–93, ASTM
D2539–93
• Detonation pressure
• Volatility and vapor pressure ASTM D5842–04(2009), ASTM D1837–11,
ASTM D323–08
• Brisance UNE 31023:1994,
• Volume of products of explosion ASTM E1248–90(2009), ASTM E1226–12a
• Power, performance, and strength, ASTM D149–09(2013)
• Sensitivity and sensitivity to initiation ASTM D6600–00
• Decomposition ASTM E1641–13, ASTM E2550–11, ASTM D7876–13,
ASTM D2879–10
• Detonation D-4814 (previously D-439), ASTM D-439/D-4814/EN228
• Toxicity (ASTM E1706)

1.3 Melting Point

The temperature at which a solid is in equilibrium with its liquid phase is called the
melting point. Classical techniques can be used to determine melting point except
for those materials which are highly sensitive, such as triacetone triperoxide
(TATP). A common method for determining the melting point is the capillary tube
method. In this method, fine powder of the compound is packed into the capillary
tube to a depth of 1–2 mm. The capillary tube containing the sample is heated
slowly, and the temperature at which the sample starts melting is noted. Often
times, the melting of the compound is spotted visually. Several devices are avail-
able to measure melting points. These are: Thiele tube, Thomas-Hoover apparatus,
and Mel-Temp system.
4 1 Properties of Insensitive Energetic Materials …

1.3.1 Thiele Tube

A Thiele tube for measurement of melting point is shown in Fig. 1.1. A silicon or
mineral oil is used in the Thiele tube as the heat transfer medium and to maintain a
constant temperature. The tube is filled to the base of the neck with oil. The
capillary tube containing the sample is attached to a thermometer so that an accurate
temperature measurement is obtained. The side arm of the Thiele tube is heated at a
slow rate. The melting point is determined through visual observation. The Thiele
tube can be used to measure melting point up to a temperature of 250 °C.

1.3.2 Thomas–Hoover Uni-Melt Device

The Thomas–Hoover Uni-Melt device, shown in Fig. 1.2, uses silicone oil as the
heating medium. With the choice of a proper type of silicon oil, temperatures up to
300 °C are possible. The oil is heated electrically and stirred continuously to
maintain a constant temperature. Depending on the design of the system, melting
point of 5–7 samples can be obtained simultaneously.

Thermometer

Sample packed
capillary tube

Oil
Filled
Thiele
tube

Fig. 1.1 A Thiele tube for measurement of melting point [3]

1.3 Melting Point 5

Fig. 1.2 A Thomas–Hoover Uni-Melt apparatus for melting point measurement [4, 5]

1.3.3 Mel-Temp Apparatus

The Mel-Temp apparatus for measurement of melting point is shown in Fig. 1.3.
The uniform heating of the sample is accomplished using an aluminum block that is
heated electrically. Several samples can be placed inside the aluminum block,
which can be heated up to a temperature of 400 °C. The melting point is determined
visually.
6 1 Properties of Insensitive Energetic Materials …

Fig. 1.3 A Mel-Temp

apparatus for melting point
measurement [6]

1.4 DSC/DTA Method

As described in the ASTM Standard E794-06, “The test method involves heating
(or cooling) a test specimen at a controlled rate in a controlled environment through
the region of fusion (or crystallization). The difference in heat flow (for DSC) or
temperature (for DTA) between the test material and a reference material due to
energy changes is continuously monitored and recorded. A transition is marked by
absorption (or release) of energy by the specimen resulting in a corresponding
endothermic (or exothermic) peak in the heating (or cooling) curve.” The operating
temperature range is −120 to 600 °C for DSC and 25–1500 °C for DTA.
Typical DSC curves for RDX and FX300 are shown in Fig. 1.4. The DSC curve for
RDX, showed two sharp peaks. The peak at 205 °C indicates the phase change of
RDX from solid to liquid, and can be designated as the melting point of RDX. The
positive peak suggests an endothermic reaction. The negative (exothermic) peak at
240 °C is attributed to the decomposition of RDX. The DSC can be an important
tool for assessment of the purity of a sample. As shown in Fig. 1.4b, The DSC
curve (Fig. 1.4) for FX-300 that is a mixture of RDX, nitrocellulose and carbon,
showed that the melting point of RDX shifted to 202 °C due to the presence of
other compounds. Also, the decomposition peak shifted to 255 °C. Figure 1.5
shows a very strong DTA peat at 260 °C due to the decomposition of RDX.
The TGA data indicated that almost 96% RDX decomposed in this temperature
range.
1.4 DSC/DTA Method 7

Fig. 1.4 DSC curves for

RDX and FX-300. A 2 mg
sample was used for both
compounds. (Hussain G,
Rees GJ (1995) Thermal
decomposition of RDX and
mixtures [7]

Enro
Exo

Temperature, oC

Fig. 1.5 DTA peat at 260 °C

due to the decomposition of
RDX [7]
8 1 Properties of Insensitive Energetic Materials …

1.5 Boiling Point

Most of the explosives decompose well before reaching the boiling point temper-
ature. Therefore, the traditional method and apparatus cannot be used and as a result
the boiling point of an explosive is not reported.

1.6 Critical Temperature, Volume, and Temperature

The direct determination of critical pressure, volume, and temperature of an

explosive is challenging. Generally, a thermodynamic model involving the equation
of state is used to estimate these values [8].

1.7 Density

The density of an explosive is expressed in a traditional manner: the mass of the

explosive per unit volume (kg/m3). Similarly, specific gravity is expressed as the
ratio of the density of the explosive to the density of water under standard con-
ditions. The specific gravity of commercial explosives ranges from 600 to
1700 kg/m3.
For explosive materials, two other densities play an important role in their
characterization:
• Package Density
• Loading Density
The package density refers to the density of an explosive as packaged in a
cartridge or tube at the mixing plant. The unit for package density is still mass per
unit volume (kg/m3).
The loading density (LD) is defined as the mass of the explosive per unit length
of the borehole at a specified borehole diameter. Therefore, LD can be mathe-
matically expressed as follows:

W
LD ¼ ð1:1Þ
L

where, W is the mass of the explosive and L is the length of the loaded hole. For free
running explosives, the unit used for loading density is often the pounds of
explosives per foot of charge length in a given size borehole [or borehole size].
High loading density can reduce sensitivity by making the mass more resistant to
internal friction. If density is increased to the extent that individual crystals are
1.7 Density 9

crushed, the explosive will become more sensitive. Denser explosives generally
provide higher detonation velocities and pressures.

1.8 Detonation Velocity

The detonation velocity is the rate of propagation of the detonation wave through
the mass of the explosive. The detonation velocity is considered to be the single
most important property for evaluating an explosive. It may be measured either
under confined or unconfined conditions. Although the measurement of the deto-
nation velocity under confined conditions is more representative of the explosion,
most manufacturers report the detonation velocity under unconfined conditions. The
detonation velocity of an explosive is dependent on the density, chemical com-
position, particle size, charge diameter, and degree of confinement. Unconfined
velocities are generally 70–80% of confined velocities.
The determination of detonation velocity is based on measuring the time
required for the detonation wave to travel between two designated points (i.e., a
certain distance). The method most often used is known as the Dautriche test
method [9]. The basic arrangement of the Dautriche test system is shown in
Fig. 1.6.
The explosive sample is placed in a confinement tube, which may or may not be
enclosed in a steel tube. Two blasting cups, one at each end, are incorporated to
mark the length of the column to be detonated. A detonation cord of known
detonation velocity is connected to these blasting cups and passed across a lead
plate as shown in Fig. 1.6. The center of the cord is marked in the lead plate. The
detonation of the explosive is initiated by the detonator or booster. The detonation
wave from this primary blast starts another detonation wave at the blast cup A,
which starts travelling through the detonation cord. Another detonation wave starts

Fig. 1.6 Basic arrangements of the Dautriche test system [9]

10 1 Properties of Insensitive Energetic Materials …

at the second blast cup B as soon as the primary wave hits it. Two detonation waves
colloids at some point on the lead plate and creates a notch. The distance between
the center of the cord and this notch, a, is measured and is used to determine the
detonation velocity using the following equation:
m
Dsampie ¼ Dcord ð1:2Þ
2a

where D sample is the detonation velocity of the test explosive, D cord is the
detonation velocity of the detonation cord, which is known, m is the length of the
charge or confinement tube (which is measured after placing the explosive in the
tube), and a is defined earlier. The derivation of Eq. 1.2 has been given by several
authors [10, 11]. The accuracy of the detonation velocity measured by the Dautriche
method is around 4–5%.
Recently, several new methods have been proposed for more accurate mea-
surement of the detonation velocity. These methods may be categorized into two
classes: Electrical and Optical methods. These methods are discussed in details by
several authors [12–14].
In the electrical method, different types of velocity probes are combined with an
electronic counter or oscilloscope [15, 16]. The optical methods involve the use of
various types of high speed cameras. [17–22].

1.9 Detonation Pressure

The detonation pressure is not measured directly; rather it is calculated from the
detonation velocity. Detonation pressure is a function of the detonation velocity and
density of an explosive. The National Park Services (NPS) developed a nomograph
to find the approximate detonation pressure of an explosive if the detonation
velocity and specific gravity are known [23]. The monograph is presented in
Fig. 1.7.
Agrawal [24] presented the following equation for calculation of the detonation
pressure (PDP):

qD2
PDP ¼ ð1:3Þ
ð k þ 1Þ

where q is the density of the explosive, D is the detonation velocity, and k is a

constant, called the polytropic exponent of detonation products. The value of k is
approximately 3 for high explosives.
Agrawal [24] also described a more accurate method to experimentally deter-
mine the detonation pressure. The method is based on impedance mismatch tech-
nique. In this method, the detonation shock wave velocity in water is measured
following detonation of the test explosive that is in contact with water. The equation
1.9 Detonation Pressure 11

Fig. 1.7 A monograph for

calculation of detonation
pressure from known
detonation velocity and
specific gravity of the
explosive

of state for water should be known. The equation for calculating the detonation
pressure is given below:

PW ðqW USW þ qX DÞ
PDp ¼ ð1:4Þ
2qW UPW

where,
PW transmitted shock pressure in water = qw USW UPW
qW density of water
USW transmitted shock velocity in water
UPW particle velocity in water
qX density of explosive
D detonation velocity of explosive
USW is obtained directly from the experimental measurement using the
Aquarium technique. UPW is related to USW by the following expression

USW  1:15
UPW ¼ ð1:5Þ
1:85

The basic experimental set-up for measurement of USW using Aquarium tech-
nique is shown in Fig. 1.8. In this method, the sample explosive charge is immersed
in distilled water. The detonator and the booster are placed outside the water
container, which may be made of glass. Following detonation of the charge, the
shock wave, travels through the water changing its optical transparency. A high
12 1 Properties of Insensitive Energetic Materials …

Fig. 1.8 Aquarium test [25]

speed camera located above the water surface records the propagation of the shock
wave front as a function of time through water. A Plexiglas block may be replaced
for water, which is also optically transparent (See Fig. 1.9).
A number of other techniques have been suggested to experimentally determine
various detonation parameters that are essential for calculation of the detonation

Fig. 1.9 Plexiglas test

method [25]
1.9 Detonation Pressure 13

pressure. These techniques include: Laser technique, Electromagnetic particle velocity

gauge technique, Laser interferometry technique and Flash X-ray photography
method. Several pressure gauges were also developed for direct measurement of
detonation pressure, including Manganin pressure gauge and polyvinylfluoride-based
pressure gauge [26–45].

1.10 Volatility

Volatility of a substance may be defined as the loss of mass per unit time at a certain
temperature. For military explosives, researchers generally agreed on the following
description: “Volatility, or the readiness with which a substance vaporizes, is an
undesirable characteristic in military explosives. Explosives must be no more than
slightly volatile at the temperature at which they are loaded or at their highest
storage temperature. Excessive volatility often results in the development of pres-
sure within rounds of ammunition and separation of mixtures into their constituents.
Stability is the ability of an explosive to stand up under storage conditions without
deteriorating. Volatility affects the chemical composition of the explosive such that
a marked reduction in stability may occur, which results in an increase in the danger
of handling. Maximum allowable volatility is 2 mL of gas evolved in 48 h”.
Although a standard method is not specified for the volatility measurement, a
Thermo Gravimetric Analyzer (TGA) may be used to determine the volatility of
explosives. From the mass loss measurement from the TGA at a certain temperature
and with the knowledge of density, the volume of the gas may be calculated at a
specified temperature.

1.11 Vapor Pressure

Methods for measuring vapor pressure can be divided into direct methods and
indirect methods. In a direct method, the actual pressure of the pure vapor in
equilibrium with liquid or solid is determined by using pressure gauges. The
accuracy of the data will depend on the choice of the pressure gauge, sample purity,
and assurance that the equilibrium condition has been achieved. In the indirect
methods, the vapor pressure is calculated from other experimentally measured
values or properties of the substances, which must have a theoretical relationship to
the vapor pressure. The indirect methods are useful for low volatile substances and
compounds that decompose before its boiling point.
14 1 Properties of Insensitive Energetic Materials …

1.11.1 Knudsen Effusion Method

One of the most used indirect-methods for the vapor pressure measurement of
low-volatile substances is the Knudsen effusion method [46, 47]. In this method, a
sample is placed in a small container with a pin-hole. The container with the sample
is placed in a high vacuum and heated to a desired temperature. It is assumed that an
equilibrium vapor pressure is established inside the container and molecules leave
the container through pin-hole into the vacuum at a constant rate. If it is assumed
that the mean free path (k) of vapor molecules is long compared to the radius of the
hole, the rate of molecules escaping through the hole would equal the rate at which
molecules would strike an area of wall equal to the hole-area if the hole were
closed. This assumption is valid for substances with a low vapor pressure which
ensures a long mean free path. The derivation of an expression for calculation of
vapor pressure from the Knudsen effusion method is given below.
The frequency of collisions of gas molecules with the wall per unit wall area is
given by:

n
c
Zwall ¼ ð1:6Þ
4

where n is the number density and
c is the average speed of the molecule. (The
number density is the ratio of the total number of gas molecules to the total gas
volume).
The ideal gas law (using the number density and the number of particles) can be
written as:

P ¼ nkT ð1:7Þ

where, k is Boltzmann’s constant. The average speed,
c, is given by:

rffiffiffiffiffiffiffiffi
8kT

c ¼ ð1:8Þ
pm

where m is the molecular mass.

If a hole of area is A, and assuming that the hole does not change the velocity
and density distribution in the gas, the number of molecules (N) entering the hole in
time h can be expressed as:

N ¼ Zwall Ah ð1:9Þ

Assuming that the same number of molecules is lost through the hole to the
vacuum space permanently, the mass lost can be expressed as:
1.11 Vapor Pressure 15

Table 1.2 Clausing factors l/r f

for cylindrical holes
0.0 1.00
0.1 0.952399
0.2 0.909215
0.5 0.801271

mass lost; ðgÞ ¼ mN ¼ m Z wall Ah ð1:10Þ

Substitution of Eqs. 1.6 and 1.7 through 1.10 gives the following expression for
vapor pressure:
rffiffiffiffiffiffiffiffiffiffiffiffi rffiffiffiffiffiffiffiffiffiffiffiffiffi
g 2 pkT g 2 pRT
P¼ ¼ ð1:11Þ
Ah m Ah M

where R is the universal gas constant and M is the molar mass.

Equation 1.11 is valid for ideal situation, i.e., the pin-hole in the container has
the zero length, which is not practical. Therefore, a molecule may enter the hole,
strike the hole wall, and go back into the vapor space inside the container. In order
to this into account, the effective area of the hole is multiplied by a correction factor,
f, called the Clausing factor and depends on the ratio of hole length to hole radius.
Iczkowski et al. [48] give the following Clausing factors for cylindrical holes
(Table 1.2).
The Clausing factor can also be approximated by:
   2
1 1
f ¼ 1  0:5 þ 0:2 ð1:12Þ
r r

where, l is the lid thickness. A schematic diagram of the apparatus is shown in

Fig. 1.10.
The system is evacuated by a turbomolecular (turbo) pump and has a base
pressure of 8  10−9 torr as read by an ion gauge. The apparatus is constructed of
stainless steel with the exception of the lower half of the tube containing the
Knudsen cell, which is made of copper to aid in heat transfer between the cell and
the constant temperature bath. The temperature bath is filled with a light silicon oil
and the temperature of the bath can be varied from 323–423 K. The apparatus was
calibrated using benzoic acid as a standard.

1.11.2 Thermogravimetry Method for Vapor Pressure

Determination

Thermogravimetry (TG) method is an indirect method for determination of the

vapor pressure. In this method, an inert gas flows over the sample with known
16 1 Properties of Insensitive Energetic Materials …

Fig. 1.10 Knudsen effusion methods for measurement of vapor pressure

surface area under a constant temperature. The free surface area of samples can be
controlled and known by melting the sample in a 12.5 mm aluminum sample cup
for the TG study. The vapor pressure is calculated from the mass loss at a constant
rate using the Langmuir equation [49]. It is noted that all these vapor pressure
calculations assumed that vapor pressure data obey the Clapeyron equation and
required reliable vapor pressure data of a standard material.
Langmuir Equation
In 1913 Langmuir developed the following equation for the vaporization rate of
tungsten as a function of temperature and vapor pressure. The Langmuir equation is
given by:
1.11 Vapor Pressure 17

rffiffiffiffiffiffiffiffiffiffiffiffiffi
dm M
¼ pa ð1:13Þ
dt 2 p RT

where

dm
dt = rate of mass loss per unit area or sublimation rate per unit area
p vapor pressure
a vaporization coefficient
M molecular weight
R gas constant
T absolute temperature

The Langmuir equation can be rearranged as follows for determination of a:

" rffiffiffiffiffi#
dm T
p¼  ½2pa ð1:14Þ
dt M

Equation 1.14 may be rewritten as follows:

p¼vk ð1:15Þ

or,

‘n p ¼ ‘n v þ ‘n k ð1:16Þ
qffiffiffi
where, v ¼ dm
dt
T
M, and k ¼ 2 p a
Price [50] plotted known vapor pressure values of several standard materials
(benzoic acid, benzophenone, phenanthrene, and acetamide) against their subli-
mation rates from a TG analysis in a log-log scale. A straight line resulted (See
Fig. 1.11) suggesting that k is a universal constant; independent of the material.
Regression analysis for p and evaporation rate.
Gückel et al. [52–55] proposed the following relationship between the rate of
mass loss and the vapor pressure of the substance.
 
dm
‘n p ¼ C ‘n þD ð1:17Þ
dt

where constants C and D are calculated from the non-linear regression. They used
twelve standard materials with their known vapor pressure data and their evapo-
ration rate (obtained by gas chromatography experiment) and a straight line was
reported when dm/dt was plotted against p in a log-log scale to determine universal
constants C and D.
18 1 Properties of Insensitive Energetic Materials …

Fig. 1.11 Calibration curve

made by Duncan and Price
[51] showing a linear
relationship between known
vapor pressure (p) of benzoic
acid (filled diamond),
benzophenone (filled
triangle), phenanthrene (filled
square) and acetamide (filled
circle) and their sublimation
rate per unit area (v) from the
gas chromatography
experiment

1.11.3 Comparative Method

Phang et al. [56] modified the TG method for the vapor pressure estimation using
only one substance of known vapor pressure. Thus, the need for the calibration
curve of p vs. v was avoided. The Langmuir equation was rearranged as follows for
two substances:
0 1
" rffiffiffiffiffi#pffiffiffiffiffiffiffiffiffi
B dm=dt C dm T 2 pR
p ¼ @h qffiffiffiffiffiffiffiffiffiiA ¼ ¼v  k ð1:18Þ
a 2 pRT
M dt M a

The Langmuir equations for a reference material or a standard material

(subscript R) and for the sample investigated (subscript S) at the same temper-
ature (T1) can be expressed as:
   
dm pffiffiffiffiffi 1 1=2
T1 ¼ aMR pR ð1:19Þ
dt R 2pR
   
dm pffiffiffiffiffi 1 1=2
T1 ¼ aMS pS ð1:20Þ
dt S 2pR

Since a is a constant value depending on the TG system and its operating

conditions, PS can be simply evaluated from a pair of evaporation rate and vapor
pressure data of the reference material as given below:
 1=2  
MR ðdm=dtÞs
pS ¼ pR ð1:21Þ
MS ðdm=dtÞR
1.11 Vapor Pressure 19

1.11.4 Vapor Pressure by Gas Chromatography Head

Space Method

Head space method involves sealing a small amount of sample (about 10 mL) in a
head space crimp top flat bottom vials fitted with septa to draw the sample using a
syringe for gas chromatography analysis. The sample vials are allowed to equili-
brate in an oven at various temperatures. A gas chromatograph oven may be used
for this purpose. Following equilibration of the sample, the vapor that is in equi-
librium with the liquid is drawn by the gas tight syringe and injected onto a gas
chromatograph equipped with an appropriate column and detector. A calibration
curve (peak area versus mg of the sample) should be prepared to determine the
amount of sample in the vapor phase. The volume of gas was withdrawn through
the septum of the equilibrated headspace vials is injected into the gas chro-
matograph and peak area is obtained. It is assumed that the vapor of the sample
compound obeys the ideal gas law ½pV ¼ ðm=M ÞRT , the vapor pressure is
calculated.
Vapor pressures of a low volatile substance, such as an explosive, can be
determined from the retention time of that substance from a gas chromatography
GC column, operating under isothermal conditions, if the retention time of several
substances of known vapor pressures that have similar chemical structure (a
homologous series) is available using the same gas chromatography column under
the same isothermal conditions. The mathematical basis for this method is described
below.
Jensen and Schall [57] noted that a relationship exists between the retention
volume (VR) and the retention time (tR) for two substances eluted on a GC column
under the same operating conditions:

VR1 tR1
¼ ð1:22Þ
VR2 tR2

The retention volume may be related to the vapor pressure by the following
equation:

VR1 p02
¼ ð1:23Þ
VR2 p01

Substitution of Eq. 1.22 into Eq. 1.23 provides a relationship between the vapor
pressure and retention time.

tR1 p02
¼ ð1:24Þ
tR2 p01

Equation 1.24 can be used to calculate the vapor pressure of Compound 2 if the
retention times are known, as well as the vapor pressure of Compound 1. However,
20 1 Properties of Insensitive Energetic Materials …

a large error may result if the vapor pressure of Compound 1 is not very accurate.
The accuracy may be increased if the vapor pressure data for several other com-
pounds in the homologous series are known along with their latent heats. The
Clausius-Clapeyron [58, 59] equation provides a relationship between the latent
heat and vapor pressure of a compound.

dp0 L
¼ ð1:25Þ
dT ðV  vÞT

where,
T absolute temperature,
L latent heat per mole,
V vapor pressure per mole,
v liquid volume per mole
Since V is a function of temperature and pressure, a relationship among V, p and
T is necessary for integration of Eq. 1.25. Assuming that the vapor obeys the perfect
gas law and v is negligible compared to V, then the following expression results:

dp0 Lp0
¼ ð1:26Þ
dT RT 2

Integration of Eq. 1.26 for compound 1 and 2, followed by some rearrangement,

the following expression is obtained:

L1
ln p01 ¼ ln p02 þ C ð1:27Þ
L2

Using Eqs. 1.24 and 1.27 can be expressed in terms of retention time as follows:
   
tR1 L1
ln ¼ 1 ln p2 þ C ð1:28Þ
tR2 L2

For a homologous series, the ratio L1/L2 may be assumed to be a constant.

Therefore, a plot of ‘n (tr1/tr2) vs. ‘n p2 should provide a straight line, from which
the vapor pressure of the unknown compound can be obtained if its retention time
under the same operating conditions is known.

1.12 Strength, Performance, and Brisance of Explosives

Brisance is “the shattering or crushing effect of an explosive measurable by the

crushing of sand or the compression of a metal cylinder and dependent upon the
rate of detonation and other factors”. Several tests are performed to determine the
1.12 Strength, Performance, and Brisance of Explosives 21

strength, performance, and brisance of explosives. Isidor Trauzl was developed by

1885 [60]. These tests provide the information for an explosive regarding its ability
to accomplish the task that is intended in the way of energy delivery.

1.12.1 Strength Tests

For determination of the strength of explosives, their performance and brisance, the
following experimental methods are used [61]:
• Lead Block Test (also known as Trauzel Test) [62–92]
• Underwater Explosion Test [93–105]
• Ballistic motor test [106–121]

1.12.1.1 Lead Block Test

The Trauzl or lead block test is conducted to determine the strength of the
explosive. Following detonation of the explosive charge, the volume increase of the
cavity into which the detonation is carried out is determined. The basic configu-
ration of the lead block is shown in Fig. 1.12.
The explosive charge, which may contain either 10 g or 10 cm3 explosives (A
constant volume of 10 cm3 is recommended by the European Commission for the
Standardization of the Tests of Explosives), is placed inside the cavity of the block
together with the detonator. The cavity is stemmed by 500 lm diameter dry sand.
The explosive charge is initiated and the expanded volume is determined. The
strength of the explosive can be expressed as work done relative to a reference
explosive and is expressed by the following expression:

Fig. 1.12 Trauzl or lead block test configuration [122]

22 1 Properties of Insensitive Energetic Materials …

Ax MAmmonit6
¼ ð1:29Þ
AAmmonit6 Mx

where, Ax and AAmmonit-6 are the work done by the test explosive and the reference
explosive, respectively, and Mx and MAmmonit-6 are their masses, respectively.

1.12.1.2 Underwater Explosion Tests

This test method is used if the charge mass of less than 10 g has to be employed in
the test. The strength of the explosive is determined from the energy release during
underwater explosion. Generally, shock wave or bubble energy is measured. As
shown in Fig. 1.13, the charge is placed inside a water-filled tank. A pressure gauge
and a triggering gauge are also placed inside the tank at a predetermined distance
from the charge.
The total energy released from explosion (ET) is calculated as a sum of shock
wave (ES) and bubble energy (EB) and can be written as:

ET ¼ ES þ EB ð1:30Þ

The shock wave energy can be calculated from the following equation:
Z
4pR2
Es ¼ k1 kC p2 dt ð1:31Þ
MB vW qW

where vW is the velocity of sound in water, [specify T and P] qW is the density of

water, MB is the mass of the charge, k1 is the amplification factor, and kc is the
constant of integration.

Fig. 1.13 Arrangement for

the underwater explosion test
to determine the strength of an
explosive [123]
1.12 Strength, Performance, and Brisance of Explosives 23

Fig. 1.14 Arrangement for

ballistic motor test to
determine the strength of the
explosive [124]

The bubble energy is obtained from the following expression:

T3
EB ¼ 2:5 ð3:28H þ 33:95Þ2:5 ð1:32Þ
MR

and H is the depth of the explosive charge (expressed in meters).

1.12.1.3 Ballistic Motor Test

As shown in Fig. 1.14, a weight or a projectile is suspended from a pendulum axis. The
explosive charge of a given mass in detonated in the motor cavity that enclosed the
projectile. The maximum swing of the mortar is recorded following ejection of the
projectile. The strength of the explosive is then calculated from the following expression:
24 1 Properties of Insensitive Energetic Materials …

AX 1  cos a
E¼ ¼  100 ð1:33Þ
AR 1  cos a0

where A is the work done by the test sample (X) and the reference explosive (R),
respectively. A is calculated from the experimental data using following equation:
 
MM
A ¼ MM Lð1  cos aÞ 1 þ ð1:34Þ
MP

where MM and MP are the mass of the mortar and the projectile, respectively. L is
the distance from the center of mass to the suspension axis, and a is the angle of the
mortar swing. Figure numbers for the figure below.

1.12.2 Performance Tests

The most common tests for determination of performance of an explosive are

double pipe and cylinder expansion tests.

1.12.2.1 Double Pipe Test [125, 126]

This test is used to determine the performance of the explosive under borehole
conditions. Standard cartridges of different length of the explosive charges are
placed inside a pipe that is equivalent to a borehole. The pipe loaded with the
charge is placed on the top of a witness steel pipe. A heavy anvil supports the
assembly as shown in Fig. 1.15a. Following the detonation, the dent on the witness
pipe is determined as shown in Fig. 1.15b. A similar test is performed for a known
explosive and the relative performance is determined.

1.12.2.2 Cylinder Expansion Test

The cylinder expansion test is performed to determine the Gurney energy, EG,
which is generally used to characterize the ability of an explosive to accelerate
metals, and µ is the ratio between the masses of the cylinder and the explosive
[127–175].
The Gurney energy is given by charge:
 Z 
1 1
EG ¼ lvm þ
2
vg dV ð1:35Þ
2 2

vm is the velocity of the wall material and vg is the velocity of the detonation
materials. If it is assumed that the velocity of the detonation materials increase
linearly in the expansion direction vg may be expressed as:
1.12 Strength, Performance, and Brisance of Explosives 25

Fig. 1.15 Cross-sectional

view of the arrangement of
the double pipe test (a), and
the determination of the dent
of the witness plate following
experimentation [125, 126]

vm r
vg ¼ ð1:36Þ
rm

where r is the radius of the cylinder at any given time and rm is the cylinder radius
initially. Integration of Eq. 1.35 using Eq. 1.36 provides the following expression
for Gurney energy.
 
1 1 2
EG ¼ lþ v ð1:37Þ
2 2 m

The wall velocity may be expressed by:

sffiffiffiffiffiffiffiffiffiffiffiffiffi
D 1
vm ¼ ð1:38Þ
2 2l þ 1

where D is the detonation velocity. The schematic of the experimental system for
determination of vm is shown in Fig. 1.16. The explosive charge is placed inside a
copper cylinder. The detonation of the charge occurs at the end of the cylinder front
by a detonator and booster. The expansion of the external radius of the cylinder is
photographed using a high speed streak camera. The increase in the cylinder radius
26 1 Properties of Insensitive Energetic Materials …

Fig. 1.16 A schematic representation of the cylinder expansion test before and after the test [214]

as the explosion progress is determined at a constant section of the cylinder. The

external radius is plotted against time to obtain the expansion curve. From this
curve, vm is obtained using Eq. 1.38.

1.12.3 Brisance

Brisance (from the French meaning to “break”) is a measure of the how rapidly the
maximum pressure is attained when an explosion takes place, and denotes the
shattering strength of the explosive. Brisance values are primarily employed in
France and the Soviet Union. There are several methods for testing brisance, since
no single brisance test is applicable for all explosives. Also, different tests can give
different values for the same explosive. Brisance is experimentally determined by
several methods:
• Sand Test [176–186]
• Plate-Dent Test [187–189]
• Lead Block Compression Test or Hess test [190–203]
• Kast test [204–211]
1.12 Strength, Performance, and Brisance of Explosives 27

1.12.3.1 Sand Test

In the sand test, approximately 400 mg of the explosive are placed in 200 g of sand
and detonated. Brisance is calculated from the amount of sand crushed by the
explosive. This test tends to give the lowest values. Ottawa sand ASTM Standard
which passes through No. 20 U.S. Standard Sieve and is retained on No. 30 U.S.
Standard Sieve is used in the test. The sand testing system is shown in Fig. 1.17.
About 80 g of sand is first poured in the cavity of the sand test bomb. It is leveled as
much as possible. The capsule containing explosive, fuse, and detonator is placed in
such a way that it just touches the sand. The rest of the 120 g sand is pour carefully
into the cavity so that the position of the test capsule is not displaced from its
position. The fuse is lighted and explosion occurs. Following detonation, the sand is
sieved to determine what has become finer than 30 mesh. The same test is con-
ducted for the detonator alone without the tested explosive. The amount of sand
crushed below 30 mesh compared to the blank test is determined and the value is
called brisance (determined by sand crushing test). The value is then compared to
TNT to provide the relative value.

Fig. 1.17 The sand test assembly. US department of Defense (1962) Military standard Explosive:
Sampling, inspection and testing. MIL-STD-650 [212]
28 1 Properties of Insensitive Energetic Materials …

1.12.3.2 Plate Dent Test

In the plate dent test, a sample of the explosive is detonated on a steel witness plate.
The hemispherical deformation of the plate is determined that provides the brisance
of the explosive. The relative brisance of the test explosive against a trinitrotoluene
charge can also be obtained. The relative brisance may be expressed by:

Dent depth from test explosive

Br ¼  100% ð1:39Þ
Dent depth from trinitroluene

Smith [213] suggested the following expression for calculation of dent depth for
explosives with density in the range of 1.58–1.64 g/cm3. The density of trinitro-
toluene in about 1.63 g/cm3.

h ¼ 7:412q0  5:375 ð1:40Þ

where h is the dent depth. The test methods currently used are in Figs. 1.18
and 1.19.

1.12.3.3 Hess Test

In this method the test explosive is placed on the top of a standard lead cylinder.
The brisance is determined from the compression of the lead cylinder due to the
shock wave originated by the detonation of the test explosives. The reduction of the
height of the lead cylinder is related to the brisance. Often time, the relative brisance
with respect to reference explosive, trinitrotoluene, is reported. The basic system is
shown in Fig. 1.20. The deformation caused by the shock wave from the detonation
is presented in Fig. 1.21.

Fig. 1.18 Set up for

measuring brisance by plate
dent method [214]
1.12 Strength, Performance, and Brisance of Explosives 29

Fig. 1.19 Determination of

the dent depth [214]

Fig. 1.20 The basic system

for Hess test [214]

1.12.3.4 Kast Method

The Kast method involves compression of a copper crusher from the detonation of
the test explosive. The copper crusher is separated from the charge by a steel piston,
which transmit the energy from the explosive to the crusher. The brisance is
determined from the decrease of the crusher height or units of crushing using Haid
and Selle table. The units of crushing are given in Fig. 1.22.
30 1 Properties of Insensitive Energetic Materials …

Fig. 1.21 The deformation of the lead block during Hess test [214]

Fig. 1.22 Basic configuration of the apparatus for Kast’s test [214]
1.13 Critical Diameter 31

1.13 Critical Diameter

The critical diameter of an explosive refers to the minimum physical diameter of a

charge necessary to sustain its own detonation wave. The critical diameter is
determined by detonating a series of charges of different diameters until sustaining
of the detonation wave propagation is observed. One such test charge is shown
in Fig. 1.23. This diameter ensures confidence and reliability that the explosive
will detonate under all conditions that are specified for the particular explosive
[215–244].

Fig. 1.23 Explosive charge configuration for determining critical diameter [245]
32 1 Properties of Insensitive Energetic Materials …

1.14 Chemical Decomposition

A chemical decomposition process may be defined as the rate at which the

decomposition of an explosive occurs. The chemical decomposition of an explosive
may take years, days, hours, or a fraction of a second. Depending on the objectives,
the decomposition rate plays a crucial role in the choice of an explosive. For
example, a slower process of decomposition may be desirable for long term storage
and stability. However, two rapid forms of decomposition; deflagration and deto-
nation, are of great interest to the users. (Group 1060, Test Methods, Chemical
Stability, MIL-STD-1751A, Department Of Defense, Test Method Standard, Safety
and Performance Test For the Qualification of Explosives (High Explosives,
Propellants, and Pyrotechnics) [246].

1.15 Deflagration [247–256]

Deflagration may be defined as the decomposition of an explosive material in which

a flame front propagates moves slowly through the explosive material, which is
characteristic of low explosive materials. The flame front generally moves at a
speed less that the speed of sound.

1.16 Detonation [257–276]

Detonation of an explosive may be described as a process in which the decom-

position reaction propagates through the explosive at a supersonic speed. Various
properties of detonation are described earlier in this chapter.

1.17 Sensitivity [277–300]

Sensitivity is an important parameter for an explosive. This refers to the ease with
which an explosive material can be ignited or detonated. The main triggers are the
shock, friction, and heat. Based on the mode of energy that needs to be supplied to
ignite or detonate an explosive, sensitivity tests may be divided into three
categories:
Mechanical Impulses: This includes impact, friction, and projectile impact. In
impact test, sensitivity is expressed in terms of the distance through which a
standard weight must be dropped to cause the material to explode. For friction tests,
sensitivity is expressed in terms of what occurs when a weighted pendulum scrapes
across the material (snaps, crackles, ignites, and/or explodes).
1.17 Sensitivity 33

1.17.1 Shock Wave Tests

Thermal Impulses: Sensitivity is expressed in terms of the temperature at which

flashing or explosion of the material occurs.

1.17.2 Mechanical Impulses

Various mechanical activities (or stimuli) can cause detonation of an explosive.

These include impact, friction, firing pin impact, etc. For safe handling and storage
of the explosive materials all these effects must be properly understood. The det-
onation of an explosive under mechanical stimuli is based on generation of heat
from these activities. The mechanical energy imparted on the explosive from the
dynamic action converts to heat energy causing local hot spots. If these hot spots
have temperature above 700 K that is sustained for more than 300 ls in an area of
diameter of 10 lm, the detonation can occur.
Several apparatus are designed for impact testing; however, all of them operate
on the same principle—a weight is dropped (or a hammer falls on the explosive) on
the test explosive. Because of this testing technique, all of these apparatus are called
the Fallhammer Apparatus. The most common apparatus that are used for impact
testing are: US Bureau of Explosive Impact Apparatus (BoE), US Bureau of Mines
Impact Apparatus (BoM), Picatinny Impact Apparatus (PA), Bundesanstalt für
Materialprüfung Apparatus (BAM).
The BoE apparatus, shown in Fig. 1.24, is capable of testing both solid and
liquid samples. The explosive sample is confined in a 0.2 inch diameter by 0.1 inch
long cylindrical cavity. An 8 lb weight [mass] is allowed to fall freely on a plunger
and plug assembly from a maximum height of 33 inch directly, that is in contact
with the test explosive charge. The sample cylinder rests on a die and anvil
assembly.
About 10-mg sample is used in the test and is loaded onto the die. Either
powdered sample or a solid wafer can be used in the test. The form of the test
sample is an important property for evaluating the results. After placing the anvil
and die, and the plug and plunger into their appropriate places, the drop weight is
released from a predetermined height. A measurement is considered positive if
either an audible report or flame is observed. A minimum of 25 tests are run to
determine the 50% point using a Bruceton procedure.
When testing liquid explosives, one drop of the test liquid is placed in a copper
cup which has been fixed in the cup positioning block. A special striker assembly is
used for the test. The end of the striker should travel up to certain distance into the
cup, but the positioning block should prevent the striker from actually touching the
liquid in the cup. The bottom of the copper cup just touches the anvil when all the
parts are assembled. This entire assembly is then placed in the same mechanism
used for solid materials and tests are conducted in a similar manner.
34 1 Properties of Insensitive Energetic Materials …

Fig. 1.24 Impact test apparatus from Bureau of explosive design (BOE) [300]

1.17.3 Friction Sensitivity

Friction is another stimulus for detonation of an explosive. The heat generated due
to the friction between explosive particles or explosive-working surface can cause
the detonation.
The pendulum friction device developed by the Bureau of Mines consists of a
steel swinging shoe which is the bob of a pendulum. The apparatus is shown in
Fig. 1.25. The friction between the shoe and anvil is controlled by controlling the
number of swings of the pendulum. A specially designed anvil is used in the test. At
the central portion of the anvil three parallel grooves are cut to prevent the test
sample from being brushed off from the surface by swinging shoe. During the test,
the test explosive charge is spread on the anvil surface. A steel shoe or one faced
with red-hair fiber (called the “hard-fiber-faced shoe”) is used. A trigger is used to
allow the shoe to be dropped upon the anvil from any desired vertical height
ranging from 50 to 200 cm. The normal height of drop used is 100 cm. This test
1.17 Sensitivity 35

Fig. 1.25 A pendulum friction device (Source Munroe CE, Tiffany JE (1931) Physical testing of
explosives at the bureau of mines explosives experiment station. Bruceton, PA. U.S. Dept. of
Commerce, Bureau of Mines, Bulletin 346, pp. 78–84) [301]

should be conducted in a temperature controlled room so that the temperature of the

anvil and shoe is 70 ± 5 F.
About 7 g of sample is spread evenly in and around the three grooves on the
anvil plate. The apparatus is adjusted with loaded weights to provide about 18 ± 1
swings across the face of the anvil before coming to rest. The shoe is then released
and the test result is noted. Twenty trials should be conducted using the steel shoe
36 1 Properties of Insensitive Energetic Materials …

or fiber shoe. The test material using the steel shoe should not react in any of the
twenty trials.
Other friction sensitivity tests that are most common include ABL Friction test
(recommended by UN) and BAM friction test (recommended by both US DOD and
UN).

1.17.4 ABL Tests [302–306]

The arrangement is shown in Fig. 1.26. In this method a thin uniform layer of the
substance is placed under the wheel on the slidi337 ng anvil. A vertical com-
pression force is applied under a non-rotating wheel, while the substance is moved
in a horizontal direction on a sliding anvil. The maximum force to be used is
1800 lb (8000 N) and the minimum is 10 lb (44 N). A pendulum strikes the anvil
and moves it at a known velocity, normally, the anvil slides 1 in (2.54 cm). The
initial velocity is determined by calibration.

1.17.5 BAM Friction Test [307–309]

In this method, the friction is generated between two porcelain objects as shown in
Fig. 1.27. A rough porcelain plate holds the sample that is moved
electro-mechanically against a stationary porcelain pistil. A force normal to the
plate is applied through the pistil and can be changed. The normal force at which
50% of initiations occur is used as the measure of the friction sensitivity.
Generally the sample is tested as received. For some explosives, a wetting agent
is added for safe handling and transportation. This type of sample is tested with the
minimum content of wetting agent. About 10 mg of the test sample is placed on the
plate. The stationary porcelain cylinder is lowered to the top the sample by using
the loading arm. A selected weight [mass] is attached to the arm to apply the force,
which may vary from 4.9 to 353.2 N. The movement of the plate, or the stroke

Fig. 1.26 The ABL test

system [306]
1.17 Sensitivity 37

Fig. 1.27 The arrangement for creation of friction between the porcelain plate and pistil

length, is 10 mm forward and backward from the initial position. The occurrence of
the initiation due to friction is determined from crackling sound, appearance of
smoke, or by the characteristic burning smell.
Although both methods can be used in evaluating safety in transport, in other
hazard assessments only the BAM test is specified (Fig. 1.28).

Fig. 1.28 A schematic diagram of the BAM apparatus [250]

38 1 Properties of Insensitive Energetic Materials …

1.18 Electrostatic Discharge (ESD) Test

This test refers to the amount of energy that is required to ignite explosives by
electrostatic stimuli. A high potential needs to be applied to generate a spark
between the test sample and the electrode. Figure 1.29 illustrates the working
principle of an ESD testing device.
Samples are tested by varying the intensity of the released electrostatic dis-
charge. The initiation point is determined whenever a flash, spark, burn, or specific
noise is detected [310–312].

1.18.1 Gap Tests-Shock Wave [313–335]

The gap test is conducted to obtain the minimum shock wave pressure that can
cause complete detonation of the explosive. The design of the experimental system
depends on the size of the booster and the sample and is called either Small Scale
Gap Test or Large Scale Gap Test system. The choice of the small or large scale gap
test facility depends on the pressure and duration of positive phase of pressure of
the generated shock wave. The determine the sensitivity to the shock wave, the
complete detonation of the explosive charge must occur, which is generally indi-
cated by the formation a clean hole in the steel witness plate that is 9.53 mm thick.
A small scale gap test system is shown in Fig. 1.30.

Fig. 1.29 Basic working principle of electrostatic discharge test system [310]
1.18 Electrostatic Discharge (ESD) Test 39

Fig. 1.30 Small scale gap

test assembly. (Source
Department Of Defense Test
Method Standard. Safety and
Performance Tests For The
Qualification Of Explosives
(High Explosives,
Propellants, And
Pyrotechnics) MIL-STD
1751A, 11 December 2001
SUPERSEDING,
MIL-STD-1751(USAF), 20
August 1982 [246]

1.18.2 Thermal Sensitivity Test [336–341]

The best way to understand the sensitivity of an explosive to heat is to determine its
ignition temperature, which is obtained by heating the sample of a given mass at a
constant rate of temperature increase until the ignition occurs. Generally, 0.2 g of
sample is placed in a test tube, which is heated in a liquid metal bath. Several
samples may be tested simultaneously depending on the size of the bath and the
electronics. A heating rate of 5 °C/min is recommended. The test tube containing
the sample is placed in the bath when the temperature of the bath containing the
sample is placed in the bath when the temperature of the bath reaches 100 °C. The
time elapsed between immersion of the tube and the ignition is known as the
induction period. The activation energy may be calculated from the knowledge of
the induction period. The test assembly is shown in Fig. 1.31.
40 1 Properties of Insensitive Energetic Materials …

Fig. 1.31 Test assembly for

determination of ignition
temperature [246]

1.19 Stability

Stability of an explosive refers to the ability to store it without deterioration for a

long period of time. The following factors generally affect the stability of an
explosive:
Chemical constitution: The chemical compounds used for the formulation of the
explosive may deteriorate or decompose to other compounds from exposure to
atmospheric oxygen, heat, and moisture. The rate of the atmospheric decomposition
will determine their stability or self life.
Temperature of storage: The temperature is one of the main parameters that
affect the stability of the explosives most. Although the rate of decomposition of
explosives increases with the increase of temperature, they should be stable at the
temperature range of −10 to +35 °C.
1.19 Stability 41

Exposure to the sun: Exposure of explosives to sun should be avoided. The

ultraviolet rays of the sun can decompose explosive compounds that contain
nitrogen groups, affecting their stability.
Electrical discharge: Static or other electrical discharge may detonate an
explosive under some circumstances. This is rather common to a number of
explosives. As a result, the safe handling of explosives and pyrotechnics almost
always requires electrical grounding of the operator.

References

1. Department of Defense (2001, December) Test method standard: safety and performance
tests for the qualification of explosives (high explosives propellants and pyrotechnics).
MIL-STD-1751A, 11 Superseding, MIL-STD-1751 (USAF), 20 August 1982
2. NATO STANAG 4170. Principles and Methodology for the Qualification of Explosive
Materials for Military Use which has associated with it NATO Allied Ordnance Publication
#7 (AOP-7) Manual of Tests for the Qualification of Explosive Materials for Military Use
3. Thiele, J (1907) Ein neuer Apparat zur Schmeltzpunktbestimmung, Berichte 40:996–997
4. LeFevre JW (2011) Measuring the melting points of compounds and mixtures: Tech 701. In:
Jeffers J (ed) CER modular laboratory program in chemistry. http://www.cerlabs.com/
experiments/10875407013.pdf
5. Organic Laboratory Techniques 4—University of Calgary. http://www.
wwwchemucalgaryca.com/courses/351/laboratory/meltingpointpdf
6. Colepamer. www.coleparmer.com/Product/Electrothermal_Mel_Temp_Melting_Point_
Apparatus_120_VAC/WU-03010-15
7. Hussain G, Rees GJ (1995) Thermal decomposition of RDX and mixtures. Fuel 74(2):273–
277
8. Reid RC, Prausnitz JM, Poling BE (1972) The properties of gases & liquids. McGraw-Hill,
New York, NY
9. Dautriche M (1907) The velocity of detonation in explosives. Compt Rend 143:641–644
10. Departmental of Defense (1970) Explosive sampling inspection and testing method T 1091.
MIL-STD-650, Department of Defense, USA
11. Persson PA (1980) EXTEST international study group for the standardization of the methods
of testing explosives. Prop Explos Pyrotech 5:23–28
12. Agrawal JP (2010) High Energy Materials Propellants Explosives Pyrotechnics.
Wiley-VCH, Germany
13. Suceska M (1995) Test methods for explosives. Springer, The Netherlands
14. Kohler J, Meyer R (1993) Explosives. VCH Publishers, New York, NY, USA
15. Cook MA, Doran RL, Morris GJ (1955) Measurement of detonation velocity by
dopplereffect at three-centimeter wavelength. J Appl Phys 16(4):426–428
16. Bussell T, Lam C (1994) An instrumentation system for the rapid measurement of run to
detonation distances. Aeronautical and Maritime Research Laboratory, Australia, Report No
DSTO-TR—0129
17. Ogata Y, Wada Y, Katsuyama K, Ma G-C (1995) Photographic measurement of the
detonation velocity of explosives by high-speed camera and its comparison with other
methods. Proc SPIE 2513:990
18. Benterou J, Udd E, Wilkins P, Roeske F, Roos E, Jackson D (2007) In-situ continuous
detonation velocity measurements using fiber-optic bragg grating sensors. Report No
UCRL-Proc-2331
42 1 Properties of Insensitive Energetic Materials …

19. Chan EM, Lee V, Mickan SP, Davies PJ (2005) Low-cost optoelectronic devices to measure
velocity of detonation in smart structures devices and systems II. In: Al-Sarawi SF
(ed) Proceedings of SPIE, vol 5649, Bellingham, WA
20. Prinse WC (2000) Development of fiber optic sensors at TNO for explosion and shock wave
measurements. Proc SPIE 4183:748–758
21. van’t Hof P (2006) Dynamic measurement of detonation pressure by use of a fiber bragg
grating. proc SPIE, 6279
22. Cheng LK, van Bree J (2011) Fiber-optic sensors in explosion and detonation experiments.
SPIE Newsroom, 1011: 17/212007050729
23. The National Park Services (NPS). U.S. Department of the Interior, USA. https://www.nps.
gov/parkhistory/online_books/npsg/explosives/Chapter2.pdf
24. Agrawal JP, Hodgson RD (2007) Organic chemistry of explosives. Wiley-VCH Verlag
GmbH
25. Suceska M (1995) Test methods for explosives (Shock Wave and High Pressure
Phenomena). 1st edn. Springer
26. Adadurov GA, Dremin AN, Kanel GI (1969) Parameters of mach reflections in plexiglas
cylinders. Zh Prikl Mekh Tekh Fiz 2:126–128
27. Bernecker RR, Clairmont AR Jr (1988) Shock initiation studies of cast plastic-bonded
explosives. In: International annual conference on ICT 19th (Combust Detonation Phenom),
41/41-41/14
28. Biss MM (2013) Energetic material detonation characterization: a laboratory-scale approach.
Propellants Explos Pyrotech 38(4):477–485
29. Chiang JC, Sanyal SK, Castanier LM, Brigham WE, Shah DO (1980) Foam as an agent to
reduce gravity override effect during gas injection in oil reservoirs. Stanford Univ, p 89
30. Cook MA, Udy LL (1961) Calibration of the card-gap test. ARS J 31:52–57
31. Dorsett HE, Brousseau P, Cliff MD (2001) The influence of ultrafine aluminum upon
explosives detonation. In: Proceedings of international pyrotech seminar 28th, pp 239–244
32. Dubovik AV, Voskoboinikov IM, Bobolev VK (1966) Role of forehead shock wave in
low-speed detonation in liquid nitroglycerin. Fiz Goreniya Vzryva 4:105–110
33. Garg DD, Kamath PV (1979) Measurement of detonation pressure of explosive shocks.
India Dep, Atomic Energy, pp 691–703
34. Heiss JF (1966) Pit-type rock salt dissolver tests in plexiglas models aimed at producing
high-purity brine. Electrochem Technol 4(11–12):560–562
35. Hlinka JW (1975) Water model for the quantitative simulation of the heat and fluid flow in
liquid-steel refractory systems. Met Soc pp 157–164
36. Ijsselstein RR (1984) A simple shock pressure transducer for measuring the performance of
explosives and explosive devices. In: Proceedings of 12th symposium on explosion
pyrotech, 3/89-83/95
37. Johnson JN (1982) Calculated shock pressures in the aquarium test. In: AIP conference on
proceedings 78 (Shock Waves Condens Matter), pp 568–572
38. Lu S, Zhang J (1993) Simple method for determining the detonation pressure in industrial
explosives. Baozha Yu Chongji 13(3):280–284
39. Majka M, Martinet J, Martin C, Berlot R (1969) Method of the temperature probe. Rev Gen
Therm 8(87):251–261
40. Miller VF (1969) Selective chromium plating of Plexiglas. Soc Plast Eng Inc, pp 521–524
41. Novikov SS, Pokhil PF, Ryazantsev YS, Sukhanov LA (1969) Characteristic feature of the
mechanism of combustion of condensed mixtures. Zh Fiz Khim 43(3):656–658
42. Sassa K, Ito I (1966) Measurement of detonation pressures of explosives by a modified
aquarium technique. Kogyo Kayaku Kyokaishi 27(4):228–233
43. Slape RJ (1975) Detonation pressures of HNS I and II final report. Mason and Hanger-Silas
Mason Co Inc, USA, p 18
44. Xu K, Yu DY, Xu YX, Zeng XF (1982) Effect of charge diameter on detonation pressure
measured by aquarium technique. In: AIP Conference on proceedings 78 (Shock Waves
Condens Matter) pp 573–577
References 43

45. Yakushev VV, Rozanov OK, Dremin AN (1968) The measurement of the polarization
relaxation time in a shock wave. Zh Eksp Teor Fiz 54(2):396–400
46. Knudsen M (1909) Effusion and the molecular flow of gases through openings. Ann Physik
28:75–130
47. Knudsen M (1909) Experimental determination of the vapor Pressure of mercury at 0 and at
higher temperatures. Ann Physik 29:179–193
48. Ickowski RP, Margrave JL, Robinson SM (1963) Clausing factor. J Phys Chem 67:229
49. Langmuir I (1916) The constitution and fundamental properties of solids and liquids part I:
Solids. J Am Chem Soc 38(11):2221–2295
50. Price DM (2001) Vapor pressure determination by thermogravimetry. Thermochim Acta
253:367–368
51. Duncan M, Price MH (1998) Calorimetry of two disperse dyes using thermogravimetry.
Thermochimica Acta 315: 19–24
52. Gückel W, Synnatschke G, Rittig R (1973) A method for determining the volatility of active
ingredients used in plant protection. Pestic Sci 4: 137
53. Gückel W, Rittig FR, Synnatschke G (1974) A method for determining the volatility of
active ingredients used in plant protection II. Applications to formulated products. Pestic Sci
5: 393
54. Gückel W, Kaüstel R, Lewerenz J, Synnatschke G (1982) A method for determining the
volatility of active ingredients used in plant protection. Part III: The Temperature
relationship between vapor pressure and evaporation rate. Pestic Sci 13: 161
55. Gückel W, Kaüstel R, Kroü R, Parg hl A (1995) A method for determining the volatility of
active ingredients used in plant protection. Part IV: An Improved Thermogravimetric
Determination Based on evaporation rate. Pestic Sci 45: 27
56. Phang P, Dollimore D, Evans SJ (2002) Thermochim Acta 392–393:119–125
57. Jensen DG, Schall ED (1966) Determination of vapor pressures of some phenoxyacetic
herbicides by gas-liquid chromatography. J Agric Fd Chem 14:123–126
58. Clausius R (1850) Ueber die bewegende Kraft der Wärme und die Gesetze welche sich
daraus für die Wärmelehre selbst ableiten lassen On the motive power of heat and the laws
which can be deduced therefrom regarding the theory of heat. Annalen der Physik (in
German) 155:500–524
59. Clapeyron MC (1834) Mémoire sur la puissance motrice de la chaleur. Journal de l’École
polytechnique (in French) 23:153–190
60. Trauzl I (1885) La Dynamite. Harvard College Library, Boston
61. Gordon WE, Everett F, Bessie R, Lepper A (1955) Lead-block test for explosives. Ind Eng
Chem 47(9):1794–1800
62. Ahrens H (1973) Nitropenta/potassium chloride reference curve for interpreting lead-block
expansion results. Explosivstoffe 21(3):72–82
63. Ahrens H (1973) Quality of lead castings for the lead-block test and checking them by
calibration with picric acid. Explosivstoffe 21(3):87–89
64. Bigourd J (1973) Bursting of blocks in the lead-block test. Explosivstoffe 21(3):82–84
65. Burlot E (1934) The lead block test for explosives. Mem artillerie franc 13:113–180
66. Chatel de Raguet de Brancion PML, Poinssot PLA, Legagneur PHMS (1967) Double-salt
explosives stable toward firedamp. Societe d’Etudes et de Recherches pour l’Amelioration
des Explosifs SERADEX, p 3
67. Comey AM, Holmes FB (1913) Methods for the determination of the effective strength of
high explosives. In: 8th international of congress of applied chemistry (Separate)
68. Dautriche (1914) Two new types of grisoutines. Meml Poudres 17: 175–177
69. Dautriche H (1912) An explosive n with five per cent potassium nitrate. Z Gesamte
Schiess-Sprengstoffwes 7:97
70. Dautriche H (1912b) An explosive n with five per cent potassium nitrate. Meml Poudres 16:
14-2069-70
71. Dautriche M (1909) Ammonium perchlorate explosives. Mem des poudres et salpetres. 14:
192-196206-133
44 1 Properties of Insensitive Energetic Materials …

72. Haeuseler E (1971) Choice of a method for determining the strength of explosives in the
lead-block test. Explosivstoffe 19(5–6):76–82
73. Haeuseler E (1973) Problem of establishing the reference curve for the lead-block test.
Explosivstoffe 21(3):71–72
74. Kast H, Haid A (1922) The explosibility of mercuric oxycyanide. Chem-Ztg 46:794–795
75. Kast H, Haid A (1922) The explosibility of mercuric oxycyanide. Z Gesamte
Schiess-Sprengstoffwes 17:116–117
76. Kuznetsov VM, Shatsukevich AF (1978) Workability of explosives. Fiz Goreniya Vzryva
14(2):120–125
77. Langenscheidt F (1913a) The manufacture of tetranitromethylaniline. Arms Explos 21:
21-2236-27
78. Langenscheidt F (1913) The manufacture of tetranitromethylaniline. Z Gesamte
Schiess-Sprengstoffwes 7:445–447
79. Le Roux A (1953) Explosive properties of tetramethyl ammonium nitrate. Meml Poudres
35:121–132
80. LeRoux A (1952) Explosive properties of the nitrate of monomethylamine. Meml Poudres
34:129–146
81. Medard L (1953) Explosive properties of nitroisobutanediol dinitrate. Meml Poudres
35:111–112
82. Mente WW (1909) Experiments with explosives regarding explosion of fire damp and coal
dust. J Soc Chem Ind (London) 28:748
83. Moreau A, Grosborne P (1973) Tests concerning the evaluation of the initiating strength of
detonators by the Hungarian method. Explosivstoffe 21(3):98–99
84. Naoum P, Aufschlager R (1924) Ammonium perchlorate. Z Gesamte
Schiess-Sprengstoffwes 19:121–123
85. Neubner R (1928) The Trauzl (lead block) test. Z Gesamte Schiess-Sprengstoffwes 23:
1-553-5672-57125-129194-128
86. Porr K (1967, Jul 06) Fluid explosive mixtures from ammonium nitrate.
Ger, DE 1244031 19670706, p 2
87. Reck W, Kiessetz C, Debik G (1962, Sep 03) Ammonium nitrate explosive. Patent DD
23657, p 2
88. Reidl HJ, Sauermilch W (1966, Jul 28) Castable high-capacity explosive mixtures.
Wasag-Chemie A-G, DE 1221945, p 2
89. Stachlewska-Wroblowa A, Okon K (1961) Properties of tertiary phosphines II Electrophilic
substitution reactions of triphenylphosphine oxides and its derivatives. Biul Wojsk Akad
Tech im Jaroslawa Dabrowskiego 10(4):14–27
90. Sucharewsky M (1925) Accuracy of the Trauzl lead-block test for measuring explosive
effect. Z ges Schiess-Sprengstoffw 20:26
91. Wang Y (2002) Description of lead nitride equivalent of detonator strength and its
application in fuse design. Huogongpin 3:24–27
92. Wang Z-Z, Wang X-G, Xia B (2007) Study on power test method of industrial explosives.
Huozhayao Xuebao 30(6): 24–26, 30
93. Aochi T, Matsunaga T, Nakayama Y, Iida M, Miyake A, Ogawa T (2000) Analysis of
underwater explosion gas products of aluminum/potassium chlorate mixtures. Kayaku
Gakkaishi 61(4):167–175
94. Aochi T, Miyake A, Ogawa T (1996) Underwater explosion test of Al/KClO3 pyrotechnic
compositions. In: Proceedings of international pyrotech seminar 22nd, pp 23–34
95. Aochi T, Miyake A, Ogawa T, Matsunaga T, Nakayama Y, Iida M (1997) Underwater
explosion characteristics of aluminum/potassium chlorate mixtures. Kayaku Gakkaishi 58
(5):202–210
96. Bjarnholt G (1980) Suggestions on standards for measurement and data evaluation in the
underwater explosion test. Propellants Explos 5(2–3):67–74
97. Chi J, Ma B (1999) Underwater explosion wave by a TWT/RDX (40/60) spherical charge.
Gaoya Wuli Xuebao 13(3):199–204
References 45

98. Hamashima H, Kato Y, Itoh S (2004) Determination of JWL parameters for non-ideal
explosive. In: AIP conference on proceedings 706 (Pt 1 Shock Compression of Condensed
Matter–2003 Part 1) pp 331–334
99. Hamashima H, Kato Y, Nadamitsu Y, Itoh S (2003) Determination of JWL parameters from
underwater explosion test for ideal and non-ideal explosives. Sci Technol Energ Mater 64
(6):248–253
100. Matsunaga T, Iida M, Aochi T, Miyake A, Ogawa T, Hatanaka S, Miyahara A (1997)
Explosive characteristics of report charges. In: Proceedings of international pyrotech seminar
23rd, pp 532–537
101. Murata K, Hatanaka S, Kato Y (2003) Risk assessment of pyrotechnic mixtures by
underwater explosion test. In: Proceedings of international pyrotech seminar 30th (Europyro
2003, vol 2), pp 478–489
102. Paszula J, Maranda A, Paplinski A, Golabek B, Kasperski J (2005) An analysis of blast
waves parameters and underwater explosion test of emulsion explosives and dynamites.
University of Pardubice, pp 721–731
103. Ruyat Y, Nakayama Y, Matsumura T, Wakabayashi K, Okada K, Miyake A, Ogawa T
Yoshida M (2004) Explosion strength of tri-n-butyl phosphate and fuming nitric acid (TBP/
FNA) mixture evaluated by underwater explosion test. Sci Technol Energ Mater 65(1): 14–
20
104. Sumiya F, Hirosaki Y, Kato Y, Wada Y, Ogata Y, Seto M Katsuyama K (2001)
Characteristics of pressure wave propagation in emulsion explosives. In: Proceedings of
annual conference of explosive blasting tech 27th (vol 2), 1–11
105. Sharon M, Boyles PE, Obney RH, Rast (1995, May 30) Miniscale ballistic motor testing
method for rocket propellants. US 5419116 A
106. Dormans R, Nakka R (2006) “¼ Scale” ballistic evaluation motor (BEM). 1st static firing
report rev. http://www.sugarshotorg.com/downloads/ssts_1st-BEM_test_reportpdf
107. Stephen WA, Warren TC, Humphrey JM, Levy S, Kroll WD (1974) Ballistic missile
propellant evaluation test motor system (super bates). Air Force Rocket Propulsion
Laboratory, USA, Ad/A-004 218
108. Fry RS (2001) Solid propellant test motor scaling chemical propulsion information agency.
The Johns Hopkins University, Whiting School Of Engineering, Columbia Maryland, USA,
DTIC Technical Report 2001, p 104
109. Rexford D, Atchley T, Sato SZ (1988, Jul 26) High strain capability ballistic test device for
solid propellant rocket motors. A Morton Thiokol Inc, US 4759215
110. Brewczyk M, Rzazewski K, Clark CW (1997) Multielectron dissociative ionization of
molecules by intense laser radiation. Phys Rev Lett 78(2):191–194
111. Cieslikowska M, Moskalewicz M, Wolszakiewicz T (2004) The examination of chosen
ballistic parameters of igniter charge BKNO3 for igniters of solid propellant rocket motors.
University of Pardubice, pp 456–463
112. Dundar D, Gullu M (2007) Use of alkyl hydantoin derivatives as binding materials in
high-energy explosives propellants and undercoatings. Tubitak-Turkiye Bilimsel ve Teknik
Arastirma Kurumu Turk, p 20
113. Frost DM, Cronin JB, Newton RU (2008) Have we underestimated the kinematic and kinetic
benefits of non-ballistic motion? Sports Biomech 7(3):372–385
114. Johansson M, de Flon J, Petterson A, Wanhatalo M, Wingborg N (2006) Spray prilling of
ADN and testing of ADN-based solid. Propellants. Eur Space Agency Spec Publ, SP SP-635
(3rd International Conference on Green Propellant for Space Propulsion and 9th
International Hydrogen Peroxide Propulsion Conference 2006), johanssn/1-johanssn/6
115. Kovalev PI, Mikhalev AN, Podlaskin AB, Tomson SG, Shiryaev VA Isaev SA (1999)
Investigation of the aerodynamic properties and flow field around hypervelocity objects in a
ballistic test range. Tech Phys 44(12): 1402–1406
116. Labock N, Labock O (2009, Jan 15) Personal portable ballistic protection for motor vehicle
occupants. USA PCT Int. Appl. (2009), WO 2009007972 A2
46 1 Properties of Insensitive Energetic Materials …

117. McFarland MJ, Palmer GR, Kordich MM, Pollet DA, Jensen JA Lindsay MH (2005a) Field
validation of sound mitigation models and air pollutant emission testing in support of missile
motor disposal activities. J Air Waste Manage Assoc 55(8): 1111–1121
118. McFarland MJ, Palmer GR, Rasmussen SL, Kordich MM, Pollet DA, Jensen JA,
Lindsay MH (2006) Field verification of sound attenuation modeling and air emission
testing in support of missile motor disposal activities. J Air Waste Manage Assoc 56
(7):1041–1051
119. Price EW (1952) Steady-state one-dimensional flow in rocket motors. J Appl Phys 23:142–
146
120. Proebster M, Schmucker RH (1986) Ballistic anomalies in solid rocket motors due to
migration effects. Acta Astronaut 13(10):599–605
121. Sandri Tussiwand G, Bandera Maggi F, De A, Luca LT (2007) Intrinsic structural-ballistic
interactions in composite energetic materials Part I experiments. Hayastani Kim Handes 60
(2):186–200
122. Meyer R, Köhler J, Homburg A (2007) Expensive. Sixth, completely revised edition.
Wiley-VCH, Germany
123. Satyavratan PV, Vedam R (1980) Some aspects of underwater testing method. Propellants
Explos Pyrotech 5(2–3):62–66
124. Baum FA, Orlenko LI, Stanyukovich KP, Chelishev VI, Shooter BI (1975) Fizika goreniya i
vzryva. Nauka, Moscow
125. Du Lownds CM, Plessis MP (1984) The double pipe test for commercial explosives I
Description and results. Propellants Explos Pyrotech 9(6):188–192
126. Du Lownds CM, Plessis MP (1985) The double pipe test for commercial explosives II
Numerical modeling and interpretation. Propellants Explos Pyrotech 10(1):5–9
127. Anderson PE, Cook P, Balas W, Davis A, Mychajlonka K (2010) An overview of combined
effects explosives formulations. In: International annual conference on ICT 41st (Energetic
Materials: for High Performance Insensitive Munitions and Zero Pollution), ander1/
1-ander1/9
128. Borisov AA, Khomik SV, Mikhalkin VN (1991) Detonation of unconfined and semicon-
fined charges of gaseous mixtures. Prog Astronaut Aeronaut 133 (Dyn Detonations Explos:
Detonations), pp 118–132
129. Broeckmann B (1998) Effective avoidance of ignition sparks electrostatic charging at
pneumatic conveyors. Chem-Anlagen Verfahren 31(10):9496
130. Cudzilo S, Maranda A, Trzcinski WA (1997) Determination of energetic characteristics of
ammonale 94/6 by using a cylinder test. In: International annual conference on ICT 28th
(Combustion and Detonation), pp 104101–104109
131. Cudzilo S, Trzcinski WA (2001) A study on detonation characteristics of pressed NTO.
J Energ Mater 19(1):1–21
132. Doherty RM, Simpson RL (1997) A comparative evaluation of several insensitive high
explosives. In: International annual conference on ICT 28th (Combustion and Detonation),
pp 3231–3223
133. Forbes JW, Glancy BC, Liddiard TP, Wilson WH (1998) Aquarium test evaluation of a
pyrotechnic’s ability to perform work in microsecond time frames. In: AIP conference on
proceedings of 429 (Shock Compression of Condensed Matter–1997), pp 759–762
134. Fuch BE (1995) Picatinny arsenal cylinder expansion test and a mathematical examination of
the expanding cylinder. Army Armament Res Dev Cent, Report (1995) (ARAED-TR-95014;
Order No. AD-A300526), pp 31
135. Han C, Liu G, Dong Y, Feng J, Wang D, Hu H (1992) Expansion movement and fracture of
a cylindrical shell due to internal explosion. North-Holland, pp 357–360
136. Hiroe T, Fujiwara K, Hata H, Yamauchi M, Tsutsumi K, Igawa T (2010) Explosively driven
expansion and fragmentation behavior for cylinders spheres and rings of 304 stainless steel.
Mater Sci Forum 638–642(Pt 2 THERMEC 2009), 1035–1040
137. Hiroe T, Fujiwara K, Kiyomura K (2004) The effect of wall configuration on deformation
and fragmentation for explosively expanded cylinders of 304 stainless steel. Mater Sci
References 47

Forum 465–466. (Explosion Shock Wave and Hypervelocity Phenomena in Materials),

pp 225–230
138. Hornberg H (1986) Determination of fume state parameters from expansion measurements
of metal tubes. Propellants Explos Pyrotech 11(1):23–31
139. Hornberg H, Volk F (1989) The cylinder test in the context of physical detonation
measurement methods. Propellants Explos Pyrotech 14(5):199–211
140. Jenkins CM, Horie Y, Lindsay CM, Butler GC, Lambert D, Welle E (2012) Cylindrical
converging shock initiation of reactive materials. In: AIP Conference on proceedings of
1426 (Shock Compression of Condensed Matter–2011 Part 1), pp 197–200
141. Kamlet MJ, Short JM, Finger M, Helm F, McGuire RR, Akst IB (1983) The chemistry of
detonations VIII Energetics relationships on the detonation isentrope. Combust Flame 51
(3):325–333
142. Koch E-C, Klapoetke TM (2012) Boron-based high explosives. Propellants Explos Pyrotech
37(3):335–344
143. Lang IF, Hung SC, Chen CY, Niu YM, Shiuan JH (1993) An improved simple method of
deducing JWL parameters from cylinder expansion test. Propellants Explos Pyrotech 18
(1):18–24
144. Levkin VV (2005, Sep 27) Production method for power hydrogen and diamonds and device
for its realization. Russia Russ, RU 2261223 C2
145. Lindsay CM, Butler GC, Rumchik CG, Schulze B, Gustafson R, Maines WR (2010)
Increasing the utility of the copper cylinder expansion test. Propellants Explos Pyrotech 35
(5):433–439
146. Makhov MN (2007) Evaluation of the explosive performance of 12-dinitroguanidine. In:
International annual conference on ICT 38th, 118/111-118/111
147. Mathieu JCE (1901, Jul 30) Carbureting apparatus for explosion-motors. U.S. US 679387 A
148. McGuire RR, Ornettas DL, Helm FH, Coon CL, Finger M (1982) Detonation chemistry: an
investigation of fluorine as an oxidizing moiety in explosives. Lawrence Livermore Natl Lab,
Livermore, CA, USA, ADA119092, p 38
149. Mitchell AR, Pagoria PF, Coon CL, Jessop ES, Poco JF, Tarver CM, Breithaupt RD,
Moody GL (1994) Nitroureas 1 Synthesis scale-up and characterization of K-6. Propellants
Explos Pyrotech 19(5):232–239
150. Murr LE, Foltz JV, Altman FD (1971) Deformation substructures and terminal properties of
explosively-loaded thin-walled stainless-steel cylinders. Phil Mag 23(185):1011–1028
151. Murr LE, Wong GI, Foltz JV (1971) Comparison of residual defect structures and hardness
in Inconel 600 following deformation by explosive shock loading cylindrical (explosive)
expansion and cold-reduction. Mater Sci Eng 7(5):278–285
152. Nagayama K, Kubota S (2003) Equation of state for detonation product gases. J Appl Phys
93(5):2583–2589
153. Polyakov VN (1993) A new concept of estimation of fracture time and crack lengths in
transmission pipelines. Inst Mater pp 1603–1609
154. Qingdong D, Bayi H, Changsheng H, Haibo H (1994) Expansion and fracture of AISI 1045
steel explosive-filled cylinders. J Phys IV 4(C8 International Conference on Mechanical and
Physical Behaviour of Materials under Dynamic Loading 1994), C8-415–C418-420
155. Rumchik C, Nep R, Butler GC, Breaux B, Lindsay C (2012) The miniaturization and
reproducibility of the cylinder expansion test. In: AIP conference on proceedings of 1426
(Shock Compression of Condensed Matter–2011 Part 1), pp 450–453
156. Sanchidrian JA, Lopez LM (2006) Calculation of the energy of explosives with a partial
reaction model comparison with cylinder test data. Propellants Explos Pyrotech 31(1):25–32
157. Sanchidrian JA, Lopez LM, Segarra P (2008) The influence of some blasting techniques on
the probability of ignition of firedamp by permissible explosives. J Hazard Mater 155
(3):580–589
158. Scovel CA, Menikoff R (2009) A verification and validation effort for high explosives at Los
Alamos National Lab. In: AIP Conference on proceedings 1195 (Pt 1 Shock Compression of
Condensed Matter–2009 Part 1), pp 169–172
48 1 Properties of Insensitive Energetic Materials …

159. Simpson RL, Urtiew PA, Ornellas DL, Moody GL, Scribner KJ, Hoffmann DM (1997)
CL-20 performance exceeds that of HMX and its sensitivity is moderate. Propellants Explos
Pyrotech 22(5):249–255
160. Stiel LI, Baker EL, Capellos C (2006) Study of detonation and cylinder velocities for
aluminized explosives. In: AIP Conference on proceedings 845 (Pt 1 Shock Compression of
Condensed Matter–2005 Part 1), pp 475–478
161. Stiel LI, Baker EL, Murphy DJ (2012) Equations of state of silicon boron and halogen
species for accurate detonation calculations. Int J Energ Mater Chem Propul 11(2):149–163
162. Sun J, Kang B, Zhang H, Liu Y, Xia Y, Yao Y, Liu X (2011) Investigation on irreversible
expansion of 135-triamino-246-trinitrobenzene cylinder. Cent Eur J Energ Mater 8(1):69–79
163. Tappan BC, Manner VW, Lloyd JM, Pemberton SJ (2012) Fast reactions of aluminum and
explosive decomposition products in a post-detonation environment. In: AIP Conference on
proceedings 1426 (Shock Compression of Condensed Matter–2011 Part 1), pp 271–274
164. Tarver CM, Tao WC, Lee CG (1996) Sideways plate-push test for detonating solid
explosives. Propellants Explos Pyrotech 21(5):238–246
165. Trebinki R, Trzcinski WA (1999) Determination of an expansion isentrope for detonation
products of condensed explosives. J Tech Phys (Warsaw) 40(4):447–504
166. Trzcinski WA (2001) Application of a cylinder test for determining energetic characteristics
of explosives. J Tech Phys (Warsaw Pol) 42(2):165–179
167. Trzcinski WA, Cudzilo S (2006) Characteristics of high explosives obtained from cylinder
test data. Hanneng Cailiao 14(1):1–7
168. Trzcinski WA, Cudzilo S, Szymanczyk L (1999) Determination of the detonation pressure
from a water test. In: International annual conference on ICT 30th, 84/81-84/13
169. Victor AC (1996) A simple method for calculating sympathetic detonation of cylindrical
cased explosive charges. Propellants Explos Pyrotech 21(2):90–99
170. Wesenberg DL, Forrestal MJ (1977) Dynamic expansion and fracture of stainless steel
cylindrical shells. San Francisco, Calif., USA, 15–19 Aug 19776 INIS-MF–4543
171. Whittaker ML, Cutler RA, Anderson PE (2011) Boride-based materials for energetic
applications. In: MRS online proceedings of library 1405 (Advances in Energetic Materials
Research)
172. Wieland MS (2010) Gurney’s journey—pipe-bomb fragments and fumes. In: Proceedings of
annual conference on explos blasting tech 36th (vol 1), pp 293–305
173. Zhang H, Xu J, Liu Y, Huang H, Sun J (2013) Effects of crystal quality and preferred
orientation on the irreversible growth of compact TATB cylindrical explosives. AIP Adv 3
(9): 092101/092101-092101/092108
174. Zimbal C, Nolde M (2010) Determination of the Gurney of civil used explosives. In:
International annual conference on ICT 41st (Energetic Materials: for High Performance
Insensitive Munitions and Zero Pollution) zimba1/1-zimba1/6 (1970) Improved
smooth-blasting explosive cartridges, Nitro Nobel AB, p 3
175. Hornberg H (1986) Determination of fume state parameters from expansion measurements
of metal tubes Propellants Explos Pyrotech 11(1): 23–31
176. Mitsui S, Watabe H, Yokogawa M, Katsuda T, Shigematsu K, Sugiyama N (1974) Liquid
explosives containing nitroglycerin as the main ingredient. Kogyo Kayaku 35(3):127–132
177. Rinkenbach WH, Burton OE (1931) Explosive characteristics of tetracene. Army Ordnance
12:120–123
178. Roberts LN (1974) Liquid explosive for well fracturing. Talley-Frac Corp, May 2, 1972 p 9
US3659652 A
179. Sakurai T (1955) The brisance of explosives VIII Propagation of shock waves in air and
powdery materials. J Ind Explosives Soc Japan 16:90–94
180. Trautmann W (1995) Low-brisance explosive for cladding and welding. Dynamit Nobel AG,
Germany, p 3
181. Dsershkovich AA, Andreev KK (1930) The properties of the nitroglycerin isomers.
Z Gesamte Schiess-Sprengstoffwes 25: 353-356400-353
References 49

182. Dubnov LV, Romanov AI (1962) Deflagration of permitted explosives in mines.

Bezopasnost Truda v Prom 6(10):20–25
183. Edwards MR, Palmer ME (2003) Mitigation of comminution effects of explosives by
particulate materials. J Appl Phys 93(5):2540–2543
184. Keshavarz MH, Seif F, Soury H (2014) Prediction of the Brisance of Energetic Materials.
Propellants Explos Pyrotech Ahead of Print
185. Blinov IF, Svetlova LM (1963) Effect of the shell on the detonation capacity of some
dinitrobenzenes. Teor Vzryvchatykh Veshchestv pp 550–557
186. Smith LC (1967) Brisance and a plate-denting test for estimation of detonation pressure.
Explosivstoffe 15(6):4–130
187. Smith LC (1967) Brisance and a plate-denting test for estimation of detonation pressure.
Explosivstoffe 15(5):10–106
188. Dynamit-Nobel A-G (1962) Ammonium nitrate explosives having improved sensitivity
brisance and power. p 7
189. Ambrozek M, Baryla S, Guga J, Kurnatowski Z, Luszczak T (1988) Storage-stable
hexogen-based plastic explosives. p 5 Abstracted and indexed from the unexamined
application Zaklady Tworzyw Sztucznych “Nitron-Erg” Pol
190. Azarkovich AE (1970) Correlation between the laboratory characteristics of explosives and
their explosive efficiency. Fiz-Tekh Probl Razrab Polez Iskop 3:64–69
191. Davydova EG (1948) Effect of moisture and sunlight on the explosive properties of TNT.
Gorn Zh 122(5):24–25
192. Matyas R, Kuenzel M, Ruzicka A, Knotek P, Vodochodsky O (2015) Characterization of
erythritol tetranitrate. Physical properties. Propellants Explos Pyrotech 40(2):185–188
193. Plucinski J, Smolenski D (1960) 246-Trinitro-3-methylnitraminotoluene (m-methyltetryl).
Chem Stosowana 4:479–499
194. Ratner SB (1947) Properties of aluminum-containing explosives. Gorn Zh 121(5):21–25
195. Sakurai T, Takei I (1952) Brisance of explosives. J Ind Explosives Soc Japan 13:138–142
196. Smida T, Denkstein J, Kaderabek V (1978) Plastic gelatinized blasting explosive with high
content of nitrates. Czech, p 3
197. Tamchyna V, Vetlicky B, Racek F, Mostak P (1984) Emulsion explosive. Czech, p 3
198. Urbanski T, Piskorz M, Maciejewski M, Cetner W (1959) Properties of tetranitromethane II
The explosive properties of binary mixtures of tetranitromethane with some combustible or
explosive substances. Biul Wojsk Akad Tech im Jaroslawa Dabrowskiego 8(42):37–41
199. Yokogawa M (1964) Combustibility of ammonium nitrate explosives Kogyo Kayaku
Kyokaishi 25(3):156–159
200. Mitsui Shiro, Watabe Harusada, Yokogawa Mutsuo, Katsuda Takeshi; Shigematsu Kenji,
Sugiyama Noboru (1974) Liquid explosives containing nitroglycerin as the main ingredient
Kogyo Kayaku 35(3): 127–132
201. Azarkovich AE (1970) Correlation between the laboratory characteristics of explosives and
their explosive efficiency. From Fiziko-Tekhnicheskie Problemy Razrabotki Poleznykh
Iskopaemykh 3:9–64
202. Calvet E (1942) Brisance of explosives New tests of the practical determination of brisance.
Ann faculte sci Marseille 16:3–13
203. Haid A, Koenen H (1930) The testing of blasting caps. Z Gesamte Schiess-Sprengstoffwes
25: 393-398433-399463-398
204. Haid A, Koenen H (1934) Explosive force and its determination II. Z Gesamte Schiess-
Sprengstoffwes 29: 11-1437-19
205. Herlin C (1914) Brisance. Z Gesamte Schiess-Sprengstoffwes 8:448–452
206. Majrich A, Sorm F (1935) Brisance and its determination. Z Gesamte
Schiess-Sprengstoffwes 30: 295-299337-240
207. Roth JF (1941) The explosive properties of mixtures of tetranitromethane and nitrobenzene:
a contribution in support of the hydrodynamic theory. Z Gesamte Schiess- Sprengstoffwes
36: 4-628-3152-25
50 1 Properties of Insensitive Energetic Materials …

208. Smolenski D, Bogdal S, Glowiak B (1961) Preparation and properties of explosive

m-hydroxytetryl salts. Zeszyty Nauk Politech Wroclaw Chem 7:3–9
209. Stadler R (1938) Analytical and technical explosive investigations on silver acetylide.
Z Gesamte Schiess-Sprengstoffwes 33: 269-272302-265334-268
210. Urbanski T (1935) Determination of the brisance of explosives. Z Gesamte
Schiess-Sprengstoffwes 30:68–71
211. Wohler L, Roth FJ (1934) The brisance of explosives. Z Gesamte Schiess-Sprengstoffwes
29: 9-1146-1874-17
212. US department of Defense (1962) Military standard Explosive: Sampling inspection and
testing MIL-STD-650
213. Smith LC (1967) On Brisance, and a Plate-Denting Test for the Estimation of Detonation
Pressure. Explosivstoffe 5(106) and (6)130
214. Suceska M (1995) Test methods for explosives. Springer Science + Business Media, LLC
215. Anshits AG, Anshits NN, Deribas AA, Karakhanov SM, Kasatkina NS, Plastinin AV,
Reshetnyak AY, Silvestrov VV (2005) Detonation velocity of emulsion explosives with
cenospheres. University of Pardubice, pp 175–179
216. Badners H, Leiber CO (1992) Method for the determination of the critical diameter of
high-velocity detonation by conical geometry. Propellants Explos Pyrotech 17(2):77–81
217. Baklanov DI, Golub VV, Ivanov KV, Krivokopytov MS (2012) Transition of combustion
into detonation within a channel with the diameter less than the critical diameter of the
existence of stationary detonation. High Temp 50(2):238–243
218. Belov GV, Bakhrakh SM, Egorshin SP, Fedorova JG, Petrushin AV, Shaverdov SA,
Jamolkin EL (2001) Initiation and parameters of trinitrotoluene explosion at impact by
fragment. Elsevier Science BV pp 893–898
219. Borisov AA, Komissarov PV, Ibragimov RK, Silakova MA, Mailkov AE, Kudryashova EL
(2004) Energies of initiation of detonation in propane- and kerosene-air mixtures by various
sources. Torus Press Ltd, pp 54–59
220. Bowden M, Maisey MP, Knowles S (2012) Shock initiation of hexanitrostilbene at
ultra-high shock pressures and critical energy determination. In: AIP conference on
proceedings of 1426 (Shock Compression of Condensed Matter–2011 Part 1) pp 615–618
221. Debenham DF, Kosecki AP (1999) Shock initiation studies of composite gun propellants. In:
International annual conference on ICT 30th 83/81-83/10
222. Dremin AN, Trofimov VS (1965) Nature of the critical diameter Symp (Int). Combust Proc
1964:839–843
223. Francois E, Sanders VE, Lloyd J, Mang J (2009) Shock sensitivity of diaminoazoxy furazan
(DAAF) using an instrumented small scale gap test. In: International annual conference on
ICT 40th (Energetic Materials) 17/11-17/10
224. Frankel MB, Milton B, Tarzana F, Harry A, Encino A, Glen D, Park CA, Gray JC (1980)
Energetic monopropellant. United States Dept of the Air Force, Washington DC, USA, 4
297 152, Oct. 27, 1981, p 31
225. Hamate Y (2007) A computational study of microstructure effects on shock ignition
sensitivity of pressed RDX. In: AIP Conference on proceedings of 955 (Pt 2 Shock
Compression of Condensed Matter–2007 Part 2) pp 923–926
226. Haskins PJ, Cook MD (2007) Detonation failure in ideal and non-ideal explosives. In: AIP
Conference on proceedings 955 (Pt 1 Shock Compression of Condensed Matter–2007 Part
1) pp 377–380
227. Higgins AJ, Pinard P, Yoshinaka AC, Lee JH, S (2001) Sensitization of fuel-air mixtures for
deflagration-to-detonation transition. ELEX-KM Publishers, pp 45–62
228. Jette FX, Higgins AJ (2007) Critical diameter prediction for steady detonation in gasless
metal-sulfur compositions. In: AIP Conference on proceedings 955 (Pt 1 Shock
Compression of Condensed Matter–2007 Part 1) pp 385–388
229. Kato Y, Murata K (2008) Detonation propagation in packed bed of metal particles saturated
with nitromethane. In: International annual conference on ICT 39th p 107/101-p107/108
References 51

230. Khomik SV, Gelfand BE, Knyazev MV (1994) Experimental determination of a critical
diameter of detonation propagation in dust suspensions. Northeast Univ Press, pp 315–319
231. Kilmer EE (1978) Detonating cord failure in the F-111 aircraft crew module escape system.
In: Proceedings of international pyrotech seminar 6th, pp 304–319
232. Klapoetke TM, Stierstorfer J (2008) Triaminoguanidinium dinitramide-calculations synthe-
sis and characterization of a promising energetic compound. Phys Chem Chem Phys 10
(29):4340–4346
233. Knystautas R, Lee JH (1988) Detonation parameters for the hydrogen-chlorine system. Prog
Astronaut Aeronaut 114(Dyn Explos) pp 32–44
234. Knystautas R, Lee JH Guirao CM (1982) The critical tube diameter for detonation failure in
hydrocarbon-air mixtures. Combust Flame 48(1): 63–83
235. Knystautas R, Lee JHS, Moen IO, Guirao CM, Urtiew P (1981) Determination of critical
tube diameters for acetylene-air and ethylene-air mixtures. Christian Michelsens Inst
Vidensk Aandsfrihet, p 84
236. Lavrov VV, Afanasenkov AN, Shvedov KK (1997) On the experimental determination of a
critical diameter and a critical detonation velocity. Publishing House of Ordnance Industry,
pp 518–525
237. Maranda A, Paplinski A, Galezowski D (2003) Investigation on detonation and thermo-
chemical parameters of aluminized. ANFO J Energ Mater 21(1):1–13
238. Maranda A, Szymanski R (2013) Testing of critical diameter and detonation velocity of
mixtures of ammonium nitrate(V) and selected organic substances. Chemik 67(1):13–18
239. Matyas R, Zeman S, Trzcinski W, Cudzilo S (2008) Detonation performance of TATP/
AN-based explosives. Propellants Explos Pyrotech 33(4):296–300
240. McKenney RL, Jr, Summers PG, Schomber PR, Whitney SD (1991) Small-scale testing of
high bulk cubical and spherical nitroguanidine for comparative evaluation. In: International
annual conference on ICT 22nd (Combust React Kinet) 2/1-2/15
241. Mendes R, Plaksin I, Campos J, Ribeiro J (2000) Double slapper initiation of the PBX. In:
AIP conference on proceedings of 505 (Shock Compression of Condensed Matter Pt 2)
pp 915–918
242. Michot C, Bigourd J (1978) Detonability of slurry blasting agents. Propellants Explos 3(1–
2):30–33
243. Moen IO, Murray SB, Bjerketvedt D, Rinnan A, Knystautas R, Lee JH (1982) Diffraction of
detonation from tubes into a large fuel-air explosive cloud. In: Symposium (Int) combust
proceedings 19th, pp 635–644
244. Pawel D, Vasatko H, Wagner HG (1969) Influence of initial temperature of the limits of
detonability. Goettingen Univ, p 71
245. UTEC Corp (2007) Explosive material critical diameter testing energetic materials business
unit. http://www.utec-corp.com/index.php/energetic-materials/critical-diameter/
246. Department of Defense (1982) Group 1060 test methods chemical stability. USA,
MIL-STD-1751A
247. Bola MS, Madan AK, Singh M, Vasudeva SK (1992) Expansion of metallic cylinders under
explosive loading. Def Sci J 42(3):157–163
248. Kong X, Wu W, Li J, Liu F, Chen P, Li Y (2013) A numerical investigation on explosive
fragmentation of metal casing using. Smoothed Particle Hydrodynamic method Mater Des
51:729–741
249. Stagg MS, Otterness RE (1995a) Effect of blasting practices on fragmentation: Full-scale
results. In: Annual meeting Minn Sect SME proceedings of 68th 215–230
250. Stagg MS, Otterness RE (1995b) Screen analysis of full-scale production blasts. In:
Proceedings of annual symposium explosive blasting Res 11th 298-313
251. Chen C-Y, Shiuan J-H, Lan IF (1994) The equation of state of detonation products obtained
from cylinder expansion test. Propellants Explos Pyrotech 19(1):9–14
252. Chen H, Touchard GG Radke CJ (1996) A linearized double layer model for laminar flow
electrification of hydrocarbon liquids in metal pipes. Institute of Electrical and Electronics
Engineers pp 411-414
52 1 Properties of Insensitive Energetic Materials …

253. Craig BG, Johnson JN, Mader CL, Lederman GF (1978) Characterization of two commercial
explosives. Los Alamos Scientific Laboratory Tech. Rep. USA, LA-7140 p 21
254. Cudzilo S, Maranda A Trzcinski WA (1997) Determination of energetic characteristics of
ammonale 94/6 by using a cylinder test. In: International annual conference on ICT 28th
(Combustion and Detonation) 104101-104109
255. Cudzilo S, Trzcinski WA (2000) A study on detonation characteristics of pressed NTO. In:
International annual conference on ICT 31st (Energetic Materials) 77/71-77/14
256. Cudzilo S, Trzcinski WA (2001) A study on detonation characteristics of pressed NTO.
J Energ Mater 19(1):1–21
257. Doherty RM, Short JM Kamlet MJ (1989) Improved prediction of cylinder test energies.
Combust Flame 76(3-4): 297-306
258. Hamashima H, Kato Y, Nadamitsu Y, Itoh S, Haid A, Koenen H (1934) Explosive force and
its determination II. Z Gesamte Schiess-Sprengstoffwes 29: 11-1437-19
259. Petel OE, Higgins AJ (2006) Comparison of failure thickness and critical diameter of
nitromethane. In: AIP conference on proceedings of 845 (Pt 2 Shock Compression of
Condensed Matter–2005 Part 2) pp 994–997
260. Petel OE, Mack D, Higgins AJ, Turcotte R, Chan SK (2007) Minimum propagation diameter
and thickness of high explosives. J Loss Prev Process Ind 20(4–6):578–583
261. Reza A, McCarthy RL (1999) Measurements to determine the effect of selected additives on
the detonability of ANFO mixtures. In Proceedings of annual conference on explosive
blasting tech 25th (vol 2) pp 249–261
262. Swinton RJ, Bussell T, McVay L (1996) A critical diameter study of the Australian
manufactured underwater explosive. Composition H6 Aeronautical Maritime Res Lab, AD
A319313, Defence Science And Technology Organization Canberra (Australia) p 13
263. Titov VM, Sil’vestrov VV, Kravtsov VV, Stadnichenko IA (1976) Investigation of some
cast TNT properties at low temperatures. Inst Hydrodynam, pp 36–46
264. Tsuchiya YN (1962) Crystal habit modification of ammonium nitrate III Application to
ammonium nitrate-fuel oil explosives. Kogyo Kayaku Kyokaishi 23:78–83
265. Vidal P, Bouton E, Pagnanini L (2012) Modeling detonation in liquid explosives: The effect
of the inter-component transfer hypothesis on chemical lengths and critical diameters.
Combust Flame 159(1):396–408
266. Vidal P, Presles HN, Gustin JL, Calzia J (1993) Detonation failure diameters and detonation
velocities of nitric acid acetic acid and water mixtures. J Energ Mater 11(2):135–153
267. Virchenko VA, Egorov AP, Fadeev AI (1993) The critical diameter of detonation of PETN
single crystal. Hanneng Cailiao 1(2):17–22
268. Whelan DJ, Bocksteiner G (1995) Velocity of detonation charge diameter and critical
diameter in unconfined RDX-driven heterogeneous explosives. J Energ Mater 13(1&2):15–
34
269. Zenow L, Tkachenko EA, Brooks NB, Lansdale RL, Lewis GE (1967) Application of
two-dimensional computations to the study of subcritical initiation and fadeout in a
homogeneous explosive. Symp Combust 11:645–655 discussion 655-646
270. Wulfman DS, Sitton O, Nixon FT, Podzimek M, Worsey G, Beistel D, Worsey P, Burch D,
Johnson M (1997) Reformulation of solid propellants and high explosives: an environmen-
tally benign means of demilitarizing explosive ordnance. Can J Chem Eng 75(5):899–912
271. Nikitin VF, Dushin VR, Phylippov YG, Legros JC (2009) Pulse detonation engines:
technical approaches. Acta Astronaut 64(2–3):281–287
272. Miyake A, Kobayashi H, Echigoya H, Arai H, Katoh K, Kubota S, Wada Y, Ogata Y,
Ogawa T (2006) Combustion and detonation properties of ammonium nitrate and activated
carbon mixtures. In: Proceedings of international pyrotech seminar 33rd pp 413–421
273. Shiromaru H, Kobayashi K, Mizutani M, Yoshino M, Mizogawa T, Achiba Y, Kobayashi N
(1997) An apparatus for position sensitive TOF measurements of fragment ions produced by
coulomb explosion. Phys Scr T T73 (8th International Conference on the Physics of Highly
Charged Ions 1996) pp 407–409
References 53

274. Lemoine D, Cherin H, Jolibois P (1994) Determination of the sensitivity of liquid explosives
submitted to mechanical threats. Int Annu Conf ICT 25th (Energetic Materials-Analysis
Characterization And Test Techniques) 81/81-81/89
275. Plaksin IY, Shutov VI, Gerasimov VM, Gerasimenko VF, Morozov VG, Karpenko II
Sokolov SS (1996) Evolution of explosion in TATB HE in the process of its expansion into
a free space followed by impact against hard barrier. In: AIP Conference on Proceedings of
370 (Pt 2 Shock Compression of Condensed Matter–1995) pp 875–878
276. Santner E (1995) Comparison of wear and friction measurements of TiN coatings.
Tribologia 26(1):7–29
277. Sapko MJ, Weiss ES, Watson RW (1989) Preferred explosives for blasting in the presence of
combustible dusts. Can Inst Min Metall, USA, pp 49–61
278. Phillips JJ (2012) A modified type-12 impact sensitivity test apparatus for explosives.
Propellants Explos Pyrotech 37(2):223–229
279. Le Roux JJPA (1990) The dependence of friction sensitivity of primary explosives upon
rubbing surface roughness. Propellants Explos Pyrotech 15(6):243–247
280. Kubota S, Ogata Y, Wada Y, Saburi T, Nagayama K (2008) Behaviors of high explosive
near the critical conditions for shock initiation of detonation. Mater Sci Forum 566
(Explosion Shock Wave and Hypervelocity Phenomena in Materials II) pp 15–22
281. Klapoetke TM, Krumm B, Nieder A, Richter O, Troegel D, Tacke R (2012)
Silicon-containing explosives: syntheses and sensitivity studies of (Azidomethyl)- Bis
(azidomethyl)- and Tris(azidomethyl)silanes. Z Anorg Allg Chem 638(7–8):1075–1079
282. Kerth J, Kuglstatter W (2001) Synthesis and characterization of
26-Diamino-35-dinitropyrazine-1-oxide (NPEX-1). In: International Annual Conference on
ICT 32nd (Energetic Materials) 166/161-166/111
283. Peterson PD, Lee KY, Moore DS, Scharff RJ, Avilucea GR (2007a) The evolution of
sensitivity in HMX-based explosives during the reversion from delta to beta phase. In: AIP
Conference on Proceedings of 955 (Pt 2 Shock Compression of Condensed Matter–2007
Part 2) pp 987–990
284. Peterson PD, Avilucea GR, Bishop RL, Sanchez JA (2007b) Individual contributions of
friction and impact on non-shock initiation of high explosives. In: AIP Conference on
Proceedings of 955 (Pt 2 Shock Compression of Condensed Matter–2007 Part 2) pp 983–
986
285. Miles G, Williams MR, Wharton RK, Train AW (1996) The development of an elevated
temperature friction sensitiveness apparatus. In: International Annual Conference pn ICT
27th (Energetic Materials) pp 3131–3114
286. Matyas R, Selesovsky J, Musil T (2012) Sensitivity to friction for primary explosives.
J Hazard Mater 213–214:236–241
287. Matyas R, Selesovsky J, Musil T (2012) Sensitivity to friction for primary explosives.
J Hazard Mater 213–214:236–241
288. Mainiero RJ, Miron Y, Kwak SSW, Kopera LH, Wheeler JQ (1996) Impact thermal and
shock sensitivity of molten TNT and of asphalt-contaminated molten TNT. In: Proceedings
of annual conference on explosive blasting tech 22nd pp 179–197
289. Ishikawa K, Abe T, Kubota S, Wakabayashi K, Matsumura T, Nakayama Y, Yoshida M
(2006) Study on the shock sensitivity of an emulsion explosive by the sand gap test. Sci
Technol Energ Mater 67(6):199–204
290. Ling P, Sakata J, Wight CA (1996) Detonation chemistry of glycidyl azide polymer. Mater
Res Soc Symp Proc 418(Decomposition Combustion and Detonation Chemistry of Energetic
Materials) pp 363–371
291. Dundar D, Gullu M (2007) Use of alkyl hydantoin derivatives as binding materials in
high-energy explosives propellants and undercoatings. Tubitak-Turkiye Bilimsel ve Teknik
Arastirma Kurumu Turk, p 20
292. Alekseevskii EV, Musin YD (1945) Instrument for determination of ignition temperature
and kinetics of oxidation of activated charcoal. Zh Prikl Khim (S-Peterburg Russ Fed) 18:
505–508
54 1 Properties of Insensitive Energetic Materials …

293. Bashkirov BG (1969) Determination of ignition temperature and duration of latent stage
during the oxidation of sulfide deposits with the use of a linear function. Geol Razvedka
Metody Izuch Mestorozhd Polezn Iskopaemykh pp 132–133
294. Edwards PW, Harrison RW (1930) Apparatus for the determination of ignition temperature
of powder substances. Ind Eng Chem Anal Ed 2:344–345
295. Hu W, Yang H, Lu J, Zhang H, Zhang J, Liu Q, Yue G (2005) Determination of ignition
temperature of coal by using thermogravimetry. In: Proceedings of international conference
on fluid bed combust 18th pp 557–562
296. Simorova T (2007) The chosen methods of determination of ignition temperature of the
wood dusts. University of Pardubice, pp 985–994
297. United Nations. Recommendations on the Transport of Dangerous Goods Tests and Criteria.
United Natio United Nations Economic Commission for Europe Allied Ordnance
Publication-7 (AOP-7) Annex 1 Description of Tests Used for the Qualification of
Explosive. Materials for Military Use Recommendations on the Transport of Dangerous
Goods: Manual of Tests and Criteria, United Nations, New York, USA
298. Department of Defense. TB 700-2 Explosives Hazard Classification Procedures Alsoknown
as NAVSEAINST 80208B Air Force TO 11A-1-47 and DLAR 82201,s, Department Of
Defense Ammunition And Explosives Hazard Classification Procedures New York, USA
299. Walker G R, Whitbread EG, Hornig DC (1966) Manual of Sensitiveness Tests Valcartier.
Quebec Canada: Canadian Armament Research and Development Establishment Published
for Tripartite Technical Cooperation Program (TTCP) Panel 0-2 (Explosives) Working
Group on Sensitiveness, pp 46–50
300. NATO (1999) NATO STANAG 4489 Explosives impact sensitivity test(s) north atlantic
treaty organization 1999-09-17
301. Munroe CE, Tiffany JE (1931) Physical Testing of Explosives at the Bureau of Mines
Explosives Experiment Station, Bruceton, PA. U.S. Dept. of Commerce. Bureau of Mines,
Bulletin 346:78–84
302. Dixon WJ, Massey FM Jr (1983) Introduction to statistical analysis, 4th edn. McGraw-Hill
Co Inc, New York
303. Applied Mathematics Panel National Defense Research Committee (1944) Statistical
Analysis for a New Procedure in Sensitivity Experiments. AMP Report No 101lR SRG-p No
40 July 1944
304. Becker KR (1972) Bureau of Mines Instrumented Impact Tester. Department of Interior
Bureau of Mines Report of Investigations, USA, 7670
305. Dixon WJ, Mood AM (1948) Method for Obtaining and Analyzing Sensitivity Data. J Am
Stat Assoc 43:109–126
306. Army Material Command (1971, January) Engineering design handbook explosive series
properties of explosives of military interest. Washington DC, AMCP-706-177, p 26
307. Harris J (1982) Friction Sensitivity of Primary Explosives. ARLCD-TR-82012, Picatinny
Arsenal, Dover, NJ, USA
308. Wharton RK, Harding JA (1994) A study of some factors that affect the impact sensitiveness
of liquids determined using the BAM Fallhammer apparatus. J Hazard Mater 37(2):265–276
309. Wharton RK, Chapman D (1997) The relationship between BAM friction and rotary friction
sensitiveness data for high explosives. Propellants Explos Pyrotech 22(2):71–73
310. Operating Manual for Model 150 ESD Sensitivity Tester Hercules Aerospace Company
Allegan Ballistics Laboratory Rocket Center West Virginia
311. Kirshenbaum MS (1976) Response of Primary Explosives to Gaseous Discharges in an
Approved Approaching Electrode Electrostatic Sensitivity Apparatus. PATR-4955 Picatinny
Arsenal, Dover, N.J. USA
312. North Atlantic Treaty Organization (2001) NATO STANAG 4490 Explosives Electrostatic
Discharge Sensitivity Test Large Scale
313. Price D, Clairmont AR Jr, Erkman JO (1974) The NOL large-scale gap test III. Compilation
of Unclassified Data and Supplementary Information for Interpretation of Results Noltr
74-40, Naval Ordnance Lab, White Oak, MD, USA, AD 0780429
References 55

314. Erkman JO, Edwards DJ, Clairmont AR Jr, Price D (1973) Calibration of the NOL
large-scale gap test; hugonoit data for polymethyl methacrylate NOLTR 73–15 April 1973.
Naval Ordnance Laboratory, White Oak, Silver Spring, Maryland, USA
315. Walker GR, Whitbread EG, Hornig DC ed (1966) Manual of Sensitiveness Tests Valcartier.
Quebec Canada: Canadian Armament Research and Development Establishment Published
for Tripartite Technical Cooperation Program (TTCP) Panel 0-2 (Explosive) Working Group
on Sensitiveness, pp 144–151
316. Ayres JN (1961) Standardization of the small scale gap test used to measure the sensitivity of
explosives. NAVWEPS Report 7342 16 Naval Surface Warfare Center, White Oak, MD,
USA
317. Price D, Liddiard TP Jr (1966) The small-scale gap test: calibration and comparison with the
large scale gap test. NOLTR 66–87 7 Naval Surface Warfare Center, White Oak, MD, USA
318. Ayres JN, Montesi LJ, Bauer RJ (1973) Small-scale gap test (ssgt) data compila-
tion:1959-1972: vo I Unclassified Explosives. NOLTR 73-132 26 Naval Surface Warfare
Center, White Oak, MD, USA
319. Hampton LD, Blum GD (1965) Maximum likelihood logistic analysis of scattered go/no-go
(quantal) data. NOLTR 64-238 26, Naval Surface Warfare Center, White Oak, MD, USA
320. Jaffe I, Beauregard RL, Amster AB (1960) The attenuation of shock in lucite. NAVORD
6876, Naval Ordnance Laboratory, White Oak, Maryland, USA, AD 241341
321. Liddiard TP, Price D (1987) The expanded large-scale gap test. NSWC TR 86-32, Naval
Surface Weapons Center, Dahigren, Virginia, USA, AD A179406
322. Tasker DG, Baker RN (1992) Experimental calibration of the NSWC expanded large scale
gap test. NSWC TR 92-54 ad A253813, Naval Surface Weapons Center, White Oak,
Maryland, USA
323. Foster C (1983) Parsons and gunger “suppression of sympathetic detonation”. In:
Proceedings of the 22nd explosive safety seminar, Houston, TX, USA
324. Glenn JG, Aubert SA, Gunger M E (1996) Development and calibration of a super large
scale gap test. WL-TR-96-7039, Shalimar, FL, USA AD B213753
325. NATO, Standardization Agreement STANAGNATO STANAG 4488 Explosives shock
sensitivity tests
326. Horst A (1987) The insensitive high explosives gap test. NSWC TR 86-058
327. Holmquist TJ (1988) Insensitive High Explosives Gap Test Data. NSWC Tr 88-282
Ad-A233 061 Strength And Fracture Characteristics OFHY-80, HY-1 00, And HY-130
Steels Subjected to Various Strains, Strain Rates,Temperatures, and Pressuresby, USA
328. Erkman JO, Edwards DJ, Clairmont AR, Jr, Price D (1973) Calibration of the nol large-scale
gap test. Hugoniot Data for Polymethyl Methacrylate NOLTR 73–15, USA
329. Tan B, Long X, Peng R, Li H, Jin B, Chu S (2011) On the shock sensitivity of explosive
compounds with small-scale gap test. J Phys Chem A 115(38):10610–10616
330. Koenig PJ, Mostert FJ (1998) A gap test driven by optimality statistics software. Propellants
Explos Pyrotech 23(2):63–67
331. Yu X, Zheng M (2011) Influence of pad or air gap between the high explosive and flyer.
University of Pardubice Institute of Energetic Materials, pp 404–411
332. Wolfson MG (1983) The MRL small scale gap test for the assessment of shock sensitivity of
high explosives. Mater Res Lab. p 26
333. Trzcinski WA, Kutkiewicz M, Szymanczyk L (2005) The use of the gap test to investigate
the shock to detonation transition in low-sensitivity explosives Part I—experimental
approach. University of Pardubice, pp 840–846
334. Ruyat Y, Nakayama Y, Matsumura T, Wakabayashi K, Liu Z-Y, Kubota S, Nakahara T,
Miyake A, Ogawa T, Yoshida M (2004) Card gap test of tri-n-butyl phosphate/fuming nitric
acid mixture. Mater Sci Forum 465–466 (Explosion Shock Wave and Hypervelocity
Phenomena in Materials) pp 319–324
335. Grant RL, Hanna NE, Van Dolah RW (1967) New gap-sensitivity methods for explosives.
U S Bur Mines Rep Invest No 6974, p 17
336. Prokosch DW et al (1994) Chemical reactivity test for thermal stability. UCRL-JC-117941
56 1 Properties of Insensitive Energetic Materials …

337. McKenney RL Jr (1998) AFRL/MNME Technical Memorandum 98 60 Modified Vacuum

Thermal Stability Apparatus
338. Knutson DT, Newman KE (1995) Processing and vulnerability evaluation of batch
manufactured RDX. IHTR 1802, Indian Head Division Naval Surface Warfare Center Indian
Head, MD, USA
339. Edwards PW, Harrison RW (1930) Apparatus for the determination of ignition temperature
of powder substances. Ind Eng Chem Anal Ed 2:344–345
340. NATO STANAG 4515 Thermal Characterization of Explosives
341. ASTM (1986) E537-86 standard test method for assessing the thermal stability of chemicals
by methods of differential thermal analysis. American Society for Testing and Materials,
Philadelphia
342. Benchabane M (1993) The discontinuous vacuum stability test (DVST). J Energetic
Materials 11(2):89–100

Additional Scholarly Articles for Further Reading

343. ASTM International (2006) Standard E 794-06: Standard test method for melting and
crystallization temperatures by thermal analysis
344. ASTM D7169–11 Standard Test Method for Boiling Point Distribution of Samples with
Residues Such as Crude Oils and Atmospheric and Vacuum Residues by High Temperature
Gas Chromatography D6730 Test Method for Determination of Individual Components in
Spark Ignition Engine Fuels by 100-Metre Capillary (with Precolumn) High-Resolution Gas
Chromatography
345. ASTM A572 / A572 M–13a Standard Specification for High-Strength Low-Alloy
Columbium-Vanadium Structural Steel A6/A6 M Specification for General Requirements
for Rolled Structural Steel Bars Plates Shapes and Sheet Piling A36/A36 M Specification for
Carbon Structural Steel A514/A514 M Specification for High-Yield-Strength Quenched and
Tempered Alloy Steel Plate Suitable for Welding A588/A588 M Specification for
High-Strength Low-Alloy Structural Steel up to 50 ksi 345 MPa Minimum Yield Point
with Atmospheric Corrosion Resistance
346. ASTM D3132-84(1996) Withdrawn Standard: ASTM D3132-84(1996) Standard Test
Method for Solubility Range of Resins and Polymers (Withdrawn 2005) Developed by
Subcommittee: D0133 WITHDRAWN NO REPLACEMENT
347. ASTM E2071–00(2010) Standard Practice for Calculating Heat of Vaporization or
Sublimation from Vapor Pressure Data
348. ASTM D4612–08 Standard Practice for Calculating Thermal Diffusivity of Rocks ASTM
D4809–13 Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by
Bomb Calorimeter (Precision Method)
349. ASTM E1148-02(2008) Withdrawn Standard: ASTM E1148-02(2008) Standard Test
Method for Measurements of Aqueous Solubility (Withdrawn 2013) ASTM D1696–95
(2011) Standard Test Method for Solubility of Cellulose in Sodium Hydroxide ASTM
D1110 - 84(2013) Standard Test Methods for Water Solubility of Wood ASTM D7553–10
Standard Test Method for Solubility of Asphalt Materials in N-Propyl Bromide
350. ASTM D2541-93(2001) Withdrawn Standard: ASTM D2541-93(2001) Standard Test
Method for Critical Diameter and Detonation Velocity of Liquid Monopropellants
(Withdrawn 2003) Historical Standard: ASTM D2541-93 Standard Test Method for
Critical Diameter and Detonation Velocity of Liquid Monopropellants SUPERSEDED
ASTM D2539-93 Historical Standard: ASTM D2539-93 Standard Test Method for Shock
Sensitivity of Liquid Monopropellants by the Card-Gap Test SUPERSEDED
351. ASTM D5842–04(2009) Standard Practice for Sampling and Handling of Fuels for
Volatility Measurement ASTM D1837–11 Standard Test Method for Volatility of Liquefied
Additional Scholarly Articles for Further Reading 57

Petroleum (LP) Gases ASTM D323–08 Standard Test Method for Vapor Pressure of
Petroleum Products (Reid Method)
352. UNE 31023:1994 Determination Of Explosive Brisance PowER (Hess MethoD)
353. ASTM E1248–90(2009) Standard Practice for Shredder Explosion Protection ASTM
E1226–12a Standard Test Method for Explosibility of Dust Clouds
354. Specification D-4814 (previously D-439) D 7055-04 Practice for Preparation (by Abrasive
Blast Cleaning) of Hot-Rolled Carbon Steel Panels for Testing of Coatings D 7072-04
Practice for Evaluating Accelerated Efflorescence of Latex Coatings
355. ASTM E1641–13 Standard Test Method for Decomposition Kinetics by Thermogravimetry
Using the Ozawa/Flynn/Wall Method ASTM E2550–11 Standard Test Method for Thermal
Stability by Thermogravimetry ASTM D7876–13 Standard Practice for Practice for Sample
Decomposition Using Microwave Heating (With or Without Prior Ashing) for Atomic
Spectroscopic Elemental Determination in Petroleum Products and Lubricants; ASTM
D2879–10 Standard Test Method for Vapor Pressure-Temperature Relationship and Initial
Decomposition Temperature of Liquids by Isoteniscope
356. ASTM D6600-00 Historical Standard: ASTM D6600-00 Standard Practice for Evaluating
Test Sensitivity for Rubber Test Methods
357. ASTM D149–09(2013) Standard Test Method for Dielectric Breakdown Voltage and
Dielectric Strength of Solid Electrical Insulating Materials at Commercial Power
Frequencies
Chapter 2
Hexanitrohexaazaisowurtzitane
(HNIW, CL-20)

Abstract Hexanitrohexaazaisowurtzitane, a nitroamine compound, has emerged as

an important insensitive energetic material. This caged compound offers several
interesting properties. This chapter discusses the properties and more importantly
the formulations using CL-20.

2.1 Introduction

Hexanitrohexaazaisowurtzitane (HNIW), commonly known as CL-20, is

2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclododecane. It is a high-energy
explosive compound and a polyazapolycyclic caged polynitramine. Structurally, it
appears like two RDX molecules fused together. CL-20 is one of the most powerful
explosives known today. Tests indicate that the formulations containing CL-20
have excellent stability, belong to hazard class 1.3, and environmentally friendly. It
was first synthesized by Nielsen [1] in 1987 at the Naval Air Warfare Center, China
Lake, CA, U.S.A. The strained/caged structure and high oxygen balance gives
CL-20 a high density and high explosive power. The six N–NO2 groups in CL-20
give a better oxidizer to fuel ratio and makes its performance better than RDX and
HMX in specific impulse, detonation velocity, enthalpy of formation, and other
parameters. It exists in five polymorphic forms, a, b, c, e, and f, and the existence
of a polymorphic phase depends on the temperature and pressure. The f–form is
formed at higher pressures. A sixth d form has also been reported. Of these six
forms, e-polymorph has higher symmetry, thus morphologically more stable at
room temperature and has the highest density (2.04 g/cm3) than the other poly-
morphs. Of the six forms, only b, c, and e have been prepared in the pure form.
CL-20 has many applications including in propulsion of strategic missiles, space
launchers and for high-lethality warheads for smart and light weapons, such as
Precision Guided Missiles, and Laser Guided Bombs. The cost of producing CL-20
is decreasing and is less than $800 per kg as reported by the USA Navy Mantech
Report of 2003 [2].

© US Government (outside the USA) 2018 59

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7_2
60 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

2.2 Synthesis

The synthesis process may be divided into two steps. The first step involves the
construction of the hexanitrohexaazaisowurtzitane cage, which is hexabenzylhexa-
azaisowurtzitane (HBIW). The chemical formula of HBIW is 2,4,6,8,10,12-
hexabenzyl-2,4,6,12-hexaazatetracyclo[5, 5, 0, 05.9, 03.11] dodecane. HBIW is
formed by the condensation reaction of glyoxal with benzylamine. Nielsen et al. [3]
and Crampton et al. [4] suggested several derivatives of benzylamine to form cage.
However, benzylamine provided the best yield for HBIW, about 80%. A number of
solvents including acetonitrile, methanol, ethanol, and isopropyl alcohol have been
tried to carry out the condensation reaction in the presence of an acid catalyst.
However, acetonitrile is found to be the best solvent. The reaction can proceed in
the temperature range of 0–25 °C [3]. Both organic and inorganic acids can be used
as catalysts.
The second step involves nitrolysis. However, direct conversion of HBIW to
CL-20 by nitrolysis cannot be carried out. The nitration of the phenyl rings is more
favorable compared to the nitration of HBIW. Therefore, debenzylation of HBIW
by catalytic hydrogenation prior to nitration is the preferred method. As a result, the
functional groups associated with nitrogen atoms are substituted by the nitro
groups.
The synthesis of CL-20 was first carried out by Nielsen and is described in the
US Patent 5693794 [1]. Later Nielsen and his co-workers used a direct conden-
sation of benzylamine with glyoxal. Crampton et al. [4] reported the synthesis of
HNIW using the same route, which was the reaction of aldehydes with amines
producing cage compounds. Both Nielsen et al. and Crampton et al. tried to find an
alternative to benzalmine, but noted that the yield of HBIW was much lower.
Debenzylation of HBIW is carried out in the presence of a catalyst. A variety of
catalysts and nitrating agents have been explored. Nielsen and his co-workers used
excess acetic anhydride for hydrogenation of HBIW forming 4,10-dibenzyl-
2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazaisowurtzitane (TADBIW) derivative.
Several researchers employed Pd or Pd supported on carbon based catalyst in a
variety of solvents for synthesis of HBIW derivatives. These include: Pd and Pd in
formic acid as a solvent [5] H2 and Pd/C in ethylbenzene [6], H2, Pd/C, and acetic
anhydride in the presence of N,N-dimethylacetamide [7]. However, the cost of
palladium is an issue and should be optimized to lower the overall cost of synthesis.
Other catalytic materials along with solvents used for synthesis are discussed
below. Ou et al. [8] have substituted ethanol for acetonitrile. This not only reduces
the cost but also the process is less toxic. In later papers, Ou et al. [9, 10] have
described the synthesis of CL-20 using benyzlamine and glyoxal. Their method
included the condensation with formic acid in acetonitrile to give CL-20. Methods
of synthesis and properties of CL-20 a highly energetic polycyclic nitramine are
surveyed (Figs. 2.1 and 2.2). Yet in another paper, Wang et al. [12] describe a
one-pot synthesis of HNIW. The starting material in this case is
tetraacetyldibenzylhexaaza-isowurtzitane (TADBIW).
2.2 Synthesis 61

Nielson et al. [13] and Latypov et al. [14] synthesized CL-20 via TADBIW
conversion to tetraacetyldinitrosohexaazaisowurtzitane (TADNIW) using N2O4 or
NOBF4 as catalyst. The resulting TADNIW was nitrated using NO2BF4. A yield of
90% was reported. However, reagents NOBF4 and NO2BF4 are costly, which are
also not environmental friendly. A mixture of nitric and sulfuric acids was used by
Hamilton et al. [15] and Bellamy [16] to nitrate both TADAIW and TADFIW to
CL-20. Zhao et al. used 95–99% nitric acid for TADAIW nitration. The optimized
reaction parameters provided 85% yield of CL-20. Surapaneni et al. [17] also used
98% nitric acid in order to improve process economics for the synthesis of CL-20.
Qian et al. [18] developed a sono-chemical method for the synthesis of CL-20
starting with TADBIW. The described two synthesis schemes using ultrasound at
30–80 kHz frequency in their experiments and obtained yields varying from 40 to
90%. The experiments were carried out at 333.15 K, mostly at 60 kHz frequency,
and 10:5:1 ratio of HNO3, N2O4, and TADBIW in ionic liquids. Their two reaction
schemes are shown in Figs. 2.3 and 2.4.
Qian et al. [19, 20] continued the use of N2O4 as a nitrating agent in their
subsequent work and reported good yield of CL-20. Sung et al. [21] studied the
reaction mechanism of nitration/nitrolysis of tetraacetylhexaazaisowurtzitane
(TAIW) with the mixture of nitric acid and sulfuric acid. According to them, two
free secondary amines of TAIW are nitrated first and then four acetyl groups of
TAIW, which were dependent on temperature.

Fig. 2.1 Synthesis mechanism for this reaction is in scheme [11]. Ar = Ph (a), C6H4Me-p (b),
C6H4Me-o (c), C6H4OMe-p (d), C6H4OMe-o (e), C6H3(OMe)2.3,4 (f), C6H4Pri-p (g),
C6H4Cl-p (h), C6H4Cl-o (i), C6H4F-o (j), C6H4Br-o (k)
62 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Fig. 2.2 Synthesis of hexanitrohexaazaisowurtzitane (CL-20) [3] and CL-20-based formulations

CH3CO-N N-COCH 3
N 2O4O3 / HNO 3 O2N-N N-NO 2
CH3CO-N N-COCH 3
((( IL O2N-N
N-NO 2
C 6H5CH2-N N-CH2C 6H5 O2N-N N-NO 2

TADBIW HNIW

Fig. 2.3 Overall reaction scheme (Qian et al. [18, 20])

Gore et al. [22] described a method for synthesis of CL-20 from 2, 6, 8,

12-tetraacetyl-4, and 10-dibenzylhexaazaisowurtzitane using debenzylation followed
by nitration. Reaction of TADBIW with cerium (IV) ammonium nitrate produced the
debenzylated product, which on nitration with HNO3/H2SO4 resulted in CL-20.
Acetylation of the debenzylated and further nitration also resulted in CL-20. Kawabe
et al. [23], and Cagnon et al. [24] patented their synthesis process for production of
CL-20. Cagnon et al. synthesized hexanitrohexaaza- isowurtzitane, in a single
reaction stage, by nitration of the substituted hexa- azaisowurtzitane derivative
formed by reaction of the a, b-dicarbonyl derivative with the primary amine. They
claimed that this route reduced the cost by eliminating the intermediate step of
making HBIW and eliminating the expensive stage of catalytic hydrogenolysis.
Kawabe et al. [23] used an expensive palladium catalyst.
2.2 Synthesis 63

CH3CO-N N-COCH 3 N2 O4 /HNO3 CH3CO-N N-COCH3

N-COCH3
CH3CO-N N-COCH 3 CH3CO-N
C 6H5CH2-N N-CH2C 6H5 ON-N N-NO

TADNSIW
TADBIW

O2 N-N N-NO2
CH3CO-N N-COCH3 N2 O4 /HNO3
O3
O2 N-N N-NO2
CH3CO-N N-COCH3
O2 N-N N-NO2
O2 N-N N-NO2

TADNIW HNTW

Fig. 2.4 Actual reaction scheme showing the intermediates [20]

In the one-pot synthesis process for HNIW described by Wang et al. [12] the
starting material was TADBIW. A yield up to 82% and a purity of CL-20 up to 98%
was claimed by the authors. This one pot method is based on the method described
earlier by Latpov et al. [25]. This is a two stage process involving nitrosation
followed by nitration in which 2,6,8,12-tetraacetyl-4,10-dibenzyl-2,4,6,8,10,12-
hexaazaisowurtzitane is converted to 2,4,6,8,10,12-hexanitro- 2,4,6,8,10,12-
hexaazaisowurtzitane, and it is claimed that the product is better than 95% pure.
Pang et al. [26] describe a synthesis route in which hexabenzylhexaazaisowurtzi-
tane is converted to HNIW and avoided the hydrogenolysis step. Although the route
of oxidative debenzylation and acetylation is less expensive, the yield is less than
the conventional process.
Chapman and Hollins [27] described the oxidation of hexa(1-pro-pentyl)hex-
aazaisowurtzitane [HPIW] by singlet oxygen. This synthesis route is a modified
procedure suggested by Herve et al. [28], although they did not synthesize CL-20.
They presented a general method for the synthesis of hexaazaisowurtzitane cages
avoiding the condensation of benzylamines. Some of the compounds synthesized
by these authors could act as precursors for the preparation of CL-20. The proce-
dure consists of the synthesis of hexaallylhexaazaiso-wurtzitane, followed by its
conversion to HPIW, and finally to HNIW. The authors present different routes to
the synthesis of HPIW and different photooxidation routes to convert HPIW to
HNIW.
The effect of several process variables and their optimization has been discussed
by Mandal et al. [29]. Their study noted that for approximate 85% yield, optimized
temperature range was 345–358 K, nitric acid concentration range from 98 to 92%,
reaction time of 1 h, and temperature during the addition of TAIW into the mixed
acid to be in the range of 298–313 K. To improve the particle size of CL-20, during
the recrystallization process, the authors have studied the effect of parameters like
addition rate of anti-solvent and rate of agitation and identified optimum conditions.
64 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Purification, recrystallization, and nano particle synthesis of CL-20 have

received a greater attention in recent years. The importance of different polymorphs
and particle size in the use of CL-20 as an insensitive explosive have been dis-
cussed by several authors [30–34].
In an unusual study of crystal transition, Song et al. [21] have looked at the effect
of solvents on crystal transformation. e-CL-20 was recrystallized from pure
(alcohol, dichloro-methane, acetone and ethyl acetate) and mixed (alcohol-acetone,
alcohol-ethylacetate, dichloromethane-acetone, dichloromethane-ethyl acetate and
acetone-ethyl acetate with different volume ratio) solvents. The resulting crystal
forms were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and
Scanning Electron Microscope (SEM).
Several authors have reviewed the synthesis of CL-20. They are: Ou et al. [8, 9],
Sysolyatin [11], Agrawal [35], and Nair et al. [36]. Chapman et al. [37] investigated
the synthesis of CL-20 as a part of their work for SERDP. Their procedure does not
involve benzylamine glyoxal condensation, a procedure followed by many inves-
tigators. A synthesis method starting from tetracetyldi-formylhexaazaisowurtzitane
(TADFIW) has been described by Jin et al. [38] in which c-HNIW was first
produced and then was converted to e-CL-20 in the solution in which nitration
reaction occurred. The yield of e-CL-20 was 91%, and the purity close to 99.5%.
Duddu and Dave [39] proposed a method to transform all other polymorphs to
e-HNIW using acetic acid and ethyl acetate as mixed solvent, and n-hexane as
nonsolvent.

2.2.1 Characterization of Polymorphs of CL-20

The e-HNIW has the highest density among all other polymorphs and thermody-
namically most stable at ambient conditions. As a result, the focus is to synthesize
e-HNIW with a maximum yield. Various properties of Cl-20 polymorphs are given
in Table 2.1. As shown in Table 2.1, these polymorphs differ from each other in the
spatial orientation of the nitro groups relative to the five- and six-membered rings of
the cage, the type of the crystal packing and the number of molecules per unit cell
[11].
Wardle and Hinshaw [40] discussed the formation of a-, b-HNIW, which mainly
depended on the solution used for recrystallization or precipitation of HNIW. The
a-HNIW was formed upon precipitation of HNIW with chloroform from its solu-
tions in sulfolane. They noted the presence of b-HNIW when crude HNIW was
recrystalized from benzene solution. However, b-HNIW is very unstable and
coverts readily to c-HNIW at 185 °C. c-HNIW can also be synthesized by the
nitrolysis of the diformyl derivative with nitric acid. Direct synthesis of d-HNIW is
not known. Although Wardle and Hinshaw initially reported that the heating of
c-HNIW at 230 °C changes it to d-HNIW. Later, based on IR spectroscopic data,
they suggested it was a structural modification rather than the formation of
d-HNIW, which is stable only at elevated pressures, and was detected during the
2.2 Synthesis 65

Table 2.1 Property and CL-20 polymorphs [11]

Property Polymorph
a b c e
Orientation of the NO2 groups at exo, exo exo, exo exo, exo exo, endo
the N(4) and N(10) Atoms
Number of molecules per unit cell 8 4 4 4
Space group Pbca Pb21a P21/n P21/n
Symmetry Orthorhombic Orthorhombic Monoclinic Monoclinic
Crystal habitus Prisms Needles Plates Prisms
Decomposition temperature, °C 260 260 260 260
Polymorphic transition – 185 (b!c) 230 (c!d) –
temperature (and type), °C
Density (g cm−3) 1.961 1.985 1.916 2.04
(2.001)a
a
The value is given for the hemihydrate of the a Polymorph

equilibrium transformation of the c-phase. Russel et al. [41] reported the presence
of f-HNIW at a high pressure during a reversible phase transition of the
c-polymorph at a pressure of (0.7 ± 0.05) GPa.
Ciezak et al. [42] examined the high pressure transition of e to c-CL-20 at room
temperature and at pressures up to 27 GPa. They obtained the vibrational spectra of
polycrystalline material and their recorded Raman spectra are shown in Fig. 2.5.
Raman profiles shown are vertically scaled for the sake of clarity. The main
region covered is from 200 to 1100 cm-1, and the range between 1200 and
1400 cm−1 is omitted. The omission in this range is explained as dominance due to
strong first-order scattering from the diamond anvils. The authors apparently omitted

Fig. 2.5 Typical Raman spectra of CL-20 in the frequency range of 200–1800 cm−1 (a) and
3000–3300 cm−1 (b) [42]
66 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

the spectral region between 1800 and 3000 cm−1 as the vibrational intensity in this
range was low. Based on their experimental data, they concluded that the e ! c
transition is purely conformational and that both the crystallographic space group
and number of molecules per unit cell are retained. They also suggest the existence
of c ! d transition at 18.7 GPa. It is clear that the spectra are pressure-induced, and
the pressure effect is prominent in the 200–400 frequency range
Gump and Peiris [43] also investigated the phase transition as a function of
pressure and temperature. They noted that e-HNIW was stable under ambient
pressure to a temperature of 120 °C. A phase transition to the c-HNIW was
observed at 125 °C and the c-HNIW remained stable until thermal decomposition
above 150 °C. The XRD measurements used to follow the phase transition are
shown in Fig. 2.6. They fitted the pressure-volume data for the e-HNIW phase at
ambient and 75 °C by the Birch–Murnaghan formalism to obtain isothermal
equations of state.
Turcotte et al. [44] explored the phase transitions using a DSC system. The DSC
curve is shown in Fig. 2.7. They noticed the presence of two peaks. The peak at
Tp = 162 ± 1 °C was assigned to a solid–solid phase transition from e ! c. The
peak at 141 ± 1 °C could not be assigned to any polymorph as there was no
reference of such a peak in the literature. Ghosh et al. [45] using raw CL-20
prepared e-CL-20 and provide density, X-ray diffraction patterns, FTIR and Raman
frequencies, DSC curve as a part of the characterization of e-CL-20.

Fig. 2.6 Phase change from e to c upon heating at ambient pressure [43]
2.2 Synthesis 67

Fig. 2.7 Endothermic phase

transition of CL-20: DSC,
5 °C min−1, pinhole pan, in
nitrogen: a 0.2 mg heated
from 30 to 190 °C; b 5 mg
with a 1 h isothermal step at
140 °C [44]

Fig. 2.8 XRD patterns of

phase change of HNIW [47]

2.2.2 Diffraction Studies

The XRD pattern is a valuable information for identifying a compound and its
polymorph. As discussed in the previous section (Fig. 2.8) the XRD was used to
understand the transition of e-HNIW to c-HNIW. Meents et al. [46] investigated
electron density of the e-polymorph of CL-20 based on high-resolution X-ray
single-crystal diffraction experiments at low temperature using synchrotron radia-
tion. The crystals were made by recrystallization from a solution in which e-HNIW
was dissolved in propanol. Based on their experimental studies and model fitting,
the authors discuss the chemical bonding and come to the conclusion that there is
no evidence to support that electron-density maxima near the C–NO2 bonds
mapped on the electron-density isosurface can be correlated with impact sensitiv-
ities. The experimental results compared well with the DFT calculated
bond-topological properties.
68 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Chen et al. [47] studied in detail the XRD pattern of a-HNIW, b-HNIW,
c-HNIW, and e-HNIW. The data are shown in Fig. 2.8 that covered 2h from 10 to
50°. According to the authors, diffraction peaks for all four polymorph were not
observed above 50°. There are more than 20 diffraction peaks in each XRD pattern
of a-, b-, c-, and e-HNIW, respectively, some of which had overlapping peaks
(Table 2.2).

Table 2.2 Important Analytic Crystallographic 2h D I%

diffraction information of parameters (o) (hkl)
a-, b-, c-, and e-HNIW
crystals [47] e-HNIW Crystal system: 12.6 12.5 94.0
Monoclinic 12.8 6.9 41.0
Space group: P21/a 13.8 6.4 94
a (nm) 1.3748 15.7 5.6 40
b (nm) 1.2596 19.9 4.4 20
c (nm) 0.8867 22.0 4.0 46
a (o) 90 25.8 3.5 52
b (o) 111.9 27.8 3.2 61
c (o) 90 29.9 3.0 47
a-HNIW Crystal system:
Orthorhombic
Space group: Pbca 12.1 7.3 77.0
a (nm) 0.9478 13.8 6.4 100
b (nm) 1.3206, 15.1 5.9 36.0
c (nm) 2.356 20.2 4.4 40
a (o) 90 28.0 3.2 67.0
b-HNIW Crystal system:
Orthorhombic
Space group: Pca21 13.6 6.5 89.0
a (nm) 0.9652 13.7 6.5 100
b (nm) 1.1644 24.2 3.7 21.0
c (nm) 1.3002 28.3 3.2 28.0
c-HNIW Crystal system: 13.9 6.3 43.8
Monoclinic 14.5 6.1 100
Space group: P21/n 15.2 5.8 41.5
a (nm) 1.3213 16.5 5.3 64.1
b (nm) 0.8161 18.6 4.8 22.6
c (nm) 1.4898 22.8 3.9 19.1
a (o) 90 34.4 2.6 37.9
b (o) 109.12 36.1 2.5 37.9
c (o) 90 42.1 2.1 40.0
2.3 Detection 69

2.3 Detection

The main focus on the detection of CL-20 is from water and soil. One of the issues
related to its detection is the fragmentation and decomposition of CL-20 in the
liquid medium including water. Cabalo and Sausa [48], by using a surface laser
photo-fragmentation- fragment detection (SPF-FD) spectroscopy at ambient tem-
perature and pressure, were able to detect various explosives including CL-20 in the
concentration range of 1–15 ng/cm2 at 1 atm and room temperature. They used a
low power, 248-nm laser photo-fragments the target molecule on the surface of a
substrate, and a low power, 226-nm laser ionizes the resulting nitric oxide fragment
by resonance-enhanced multi-photon ionization by means of its A-X (0,0) transi-
tions near 226 nm. The lower limit of detection for CL-20 was 7.1 ng/cm2 at
248 nm. A HPLC coupled with a UV detector is used frequently to identify and
quantify CL-20 in a solution. As noted by Larson et al. [49] the detection of CL-20
in a variety of environmental samples requires matrix-specific sample preparation,
separation by reverse-phase high performance liquid chromatography, and ultra-
violet detector. Also, most of these methods follow USEPA SW-846 Method 8330
for the determination of explosives in waters and soils. Using a chromatographic
column and UV-VIS detector, Larson et al. separated and detected CL-20 from the
solution [49]. The UV spectrum of CL-20 in acetonitrile is shown in Fig. 2.9.
A number of researchers have used a combination of HPLC and various other
detectors to detect CL-20 [50, 51]. Anthony et al. [52] used EPA 8330A method to
detect CL-20 in soil samples. The HPLC was equipped with a Supelcosil LC-CN
column for separation of CL-20 and a Diode Array Detector set at 230 nm (lmax)
was used for detection of CL-20. An ultra HPLC also appears to be promising for
separation of energetic materials including Cl-20 [53]. Oehrle [54] used USEPA
SW-846 Method 8330 for analysis of CL-20 in the presence of 14 nitroaromatics
and nitramine. Along with HPLC, he used a photodiode array detection system for

Fig. 2.9 Absorbance curve

of 2.25  10−3 M RDX and
CL-20 in the 190- to 290-nm
range [48]
70 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

CL-20 peak identification. The analysis for CL-20 was accomplished in less than
30 min using an isocratic HPLC mobile phase of water and isopropanol.
Persson et al. [55] used a HPLC method for qualitative and quantitative analysis
of a mixture of RDX, 2,4,6-TNT, 2,4-DNT, HMX, PETN, Tetryl, HNS, TNAZ and
HNIW. A programmable multi-wavelength detector in the UVNIS range was used
for detection of these explosives in less than 10 min. The detection limit for HNIW
was was less than 5 ng.
NMR characterization has been carried out [56] and coupling constants have
been determined. Agilent Technologies prposed a APCI LC/MS/MS based methods
for deetction of TNT, RDX, and CL-20. According to them, CL-20 yields two
intense product ions. The major product ion is m/z 154 or a loss of 319 mass units
(C5H5O8N9). The mass spectrum is given in Fig. 2.10.

2.4 Physical and Thermal Properties

Physical, and thermal properties of CL-20 are given in Table 2.3. In addition to the
data presented in this table, other properties such as solubility, vapor pressure, ideal
gas heat capacity and entropy are also discussed in the following sections
(Tables 2.4 and 2.5)

Fig. 2.10 HPLC chromatogram for a nine compound explosive mixture (measurement parameters
as in Table) [55]
2.4 Physical and Thermal Properties 71

Table 2.3 Properties of CL-20

CAS number 135285-90-4
IUPAC name 5,2,6-(Iminomethenimino)-1H-imidazo[4,5-b]pyrazine,
octahydro-1,3,4,7,8,10-hexanitro-
Other names 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatetracyclododecane;
2,4,6,8,10,12-Hexanitrohexaazaisowurtzitane; CL 20; HNIW;
Hexanitrohexaazaisowurtzitane; LX 19; RX 39AB; RX 39AC
Chemical structure NO2
NO2
O2N
N N
N

N N
N
O2N NO2
NO2
Molecular mass 438.23, Daltons
Density 2.04, g/cm3 @ 298.15 K
Melting point 513 K [57]
Boiling point 862 K [57]
Acentric factor 2.347 [57]
Critical temperature 1058 K [57]
Critical pressure 48.9 bar [57]
Dipole moment 1.016 debye [58]
Enthalpy of fusion 13.7 [57] and 42.7 [59] kJ/mole
Enthalpy of formation 141.0 kcal/mole
(gas phase)
Enthalpy of sublimation 150–170 kJ/mole
Enthalpy of −311 kJ/mole
vaporization
Aqueous solubility 3.86−3; 2.91−3 g/l @ 298.15 K [60]
Log KOW 1.92 [51] 1.375 and 4.14 {Predicted values}

Table 2.4 Enthalpy of Material DHcombustion (106J/ DHformation (103J/

combustion and formation mo1) mol)
[61]
b-CL-20 −3.649 +431.0 ± 13
e-CL-20 −3.596 +377.4 ± 13
72 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Table 2.5 Enthalpy of detonation of CL-20 [61]

Material q(g/cm3) J/g(a) J/cm3 TMD(b)J/J/cm3
e-CL-20 1.96 Expt. 6.234 ± 63 12,219 ± 123 12,717 ± 129
e-CL-20 1.96 Calc. 6.029 ± 146 11,817 ± 286 12,301 ± 298
(a)
25 °C, H2O(liquid)
(b)
TMD is the theoretical maximum density

2.4.1 Vapor Pressure

Only a few experimental vapor pressure data are reported in the literature. Greenlief
et al. [62] obtained the data at the low pressure range using the Knudsen effusion
method. The data are shown in Table 2.6.
Sinditskii et al. [63] while determining the kinetic parameters of combustion of
four solid rocket propellant oxidizers and other energetic compounds also obtained
the vapor pressure data including that of CL-20 above 600 K. Sinditskii et al.
compiled the vapor pressure data for CL-20 from the literature (see Fig. 2.11), and
noted significant differences in the reported values.
Both Greenlief et al. [62] and Sinditskii et al. [63] correlated the vapor pressure
data according to a Clausius-Clapeyron type equations. The equations along with
their best fit constants are given below:

17;715
Solid: ‘nP ¼ 25:328  ; ðfor 660775 KÞ
T
13;085
Liquid: ‘nP ¼ 19:337  ; ðfor 775960 KÞ
T

The equation provided by Greenlief is given below:

9087:9
LnP ¼ 9:552 
T

This equation provided a maximum deviation of 5% and an average absolute

deviation of 4%.
Boddu et al. [64] calculated the vapor pressure of CL-20 using an equation of
state approach. However, their predicted values are an order of magnitude lower
compared to our experimental data [62].

Table 2.6 Experimental vapor pressure data, P in Pascals. [62]

Temperature (K) 383.15 393.15 395.15 405.15 405.15
Vapor pressure (Pa) 7.067−07 1.219−06 1.528−06 2.435−06 2.659−06
2.4 Physical and Thermal Properties 73

2.4.2 Heat Capacity and Entropy Data

Table 2.7 lists the ideal gas heat capacity and entropy values evaluated by Osmont
et al. [65] based on Ab-Inito calculations.

2.5 Solubility

The aqueous solubility of CL-20 has been measured as a function of temperature by

Monteil-Rivera et al. [51], and by Karakaya et al. [66]. Tables 2.8 and 2.9 list their
data. The results from these two sets of data do not agree closely, and the difference
between the two sets of data increased with the increase in temperature. This could
be due to the analytical techniques used, the purity of the chemical, and the degree
of conversion of e-CL-20 to other phases, particularly the c-phase. Holtz et al. [67]

Table 2.7 Ideal gas heat capacity and entropy [65]

T (K) 300 400 500 600 800 1000 1500
Cop (cal mol−1 K−1) 91.1 114.2 132.6 146.8 166.1 178.1 193.4
T (K) 2000 2500 3000 3500 4000 4500 5000
Cop (cal mol−1 K−1) 200.2 203.7 205.7 206.9 207.8 208.3 208.8
T (K) 300 400 500 600 800 1000 1500
So (cal mol−1 K−1) 167.3 196.8 224.3 249.8 295.0 333.4 409.0
T (K) 2000 2500 3000 3500 4000 4500 5000
So (cal mol−1 K−1) 465.7 510.8 548.2 580.0 607.7 632.2 654.2

Table 2.8 Aqueous Solubility of CL-20

solubility of CL-20 as a
Temperature (°C) (mg/L) Mole fraction
function of temperature [68]
4 2.27 (± 0.09) 9.33 10−8
19.5 3.11 (± 0.06) 1.41 10−7
25 4.33 (± 0.04) 178 10−7
30 5.46 (± 0.02) 2.26 10−7
35 6.69 (± 0.01) 2.86 10−7
39 8.10 (± 0.06) 3.33 10−7
45 11.30 (± 0.25) 4.64 10−7
50 14.16 (± 0.47) 5.82 10−7
55 17.37 (± 0.17) 7.14 10−7
60 23.98 (± 0.41) 9.85 10−7
65 32.36 (± 1.03) 1.33 10−6
69 39.68 (± 0.25) 1.63 10−6
74 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Table 2.9 Aqueous solubility (S) of CL-20 as a function of temperature [68]

t (°C) 5 10 15 20 30 40 50 60
S (mg/L) 1.97 2.12 2.48 3.16 4.89 7.39 11.62 18.48

observed a transition in the solubility for CL-20 in different solvents. The solubility
of Cl-20 in thirteen solvents—acetone, bis(fluorodinitroethy1) formal, ethanol,
ethyldinitropentanoate, ethyl acetate, ethylene glycol, FM-1 (FM-1 is a liquid
explosive composedof 25% FEFO, 25% bis(dinitropropy1) formal, and 50%
fluorodinitroethyldinitropropylformal (by mole percent), methylene chloride,
nitroglyceridtriacetin75/25 (NG/TA), nitroplasticizer (NP), triethyleneglycol dini-
trate, trimethylolethane tri-nitrate, and water were measured. The solubility-
temperature relation for each solvent was provided by them.
The solubility data collected by Monteil-Rivera et al. [51] are shown in
Table 2.9 and graphically in Fig. 2.12. During measuremnets, the authors found
that CL-20 decomposed in non-acidified water upon contact with glass containers to
−
give NO 2 (2 equiv.), N2O (2 equiv.), and HCOO (2 equiv.).

2.6 Decomposition and Destruction

Thermal Decomposition
Thermal decomposition of HNIW starts above 210 °C. Turcotte et al. [68]
studied thermal behavior of CL-20 under various conditions using different tech-
niques that included DSC, TG, Heat Flux Calorimetry, Accelerating Rate
Calorimetry, and simultaneous TG-DTA-FTIR-MS analysis. NO2 is the most sig-
nificant product of the decomposition. Other compounds that are identified from
FTIR included N2O, CO2, HCOOH, HNCO, H2O, HCN, CO and NO. The gaseous
products; CO2, N2O, NO2, HCN, NO and CO are result of secondary decompo-
sition reactions. They also noted that the heating rate and the purge gas used during
heating had no effect on the decomposition products or the mass loss, which was
between 80 and 98% of the initial mass. Korsounskii et al. [70] studied the thermal
decomposition characteristics along with the kinetics for HNIW. As expected, the
rate of mass loss of CL-20 was dependent on temperatures and found a final mass
loss of about 80% in air within 200 min in the temperature range of 183–211 °C. In
comparison, HMX did not show any decomposition at 220 °C within 200 min.
Based on the IR spectrum, the authors conclude that the hemolytic cleavage of the
N–NO2 bond to be the primary cause of HNIW decomposition. The effect of
particle size on thermal decomposition of CL-20 has been discussed by Dong et al.
[71]. They compared the decomposition steps for isothermal and non-isothermal
decomposition for 40 and 230 lm particles. The 230 lm particles decomposed in
two steps under non-isothermal conditions, where as it was a one step decompo-
sition for smaller particles. The main products identified using FTIR were NO,
2.6 Decomposition and Destruction 75

N2O, CO2, and a small amount of NO2 and C2N2H2. During isothermal decom-
position, the decomposition products from larger HNIW particles at 204 °C were
same as that observed in the first step of the non-isothermal decomposition.
Several researchers focused on the decomposition kinetics and developed
expressions for the reaction rates. Korsounskii et al. [70] found that the solid state
decomposition follows first-order kinetics and that it is an autocatalytic decompo-
sition. The thermogravimetry analysis in a narrow temperature range of 458–477 K
resulted in an activation energy of 151.7 kJ/mol and a frequency factor of
1013.6 s−1. The decomposition reaction rate is represented by:

dx
¼ k 1 ð 1  aÞ þ k 2 að 1  aÞ
dt

m0  m
a¼
m0  m1

where m0 is the weight of the starting sample, m is its weight at time t and m1 is the
weight of the sample at the end of experiment and k1 and k2 are given by:

k1 ¼ 1020:50:8 eð RT Þ
53;400  1500

k2 ¼ 1017:31:4 eð RT Þ
44;700  2900

Bohn [72] provides a general model for isothermal decomposition of solid

energetic materials, and verified his model with data on e-CL-20. Kinetic param-
eters and Arrhenius parameters are developed. The following expression was
suggested for approximation of the HNIW decomposition during which a mass loss
of 0–11% would occur.
mC
MLðt; T Þ ¼ O þ ½1  MAr ðt; T Þ  100%
mA

The parameter, O, stands for an offset not caused by the decomposition of

compound A.
Figure 2.13 shows some of the results of this study. The solid lines in Fig. 2.13
show the model calculations, and dots represent the experimental data over a range
of temperatures and time. Based on the model and experimental data Bohn con-
cludes that the thermal decomposition of HNIW is autocatalytic.
Qasim et al. [73] carried out theoretical computations using MOPAC [Molecular
Orbital PACkage] quantum mechanical and classical force field mechanics to assess
the type of bond degradation in CL-20. The FTIR and UV/FTIR were used to follow
the decomposition of HNIW and the data were used for theoretical calculations, and
concluded that the breakage of C–N bonds to be a plausible mechanism. In addition,
they computed the dipole moment and enthalpies of formation. The values of the
enthalpies of formation show that the PM3 model to be better than MNDO and AM1
76 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

models [73]. Qasim et al. [73] also reviwed the research work carried out to
understand structural relationships and degradation mechanisms of current and a
number of emerging explosives, including nitroaromatics, cyclic and cage cyclic
nitramines, and a nitrocubane. The competitive degradation mechanisms by free
radical oxidative, reductive and alkali hydrolysis were studied, that included,
2,4,6-trinitrotoluene (TNT); 1,3,5-trinitrobenzene (TNB); 2,4,6-trinitrophenol (TNP
or picric acid); hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX); octahydro-1,3,5,7-
tetranitro-1,3,5,7-tetrazocine (HMX); 2,4,6,8,10,12-hexanitro- hexa-azoisowurtzitane
(CL-20); and 2,4,6,8-tetranitro1,3,5,7-tetraaza-cubane (TNTAC), and octonitrocubane
(ONC).
The thermal decomposition study of CL-20 (hexanitrohexaazaisowurtzitane)
using pyrolysis GC/MS was carried out mainly by electron impact (EI) mode.
Chemical ionization (CI) mode was used for further confirmation of identified
species. Mass spectrum of CL-20 decomposition products predominantly revealed
fragments with m/z 81 and 96 corresponding to C4 H5 N2þ and C4H4N2O+ ions,
respectively. The total ion chromatogram (TIC) of CL-20 pyrolysis shows a peak
within the first 2 min due to the presence of low molecular weight gases. Peaks
corresponding to several other products were also observed including the atmo-
spheric gases. Cyanogen formation (C2N2, m/z 52) observed to be enriched at the
scan number 300–500. The low molecular mass range decomposition products
formed by cleavage of C–N ring structure were found in majority. Additional
structural information was sought by employing chemical ionization mode. The
data generated during this study was instrumented in determining decomposition
pathways of CL-20, and it is shown in Fig. 2.14 [76].

2.7 Hydrolysis of Hexanitrohexaazaisowurtzitane

HNIW can also be degraded through a hydrolysis reaction. Pavlov et al. [74]
investigated the hydrolysis of the a, b, and e polymorphs of 2,4,6,8,10,12-
hexanitro-2,4,6,8,10,12-hexa azaiso-wurtzitane in dilute buffered aqueous solutions
over a pH range of 4–10 and at 35, 43, 50, 58 and 65 °C, with starting concen-
trations of CL-20 at one half the solubility limit for the respective temperature.
Figure 2.15 shows the hydrolysis rates at 50 °C at different pH values. In all cases,
an overall first-order kinetic behavior was observed. The rate constants, half-lives,
activation energies, and Arrhenius pre-exponential factors were determined. The
latter was found to vary linearly with pH [74]. Specifically for each polymorph, the
observed pseudo-first order hydrolytic rate constants at any pH and temperature in
sub-solubility regions are as follows:

d ½Ct 
¼ k0 ½Ct 
dt
2.7 Hydrolysis of Hexanitrohexaazaisowurtzitane 77

Fig. 2.11 Vapor pressure as a function of reciprocal temperature: vapor pressure above solid (1)
and liquid CL-20 (2), and CL-20 surface temperatures [63]

 

55748
ka0 ¼ 9:439  105 pH þ 6:905  106 exp 
8:314  T
 

61530
kb0 ¼ 5:085  105 pH þ 2:332  105 exp 
8:314  T
 

56276
ke0 ¼ 6:662  104 pH þ 4:875  105 exp 
8:314  T

Santiago et al. [75] studied the chemical remediation of soils containing CL-20
by alkaline hydrolysis. Their study is confined to lower concentration of CL-20,
shorter time periods but at higher pH values compared to the study of Pavlov et al.
[74]. From their results, alkaline hydrolysis appears to be faster, and removal
greater than 90% was reported.

2.8 Biodegradation

Trott et al. [77] examined CL-20 in soil microcosms to determine its biodegrad-
ability. CL-20, after incubation with a variety of soils disappeared in all microcosms
except in the controls in which microbial activity had been inhibited. CL-20 was
degraded most rapidly in garden soil. After 2 days of incubation, about 80% of the
78 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

initial CL-20 had disappeared. A CL-20-degrading bacterial strain, Agrobacterium

sp. strain JS71, was isolated from enrichment cultures containing garden soil as an
inoculum, succinate as a carbon source, and CL-20 as a nitrogen source. Growth
experiments revealed that strain JS71 used 3 mol of nitrogen per mol of CL-20.
Jenkinks et al. [60] found that the half-life of CL-20 is dependent on the soil
type. The rate of loss and estimation of the half-lives of several explosives were
carried out by exposing them to three test soils. The mean concentrations obtained
at each time period were plotted as the ‘n (C/Co) versus time (t), where C is the
concentration at time t and Co is the initial concentration at time zero. Assuming, a
first-order rate process, the half-life was determined using the following simple rate
equation

‘nðC=CoÞ ¼ kt

where k is the rate constant equal to the slope of the relationship. It may be noted
that when the rate is first order, the half-life is independent of the starting con-
centration. Their finding is given in Table 2.10.
Crocker et al. [78] hypothesized that the biodegradation of cyclic nitramines
such as CL-20 takes place by one or more of the mechanisms such as the formation
of a nitramine free radical and loss of nitro functional groups, by the reduction of
nitro functional groups, by direct enzymatic cleavage, by a-hydroxylation, and/or
by hydride ion transfer. The intermediates formed by one or more of the pathways
spontaneously decompose in water producing nitrite, nitrous oxide, formaldehyde,
or formic acid as common end products. They summarize in a table the degrading
bacteria and possible biochemical mechanisms for degradation of TNT, RDX,
HMX, and CL-20, and show the pathways of degradation mechanism.
Both aerobic and anaerobic bacteria have been used to study the degradation of
CL-20. Among the several bacteria used by the NRC Group of Canada,
Phanerochaete chrysosporium and Irpex lacteus were found to degrade CL-20 [79].
Both P. chrysosporium and I. lacteus were able to remove almost all the nitramine
after 25 days of incubation, and no CL-20 intermediates were detected. The pro-
posed degradation pathway based on several publications [80, 81] by this group is
shown in Fig. 2.16. They found that CL-20 transforms via an N-denitration
mechanism, and putative doubly denitrated CL-20 inter–mediates and finally to the

Table 2.10 Half-life Analyte FG CG YTC

estimates (days) in three test
soils [60] HMX 133 433 2310
TNAZ <1 <1 <1
RDX 94 98 154
CL-20 69 267 144
NG 0.49 <1 <1
PETN 2.4 0.45 1.4
FG Fort Greely soil; CG Camp Guernsey soil; YTC Yakima
Training Center soil
2.8 Biodegradation 79

Fig. 2.12 Temperature-solubility of CL-20 in water

Fig. 2.13 Isothermal TGA data of e-HNIW [72]

80 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Fig. 2.14 Decomposition mechanism of CL-20 [76]

2.8 Biodegradation 81

Fig. 2.15 Hydrolysis of a-CL-20 at 50 °C (●: data at pH 4; ○: data at pH 5.5; ▼: data at pH 7;

Δ: data at pH 8; ■: data at pH 9; □: data at pH 10; —: exponential decay models) [74]

end products nitrous oxide (N2O), formate (HCOO−), ammonia (NH3), and glyoxal
(CHOCHO) as shown in Fig. 2.16 (Figs. 2.13, 2.14, and 2.15).

2.9 Spectroscopy

Kholod et al. [82] have carried out the B3LYP/6-31+G(d,p) level of theory studies
to simulate IR and Raman spectra of different polymorphs of HNIW, and compared
the theoretical values with experimental data of both IR and Raman spectra. They
also found that the most stable conformers of CL-20, which correspond to exper-
imentally obtained polymorphs, the pattern b > a and c > e>f for relative stability.
Table 2.11 reproduced from their paper shows the assignments for IR and Raman,
and experimental values. Experimental FTIR spectrum of a standard CL-20 sample
obtained by Qasim et al. [83] as well as some characteristic bands in the experi-
mental FTIR [84] spectra. Goede et al. [85] used FT-Raman to characterize the four
stable phases of CL-20. They also report reported over the region from
0–4000 cm−1 and assigned the most predominant Raman. They use this method for
detecting polymorphic impurities in e-CL-20, and the detection level for poly-
morphic impurities was determined to be below 2%.
82 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Fig. 2.16 Structure of CL-20 NO2

NO2 N N
(1) and CL-20 denitration NO2 N N NO2
products (2a and 2b) observed
during treatment with FeO NO2 N
N NO2
[79, 80] or with
nitro-reductase [81] 1 Cl-20

NO2-

NO2-

NO2 NO2 NO2

NO2 NO2
N N N N
N N

N N N
N N N
NO2
NO2 NO2

2a Doubly denitrated Cl-20 2b Isomer of compound 2a

Abiotic secondary decomposioon

CHOCHO + N2O + HCOO- + NH3

2.10 Formulations and Detonation Characteristics

According to Simpson et al. [61] the explosive performance of e-CL-20 is

approximately 14% greater than HMX making it the most powerful explosive ever
tested. They determined a number of detonation properties of CL-20 and compared
with other explosives. Various detonation and morphological properties are sum-
marized in Tables 2.12–2.17). They have also provided information on calorimetric
and thermal properties, Jones-Wilkins-Lee equation of state to correlate the deto-
nation parameters, and comparison with other explosive materials.
2.10 Formulations and Detonation Characteristics 83

Table 2.11 Experimental and spectra of pure CL-20 polymorphs and the FTIR spectrum of a
standard CL-20 sample [82]
FTIR Raman
e a b c f CL-20 e a b c
– 3038 3043 w 3048 3058 s 3055 m 3062 m
vs
3031 3016 w 3031 m 3036 m 3045 m 3044 m
1603 1605 s 3020 w 3028 m 3035 m 3035 w
1568 1589 s 2924 w
1541 1566 s
1379 1381 w
1346
1332 1327 s
1284 1285
vs
1263 1265
vs
1229 1219
sh
1191.7 1184 1190 m 1192 w 1188 w 1080 w
1182.5 1169.6 1178.6 1180.4 1180 w 1180 m 1170 m 1175 m
1168.1 1171.8
1154.4 1153 1161 1150 m 1155 m 1048 m
1139.2 1138 1135 m 1130 w
sh
1125.1 1121.1 1106.1 1126 m 1125 s 1120 1125 w 1020 w
sh
1087.2 1119.8 1094.7 1080.4 1115 w 1105 m
1118.3 1088 m 1085 m 1095 1090 1083 m
vs vs
1094.9
1082
1078.3
1072.8 1060 s
1051.6 1052.4 1052.3 1043.8 1038 1045 s 1055 1054 s 1055 s
vs
1022.1 1010 1020 w
998.7 990.7 991.8 1000 s 1000 s
980.9 989.2 970.6 970 980 m
953 959.2 958.8
951.7
949.1
947.7
(continued)
84 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Table 2.11 (continued)

FTIR Raman
e a b c f CL-20 e a b c
944.4 945.2 944.9 946 941 s
938.3 938.1
913.2 904.3 907.7 909.4 904 910 sh
w
900.3 938.1
883.8 881.7 882.9 879.2 875 883 s
855.4 860.2 835.4 858.3 856 m 857 w 861 w 854 w 861 w
831.6 835.4 834.4 833 829 m 832 m 842 m 835 m 849 m
820.2 825.3 831.7 818 m 820 s 825 w 836 w
800 791 w 895 w 805 w 895 w
764.9 766.8 764.1 770 764.9 792 w
758.2 757.7 755.8 755 756 s 755 w 762 w 763 w 762 w
751.4 751.1
744.5 746.5 746.4 741 745 741 s
738.2
723.9 718 718.9 719.5 721 s
705.1 706 sh
660 sh
283 w 284 w 287 w
267 w 270 w

Table 2.12 Small scale safety test results

Material Impact(a) (cm) Friction(b) (kg) Spark(c) CRT(d) (cm3/g)
(e)
b-CL-20 14 6.4 no rxn 0.24
e-CL-20(f) 12–16 6.4–7.2 no rxn 0.16
e-CL-20(g) 17 6.4 no rxn 0.10
e-CL-20(h) 21 6.2 no rxn na
(a)
2.5 kg Type 12 tool with 35 mg pressed samples
(b)
Julius-Peters-Berlin 21 friction machine. One reaction in ten tries
(c)
Ten tries at 1 J with 510 R in line resistance
(d)
22 h at 120 ”C under 1 atm He
(e)
LLNL synthesized CL-20
(f)
Aerojet synthesized CL-20. The median value is approximately 15 cm
(g)
Thiokol synthesized CL-20
(h)
Thiokol synthesized CL-20. Ground by NAWC, China Lake, to 3-5 pm

Table 2.13 Heats of combustion and formation [61]

Material DHcombustmn (106 J/mo1) DHformatlon (103 J/mol)
b-CL-20 −3.649 +431.0 ± 13
e-CL-20 −3.596 +377.4 ± 13
2.11 CL-20 Based Formulations 85

Table 2.14 Calorimetric heat of detonation of CL-20 [61]

Materials p (g/ J/g(a) J/cm3 J/cm3 at
cm3) TMD(b)
e-CL-20 experimental 1.96 6.234 ± 63 12,219 ± 123 12,717 ± 129
e-CL-20 experimental 1.96 6.029 ± 146 11,817 ± 286 123,013 ± 298
estimated from products

Table 2.15 Performance characteristics of explosive components [86]

Substance DHf Q (g/ Dcalc Pcj DE at V/V9 = 6.5 Vgas at 1 bar
(kcal/ cm3) (m/s) (GPa) (kj/cm3) (cm3/g)
kg)
TNT −70.5 1.654 6881 19.53 −5.53 738
RDX 72.0 1.816 8977 35.14 −8.91 903
HMX 60.5 1.910 9520 39.63 −9.57 886
PETN −407.4 1.778 8564 31.39 −8.43 852
TATB −129.38 1.937 8114 31.15 −6.94 737
HNS 41.53 1.745 7241 23.40 −6.30 709
NTO −237.8 1.930 8558 31.12 −6.63 768
TNAZ 45.29 1.840 9006 36.37 −9.39 877
CL-20 220.0 2.044 10065 48.23 −11.22 827

Table 2.16 Insensitive munitions properties of and new energetic materials [86]
Substance Friction sensitivity (N) Impact sensitivity (Nm) Deflagration point (°C)
TNT 353 15 300
RDX 120 7.4 230
HMX 120 7.4 287
CL-20 54 4 228
The materials data sheet from Société nationale des poudres et explosifs, France (SNPE) lists the
following properties for CL-20:
Deflagration temperate: 220–225 °C
Decomposition temperate: 213 °C
Maximum Decomposition temperate: 249 °C
Heat of Decomposition: 2300 J/g
Detonation velocity: 9650 m/s (experimental value)
Vacuum test, 193 h at 100 °C: 0.4 cm3/g

2.11 CL-20 Based Formulations

Various CL-20 based formulations are available for use in both propellants and
explosives. A large number of CL-20-based plastic bonded explosives (PBXs) are
developed to enhance the explosive powers, and the burning rate in the case of
propellants. Nair et al. [87] carried out thermal and sensitivity studies on CL-20
86 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Table 2.17 Properties of CL-20 Polymorphs [86]

Property c-CL-20 a-CL-20 b-CL-20 e-CL-20 HMX
Density (g/cm3) 1.92 1.97 1.99 2.04 1.91
Detonation velocity (m/s) 9380 9380 9380 9660 9100
Phase transition temperate (°C) 260 170 163 177 280

Table 2.18 Density and velocity of detonation of selected CL-20-based PBXs [87–90]
Composition Density (g/ Detonation
cm3) velocity [mm/(l
sec)]
96% CL-20; 1% Hy Temp; 3% DOA 1.901 9.018
96% HMX; 1% Hy Temp; 3% DOA 1.792 8.748
RX-39-AA&AB: 95.5–95.8% CL-20; estane 1.942 ± 0.001 9.208
PBXC-19: 95% CL-20; EVA 1.896 ± 0.002 9.083
PATHX-1: 88–95% CL-20; estane 1.868–1.944 8.89–9.37
PATHX-2: 92–95% CL-20; estane 1.869–1.923 8.85–9.22
PATHX-3: 85–94% CL-20; estane 1.871–1.958 8.91–9.50
LX-19: 95% CL-20; estane 1.959 9.44
LX-14: 95% HMX; estane 1.835 8.79
PBXCLT-1:49-70% CL-20; 48-27% energetic 1.906 8.384–9.102
material HNJ and 3% polymeric binder PVB
PBXCL-1: 97% CL-20; 3% PVB 1.921 9.102
66.8–72.1% CL-20; HTPB 1.648–1.710 8.325–8.470
66.8–72.1% HMX; HTPB 1.575–1.618 8.030–8.107
32% CL-20; 48% TEX; 20% HTPB 1.595
32% HMX; 48% TEX; 20% HTPB 1.560

coated with several polymers—Ethylene vinyl acetate (EVA), copolymer of poly-

butylene terephthalate polyether glycol (hytrel), polyurethane-ester-MDI (Estane),
hexafluoropropylene vinylidine fluoride copolymer (Viton) and polyurethane (PU).
Their results are given in Table 2.18 [87–90].
As shown in Table 2.18, CL-20 based formulations have 12–15% higher
velocity of detonation compared to the corresponding HMX based formulations.
CL-20 is also found to be a superior alternative to RDX and HMX for applications
in low signature rocket propellants. CL-20 based propellants showed a 35–110%
higher burning rates than those of HMX-based propellants. Golfier et al. [91] noted
that the Isp of CL-20–glycidyl azide polymer (GAP) propellants is 251 s, compared
to 242 s for the corresponding RDX-based propellant.
Li and Brill [92] discuss nanostructured energetic compounds of CL-20. They
found that the cryogel method enabled them to load up to 90% of CL-20 (by mass)
in energetic polymer matrices composed of single precursors of GAP polyol, NC,
and THMNM and their mixed precursors. One of the objectives for development of
2.11 CL-20 Based Formulations 87

Fig. 2.17 Drop weight impact test data of energetie polymer gels and composite energetie gels
CL-20 in the 50–70% by weight rang appear to have a notable reduction in scnsitivy [92]

Table 2.19 Burning rates of CL-20-incorporating rocket propellants [69, 91–93]

Composition Burning rate (mm/sec) n
60% CL-20; 40% PGA 11.5–23 (7–15 MPa) 0.92
60% HMX; 40% PGA 6–11 (7–15 MPa) 0.89
60% CL-20; 40% GAP 1 3.4–27.2 (7–15 MPa) 0.94
60% HMX; 40% GAP 7.2–13.6 (7–15 MPa) 0.91
60% CL-20; 40% GAP 20.0–32.4 0.48
(catalyzed) (7–20 MPa)
60% RDX; 40% GAP 14.6–21.4 0.37
(catalyzed) (7–20 MPa)
70% CL-20; 20% GAP; 15 0.57
10% BDNPF/A (7 MPa)
Note n is the exponent in the power law of the burning rate, PGA is polyglycol adipate, and GAP is
a glycidyl azide polymer

this product was to reduce the sensitivity of the formulations. The sensitivity
determine by the drop test is shown in Fig. 2.17 (Table 2.19).
Mueller [94] has studied several formulations of CL-20 and RDX with nitro-
cellulose, BDNPA/F, EPX, and a stabilizer, and compared the properties of these
two explosives. Mueller has presented thermodynamic and chemical stability data
along with 40-mm gun simulation data as a function of temperature.
Besides using CL-20 as an explosive, it is also used as a propellant. It is being
tested as an alternative to ammonium perchlorate in missile and space applications.
Golfier et al. [89] found that CL-20 propellants offer 7% superior Isp (251 s)
compared to RDX-based formulations. Weiser et al. [95] found that the CL-20/
glycidylazide polymer-(GAP) propellants exhibit burning rates twice those of
88 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

HMX/GAP propellants. Attempts have been made to ballistically modify CL-20

formulations, but specific information about the modifiers is not available. Nair
et al. [96] have studied CL-20 based composites as double-based propellants. With
corporate 17.5% aluminum based on their theoretical evaluation of Isp. In another
paper, Thepenier and Fanblanc [97] compare the characteristics of several com-
pounds and show the superiority of CL-20 with respect to density, enthalpy of
formation, and oxygen balance. In addition this paper provides information on a
wide variety of fields from new raw materials (energetic binders, plasticizers,
oxidizers) through new propellants and new processes to new tools for designing
grains. Unlike many other propellants, the CL-20 propellant exhaust is free of lead,
acids, and aluminum oxide emissions. The absence of halogens like in ammonium
perchlorate makes CL-20 products of combustion more environmentally friendly.

2.12 Toxicity

Kuperman et al. [98, 99] have reported the Enchytraeid Reproduction Test, and
found that toxicities for E. crypticus adult survival and juvenile production sig-
nificantly increased in weathered and aged treatments compared with toxicity in
freshly amended soil, based on 95% confidence intervals. The EC50 and EC20
values for juvenile production were 0.3 and 0.1 mg kg-1 for CL-20 freshly amended
into soil, and 0.1 and 0.035 mg kg-1, respectively, for weathered and aged CL-20
treatments.

2.13 Conclusion

CL-20 has attracted a great deal of attention in the recent years as a powerful
insensitive explosive. Current literature search revealed that several countries are
working on this explosive mainly on the synthesis, scale-up, and cost reduction.
There is little work on properties, detection, toxicity, and remediation of contam-
inated sites should this be made in large quantities.

References

1. Nielsen AT (1997) Caged polynitramine compound. US Patent 5693794

2. USA Navy Manteca (2004) Report of 2003. Dept of Navy, Fiscal Year 2003 Rpt
3. Nielsen AT, Nissan RA, Vanderah DJ, Coon CL, Gilardi RD, George CF, Lippen-Anderson
JF (1990) Polyazapolycyclics by condensation of aldehydes with amines 2 Formation of
2,4,6,8,10,12-Hexabenzyl-2,4,6,8,10,12-hexaazatetra – cyclo [55000] dodecanes from
glyoxal and benzylamines. J Org Chem 55(5):1459–1466
References 89

4. Crampton MR, Hamid J, Millar R, Ferguson G (1993) Studies of the synthesis, protonation and
decomposition of 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazatetracyclo[55005,903,11]do-
decane (HBIW). J Chem Soc Perkin Trans 2(5):923–929
5. Edwards WW, Wardle RB (1998) Process for making 2,4,6, 8,10,12- hexanitro- 2,4,6,8,10, 12-
hexa azatetracyclo 550 0 5,9 0 3,11] –dodecane. EP 1153025 A2 (WO2000052011A2), US
Patent 5739325
6. Kodama T (1994) Preparation of hexakis (trimethylsilylethylcarbamyl) hexaazaisowurtzi-
tane. JP06321962A
7. Kodama T, Tojo M, Ikeda M (1996) Acylated hexaazaisowurtzitane derivatives and process
for producing the same. WO9623792A1
8. Ou Y-x, Xu Y-j, Liu L-h, Zheng F-p, Wang C, Chen J-t (1999) Comparison of acetonitrile
process with ethanol process for synthesis of hexabenzylhexaazaisowurtzitane. Hanneng
Cailiao 7(4):152–155
9. Ou Y, Xu Y, Chen B, Liu L, Wang C (1999) Synthesis of hexanitrohexaazaisowurtzitane
from tetraacetyldiformylhexaazaisowurtzitane. Proc Int Pyrotech Semin 26th:406–411
10. Ou Y, Meng Z, Liu J (2007) Advance in high energy density compound CL-20-
developments of synthesis route and production technologies of CL-20. Huagong Jinzhan 26
(6):762–768
11. Sysolyatin SV, Lobanova AA, Chernikova YT, Sakovich GV (2005) Methods of synthesis
and properties of hexanitrohexaazaisowurtzitane. Russ Chem Rev 74(8):757–764. doi:10.
1070/RC2005v074n08ABEH001179
12. Wang C, Ou Y-X, Chen B-R (2000) One pot synthesis of hexabenzylhexaazaiso-wurtzitane.
Beijing LigongDaxueXuebao 20(4):521–523
13. Nielsen AT, Chafin AP, Christian SL, Moore DW, Nadler MP, Nissan RA, Vanderah DJ
(1998) Synthesis of polyazapolycyclic caged polynitramines. Tetrahedron 54(39):11793–
11812. doi:10.1016/S0040-4020(98)83040-8
14. Larson SL, Felt DR, Davis JL, Escalon L (2002) Analysis of CL-20 in environmental
matrices: water and soil. J Chromatogr Sci 40(4):201–206. doi:10.1093/chromsci/404201
15. Hamilton RS, Sanderson AJ, Wardle RB, Warner KF (2000) Studies of the crystallization of
CL-20. International Annual Conference of ICT [Institut ChemischeTechnologie], 31st
(Energetic Materials), 21/1–21/8
16. Bellamy AJ (1995) Reductive debenzylation of hexabenzylhexaazaisowurtzitane.
Tetrahedron 51(16):4711–4722
17. Surapaneni R, Damavarapu R, Kumar RA, Dave PR (2000) Process improvements in CL-20
manufacture. International Annual Conference of ICT, 31st (Energetic Materials), 108/1–
108/4
18. Qian H, Ye Z-W, Lv C-X (2007) Efficient and facile synthesis of hexanitrohexaaza-
isowurtzitane (HNIW) for high energetic materials. Lett Org Chem 4(7):482–485
19. Qian H, Chunxu LV, Zhiwen YE (2008) Synthesis of CL-20 by clean nitrating agent
dinitrogen pentoxide. J Indian Chem Soc 85(4):434–439
20. Qian H, Ye Z-W, Lu C-X (2008) Synthesis of CL-20 via nitration and nitrolysis of
2,6,8,12-tetraacety l-2,4,6,8,10,12-hexaazaisowurtzitane with N2O5/HNO3. Yingyong
Huaxue 25(3):378–380
21. Song ZW, Yan QL, Li XJ, Qi XF, Lim M (2010) Crystal transition of CL-20 in different
solvents. Chin J Energ Mater 6:648–653
22. Gore GM, Sivabalan R, Nair UR, Saikia A, Venugopalan S, Gandhe BR (2007) Synthesis of
CL-20: By oxidative debenzylation with cerium (IV) ammonium nitrate (CAN). Indian J
Chem, Sect B: Org Chem Incl Med Chem 46B(3):505–508
23. Kawabe S, Miya H, Kodama T, Miyake N (2007) Process for the preparation of
1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane. US 6297372 B1, EP 0547735
24. Cagnon G, Eck G, Herve G, Jacob G (2007) Method for making new polycyclic polyamides
as precursors for energetic polycyclic polynitramine oxidizers. US Patent 7279572
90 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

25. Latypov NV, Wellmar U, Goede P, Bellamy AJ (2000) Synthesis and Scale-Up of
2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane from 2,6,8,12-Tetraacetyl-4,10-
dibenzyl-2,4,6,8,10,12- hexaazaisowurtzitane (HNIW, CL-20). Org Proc Res Dev 4(3):156–158
26. Pang S-P, Yu Y-Z, X-Q Zhao () A novel synthetic route to hexanitrohexa- azaisowurtzitane.
Propellants, Explosives, Pyrotechnics 30(6):442–444
27. Chapman RD, Hollins RA (2008) Benzylamine-Free, heavy-metal-free synthesis of CL-20
via hexa(1-propenyl)hexaazaisowurtzitane. J Energ Mater 26(4):246–273
28. Herve G, Jacob G, Gallo R (2006) Preparation and structure of novel hexaazaisowurtzitane
cages. Chem Eur J 12(12):3339–3344
29. Mandal AK, Pant CS, Kasar SM, Soman T (2009) Process Optimization for Synthesis of
CL-20. J Energ Mater 27(4):231–246. doi:10.1080/07370650902732956
30. Lu L, Xu B, Ma Z, Yue H, Mu W, Ou Y (2007) New method for synthesis and crystallizing
of HNIW in nitric acid. In: Huang P, Wang Y, Li S (eds) 2007 Science Press, Proc Intl
Autumn Seminar on Propellants, Explosives and Pyrotechnics, 7th, Xi’an, China, Oct 23–
26, pp 64–65
31. Wang J, Li J, An C, Hou C, Xu W, Li X (2012) Study on ultrasound- and spray-assisted
precipitation of CL-20. Propellants, Explos, Pyrotech 37(6):670–675
32. van der Heijden AEDM, Bouma RHB (2004) Crystallization and characterization of RDX,
HMX, and CL-20. Cryst Growth Des 4(5):999–1007
33. Bellamy AJ (2003) A simple method for the purification of crude hexanitrohexaaza-
isowurtzitane (HNIW or CL20). Propellants, Explos, Pyrotech 28(3):145–152
34. Degirmenbasi N, Peralta-Inga Z, Olgun U, Gocmez H, Kalyon DM (2006) Recrystallization
of CL-20 and HNFX from solution for rigorous control of the polymorph type: part II,
experimental studies. J Energ Mater 24(2):103–139. doi:10.1080/07370650600672090
35. Agrawal JP (2011) High Energy Materials. Wiley, Weinheim, Germany
36. Nair UR, Sivabalan R, Gore GM, Geetha M, Asthana SN, Singh H (2005)
Hexanitrohexaazaisowurtzitane (CL-20) and CL-20-based formulations (Review).
Combust Explosion Shock Waves 41:121–132
37. Chapman RD, Hollins RA, Groshens TJ, Nissan DA (2006) Benzylamine-Free,
heavy-metal-free synthesis of CL-20. SERDP seed Prohect WP-1518
38. Jin S, Shu Q, Chen S, Shi Y (2007) Preparation of e-HNIW by a one-pot method in
concentrated nitric acid from tetraacetyldiformylhexaazaisowurtzitane. Propellants, Explos,
Pyrotech 32(6):468–471
39. Duddu R, Dave PR (1999) Processes and Compositions for Nitration of N-Substituted
Isowurtzitane Compounds. Paten WO9957104, USA
40. Wardle RB, Hinshaw JC (2000) Synthesis and reactions of hexaazaisowurtzitane-type
compounds in synthesis of hexanitrohexaazaisowurtzitane (HNIW) explosive. In: Cordant
Technologies Inc, USA, Division of US Ser No 292 028, pp 8
41. Russell TP, Miller PJ, Piermarini GJ, Block S (1992) High-pressure phase transition in
c-hexanitrohexaazaisowurtzitane. J Phys Chem 96(13):5509–5512
42. Ciezak JA, Jenkins TA, Liu Z (2007) Evidence for a high-pressure phase transition of
e-2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20) using vibrational spectroscopy.
Propellants, Explos, Pyrotech 32(6):472–477. doi:10.1002/prep200700209
43. Gump JC, Peiris SM (2008) Phase transitions and isothermal equations of state of epsilon
hexanitrohexaazaisowurtzitane (CL-20). J Appl Phys 104(8):083509/1–083509/5. doi:10.
1063/1.2990066
44. Turcotte R, Vachon M, Kwok QSM, Wang R, Jones DEG (2005) Thermal study of HNIW
(CL-20). Thermochim Acta 433:105–115
45. Ghosh M, Venkatesan V, Sikder AK, Sikder N (2012) Preparation and characterisation of
e-CL-20 by solvent evaporation and precipitation methods. Def Sci J 62(6):390–398
46. Meents A, Dittrich B, Johnas SKJ, Thome V, Weckert EF (2008) Charge-density studies of
energetic materials: CL-20 and FOX-7. Acta Crystallogr B 64(Pt 1):9–42
47. Chen H, Chen S, Li L, Jin S (2008) Quantitative determination of e-phase in polymorphic
HNIW using diffraction patterns. Propellants, Explos, Pyrotech 33:467–471
References 91

48. Cabalo JB, Sausa RC (2005) Explosive residue detection by laser surface photo-
fragmentation–fragment detection spectroscopy: II In Situ and Real-time Monitoring of
RDX, HMX, CL20, and TNT, by an Improved ion probe. Report ARL-TR-3478
49. Larson SL, felt DR, Escalon L, JD Davis, Hansen LD (2001) Analysis of CL-20 in
environmental matrices water and soil. ERDC/EL TR-01-21
50. Liu Y, Chen S, Luo S (2000) HPLC method for analysis of CL-20 in explosive mixture.
Huaxue Yanjiu Yu Yingyong 12(4):446–448
51. Monteil-Rivera F, Paquet L, Deschamps S, Balakrishnan VK, Beaulieu C, Hawari J (2004)
Physico-chemical measurements of CL-20 for environmental applications Comparison with
RDX and HMX. J Chromatogr A 1025(1):125–132. doi:10.1016/jchroma200308060
52. Anthony JS, Davis EA, Haley MV, Kolakowski JE, Kurnas CW, Phillips CT, Simini M,
Kuperman RG, Checkai RT (2004) HPLC determination of hexanitrohexaazaisowurtzitane
(CL 20) in soil and aqueous matrices. US Army Res Dev Eng Command Edgewood chem
Bio Center, ECBE-TR, p 403
53. Makarov A, LoBrutto R, Christodoulatos C, Jerkovich A (2009) The use of ultra
high-performance liquid chromatography for studying hydrolysis kinetics of CL-20 and
related energetic compounds. J Hazard Mater 162(2–3):1034–1040. doi:10.1016/
jjhazmat200805157
54. Oehrle SA (1994) Analysis of CL-20 and TNAZ in the presence of other nitroaromatic and
nitramine explosives using HPLC with photodiode array (PDA) detection. J Energ Mater 12
(4):22–211. doi:10.1080/07370659408018651
55. Persson B, Ostmark H, Bergman H (1997) An HPLC method for analysis of HNIW and
TNAZ in an explosive mixture. Propellants, Explos, Pyrotech 22(4):238–239
56. Agilent Technology, LC/MS Application Note, April 2004
57. Toghiani RK, Toghiani H, Maloney SW, Boddu VM (2008) Prediction of physicochemical
properties of energetic materials. Fluid Phase Equilib 264:86–92
58. Qasim MM, Furey J, Fredrickson HL, Szecsody J, McGrath C, Bajpai R (2004) Semiempirical
predictions of chemical degradation reaction mechanisms of CL-20 as related to molecular
structure. Struct Chem 15(5):493–499. doi:10.1023/B:STUC000003790727898f5
59. Zeman S, Jalovy Z (2000) Heats of fusion of polynitro derivatives of polyazaisowurtzitane.
Thermochim Acta 345(1):31–38
60. Jenkins TF, Bartolini C, Ranney TA (2003) Stability of CL-20,TNAZ, HMX, RDX,NG, and
PETN in moist, unsaturated soil. ERDC/CRREL TR-03-7
61. Simpson RL, Urtiew PA, Ornellas DL, Moody GL, Scribner KJ, Hoffmann DM (1997)
CL-20 performance exceeds that of HMX and its sensitivity is moderate. Propellants,
Explos, Pyrotech 22(5):249–255
62. Greenlief CM, Ghosh TK, Viswanath DS, Boddu VM (2010) Vapor Pressure of
Hexanitrohexaazaisowurtzitane (HNIW, CL-20). Report to Leonard Wood Institute,
LWI-101.1, MO, USA
63. Sinditskii VP, Egorshev VY, Berezin MV, Serushkin VV, Milekhin YM, Gusev SA,
Matveev AA (2003) Combustion characteristics of the high-energy cage hexanitrohexaaza-
isowurtzitane nitramine. Khim Fiz 22(7):69–74
64. Boddu VM, Maloney SW, Toghiani RK, Toghiani H (2010) Prediction of physicochemical
properties of energetic materials for identification of treatment technologies for waste
streams. U.S. Army Engineer Research and Development Center, ERDC/CERL TR-10-27
65. Osmont A, Catoire L, Gökalp I, Yang V (2007) Ab initio quantum chemical predictions of
enthalpies of formation, heat capacities, and entropies of gas-phase energetic compounds.
Combust Flame 151:262–273
66. Karakaya P, Sidhoum M, Christodoulatos C, Nicolich S, Balas W (2005) Aqueous solubility
and alkaline hydrolysis of the novel high explosive hexanitrohexaazaisowurtzitane (CL-20).
J Hazard Mater 120(1–3):183–191
67. von Holtz E, Ornellas D, Foltz MF, Clarkson JE (1994) The solubility of e-CL-20 in selected
materials. Propellants, Explos, Pyrotech 19:206–212
92 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

68. Turcotte R, Vachon M, Kwok QSM, Wang R, Jones DEG (2005) Thermal study of HNIW
(CL-20). Thermochim Acta 433(1–2):105–115
69. Highsmith T, Johnston H (2004) Continuous process for preparing alkoxynitroarenes.
ALLIANT TECHSYSTEMS INC., MINNESOTA, US 10/338,767, USA
70. Korsounskii BL, Nedel’ko VV, Chuk anov NV, Larikova TS, Volk F (2000) Kinetics of
thermal decomposition of hexanitrohexaazaisowurzitane, Russ Chem Bull 49:812–817
71. Ding T, Yang H, Zhang Y (2013) Thermal decomposition of CL-20/RDX mixed system.
Huaxue Tuijinji Yu Gaofenzi Cailiao 11(6):84–86
72. Bohn MA (2002) Kinetic description of mass loss data for the assessment of stability,
compatibility and aging of energetic components and formulations exemplified with e-CL20.
Propellants, Explos, Pyrotech 27(3):125–135
73. Qasim MM, Moore B, Taylor L, Honea P, Gorb L, Leszczynski J (2007) Structural
characteristics and reactivity relationships of nitroaromatic and nitramine explosives—a
review of our computational chemistry and spectroscopic research. Int J Mol Sci 8:1234–
1264
74. Pavlov J, Christodoulatos C, Sidhoum M, Nicolich S, Balas W, Koutsospyros A (2007)
Hydrolysis of hexanitrohexaazaisowurtzitane (CL-20). J Energ Mater 25(1):1–18
75. Santiago L, Felt DR, Davis JL (2007) Chemical remediation of an ordnance-related
compound: thealkaline hydrolysis of CL-20. ERDC/El TR-07-18 Report
76. Naik NH, Gore GM, Gandhe BR, Sikder AK (2008) Studies on thermal decomposition
mechanism of CL-20 by pyrolysis gas chromatography-mass spectrometry (Py-GC/MS).
J Hazard Mater 159(2–3):5–630
77. Trott S, Nishino SF, Hawari J, Spain JC (2003) Biodegradation of the nitramine explosive
CL-20. Appl Environ Microbiol 69(3):1871–1874
78. Crocker FH, Indest KJ, Fredrickson HL (2006) Biodegradation of the cyclic nitramine
explosives RDX, HMX, and CL-20. Appl Microbiol Biotechnol 73(2):274–290; Fournier D,
Monteil-Rivera F, Halasz A, Bhatt M, Hawari J (2006) Degradation of CL-20 by white-rot
fungi Chemosphere 63(1):175–181
79. Balakrishnan VK, Monteil-Rivera F, Gautier MA, Hawari J (2004) Sorption and stability of
the polycyclic nitramine explosive CL-20 in soil. J Environ Qual 33(4):1362–1368
80. Balakrishnan VK, Monteil-Rivera F, Halasz A, Corbeanu A, Hawari J (2004)
Decomposition of the Polycyclic Nitramine Explosive, CL-20, by Fe0. Environ Sci
Technol 38(24):6861–6866
81. Bhushan B, Paquet L, Spain JC, Hawari J (2003) Biotransformation of 2,4,6,8,10,12-
hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) by denitrifying Pseudomonas sp
strain FA1. Appl Environ Microbiol 69(9):5216–5221
82. Kholod Y, Okovytyy S, Kuramshina G, Qasim M, Gorb L, Leszczynski J (2007) An analysis
of stable forms of CL-20: a DFT study of conformational transitions, infrared and Raman
spectra. J Mol Struct 843(1–3):14–25
83. Qasim M, Fredrickson H, Honea P, Furey J, Leszcznski J, Okovytyy S, Szecsody J,
Kholod Y (2005) Prediction of CL-20 chemical degradation pathways, theoretical and
experimental evidence for dependence on competing modes of reaction. SAR QSAR
Environ Res 16:495–515
84. Foltz MF (1994) Thermal stability of e-hexanitrohexaazaisowurtzitane in an Estane
formulation. Propellants, Explos, Pyrotech 19(2):63–69
85. Goede P, Latypov NV, Oestmark H (2004) Fourier transform Raman Spectroscopy of the
four crystallographic phases of a, b, c and e 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-
hexaazatetracyclo[55005,903,11]dodecane (HNIW, CL-20). Propellants, Explos, Pyrotech
29(4):205–208
86. Ulrich TF (2005) Energetic materials: particle processing and characterization. Wiley, New
York
87. Nair UR, Gore GM, Sivabalan R, Satpute RS, Asthana SN, Singh H (2004) Studies on
polymer coated CL-20-the most powerful explosive J Polym Mater 21(4):377–382
References 93

88. Nair UR, Sivabalan R, Gore GM, Dudek K, Marecek P, Vavra P (2000) Laboratory testing
of HNIW mixtures. Proc. 31st Int Conf ICT, Karlsruhe, June 27–30 (2000), pp 110/1–110/6
89. Mezger MJ, Nicholich SM, Geiss DA et al (1999) Performance and hazard characterzation
of CL-20 formulations. In: Proceedings of 30th International Annual Conference of ICT,
Karlsruhe, June 29–July 2 (1999), pp. 4/1–4/14
90. Tian Y, Xu R, Zhou Y, Nie F (2001) Study on formulation of CL-20. In: Procecings of 4th
International Autumn Seminar on Propellants, Explos, Pyrotech Shaoxing, China, pp 43–47
91. Golfier M, Graindorge H, Longevialle Y, Mace H (1998) New energetic molecules and their
applications in the energetic materials. In: Proceedings of 29th International Annual Conf. of
ICT, Karlsruhe, 30 June–3 July 1998, pp 3/1–3/17
92. Li J, Brill TB (2006) Nanostructured energetic composites of CL-20 and binders synthesized
by sol gel methods. Propellants, Explos, Pyrotech 31:61–69
93. Wagstaff DC (2002) Desensitization of energetic materialsby energetic plasticizer, Brit. UK
Pat. Appl GB 2374867 A1, 30 October 2002
94. Mueller D (1999) New gun propellant with CL-20. Propellants, Explos, Pyrotech 24(3):176–
181. doi:10.1002/(SICI)1521-4087(199906)24:03<176:AID-PREP176>30CO;2-4
95. Weiser V, Eisenreich N, Eckl W, Eisele S, Menke K (2000) Burning behavior of CL-20/
GAP and HMX/GAP rocket propellants. In: International Annual Conference on ICT 31st
(Energetic Materials), pp 144/141–144/146
96. Nair UR, Gore GM, Sivabalan R, Divekar CN, Asthana SN, Singh H (2004) Studies on
advanced CL-20-based composite modified double-base propellants. J Propul Power 20
(5):952–955; Thepenier J, Fanblanc G (2001) Acta Austronautica, 38:245
97. Thepenier J, Fanblanc G (2001) Advanced technologies available for future solid propellant
grains. Acta Austronautica 48(5–12):245–255
98. Kuperman RG, Checkai RT, Simini M, Phillips CT, Anthony JS, Kolakowski JE,
Kumas CW, Davis EA (2006) U S Army Research, Development and Engineering.,
ECBC-TR-485
99. Kuperman RG, Checkai RT, Simini M, Phillips CT, Anthony JS, Kolakowski JE, Davis EA
(2006) Toxicity of emerging energetic soil contaminant CL-20 to potworm Enchytraeus
crypticus in freshly amended or weathered and aged treatments. Chemosphere 62(8):1282–
1293

Additional Scholarly Articles for Further Reading

100. Agrawal JP, Walley SM, Field JE (1998) A high-speed photographic study of the impact
initiation of hexanitro-hexaaza-isowurtzitane and nitrotriazolone. Combust Flame 112(1/
2):62–72. doi:10.1016/S0010-2180(97)81757-9
101. Aldoshin SM, Aliev ZG, Goncharov TK (2014) Crystal structure of 2,4,6,8,10,12-hexanitro-
2,4,6,8,10,12-hexaazaisowurtzitane solvate with e-caprolactam. J Struct Chem 55(4):709–
712. doi:10.1134/S0022476614040179
102. Aldoshin SM, Aliev ZG, Goncharov TK, Korchagin DV, Milekhin YM, Shishov NI (2011)
New conformer of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20).
Crystal and molecular structures of the CL-20 solvate with glyceryl triacetate. Russ Chem
Bull 60(7):1394–1400. doi:10.1007/s11172-011-0209-5
103. Aldoshin SM et al (2014) Crystal structure of cocrystals 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-
hexaazatetracyclo[5.5.0.05.9.03.11]dodecane with 7H-tris-1,2,5-oxadiazolo(3,4-b:3′,4′-d:3″,4″-
f)azepine. J Struct Chem 55(2):327–331. doi:10.1134/S0022476614020206
104. Alnemrat S, Hooper JP (2013) Predicting temperature-dependent solid vapor pressures of
explosives and related compounds using a quantum mechanical continuum solvation model.
J Phys Chem A 117(9):2035–2043. doi:10.1021/jp400164j
94 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

105. Alnemrat S, Hooper JP (2014) Predicting solubility of military, homemade, and green
explosives in pure and saline water using COSMO-RS. Propellants, Explos, Pyrotech 39
(1):79–89. doi:10.1002/prep.201300071
106. Ammon HL (2008) Updated atom/functional group and atom_code volume additivity
parameters for the calculation of crystal densities of single molecules, organic salts, and
multi-fragment materials containing H, C, B, N, O, F, S, P, Cl, Br, and I. Propellants,
Explos, Pyrotech 33(2):92–102. doi:10.1002/prep.200700054
107. Amwele HR, Papirom P, Chukanhom K, Beamish FHW, Petkam R (2015) Acute and
subchronic toxicity of metal complex azo acid dye and anionic surfactant oil on fish
Oreochromis niloticus. J Environ Biol 36(1):199–205, 7p
108. Andelkovic-Lukic M (2000) New high explosive—polycyclic nitramine hexanitrohexaaza-
isowurtzitane (HNIW, CL-20). Naucno-Teh Pregl 50(6):60–64
109. Anderson SR, am Ende DJ, Salan JS, Samuels P (2014) Preparation of an energetic-energetic
cocrystal using resonant acoustic mixing. Propellants, Explos, Pyrotech 39(5):637–640
doi:10.1002/prep.201400092
110. Atwood AI et al (1999) Burning rate of solid propellant ingredients, part 1: pressure and
initial temperature effects. J Propul Power 15(6):740–747. doi:10.2514/2.5522
111. Paromov AE, Sysolyatin SV, Gatilov YV (2016) An acid-catalyzed cascade synthesis of
oxaazatetracyclo [5.5.0.03,11.05,9]dodecane derivatives. J Energ Mater. doi:10.1080/
07370652.2016.1194499
112. Atwood AI et al (1999) Burning rate of solid propellant ingredients, part 2: determination of
burning rate temperature sensitivity. J Propul Power 15(6):748–752. doi:10.2514/2.5523
113. Aubuchon CM, Rector KD, Holmes W, Fayer MD (1999) Nitro group asymmetric stretching
mode lifetimes of molecules used in energetic materials. Chem Phys Lett 299(1):84–90.
doi:10.1016/S0009-2614(98)01241-X
114. Balakrishnan VK, Halasz A, Hawari J (2003) Alkaline Hydrolysis of the cyclic nitramine
explosives RDX, HMX, and CL-20: new insights into degradation pathways obtained by the
observation of novel intermediates. Environ Sci Technol 37(9):1838–1843. doi:10.1021/
es020959h
115. Balakrishnan VK, Monteil-Rivera F, Gautier MA, Hawari J (2004) Sorption and stability of
the polycyclic nitramine explosive CL-20 in soil. J Environ Qual 33(4):1362–1368. doi:10.
2134/jeq2004.1362
116. Balakrishnan VK, Monteil-Rivera F, Halasz A, Corbeanu A, Hawari J (2004)
Decomposition of the polycyclic nitramine explosive, CL-20, by FeO. Environ Sci
Technol 38(24):6861–6866. doi:10.1021/es049423h
117. Bardai G, Sunahara GI, Spear PA, Martel M, Gong P, Hawari J (2005) Effects of dietary
administration of CL-20 on Japanese Quail Coturnix coturnix japonica. Arch Environ
Contam Toxicol 49(2):215–222. doi:10.1007/s00244-004-0231-9
118. Bardai GK et al (2006) In vitro degradation of hexanitrohexaazaisowurtzitane (CL-20) by
cytosolic enzymes of Japanese quail and the rabbit. Environ Toxicol Chem 25(12):3221–
3229. doi:10.1897/06-068R.1
119. Bayat Y et al (2013) Synthesis of 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane
using Melaminium-tris(hydrogensulfate) by a Simple One-pot Nitration Procedure.
Propellants, Explos, Pyrotech 38(6):745–747. doi:10.1002/prep.201300034
120. Bayat Y, Mokhtari J, Farhadian N, Bayat M (2012) Heteropolyacids: an efficient catalyst for
synthesis of CL-20. J Energ Mater 30(2):124–134. doi:10.1080/07370652.2010.549539
121. Bayat Y, Pourmortazavi SM, Ahadi H, Iravani H (2013) Taguchi robust design to optimize
supercritical carbon dioxide anti-solvent process for preparation of 2,4,6,8,10,12-hexanitro-
2,4,6,8,10,12-hexaazaisowurtzitane nanoparticles. Chem Eng J 230:432–438 doi:10.1016/j.
cej.2013.06.100
122. Bayat Y, Soleyman R, Zarandi M (2015) Synthesis and characterization of novel
2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (2,4,6,8,10,12-hexanitro-
2,4,6,8,10,12-hexaazatetracyclo dodecane based nanopolymer-bonded explosives by
microemulsion. J Mol Liq 206:190–194. doi:10.1016/j.molliq.2015.02.019
Additional Scholarly Articles for Further Reading 95

123. Bazaki H, Kawabe S, Miya H, Kodama T (1998) Synthesis and sensitivity of

hexanitrohexaaza-isowurtzitane (HNIW). Propellants, Explos, Pyrotech 23(6):333–336.
doi:10.1002/(SICI)1521-4087(199812)23:6<333:AID-PREP333>3.0.CO;2-X
124. Behler KD, Pesce-Rodriguez R, Cabalo J, Sausa R (2013) Infrared spectroscopy and density
functional theory of crystalline b-2,4,6,8,10,12-hexanitrohexaaziosowurtzitane (b CL-20) in
the region of its C-H stretching vibrations. Spectrochim Acta, Part A 114:708–712. doi:10.
1016/j.saa.2013.05.075
125. Behrens R (2005) Thermal decomposition processes of energetic materials in the condensed
phase at low and moderate temperatures. Adv Ser Phys Chem 16(Overviews of Recent
Research on Energetic Materials):29–73
126. Bhushan B, Halasz A, Hawari J (2004) Nitroreductase catalyzed biotransformation of
CL-20. Biochem Biophys Res Commun 322(1):271–276. doi:10.1016/j.bbrc.2004.07.115
127. Bhushan B, Halasz A, Spain JC, Hawari J (2004) Initial reaction(s) in biotransformation of
CL-20 is catalyzed by salicylate 1-monooxygenase from Pseudomonas sp. strain ATCC
29352. Appl Environ Microbiol 70(7):4040–4047. doi:10.1128/AEM.70.7.4040-4047.2004
128. Bhushan B, Halasz A, Thiboutot S, Ampleman G, Hawari J (2004) Chemotaxis-mediated
biodegradation of cyclic nitramine explosives RDX, HMX, and CL-20 by Clostridium
sp. EDB2. Biochem Biophys Res Commun 316(3):816–821. doi:10.1016/j.bbrc.2004.02.120
129. Bolton O, Simke LR, Pagoria PF, Matzger AJ (2012) High power explosive with good
sensitivity: A 2:1 cocrystal of CL-20:HMX. Cryst Growth Des 12(9):4311–4314. doi:10.
1021/cg3010882
130. Bonin PML, Bejan D, Radovic-Hrapovic Z, Halasz A, Hawari J, Bunce NJ (2005) Indirect
oxidation of RDX, HMX, and CL-20 cyclic nitramines in aqueous solution at boron-doped
diamond electrodes. Environ Chem 2(2):125–129. doi:10.1071/EN05006
131. Boudreau AE, Hoatson DM (2004) Halogen variations in the paleoproterozoic layered
mafic-ultramafic intrusions of East Kimberley, Western Australia: implications for platinum
group element mineralization. Econ Geol 99(5):1015–1026
132. Bresler PI (1966) Gas analyzer for determination of chlorine concentrations in gas mixtures.
Zavod Lab 32(6):7–766
133. Bunte G, Pontius H, Kaiser M (1999) Analytical characterization of impurities or byproducts
in new energetic materials. Propellants, Explos, Pyrotech 24(3):149–155. doi:10.1002/(SICI)
1521-4087(199906)24:03<149:AID-PREP149>3.0.CO;2-4
134. Byrd EFC, Chabalowski CF, Rice BM (2007) An Ab initio study of nitromethane, HMX,
RDX, CL-20, PETN, and TATB. Science Press, pp 696–700
135. Byrd EFC, Rice BM (2006) Improved prediction of heats of formation of energetic materials
using quantum mechanical calculations. J Phys Chem A 110(3):1005–1013
136. Byrd EFC, Rice BM (2007) Ab initio study of compressed 1,3,5,7-tetranitro-1,3,5,7-
tetraazacyclooctane (HMX), cyclotrimethylenetrinitramine (RDX), 2,4,6,8,10,12-
hexanitrohexaazaisowurzitane (CL-20), 2,4,6-trinitro-1,3,5-benzenetriamine (TATB), and
pentaerythritol tetranitrate (PETN). J Phys Chem C 111(6):2787–2796. doi:10.1021/
jp0617930
137. Bywater WG, Coleman WR, Kamm O, Merritt HH (1945) Synthetic anticonvulsants.
Preparation and properties of some benzoxazoles. J Am Chem Soc 67:7–905. doi:10.1021/
ja01222a008
138. Campbell JA, Szecsody JE, Devary BJ, Valenzuela BR (2007) Electrospray ionization mass
spectrometry of hexanitrohexaazaisowurtzitane (CL-20). Anal Lett 40(10):1972–1978.
doi:10.1080/00032710701484459
139. Chambers RD, Musgrave WKR, Urben PG (1975) Chlorination of perfluorodiazines.
J Fluorine Chem 5(3):6–275. doi:10.1016/S0022-1139(00)82489-6
140. Chan RKS, Anselmo KJ, Reynolds CE, Worman CH (1978) Diffusion of vinyl chloride
from PVC packaging material into food simulating solvents. Polym Eng Sci 18(7):6–601.
doi:10.1002/pen.760180709
141. Chang C-L, Lee J-S, Hsu C-K, Shieh B (2001) Thermal decomposition properties of CL-20
and NTO. Proc NATAS Annu Conf Therm Anal Appl 29th:685–690
96 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

142. Chapman RD, Hollins RA (2008) Benzylamine-Free, heavy-metal-free synthesis of CL-20

via hexa(1-propenyl)hexaazaisowurtzitane. J Energ Mater 26(4):246–273. doi:10.1080/
07370650802182385
143. Chernyshev EA, Mironov VF, Petrov AD (1960) New method of preparation of
organosilicon monomers by high temperature condensation of alkenyl chlorides, aryl
chlorides, and olefins with hydrosilanes. Izv Akad Nauk SSSR, Ser Khim:2147–2156
144. Chung K-H, Kil H-S, Choi I-Y, Chu C-K, Lee I-M (2000) New precursors for
hexanitrohexaazaisowurtzitane (HNIW, CL-20). J Heterocycl Chem 37(6):1647–1649.
doi:10.1002/jhet.5570370640
145. Clawson JS, Anderson KL, Pugmire RJ, Grant DM (2004) 15 N NMR Chemical Shift
Tensors of Substituted Hexaazaisowurtzitanes: The Intermediates in the Synthesis of CL-20.
J Phys Chem A 108(14):2638–2644. doi:10.1021/jp0373999
146. Collet C, Dervaux M, Werschine M (2011) B2514A: a novel enhanced blast explosive. Proc
Int Pyrotech Semin 37th(EUROPYRO 2011):72–84
147. Crocker FH, Indest KJ, Fredrickson HL (2006) Biodegradation of the cyclic nitramine
explosives RDX, HMX, and CL-20. Appl Microbiol Biotechnol 73(2):274–290. doi:10.
1007/s00253-006-0588-y
148. Crocker FH, Thompson KT, Szecsody JE, Fredrickson HL (2005) Biotic and abiotic
degradation of CL-20 and RDX in soils. J Environ Qual 34(6):2208–2216. doi:10.2134/
jeq2005.0032
149. DeTata D, Collins P, McKinley A (2013) A fast liquid chromatography quadrupole
time-of-flight mass spectrometry (LC-QToF-MS) method for the identification of organic
explosives and propellants. Forensic Sci Int 233(1–3):63–74. doi:10.1016/j.forsciint.2013.
08.007
150. Divekar CN, Sanghavi RR, Nair UR, Chakraborthy TK, Sikder AK, Singh A (2010)
Closed-vessel and thermal studies on triple-base gun propellants containing CL-20. J Propul
Power 26(1):120–124. doi:10.2514/1.40895
151. Doriath G (1995) Energetic insensitive propellants for solid and ducted rockets. J Propul
Power 11(4):82–870. doi:10.2514/3.23912
152. Dorofeeva OV, Suntsova MA (2015) Enthalpy of formation of CL-20. Comput Theor Chem
1057:54–59. doi:10.1016/j.comptc.2015.01.015
153. Dubovik AV, Kozak GD, Aleshkina EA (2007) Theoretical estimation of explosion hazard
of NTO, FOX-7, TNAZ, and CL-20. University of Pardubice, pp 484–495
154. Dumas S, Gauvrit JY, Lanteri P (2012) Determining the polymorphic purity of e-CL20
contaminated by other polymorphs through the use of FTIR spectroscopy with PLS
regression. Propellants, Explos, Pyrotech 37(2):230–234. doi:10.1002/prep.200900090
155. Dziura R, Kazimierczuk R, Skupinski W, Pienkowski L, Grzelczyk S (2003) Reductive
debenzylation in synthesis of hexanitrohexaazaisowurtzitane (HNIW, CL-20). Organika:31–43
156. Elbeih A, Zeman S, Jungova M, Vavra P (2013) Attractive nitramines and related PBXs.
Propellants, Explos, Pyrotech 38(3):379–385. doi:10.1002/prep.201200011
157. Fournier D, Monteil-Rivera F, Halasz A, Bhatt M, Hawari J (2006) Degradation of CL-20 by
white-rot fungi. Chemosphere 63(1):175–181. doi:10.1016/j.chemosphere.2005.06.052
158. Gar KA (1958) Field trials of 65% chlorten. Org Insektofungitsidy i Gerbitsidy:208–230
159. Geetha M, Nair UR, Sarwade DB, Gore GM, Asthana SN, Singh H (2003) Studies on
CL-20: The most powerful high energy material. J Therm Anal Calorim 73(3):913–922
160. Ghosh M et al (2014) Probing crystal growth of e- and a-CL-20 polymorphs via metastable
phase transition using microscopy and vibrational spectroscopy. Cryst Growth Des 14
(10):5053–5063. doi:10.1021/cg500644w
161. Ghule VD, Jadhav PM, Patil RS, Radhakrishnan S, Soman T (2010) Quantum-chemical
studies on hexaazaisowurtzitanes. J Phys Chem A 114(1):498–503. doi:10.1021/jp9071839
162. Gnirke AU, Weidle UH (1998) Investigation of prevalence and regulation of expression of
progression associated protein (PAP). Anticancer Res 18(6A):4363–4369
163. Gnirke AU, Weidle UH (1998) Investigation of prevalence and regulation of expression of
progression associated protein (PAP). Anticancer Res 18(6A):4363–4369
Additional Scholarly Articles for Further Reading 97

164. Goede P, Latypov NV, Oestmark H (2004) Fourier transform Raman Spectroscopy of the
four crystallographic phases of a, b, c and e 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-
hexaazatetracyclo[5.5.0.05,9.03,11]dodecane (HNIW, CL-20). Propellants, Explos,
Pyrotech 29(4):205–208 doi:10.1002/prep.200400047
165. Golofit T, Zysk K (2015) Thermal decomposition properties and compatibility of CL-20
with binders HTPB, PBAN, GAP and polyNIMMO. J Therm Anal Calorim 119(3):1931–
1939. doi:10.1007/s10973-015-4418-2
166. Gong P, Sunahara GI, Rocheleau S, Dodard SG, Robidoux PY, Hawari J (2004) Preliminary
ecotoxicological characterization of a new energetic substance, CL-20. Chemosphere 56
(7):653–658. doi:10.1016/j.chemosphere.2004.04.010
167. Granito C, Schultz HP (1963) Decarboxylation studies. II. Preparation of alkyl phenyl
ketones. J Org Chem 28:81–879. doi:10.1021/jo01038a521
168. Greenberg BL, Kalyon DM, Erol M, Mezger M, Lee K, Lusk S (2003) Analysis of
slurry-coating effectiveness of CL-20 using grazing incidence x-ray diffraction. J Energ
Mater 21(3):185–199. doi:10.1080/716100383
169. Groom CA, Halasz A, Paquet L, D’Cruz P, Hawari J (2003) Cyclodextrin-assisted capillary
electrophoresis for determination of the cyclic nitramine explosives RDX, HMX and CL-20.
Comparison with high-performance liquid chromatography. J Chromatogr, A 999(1–2):17–
22 doi:10.1016/S0021-9673(03)00389-3
170. Hakansson K, Coorey RV, Zubarev RA, Talrose VL, Hakansson P (2000) Low-mass ions
observed in plasma desorption mass spectrometry of high explosives. J Mass Spectrom 35
(3):337–346
171. Hawari J, Deschamps S, Beaulieu C, Paquet L, Halasz A (2004) Photodegradation of CL-20:
insights into the mechanisms of initial reactions and environmental fate. Water Res 38
(19):4055–4064. doi:10.1016/j.watres.2004.06.032
172. Hoffmann RW, Sieber W, Guhn G (1965) Decomposition of 1,2,3-benzothiadiazole
1,1-dioxide. Chem Ber 98(11):8–3470
173. Hultquist ME et al (1951) N-Heterocyclic benzenesulfonamides. J Am Chem Soc 73:66–
2558. doi:10.1021/ja01150a042
174. Isayev O, Gorb L, Qasim M, Leszczynski J (2008) Ab initio molecular dynamics study on
the initial chemical events in nitramines: thermal decomposition of CL-20. J Phys Chem B
112(35):11005–11013. doi:10.1021/jp804765m
175. Kaste PJ, Rice BM (2004) Novel energetic materials for the future force: the army pursues
the next generation of propellants and explosives. AMPTIAC Q 8(4):85–89
176. Keshavarz MH, Yousefi MH (2008) Heats of sublimation of nitramines based on simple
parameters. J Hazard Mater 152(3):929–933. doi:10.1016/j.jhazmat.2007.07.067
177. Kholod Y et al (2006) Are 1,5- and 1,7-dihydrodiimidazo[4,5-b:4’,5’-e]pyrazine the main
products of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) alkaline
hydrolysis? A DFT study of vibrational spectra. J Mol Struct 794(1–3):288–302. doi:10.
1016/j.molstruc.2006.02.061
178. Kholod Y, Kosenkov D, Okovytyy S, Gorb L, Qasim M, Leszczynski J (2008) CL-20
photodecomposition: Ab initio foundations for identification of products. Spectrochim Acta,
Part A 71A(1):230–237. doi:10.1016/j.saa.2007.12.021
179. Kim J-H, Park Y-C, Yim Y-J, Han J-S (1998) Crystallization behavior of hexanitrohex-
aazaisowurtzitane at 298 K and quantitative analysis of mixtures of its polymorphs by FTIR.
J Chem Eng Jpn 31(3):478–481. doi:10.1252/jcej.31.478
180. Kim J-H, Park Y-C, Yim Y-J, Han J-S (1998) Crystallization behavior of hexanitrohex-
aazaisowurtzitane at 298 K and quantitative analysis of mixtures of its polymorphs by FTIR.
J Chem Eng Jpn 31(3):478–481. doi:10.1252/jcej.31.478
181. Klapotke TM, Ang H-G (2001) Estimation of the crystalline density of nitramine (N-NO2
based) high energy density materials (HEDM). Propellants, Explos, Pyrotech 26(5):221–
224. doi:10.1002/1521-4087(200112)26:5<221:AID-PREP221>3.0.CO;2-T
182. Klapötke TM, Witkowski TG (2016) Covalent and Ionic Insensitive High-Explosives.
Propellants, Explos, Pyrotech 41:470–483. doi:10.1002/prep.201600006
98 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

183. Knox-Holmes B (1993) Biofouling control with low levels of copper and chlorine.
Biofouling 7(2):66–157. doi:10.1080/08927019309386250
184. Koslik P, Stas J, Wilk Z, Zakrzewski A (2007) Research of high explosives based on RDX,
HMX and CL-20 in the small scale underwater test examination. Cent Eur J Energ Mater 4
(3):3–13
185. Koutsospyros A, Christodoulatos C, Panikov N, Malcheva O, Karakaya P, Nicolich S (2004)
Environmental relevance of CL-20: preliminary findings. Water Air Soil Pollut Focus 4(4–
5):459–470. doi:10.1023/B:WAFO.0000044818.76609.e9
186. Li H, Shu Y, Gao S, Chen L, Ma Q, Ju X (2013) Easy methods to study the smart energetic
TNT/CL-20 co-crystal. J Mol Model 19(11):4909–4917. doi:10.1007/s00894-013-1988-4
187. Li J, Brill TB (2007) Kinetics of solid polymorphic phase transitions of CL-20. Propellants,
Explos, Pyrotech 32(4):326–330. doi:10.1002/prep.200700036
188. Lizlovs EA, Bond AP (1975) Effect of low-temperature aging on corrosion resistance of
chromium-molybdenum (18Cr-2Mo) titanium-stabilized ferritic stainless steel.
J Electrochem Soc 122(5):93–589. doi:10.1149/1.2134271
189. Maksimowski P, Skupinski W, Szczygielska J (2013) Comparison of the crystals obtained
by precipitation of CL-20 with different chemical purity. Propellants, Explos, Pyrotech 38
(6):791–797. doi:10.1002/prep.201300064
190. Marvin KW, Fujimoto W, Jetten AM (1995) Identification and characterization of a novel
squamous cell-associated gene related to PMP22. J Biol Chem 270(48):16–28910. doi:10.
1074/jbc.270.48.28910
191. Mathieu J, Stucki H (2004) Military high explosives. Chimia 58(6):383–389. doi:10.2533/
0000942904777677669
192. Meents A, Dittrich B, Johnas SKJ, Thome V, Weckert EF (2008) Charge-density studies of
energetic materials: CL-20 and FOX-7. Acta Crystallogr Sect B: Struct Sci 64(4):519.
doi:10.1107/S0108768108017497
193. Millar DIA et al (2012) Crystal engineering of energetic materials: Co-crystals of CL-20.
CrystEngComm 14(10):3742–3749. doi:10.1039/c2ce05796d
194. Molt RW, Bartlett RJ, Watson T, Bazante AP (2012) Conformers of CL-20 explosive and
ab initio refinement using perturbation theory: implications to detonation mechanisms.
J Phys Chem A 116(49):12129–12135. doi:10.1021/jp305443h
195. Monteil-Rivera F et al (2009) Fate of CL-20 in sandy soils: degradation products as potential
markers of natural attenuation. Environ Pollut 157(1):77–85
196. Naik NH, Gore GM, Gandhe BR, Sikder AK (2008) Studies on thermal decomposition
mechanism of CL-20 by pyrolysis gas chromatography-mass spectrometry (Py-GC/MS).
J Hazard Mater 159(2–3):630–635. doi:10.1016/j.jhazmat.2008.02.049
197. Namasivayam C, Kanagarathinam A (1992) Distillery wastewater treatment using waste iron
(3+)/chromium(3+) hydroxide sludge and polymer flocculants. J Environ Sci Health, Part A
A 27(7):37–1721
198. Nedelko VV et al (2000) Comparative investigation of thermal decomposition of various
modifications of hexanitrohexaazaisowurtzitane (CL-20). Propellants, Explos, Pyrotech 25
(5):255–259. doi:10.1002/1521-4087(200011)25:5<255:AID-PREP255>3.0.CO;2-8
199. Oehrle SA (1996) Analysis of nitramine and nitroaromatic explosives by micellar
electrokinetic capillary chromatography (MECC). J Energ Mater 14(1):47–56. doi:10.
1080/07370659608216057
200. Ogata Y, Kawasaki A, Nakagawa K (1964) Kinetics of the formation of benzoguanamine
from dicyandiamide and benzonitrile. Tetrahedron 20(12):61–2755. doi:10.1016/S0040-
4020(01)98493-5
201. Okovytyy S, Kholod Y, Qasim M, Fredrickson H, Leszczynski J (2005) The Mechanism of
Unimolecular Decomposition of 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane.
A computational DFT study. J Phys Chem A 109(12):2964–2970. doi:10.1021/jp045292v
202. Patel AR, Oneto JF (1963) Basic 1,3-dioxolanes. J Pharm Sci 52(6):92–588. doi:10.1002/
jps.2600520618
Additional Scholarly Articles for Further Reading 99

203. Paulin A, Jobson BA, Vukcevic S (1981) Chlorination of alumina-containing materials in

fluidized bed. Trav Com Int Etude Bauxites, Alumine Alum 16:70–161
204. Peralta-Inga Z, Degirmenbasi N, Olgun U, Gocmez H, Kalyon DM (2006) Recrystallization
of CL-20 and HNFX from solution for rigorous control of the polymorph type: part I,
mathematical modeling using molecular dynamics method. J Energ Mater 24(2):69–101.
doi:10.1080/07370650600672082
205. Pivina T, Korolev V, Khakimov D, Petukhova T, Ivshin V, Lempert D (2012) Computer
simulation of decomposition mechanisms for CL-20, hydrazine, and their binary system.
Propellants, Explos, Pyrotech 37(4):502–509. doi:10.1002/prep.201100098
206. Reeves CC Jr, Miller WD (1978) Nitrate, chloride and dissolved solids, Ogallala aquifer,
west Texas. Ground Water 16(3):73–167. doi:10.1111/j.1745-6584.1978.tb03218.x
207. Robidoux PY et al (2004) Acute and chronic toxicity of the new explosive CL-20 to the
earthworm (Eisenia andrei) exposed to amended natural soils. Environ Toxicol Chem 23
(4):1026–1034. doi:10.1897/03-308
208. Sandor A (1964) Thermionic emission from barium-coated ultrapure nickel in the emission
microscope. J Electron Control 17(4):91–377. doi:10.1080/00207216408937712
209. Sandor A (1964) Thermionic emission from barium-coated ultrapure nickel in the emission
microscope. J Electron Control 17(4):91–377. doi:10.1080/00207216408937712
210. Sausa RC, Cabalo JB (2012) The detection of energetic materials by laser photoacoustic
overtone spectroscopy. Appl Spectrosc 66(9):993–998. doi:10.1366/12-06699
211. Schefflan R, Kovenklioglu S, Kalyon D, Redner P, Heider E (2006) Mathematical model for
a fed-batch crystallization process for energetic crystals to achieve targeted size distributions.
J Energ Mater 24(2):157–172. doi:10.1080/07370650600672058
212. Sikder AK, Sikder N, Gandhe BR, Agrawal JP, Singh H (2002) Hexanitrohexaazaisowurtzitane
or CL-20 in India: synthesis and characterisation. Def Sci J 52(2):135–146
213. Sinditskii VP, Burzhava AV, Sheremetev AB, Aleksandrova NS (2012) Thermal and
combustion properties of 3,4-bis(3-nitrofurazan-4-yl)furoxan (DNTF). Propellants, Explos,
Pyrotech 37(5):575–580. doi:10.1002/prep.201100095
214. Sinditskii VP, Egorshev VY, Serushkin VV, Filatov SA, Chernyi AN (2012) Combustion
mechanism of energetic binders with nitramines. Int J Energ Mater Chem Propul 11(5):427–
449. doi:10.1615/IntJEnergeticMaterialsChemProp.2013005557
215. Singh H (2005) Current trend of R&D in the field of high energy materials: an overview.
Explosion 15(3):120–132
216. Sivabalan R, Gore GM, Nair UR, Saikia A, Venugopalan S, Gandhe BR (2007) Study on
ultrasound assisted precipitation of CL-20 and its effect on morphology and sensitivity.
J Hazard Mater 139(2):199–203. doi:10.1016/j.jhazmat.2006.06.027
217. Souers PC et al (2001) Detonation energies from the cylinder test and CHEETAH V3.0.
Propellants, Explos, Pyrotech 26(4):180–190 doi:10.1002/1521-4087(200110)26:4<180::
AID-PREP180>3.0.CO;2-K
218. Steinmetz I, Rott L, Boer C (1966) Enrichment of ground waters with surface waters.
Hidrobiologia 7:195–201
219. Strigul N, Braida W, Christodoulatos C, Balas W, Nicolich S (2005) The assessment of the
energetic compound 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20)
degradability in soil. Environ Pollut 139(2):353–361. doi:10.1016/j.envpol.2005.05.002
220. Suzuki J et al (1984) Performance of Shimadzu clinical chemistry analyzer CL-20.
Shimadzu Hyoron 41(4):45–229
221. Szecsody JE, Girvin DC, Devary BJ, Campbell JA (2004) Sorption and oxic degradation of
the explosive CL-20 during transport in subsurface sediments. Chemosphere 56(6):593–610.
doi:10.1016/j.chemosphere.2004.04.028
222. Talawar MB et al (2006) Effect of organic additives on the mitigation of volatility of
1-nitro-3,3’-dinitroazetidine (TNAZ): Next generation powerful melt castable high energy
material. J Hazard Mater 134(1–3):8–18. doi:10.1016/j.jhazmat.2003.10.008
223. Talawar MB, Sivabalan R, Polke BG, Nair UR, Gore GM, Asthana SN (2005) Establishment
of process technology for the manufacture of dinitrogen pentoxide and its utility for the
100 2 Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

synthesis of most powerful explosive of today—CL-20. J Hazard Mater 124(1–3):153–164.

doi:10.1016/j.jhazmat.2005.04.021
224. Tappan AS, Basiliere M, Ball JP, Snedigar S, Fischer GJ, Salton J (2010) Linear actuation
using milligram quantities of CL-20 and TAGDNAT. Propellants, Explos, Pyrotech 35
(3):207–212. doi:10.1002/prep.201000025
225. Tappan BC, Brill TB (2003) Thermal decomposition of energetic materials 86. Cryogel
synthesis of nanocrystalline CL-20 coated with cured nitrocellulose. Propellants, Explos,
Pyrotech 28(5):223–230 doi:10.1002/prep.200300009
226. Thiboutot S, Brousseau P, Ampleman G, Pantea D, Cote S (2008) Potential use of CL-20 in
TNT/ETPE-based melt cast formulations. Propellants, Explos, Pyrotech 33(2):103–108.
doi:10.1002/prep.200700223
227. Tian Q et al (2013) Thermally induced damage in hexanitrohexaazaisowurtzitane. Cent Eur J
Energ Mater 10(3):359–369
228. Tomas-Alonso F, Rubio AM, Alvarez R, Ortuno JA (2013) Dynamic potential response and
SEM-EDX studies of polymeric inclusion membranes based on ionic liquids. Int J
Electrochem Sci 8(4):4955–4969
229. Urbelis JH, Young VG, Swift JA (2015) Using solvent effects to guide the design of a CL-20
cocrystal. CrystEngComm 17(7):1564–1568. doi:10.1039/C4CE02285H
230. Van der Heijden AEDM (1998) Crystallization and characterization of energetic materials.
Curr Top Cryst Growth Res 4:99–114
231. van der Heijden AEDM, Bouma RHB, van der Steen AC (2004) Physicochemical
parameters of nitramines influencing shock sensitivity. Propellants, Explos, Pyrotech 29
(5):304–313. doi:10.1002/prep.200400058
232. van der Heijden AEDM, Bouma RHB, van der Steen AC (2004) Physicochemical
parameters of nitramines influencing shock sensitivity. Propellants, Explos, Pyrotech 29
(5):304–313. doi:10.1002/prep.200400058
233. Viswanath DS, Reinig M, Ghosh TK, Boddu VM (2010) Vapor pressure of nitro
compounds, vol Pt. 1. University of Pardubice, Institute of Energetic Materials, pp 306–309
234. Viswanath JV, Venugopal KJ, Rao NVS, Venkataraman A (2016) An overview on importance,
synthetic strategies and studies of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane
(HNIW). Defence Technol 12(5), October 2016, pp 401–418
235. Volk F, Bathelt H (1997) Influence of energetic materials on the energy-output of gun
propellants. Propellants, Explos, Pyrotech 22(3):120–124. doi:10.1002/prep.19970220305
236. Volk F, Bathelt H (1995) Influence of energetic materials on the energy-output of gun
propellants. Am Defense Preparedness Assoc: 82–89
237. von Holtz E, Ornellas D, Foltz MF, Clarkson JE (1994) The solubility of e-CL-20 in selected
materials. Propellants, Explos, Pyrotech 19(4):12–206. doi:10.1002/prep.19940190410
238. Wu Y, Ou Y, Liu Z, Liu J, Meng Z, Chen B (2004) Theoretical studies on the possible
conformers and properties of tetranitrodiazidoacetylhexaazaisowurtzitane (TNDAIW). Sci
China, Ser B: Chem 47(5):414–419. doi:10.1360/04yb0046
239. Xing X et al (2015) Thermal decomposition behavior of hexanitrohexaazaisowurtzitane and
its blending with BTATz (expand) and Al by microcalorimetry. J Therm Anal Calorim:
Ahead of Print. doi:10.1007/s10973-015-4431-5
240. Yazici R, Kalyon D (2005) Microstrain and defect analysis of CL-20 crystals by novel x-ray
methods. J Energ Mater 23(1):43–58. doi:10.1080/07370650590920287
241. Zhang C et al (2014) Evident hydrogen bonded chains building CL-20-based cocrystals.
Cryst Growth Des 14(8):3923–3928. doi:10.1021/cg500796r
242. Zhang P, Guo X-Y, Zhang J-Y, Jiao Q-J (2014) Application of liquid paraffin in castable
CL-20-based PBX. J Energ Mater 32(4):278–292. doi:10.1080/07370652.2013.862318
243. Zubarev RA, Hakansson P, Hakansson K, Talrose VL (1998) Matrix assisted particle
desorption techniques: use of explosive matrixes. Adv Mass Spectrom 14:B061920/1–
B061920/8
Chapter 3
FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

Abstract FOX-7 (1,1-diamino-2,2-dinitroethylene) was first synthesized in 1998

by the FOA Defense Research Establishment (Sweden). Synthesis of the FOX-7
and its structural, spectroscopic, and explosive properties are described in this
chapter. The chemical reactivity of FOX-7 towards nucleophilic substitution
(transamination), electrophilic substitution, and acid-base properties, thermal
behavior (phase transformations and thermal decomposition, molecular structure
and physical properties, other energetic molecules that are structurally related to
FOX-7 are also summarized in this chapter.

3.1 Introduction

1,1-diamino-2,2-dinitroethylene, (better known as DADE or FOX-7), is a relatively

new explosive with a high performance and low sensitivity. It is a high energy
density material with low friction and low impact sensitivity. FOX-7 was synthe-
sized first in 1998 by the defense establishment in Sweden, and derives the name
FOX-7 because the Swedish Defense Research Agency is known as FOI, and
I being replaced by X to convey that it is an eXplosive as in RDX and HMX. It has
a large activation barrier for detonation. Its detonation characteristics are similar to
that of RDX, but its sensitivity is lower than TNT. It is structurally similar to
several other energetic compounds but much simpler to synthesize. The chemical
structure of FOX-7 along with RDX and HMX is shown in Fig. 3.1. These unique
combinations of properties arise because of the structure of FOX-7 with molecular
packing consisting of strong hydrogen bonding, and the layered packing indicative
of weak van der Waals interactions.
FOX-7 is classified as an insensitive high explosive. FOX-7 is thermally stable
with an activation energy of 56 kcal/mole compared to 40 kcal/mole for RDX and
35 kcal/mole for HMX [1]. FOX-7 is a symmetric molecule with a simple crystal

© US Government (outside the USA) 2018 101

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7_3
102 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

(a) FOX-7 (b) RDX (c) HMX

Fig. 3.1 Chemical structure of 1,1-Diamino-2,2-dinitroethylene (FOX-7)

structure, which makes it easier to model compared to many other energetic

materials. It is slightly soluble in common organic solvents and water, but readily
dissolves in dipolar aprotic solvents such as dimethyl sulfoxide, N,N-dimethyl
formamide and 1-methyl-2-pyrrolidinone.
FOX-7 exists in three forms depending upon the temperature [2]. Solid FOX-7 is
trimorphic with the a-phase stable on heating up to 388 K, the b-phase from 388 to
435 K, and the c-phase from about 435 K until thermal decomposition at 504 K [3].
The thermal behavior of DADE has been studied by several researchers [1, 4–6].

3.2 Synthesis

FOX-7 was first synthesized by Latypov et al. [7] by reacting 2-(dinitro- methylene)-
4,5-imidazolidinedione with aqueous ammonia solution. They also studied the syn-
thesis of FOX-7 by nitration of 4,6-dihydroxy-2-methylpyrimidine, followed by
hydrolysis of the resulting intermediate 2-dinitromethylene-5,5-dinitropyrimidine-
4,6-dione [8]. Jalovy et al. [9] synthesized FOX-7 by the hydrolysis of
2-dinitrodinitromethylene)-4,5-imidazolidinedione. Swedish Defense Establishment
[10] used 2-methyl-pyrimidine-4,6-di-one is the method currently used for the pro-
duction of FOX-7 on a production scale. Ostmark et al. [11] at have studied various
properties that affect the sensitivity of DADE. In addition, Lochert [6] described three
different methods followed by the Swedish Defense Establishment for the synthesis
of DADE. These three reactions are shown in Fig. 3.2.
The first reaction path produced a highly sensitive intermediate and concluded to
be non-preferable synthesis path for producing DADE. The second path was sat-
isfactory, but the yield was rather low, about 38%. This second reaction path was
scaled up in the laboratory to produce about 50 g of DADE. Lochert [6] carried out
a cost analysis for this synthesis route and reported that the cost of production of
DADE by the new route can be half of the cost of the commercial product at that
time. Based on the analysis, Lochert [6] estimated that it costs AU$ 2930 to make
3.2 Synthesis 103

Reaction Path 1

Reaction Path 2

Fig. 3.2 Three reaction paths followed by FOI for synthesis of DADE [6]

1 kg of DADE, and cost of the commercial product at that time was AU$ 5800/Kg.
The chemicals and the quantities used in the cost calculation are given in Table 3.1.
During laboratory scale experimentation, another problem was encountered;
frothing of the solution [5, 6, 12–15]. To avoid this problem, a third synthesis route
was developed, which also provided higher yield (Table 3.2).
104 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

Reaction Path 3

Fig. 3.2 (continued)

Table 3.1 Amounts of Item Amount required

various materials estimated
for production of 50 g of Methanol 7500 mL
FOX-7 via FOI reaction Sodium Methoxide (30%) 1070 mL
path 2 [6] Acetamidine Hydrochloride 168 g
Diethyl Oxalate 258 g
Hydrochloric Acid 375 mL
Sulfuric Acid 940 mL
Nitric Acid 205 mL
Ammonia 190 mL

Trzcinski et al. [16] synthesized DADE by following the method suggested by

Chylek et al. [17], which was a modification of the method proposed by Latypov
et al. [8]. In this process, DADE was synthesized via 2-methylpyrimidine-4,6
(3H,5H-dione (1), which was prepared by the condensation of acetamidine
hydrochloride with diethyl malonate as shown in Fig. 3.3. The process was similar
to that used by the Sweden Defence Establishment [1]. The final product, DADE,
was obtained by nitration and hydrolysis. The authors provided a detailed expla-
nation of the reaction paths, the crystallization process using water/
N-methyl-2-pyrrolidone mixture, the particle size distribution of the finished pro-
duct, and SEM micrographs. The size and distribution of particles depended on the
crystallization process, which is discussed in the following section.
Figure 3.4 shows two different synthesis schemes used by Anniyappan et al. [5].
In the first method, they nitrated 2-methylimidazol (7) with mixed acid to yield
intermediate 2-dinitromethylene-4,4-dinitro-5-imidazolidinone, (8) that decom-
posed at room temperature to give the compound (6), which was converted to
FOX-7 by amination.
Temperature control was important in the nitration step. The product was isolated as
a solid. The product yield was low (<15%). In the second method, acetamidine
hydrochloride (9) was reacted with diethyl oxalate (10) to give a mixture of 2-methoxy-
2-methyl-4,5 imidazolidinedione (11) and 2-methyl-4,5-imidazolidinedione (12). This
3.2 Synthesis 105

Table 3.2 A summary of various synthesis routes explored by researchers

Authors Synthesis Route Yield
Cai et al. [12] 13%

81.1%

Cai et al. [14]

cardoxylic acid yield of 2

(%)
Formic acid 94.6
Acetic acid 95.8
Propanoic acid 95.8
n-butanoic acid 96.6
a Carboxylic acid (200 ml), 2-(dinitromethylene)-4,5-imidazolidinedione Formic acid 94.6
(0.01 mol), reaction 30 min, T = 25 oC.

product mixture11 and 12 or 11 alone was nitrated by mixed acid to from 2-(dini-
tromethylene)-4,5-imidazolidinedione (6) which was subsequently converted to FOX-7
as shown in Fig. 3.4. They describe other methods in their paper, and also the
preparation of salts of DADE. Table 3.2 shows a summary of synthesis processes used
by various researchers.
The synthesis of FOX-7 by transacylation reactions based on the hydrolysis and
methanolysis has been reported by Dewey [18]. The report contains environmental
fate and transport parameters for several compounds such as AP, ADNA,
ADNDNA, DNNC, and HCO. The same results, as has been reported by Dewey,
106 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

Table 3.2 (continued)

R R

HN NH
RNH 2
O2N NO 2
l l

Lochert [6]
O2N NO 2 R'
H2NR'NH 2 HN NH

O2N NO 2
R, R' = alkyl, aryl

Anniyappan.et al [5]

have also been reported by Clausen et al. [19]. There appears to be some dis-
crepancies as for instance the melting point is reported as 478-543 K based on the
work of different investigators. This is a classic example of the discrepancies in
values of physical properties existing for different explosives.
3.2 Synthesis 107

Fig. 3.3 Reaction scheme of coworkers [16]

Fig. 3.4 Different routes for the synthesis of FOX-7 [5]

108 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

Zhou et al. [20] describe the synthesis procedure starting with 2-methylimidazole.
They also determined density (1.885 g cm−3) detonation velocity (8047 m s−1 at
q = 1.696 g cm−3), friction sensitivity of 10% (3.92 MPa, 90°), impact sensitivity
of 6% (10 kg, 25 cm), H2O of 89.1 cm (5 kg), vacuum stability test of 0.14 mL/5 g
(100 °C, 48 h), explosion temperature of 285 °C (5 s delay).
In the recent years, Cai et al. [12–15] have used different synthesis routes, scaled
up the preparation to 7 kg/batch, and compared the properties with other explosives.
Bladek et al. used thin layer chromatography to monitor FOX-7 during its
synthesis [21]. The analytical parameters involved in quantitative determination are
examined. The authors also examined the effect of water concentration and found
an improvement in the yields during the nitration step. Orzechowski et al. [22]
discuss crystallization of from DMF, DMSO, and DMSO + water. They also
provide the solubility of FOX-7 in these two solvents from 293 to 363 K. They
synthesized FOX-7 by reacting dioctylmalonate with acetamidine hydrochloride in
thesolution of sodium methylate, and nitration of obtained 2-methylpyrimidyne 4,6
(3H,5H)-dione. Several examples of the crystallization step are provided together
with SEM photomicrographs and particle size distribution, and conclude that the
best results in terms of particle size and density were obtained using a mixture of
DMSO + water as the solvent.
Goh et al. [23, 24] who discussed the synthesis starting from 2-methylpyrimidyne
4,6-dione and report yields close to 80%; of Goh and Kim [25] who discussed the
nitration of 4,6-Dihydroxy -2-methylpyrimidine using dichloromethane as a solvent,
and on hydrolysis of the nitrated product, 4,6-dihydroxy-5,5-dinitro-2-(dini-
tromethylene)-2,5-dihydro pyrimidine, report yields of 90%. The reactions were
carried out at temperatures between 293 and 313 K and hydrolysis time of 2 h. They
also discuss different schemes of nitration, and ratio of reactants used, and other
reaction parameters, and of Bellamy [26] who summarized the discovery, synthesis,
structure, and isomers together with an account of spectroscopic and explosive
properties, and chemical reactions of FOX-7.

3.3 Crystallization/Recrystallization

Particle size, along with crystal quality and morphology, play an important role in
determining the sensitivity of an explosive. The size of the crystals affects the
packing density, and, therefore, the performance. The crystals should have mini-
mum defects to maximize its detonation properties. As a result, a number of
recrystallization techniques were proposed that can reliably produce crystals of
desirable size in a consistent manner. The parameters that affect the crystal shape,
size, and its particle size distribution include: solvent type, cooling rate, stirring
rate, and method of stirring, such as sonic method with different frequencies.
Trzcinski et al. [16] used a mixture of water/N-methyl-2-pyrrolidone in a ratio of
75/25 and a cooling rate of 0.3 K/min to recrystallize DADE. They used vigorous
mechanical stirring during the recrystallization process. Particles of diameter in the
3.3 Crystallization/Recrystallization 109

range of 100 to 600 lm with a normal distribution were obtained. The particle
diameter ranged from 2 to 18 lm with a peak around 7 lm when DADE was
recrystallized from NMP into water at an ambient temperature. The FOX-7 crystals
are shown in Fig. 3.5 and their size distribution is presented in Fig. 3.6.
Orzechowski et al. [22] discuss crystallization of DADE from DMF, DMSO, and
DMSO+water solvent. They also provide the solubility of FOX-7 in these two
solvents from 293 to 363 K. Teipel et al. [27] evaluated several solvents and
solvent/anti-solvent mixture for recrystallization of DADE. They noted that solvent
has significant effect on particle shape, surface texture, size and yield. Solvents used
in their study included N-methyl pyrrolidinone (NMP), NMP/water mixtures and N,
N-dimethyl formamide (DMF), c-butyrolactone (GBL) and acetonitrile. The mean
particle size varied from one run to another run, leading them to conclude that
standard cooling-type recrystallization processes are not a preferable approach.
Depending on the solvent used, different types of morphologies of recrystallized
DADE were observed: rhombic, flat, or rectangular. Several researchers tried to
optimize the process parameters that can produce the best crystals in a consistent
manner. The parameters were optimized in terms of solvents, stirring rate and
cooling rate, and the use of anti-solvent. The goal was to produce near spherical
particles or particles that can provide the best packing density.
Solvents used for the recrystallization not only affected the particle sizes and
morphology, but also the detonation properties. Fuhr and Mikonsaari [28] showed
that not only yield of FOX-7 depended on the choice of solvent, but also the impact
and friction sensitivity. Their results are given in Table 3.3.
Several researchers have suggested the use of sonication using ultrasound as a
stirring method during recrystallization process. Ultrasonic cavitation induces
nucleation providing a dominant mechanism of crystal inception. A better control
over the crystal size and morphology was achieved. The particle sizes of DADE
produced from different solvent when 20 kHz ultrasound was applied are given in
Table 3.4 [29]. The application of ultrasound appeared to improve crystal quality in
comparison to traditional recrystallization. The frequency of the ultrasound affected

Fig. 3.5 FOX-7 crystals prepared by recrystallization method are shown in two magnification
scale [16]
110 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

Fig. 3.6 Particle size distribution of FOX-7 crystals following their recrystallization [16]

Table 3.3 Properties of the recrystallized FOX-7 [28]

FOX-7 NMP/water NMP/water+antisolvent
Mean particle size (lm) 213 273
Span (90/10) 1.445 0.506
Rate of yield 50% 80%
Impact sensitivity (N m) 25 35
Friction sensitivity (N) 240 192

the particle size and is explained in Table 3.5. The SEM micrographs of particles
[29] produced under three conditions are given in Fig. 3.7. Less agglomeration or
twinning, and more spherical shape were noted.
3.3 Crystallization/Recrystallization 111

Table 3.4 Effect of solvent on the recrystallization of FOX-7 from various solvents using 20 kHz
ultrasound for production of 3 g materials [29]
Solvent Particle size (lm) Morphology
d (0.1) d (0.5) d (0.9)
NMP/H2O (50:50) 10 29 66 Sharp blocks
GBL 7 16 30 Rounded plates
DMF 3 11 25 Rounded oblongs
DMF/H2O (75:25) 12 35 78 Sharp blocks
Acetonitrile 30 59 103 Rounded blocks

Table 3.5 Effect of frequency of ultrasound on FOX-7 recrystallization [29]

Expt. Method Particle size (mm) Morphology
Application of Scale Cooling rate d d d
ultrasound (g) (oC/min) (0.1) (0.5) (0.9)
#1 None 10 0.5 113 278 543 Blocky,
jagged
#2 None 100 2.0 86 213 445 Blocky
#3 45 kHz continuous 10 0.5 30 59 105 Rounded,
rhombic
#4 45 kHz continuous 10 1.0 – <601 – Blocky
#5 45 kHz continuous, 10 0.5 45 95 183 Rhombic
with surfactant
#6 45 kHz pulsed at 100 0.5 48 98 186 Smooth,
15 min intervals rhombic
#7 20 kHz continuous 100 0.5 65 105 170 Blocky
#8 20 kHz continuous 100 2.0 27 59 121 Blocky

Fig. 3.7 SEM images of FOX-7 (a) No ultrasound (b) 45 kHz ultrasound (c) 20 kHz ultrasound
[29]
112 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

They [29] synthesized FOX-7 by reacting dioctylmalonate with acetamidine

hydrochloride in the solution of sodium methylate, and nitration of obtained
2-methylpyrimidyne 4,6(3H,5H)-dione. Several examples of the crystallization step
are provided together with SEM photomicrographs and particle size distribution,
and conclude that the best results in terms of particle size and density were obtained
using a mixture of DMSO + water as the solvent.

3.4 Structure

3.4.1 Polymorphic Forms

FOX-7 has three polymorphic forms: a, b, and c. Evers et al. [3] found that the a
and b polymorphic transformation in FOX-7 to be first order transition with the
crystal symmetry changing from monoclinic to orthorhombic with a decrease in
density from 1.86 to 1.82 g cm−1 and a ΔH*584 J mol−1. The molecules in the
crystal are arranged in a wave-like structure similar to the (0001) basal-plane of
graphite, and the crystal structure determined by Evers et al. is shown in Fig. 3.8.
Crawford et al. [2] studied transformation of a and b phases to c-FOX-7 using a
DSC over a temperature range of 380–450 K. They noted that the transformation to
c-form takes place around 435 K, and was found to be stable up to 504 K. There
are small differences in physicochemical properties between the a-monoclinic to
b-orthorhombic phase compared to the trimorphic c-phase. The authors prepared
c-FOX-7 by slowly heating b-FOX-7. The authors have also carried out a detailed

Fig. 3.8 Crystal structure of FOX-7 [3]

3.4 Structure 113

Fig. 3.9 DSC of FOX-7

between 373 and 463 K with
endotherms showing the a–b
and b–c phase transitions at
388(1) K and *435 K [2]

study of the structure of the c-phase. The paper provides lattice parameters as a
function of temperature, DSC over a temperature range of 380–450 K, unit cell
volumes for the three phases, and other useful information.
Welch [30] using data from DSC measurements showed that the polymorphic
transformations is temperature dependent and can transform from a to b at 388 K
and b to c around 435 K (see Fig. 3.9). In addition, Welch also provides detailed
crystallographic data for a, b, and c phases.

3.4.2 Crystal Structure

The molecules in the crystal are arranged in a wave-like structure similar to the
(0001) basal-plane of graphite. This may be due to the extensive intermolecular
hydrogen bonding within the layers and ordinary van der Waals interactions
between the layers. The wave like structure was determined by Evers et al. [3] and
is shown in Fig. 3.8. Further study of the crystal structure was carried out by a
number of researchers using x-ray diffraction technique and other spectrometric
method such as the Raman spectrometry.
Bemm and Ostmark [31] carried out a general x-ray diffraction studies of FOX-7
to determine the crystal parameters. Although, they did not identify any poly-
morphic phase for their sample, later Zhao and Liu [32] indicated that the data was
for a-phase. These parameters are given in Table 3.6.
Crawford et al. [2] carried out a detailed study of the structure of the b and
c-phase and provided lattice parameters at various temperature. They prepared
single crystal of b and c-FOX-7 to study the diffraction pattern. The results are
given in Table 3.7.
Zhao and Liu [32] calculated various lattice parameters for a-phase using the
density functional theory (DFT) within local density approximation (LDA) as well
as generalized gradient approximation (GGA) to simulate the structural and
114 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

Table 3.6 Crystal lattice parameters [31]

C2H4N4O4 Mo Ka radiation
Mr = 148.09 k = 0.71073 Å
Monoclinic P21/n Cell parameters from 3831 reflections
a = 6.941 (1) Å h = 3.4-25.9°
b = 6.569 (1) Å l = 0.181 mm−1
c = 11.315 (2) Å T = 173 (2) K
b = 90.55 (2)° Prismatic
V = 515.9 (1) Å3 0.30
0.30
0.20 mm
Z=4 Yellow
D1 = 1.907 Mg m−3
Dm not measured

Table 3.7 Crystallographic data for select explosives

Properties FOX-7 RDX HMX c-FOX-7
T (K) 403 413 423 200
Phase b b b c
Crystal system Orthorhombic Orthorhombic Orthorhombic Monoclinic
Space group P212121 P212121 P212121 P21/n
a (pm) 698.6 (1)a 698.6 (1) 698.6 (1) 1335.4 (3)
b (pm) 666.0 (2) 667.1 (2) 668.6 (2) 689.5 (1)
c (pm) 1167.4 (3) 1168.1 (3) 1168.7 (3) 1205.0 (2)
b (°) 111.102 (8)
V (106 pm3) 543.1 (2) 544.4 (2) 545.9 (2) 1035.0 (3)
Z 4 4 4 8
Dcalc (g cm−3) 1.811 (1) 1.807 (1) 1.802 (1) 1.901 (1)
Reflections
Measured 2897 2913 2902 3620
Unique 1127 1127 1137 2021
R(r) 0.0289 0.0296 0.0282 0.0602
R(Fo) 0.0592 0.0600 0.0575 0.1118b
2
Rw(Fo) 0.1784 0.1858 0.1749 0.3387b
GOF 1.096 1.118 1.117 1.116
Highest rest electron densityc +0.31/−0.24 +0.33/−0.22 +0.28/−0.24 0.63/−0.58
Obtained from single crystal investigations [2]
a
Experimental uncertainties in parentheses
b
The high R-values result from the two phase transitions performed on the single crystal, first a/b
at 390 K, second b/c at 440 K and then quenching to 200 K
c
In e/106 pm3
3.4 Structure 115

Table 3.8 Attice parameters and unit cell volume of a-phase crystalline FOX-7 [32]
a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å)3
Exp. [3] 6.94 6.56 11.31 90.0 90.55 90.0 515.9
Exp. [4] 6.94 6.64 11.34 90.0 90.61 90.0 522.3
Exp. [8] 6.93 6.62 11.23 90.0 89.48 90.0 514.6
Exp. [9] 6.92 6.55 11.27 90.0 90.06 90.0 511.2
LDA 6.74 6.18 11.05 90.0 90.69 90.0 460.5
GGA 7.19 7.54 11.49 90.0 91.96 90.0 623.0
Mean 6.96 6.83 11.27 90.0 91.32 90.0 535

Table 3.9 Selected bond lengths (nm) and bond angle (°) [33] Bond length
Bond length
C(1)—C(2) 0.1492(2) N(4)—C(2) 0.1376(2) O(4)—N(4) 0.12525(18)
N(1)—C(1) 0.1342(2) O(1)—N(3) 0.12586(19) N(5)—C(3) 0.1315(2)
N(2)—C(1) 0.1277(2) O(2)—N(3) 0.12469(18) N(6)—C(3) 0.1325(2)
N(3)—C(2) 0.1360(2) O(3)—N(4) 0.12375(19) N(7)—C(3) 0.1321(2)
Bond angle
N(1)–C(1)–N(2) 121.1(2) N(3)–C(2)–N(4) 121.86(16) O(4)–N(4)–C(2) 116.17(15)
N(1)–C(1)–C(2) 115.21(18) O(1)–N(3)–C(2) 116.47(15) O(3)–N(4)–O(4) 120.28(15)
N(2)–C(1)–C(2) 123.61(18) O(2)–N(3)–C(2) 123.23(15) N(5)–C(3)–N(6) 121.4(2)
N(3)–C(2)–C(1) 119.87(16) O(1)–N(3)–O(2) 120.30(15) N(5)–C(3)–N(7) 119.87(19)
N(4)–C(2)–C(1) 118.20(16) O(3)–N(4)–C(2) 123.55(15) N(7)–C(3)–N(6) 118.75(19)

electronic properties of FOX-7 crystal under high-pressure up to 4 GPa. Their

calculated lattice parameter data are shown in Table 3.8 along with the experi-
mental data from four researchers. A good agreement of the experimental data with
the theory was reported.
Xu et al. [33] used B3LYP, HF and MP2 methods to elucidate the crystal
structure. They reported the bond lengths and bond angles between various atoms
within the structure. This information is useful in determining the reactivity of
FOX-7. For example, FOX-7 can react with some nucleophiles and strong alkalis to
obtain new energetic compounds. The bond lengths and bond angles between
various atoms within the structure are given in Table 3.9.

3.5 Thermophysical Data

A limited number of experimental data for fundamental properties of FOX-7 are

available in the literature. This may be due to the difficulties in conducting
experiments with FOX-7 due its sensitivity and decomposition characteristics.
116 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

The experimental data for fundamental properties are given in Table 3.10. The lack
of experimental data due to difficulties associated with conducting experiments led
several researchers to use various thermodynamic model and approaches to estimate
these properties. Dewey [18] used EPI (Estimation Program Interface) SuiteTM to
estimate various fundamental properties of FOX-7. EPI (Estimation Program
Interface) SuiteTM is a publicly available Windows® based suite of physical/
chemical property and environmental fate estimation models developed by the US
Environmental Protection Agency (EPA). EPI Suite is comprised of individual
chemical/physical estimating modules; each designed to estimate a specific physical
or chemical property of a given structure. The estimated values of various prop-
erties of FOX-7 by the EPI suite are given in Table 3.11.

Table 3.10 Values for some fundamental properties of FOX-7 [34]

Bioconcentration factor 1.0
Boiling point (°C) 194.6 ± 40.0
Density (g/cm3) 1.688 ± 0.06 @ 298.15 K and 760 torr
Enthalpy of vaporization (kJ/mol) 43.08 ± 3.0
Flash point (°C) 71.5 ± 27.3
Koc 1.0 @ pH = 1
Vapor pressure 0.438 torr @ 298.15 K

Table 3.11 Summary of FOX-7 literature values and EPI Suite input and output [18, 34]
Molecular formula C2H4N4O4 Molecular weight (g/ 148.08
mol)
Literature value SMILES only SMILES and MP
Physical state
Melting point (oC) 205.0 83.37 83.37
Boiling point (oC) NA 287.51 287.51
Solubility, Water (mg/L) NA 1.06 1.06
Partion coefficients
Log Kow NA −2.86 −2.86
Koc NA 30.6 30.6
Vapor Pr. (mm Hg, 25 °C) NA 0.00104 4.70−5
Henry’s Law Constant (atm-m3/mole) NA 1.43−12 1.43−12
Half-life in Air (hr) NA 5.85 5.85
Half-life in Water (hr) NA 360 360
Half-life in Soil (hr) NA 360 360
Half-life in Sediment (hr) NA 1440 1440
Daphnid LC50 (mg/L) NA 2073.6 2073.6
Density (g/cm3) 1.86 1.87 [6]
Enthalpy of formation (kcal/mole) −32 [6]
3.5 Thermophysical Data 117

Kim et al. [35] proposed a simplified model based on molecular surface elec-
trostatic potentials to predict the densities of high energetic molecules in the solid
state, and compared with experimental values. Their value varied from 1.752 to
1.803 g cm–3 depending on the regression technique used, where as the experi-
mental value is 1.883 g cm–3 [6].
Xu et al. [36] determined specific heat of c-FOX-7 both experimentally and
theoretically. A Micro-DSCIII apparatus (SETARAM, France) was used for con-
tinuous measurement of the specific heat. They used 442.37 mg of sample and a
heating rate of 0.15 °C min−1 from 10 to 80 °C. The heat capacity was calculated
from the following expression on a continuous basis:

As  Ab
Cp ¼
m
b

where Cp is the specific heat capacity, As and Ab are the heat flows of the sample
and blank, ms is the amount of the sample, and b is the heating rate.
For theoretical determination of the specific heat, they first obtained the opti-
mized parameters for the crystal structure using a software and obtained the fre-
quencies at various temperatures. Then various thermodynamic properties were
calculated based on the statistical thermodynamic methods. Their measured specific
heat and calculated values are presented in Table 3.12.
As can be seen from the table, the calculated values are always lower than the
experimental values by 18.36–21.49%, which they attributed to the consideration of
only gas-phase molecule in the calculation process. The authors stated that mole-
cules at the solid phase should be considered for better estimation of the specific
heats.

Table 3.12 Experimental Temperature (K) Specific heat

and theoretical specific heat,
Experimental Theoretical
Units: J mol−1 K−1 [36]
283.0 266.6 217.7
288.0 272.0 220.1
293.0 277.1 222.5
298.0 281.9 224.9
303.0 286.4 227.4
308.0 290.7 229.8
313.0 294.7 232.2
318.0 298.4 234.6
323.0 301.8 237.0
328.0 305.0 239.5
333.0 307.9 241.9
338.0 310.5 244.3
343.0 312.8 246.7
348.0 314.9 249.1
353.0 316.7 251.5
118 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

They also fitted the experimental data to the following temperature dependent
expression:

Cp ¼ 2:3346 þ 2:0290
102 T  2:6476
105 T 2 ; ð283KhTh353K Þ

where Cp is inJ g1 K 1 .

Zerilli and Kuklja [37] carried out Ab Initio calculations to estimate various
thermodynamic properties of FOX-7. They calculated a complete equation of state
from first principles in the temperature range of 0–400 K and for specific volumes
from 61 to 83 cm3/mol. The properties calculated by them included
pressure-volume data, heat capacity as a function of temperature at different specific
volumes, and bulk modulus. They compared the pressure-volume data at 300 K
with the experimental data reported by Peiris et al. [38] Figs. 3.10, 3.11, 3.12, 3.13
and 3.14 show various computed values.

Fig. 3.10 Pressure-volume

relation at 0 K calculated with
HartreeFockself-consistent
field energy including
vibrational. Mode zero point
energy [37]

Fig. 3.11 Calculated 300 K

isotherm compared to
experimental data of Peiris
et al. [37]
3.5 Thermophysical Data 119

Fig. 3.12 Calculated specific

heat as a function of
temperature for different cell
volumes [37]

Fig. 3.13 Calculated bulk modulus as function of temperature for different cell volumes [37]

Charge density calculations have been carried out by Meents et al. [39, 40] from
single crystal diffraction studies. The results of comparison of theoretical and
experimental electrostatic potentials do not show any correlation of electron density
with impact sensitivities.
Sun et al. [41] used the density functional theory to calculate various funda-
mental properties of FOX-7. These included specific heats, entropies, and also
applied correction to enthalpies. The interaction between FOX-7 and water was also
evaluated to study the dimmers of FOX-7. Table 3.13 lists the thermodynamic
properties of FOX-7 calculated by Sun et al.
120 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

200 x 10 -6 0.0002

3
81.0 cm /mol
Thermal Expansion (K )
-1

-6 3
150 x 10 76.3 cm /mol 0.00015
3
71.8 cm /mol
3
67.4 cm /mol
3
63.3 cm /mol
100 x 10 -6 0.0001

50 x 10 -6 5 10
-5

0 0
0 50 100 150 200 250 300 350 400
Temperature (K)

Fig. 3.14 Calculated thermal expansion for different cell volumes [37]

Table 3.13 Thermodynamic Temp (K) Cop SoT (J/mol/K) HoT (kJ/mol)
properties [41]
200 114.57 345.50 14.15
298.15 152.46 398.55 27.32
500 208.92 491.86 64.25
700 242.90 568.02 109.71

3.5.1 Solubility of FOX-7

The characteristics of FOX-7 synthesized by above methods depend on the crys-

tallization step. Solvents and solubility of FOX-7 in these solvents are an important
factor on the selection of the solvent. Fuhr and Mikonsaari [28] studied the crys-
tallization of FOX-7 using n-methyl pyrrolidone (NMP), dimethylformamid
(DMF) and mixtures of NMP/water [28, 29]. The solubility data of FOX-7 in these
solvents are shown in Fig. 3.15.
The crystallization process is temperature dependent. The temperature should be
maintained constant during the crystallization process to obtain uniform shape and
size of the particles. The partial molal enthalpies of FOX-7 in DMSO at 298.15 K,
kinetics of dissolution, and other thermodynamic properties have been measured
and discussed by Xing et al. [42]. They noted that the dissolution of FOX-7 in
DMSO is an exothermic process. Therefore, the enthalpy change during the dis-
solution process should be known. They provided the partial molal enthalpies of
FOX-7 in DMSO at 298.15 K and kinetics of dissolution. The partial molal
enthalpies are given in Table 3.14.
Xing et al. [42] suggested an empirical expression for calculation of enthalpies
of dissolution and is given below:
3.5 Thermophysical Data 121

Fig. 3.15 Solubility of FOX-7 in NMP and NMP-water mixtures [29]

Table 3.14 The enthalpies of dissolution of FOX-7 in DMSO [42]

b
102 b1/2 DdissH (kJ/mol) Ddiss Hpartial Ddiss Happarent
(mol/kg) Found Calculated (kJ/mol) (kJ/mol)
2.14 0.146 −8.64 −8.58 −18.04 −16.48
2.50 0.158 −8.81 −8.80 −17.28 −16.66
3.00 0.173 −8.83 −8.79 −15.71 −16.60
3.18 0.178 −8.73 −8.72 −15.04 −16.56
3.68 0.192 −8.38 −8.37 −12.98 −16.22

Ddiss H ¼ 8:2146  207:343 b1=2 þ 629:7194 b

where b represents the concentration of the solution after FOX-7 dissolved in

DMSO.

3.6 Detection

There appears to be very little attention paid to the detection of FOX-7. From the
homeland security point of view, it will be necessary to detect it at very low
concentrations. Majano et al. [43] studied detection of FOX-7 by stabilizing it in the
122 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

pores of MFI-type nanocrystals. The presence of FOX-7 was determined using

XRD, IR, and Raman spectroscopy. Although this method may be useful in lab-
oratory setting, the detection of field sample may not be feasible. The immobi-
lization of field samples into the pores of MFI-type nanocrystals may not be
feasible.
Ottis and Benova [44] applied UV spectroscopy and HPLC for analysis of
FOX-7 determination of FOX-7 and its precursors used for its synthesis. All
experiments were conducted using acetone solutions with a concentration of 0.3 g/
L, and 10 lL samples of the solutions were applied on the start line of chro-
matoplates (band width 4 mm). Normal and reversed phase systems were used.
They were able to separate various compounds using a two-step elution process,
which were: Step 1: methanol/dichloromethane (3:2 v/v), range of elution–2 cm,
and Step 2: carbon tetrachloride/acetonitrile (3:2 v/v), range of elution–6 cm. The
chromatograph is shown in Fig. 3.16. They also developed a calibration curve for
the quantification purpose.
Dorsett [45] studied fragmentation of FOX-7 in an electron impact mass spec-
trometer (EIMS). EIMS involves ionizing molecules in a sample by bombarding
with electron. Each molecule exhibits its distinct mass/charge (m/z) ratio of the
resulting fragments. The known fragmentation pattern may be used to identify

Fig. 3.16 A chromatograph of a mixture of compounds containing FOX-7 Chromatogram of the

analytes: (1) 2-methylpyrimidine-4,6(1H,5H)-dione; (2) 2-dinitromethylene-5,5-dinitropyrimidine-
4,6(1H,3H)-dione; (3) 2-methyl-5-nitropyrimidine-4,6(1H,5H)-dione; (4) FOX-7; A, absorbance
[a.u.]; z, range of elution [mm] [44]
3.6 Detection 123

Table 3.15 EI-MS spectra for FOX-7 subjected to 20 and 70 eV electron impact energies [45]
M/z 20 eV peak int (%) 70 eV peak int (%) Possible species
18 n/a 20.0 H2O
27 n/a 4.9 HCN
28 n/a 33.2 CO, N2
29 n/a 6.0
30 n/a 32.5 NO
41 – 4.9
42 3.5 16.2
43 13.3 100.0 C(NH)(NH2), CNO
44 100.0 80.0 C(NH2)3, CO2
45 37.3 1.9
46 0.7 7.9 NO2
53 – 12.8
54 0.6 3.4
55 – 9.1
60 24.1 <0.5
69 – 33.2
70 – 6.4
72 – 9.1
86 – 21.9
88 25.2 <0.5 C(NO)(NO2)
89 1.0 <0.5
130 – <0.2
148 21.2 69.4 FOX-7
149 1.5 12.5 FOX-7 + H
1 eV = 1.602
10−19 J = 23.06 kcal/mol

FOX-7 in a sample. The fragmentation of FOX-7 depends on the electron beam

strength. The major m/e peaks observed in 70 and 20 eV spectra are given in
Table 3.15.

3.7 Decomposition and Destruction

As the temperature is increased above 200 °C, decomposition, without melting,

begins to occur. The thermal behavior of FOX-7 at temperatures below 200 °C has
already been described above.
Sinditskii et al. [46] carried out thermal decomposition studies and found that the
burning rate of FOX-7 is slower than RDX. The initial stages of decomposition,
revealed that FOX-7 to be more thermally stable than RDX.
124 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

The authors suggested that the decomposition of FOX-7 depends on its purity
and also on the presence of crystalline phases in the sample. They noted that when a
sample of FOX-7 is consisted of two phases, part crystalline and part amorphous,
the amorphous phase decomposes first as indicated by the first DSC peak leaving
the original crystalline part. The relative amounts of these two phases are dependent
on the synthesis process conditions.
The products formed during decomposition of FOX-7 have been studied by a
number of researchers using FTIR (Fourier Transform Infrared Spectroscopy) and
laser-induced breakdown spectroscopy (LIBS). The FTIR analysis showed the
presence of CO2, HCN, N2O, NO2, HOCN, H2O and NO during the first stage of
decomposition as suggested by selected ion flow tube mass spectrometry
(SIFT-MS), while HNO2 and HCOOH are produced in the second decomposition.
The apparent activation energies for the two steps are reported as 238.3 and
322.4 kJ mol−1, respectively.
Civis et al. [47] used a combination of laser-induced breakdown spectroscopy
(LIBS) and SIFT-MS to study the decomposition of c-FOX-7. They observed
several atomic transitions and molecular electronic bands in the LIBS emission
spectra of the FOX-7 during decomposition. Based on the decomposition products,
they suggested a decomposition path, which is shown in Fig. 3.17.
Civis et al. [47] identified directly H2O, NH3, HCN from their experimental
results (HNC isomer could not be distinguished by SIFT-MS), and NO, CO, and
HONO stable molecules from theoretical calculation. CO molecules cannot be
detected by SIFT-MS. They also reported that production of two molecules of N2,
CO, and H2O from the FOX-7 molecule is exothermic (117 kcal/mol). In addition,
they also observed C2H5OH in a relatively high concentration (several parts per
million. The formation mechanism of ethanol is proposed in Scheme 1 as a reaction
path in which the structure (D) does not fragment directly to CO, HNC, and NH2
but where only the C–N bonds dissociate (Fig. 3.18).

3.8 Spectroscopy

The understanding of the spectroscopic properties of FOX-7 is important for the

analysis and development of detection systems. Dorsett [45] used B3LYP func-
tional in conjunction with Dunning’s correlation consistent basis sets cc-pVDZ and
aug-cc-pVDZ3 for calculating geometric parameters and compared with available
experimental data. Besides geometric parameters and vibrational frequencies, the
author also evaluated configurational energies and enthalpies of various reaction
species and are given in Tables 3.16 and 3.17.
Welch [30] investigated the spectroscopic behavior of FOX-7 using DSC,
temperature resolved Raman spectroscopy, powder and single crystal X-ray
diffraction studies. The DSC data agreed well with the literature data. Raman
 3.8 Spectroscopy

Fig. 3.17 The thermal decomposition path for FOX-7 [47]

125
126 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

Fig. 3.18 CO2-Laser induced thermal decomposition mass spectrum FOX-7, 100 W 80 MS (The
region m/z 38 and 42 is entirely dominated by solvent peaks and has therefore been removed) [47]

Table 3.16 Selected geometric parameters for FOX-7 (Å, degrees) [45]
Parameter Expt. [13] Calc. Parameter Expt. [13] Calc.
C=C 1.456 1.430 N–H(t) 0.88, 0.87 1.008
C–NH2 1.319, 1.325 1.344 N–H(s) 0.84 1.018
C–NO2 1.399, 1.426 1.433 N–O(t) 1.252, 1.242 1.255
O(s)–H(s) 1.97, 2.03 1.790 N–O(s) 1.249, 1.242 1.222
<H2N–C–NH2 118.4 117.7 <O–N–O 120.9, 121.0 122.4
<O2N–C–NO2 116.3 116.9 <H(t)–N–C 121.0, 121.1 120.3
<H2N–C=C 120.7, 120.8 121.1 <H(s)–N–C 119.8, 121.9 117.0
<O2N–C=C 119.8, 123.9 121.6 <O(s)–N–C 118.6, 118.9 117.9
<H–N–H 118.3, 118.1 122.2 <O(t)–N–C 120.1, 120.4 119.7
<H2N–C=C– 172.9, 177.8 169.2
NO2
<H(t)–N–C–C −179.6, −178.3 −170.4 <O(t)–N–C–C 171.0,143.6 156.0
<H(s)–N–C–C 0.5, 10.1 2.1 <O(s)–N–C– −5.8, −34.3 −21.7
C
T terminal bond (bond nearly parallel to C=C axis), s side bond

spectra of a, b, and c FOX-7 are shown in Figs. 3.19 and 3.20. Detailed expla-
nation of the spectra and the transitions that occur from one phase to another have
been discussed by Welch [30].
Majano et al. [43] have also contributed to IR, Raman, NMR and XRD of
FOX-7 in MFI-type nanocrystalline zeolites.
3.8 Spectroscopy 127

Table 3.17 Vibrational normal modes [45]

Freq Type Freq Type
61 C=C stretch + NO2 scissor 806 NO2–C–NO2 scissor + N–O stretch
88 NH2–C–NH2 rock + N–H(t) stretch 870 N–O(s) stretch + N–O(t) oop rock
114 NH2–C–NH2 rock + N–H(t) stretch 1068 C–NH2 torsion + N–H(s) stretch
212 C=C stretch + N–H(t) stretch 1083 C–NH2 torsion + N–H(s) stretch
266 N–H(t) stretch 1149 NH2–C–NH2 bend
296 C–N stretch + N–H(t) stretch 1214 C–NH2 torsion + C–NO2 stretch
335 C–N stretch 1272 C–NO2 bend
376 N–H(t) stretch 1341 C–NO2 bend + N–H(t) oop rock
387 N–H(t) stretch 1481 N–H(s) stretch + NH2–C–NH2 bend
442 NH2 torsion + N–H stretch 1519 C–NH2 stretch + N–H oop rock
465 C=C stretch + NO2–C–NO2 scissor 1565 N–H(s) stretch + C–NH2 bend
471 C=C torsion 1602 C–N stretch + NO2 stretch
610 C–NH2 torsion + C–N stretch 1624 NH2–C–NH2 bend + C–NH2 bend
643 N–H(s) stretch + NH(s) rock 1632 C–NH2 bend
690 C=C stretch + NH2–C–NH2 scissor 3446 C–NH2 bend + C–NH2 rock
751 NO2–C–NO2 rock + N–O stretch 3460 C–NH2 bend + C–NH2 rock
751 N–H(s) stretch + NH(s) rock 3681 N–H(t) rock
771 C=C stretch + NO2–C–NO2 scissor 3683 N–H(t) rock
Frequencies in wavenumbers (cm−1)
t terminal bond; s side bond; oop out of plane

Fig. 3.19 Raman spectra of a- and b-FOX-7 over the temperature range 298–398 K [29]
128 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

Fig. 3.20 Raman spectra of b- and c-FOX-7 over the temperature range 423–448 K [29]

3.9 Detonation Properties

Detonation properties of FOX-7 measured by various researchers and their com-

parison with other explosives are complied in Table 3.18. Although FOX-7 has the
detonation pressure and velocity similar to that of RDX, it is much less sensitive as
indicated by the drop weight test and friction test. For a better understanding of the
detonation characteristics of FOX-7, its detonation properties are compared with
other explosives in Table 3.19. Anniyappan et al. [5] also compared the detonation
properties of FOX-7 with several other explosives and the results are given in the
same Table 3.19. They included the thermal stability properties and compared with
RDX, TEX, and TATB. Although it is less stable thatn TEX and TATB, but it is
more stable compared to RDX. Latypov et al. [4], besides synthesizing DADE,
carried out sensitivity tests and compared them with RDX. Their results are shown
in Table 3.18.

Table 3.18 Comparison of RDX DADE

FOX-7 with RDX
Dropweight test (cm) 38 126
Friction test (N) 120 >350
Detonation pressurea (GPa) 34.63 33.96
Detonation velocitya (m/s) 8869 8930
a
Calculated values
3.9 Detonation Properties 129

Table 3.19 Explosive properties of FOX-7 in comparison with RDX, TEX and TATB
Properties FOX-7 RDX TEX TATB
Detonation velocity (m/s)a 9090 8800 8749 8108
Detonation pressure (GPa)a 36.6 34.7 36.5 31.1
Drop weight test (cm) 126 38 177 170
Friction test (kg) >36 12 >36 >36
Thermal stability (oC) 240 215 285 287
a
Calculated values by Cheetah v 2.0

Table 3.20 Sensitivity test data for three batches of FOX-7 synthesized by two different research
group and its comparison with RDX data [49]
Test FOX-7 (Bofors FOX-7 (Bofors FOX-7 RDX
20017011)c 20017002)d (DSTO)e
Rotter impact 100 100 110–140 80
(F of I)
BAM friction 240 240 168–288 *120
(N)
ESDa, Ignition 4.5 4.5 4.5 4.5
(J)
ESDa, No 0.45 0.45 0.45 0.45
Ignition (J)
VTSb (mL/g) 0.28 – <0.1 <0.1
Temp of 217 – 226 223
Ignition (°C)
Beckford fuse Ignition – Fails to Fails to
ignition ignition
Train test Ignition – Ignition Ignition
a
Electrostatic discharge
b
Vacuum thermal stability (perfumed at 100 °C for 48 h)
c
Bofors, not recrystallized
d
Bofors, recrystallized
e
Synthesizes at DSTO, not recrystallized

Trzcinski et al. [16] have measured detonation velocity, detonation pressure, and
calorimetric heat of explosion as well as the accelerating ability.
Theoretical study of Sorescu et al. [48] reveals that Fox-7 can be adsorbed on
aluminum and oxidized aluminum surfaces. The adsorption of FOX-7 on aluminum
surface provides an energy of 69.5 kcal/mol compared to the aluminum surface.
Chen et al. [49] studied the sensitivity of FOX-7 using DSC-TG combination,
and found the friction sensitivity to be 68% or less and impact sensitivity to be more
than 25 J (Table 3.20).
Charge density calculations have been carried out by Meents et al. [39] from
single crystal diffraction studies. The results of comparison of theoretical and
experimental electrostatic potentials do not show any correlation of electron density
with impact sensitivities.
130 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

3.10 Cylinder Test

The cylinder test was conducted by several researchers and their findings are dis-
cussed below. Karlsson et al. [1] used a copper cylinder of 300 mm in length and
30.2 mm in diameter, and a shell thickness of 2.52 mm. The charge was FOX-7
containing 1.5 w% wax and had a density of 1.756 g/cm3. Their experimental
cylinder is shown in Fig. 3.21. The detonation velocity was estimated to
8.335 ± 0.025 mm/ls. They used a HI-Dyna2d modeling for comparison with the
experimentally derived cylinder wall motion. The calculated and experimental
values are presented in Fig. 3.22. Also, the of detonation velocity calculated using
CHETTA, BKWC, gave a velocity of 8.266 mm/ls, which is in good agreement
with the experimental value.
Trzcinski et al. [16] estimated t.he detonation energy from the cylinder test data.
They used a cylinder of same dimension as Karlsson et al. [1] to conduct the test.
The test results are given in Fig. 3.23. They recorded a detonation velocity of
8325 ± 50 m/s, Gurney energy of 3540 ± 100 j/g, and Gurney velocity of
2660 ± 40 m/s for FOX-7.

Fig. 3.21 Radial expansion of the cylinder wall during cylinder test of FOX-7 [1]

Fig. 3.22 Radial velocity

along the wall during the
cylinder test of FOX-7 [1]
3.10 Cylinder Test 131

The data from the cylinder test was used to determine the detonation pressure
using the Jones, Wilkins and Lee equation of the isentrope. The equation can be
written as:

p ¼ AeR1 V þ BeR2 V þ CV ð1-Þ

where A, B, C, R1, R1 and x are constants for a given explosive, V = v/v0, v = 1/q0.
The constants for the JWL equation are given in Table 3.21.
A comparison among various computational methods is also provided by them.
The computational methods included the JWL isentrope calculation, the
CHEETAH(BKWC) code, and a constant isentrope (g = 3.22). The comparison is
shown in Fig. 3.24. The detonation parameters provided by Trzcinski et al. [16] are
given in Table 3.22.

Fig. 3.23 Radial displacement of the external surface of the tube versus an axial co-ordinate [16]

Table 3.21 JWL isentrope Explosive characteristics JWL isentrope constants

of DADNE [50]
q0 = 1780 kg/m 3
A = 1414.339 GPa
D = 8325 m/s B = 21.6637 GPa
cCJ = 3.35 C = 1.23412 GPa
pCJ = 28.4 GPa R1 = 5.54
E0 = 8.9 GPa R2 = 1.51
x = 0.32
132 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

4 4

2 Yof = 3.22 2
JWL - experiment
JWL - CHEETAH
0 0
ln(p), GPa

-2 -2

-4 -4

-6 -6

-8 -8
0 1 2 3 4 5 6
ln(ν/ν0 )

Fig. 3.24 Constant c and JWL isentropes for detonation products of DADE [16]

Table 3.22 Experimental Test D (m/ c PCI Dt ci PCJ,t

and calculated detonation no s)
properties of DADE [16]
1 8405 3.31 29.2 8453 3.335 29.34
2 8375 3.39 28.4

Table 3.23 CHEETAH JWL parameter Value

QRX080 JWL constants [50]
A (GPa) 545.35
B (GPa) 5.97
C (GPa) 1.08
R1 4.09
R2 1.06
x 0.3143

Cullis and Townsley [50] used CHEETAH to estimate the JWL parameters for a
FOX-7 formulation that contained 95% FOX-7 and 5% binder (Table 3.23).
The detonation velocity predicted by CHEETAH was 8.434 km/s, which was
greater than the average value obtained experimentally, which was 8.28 km/s.
3.10 Cylinder Test 133

Fig. 3.25 Cylinder wall expansion predicted from CHEETA for QRX080 using JWL equation
[50]

Fig. 3.26 Cylinder wall velocity predicted by using CHEETAH with JWL equation [50]

Using the CHEETAH QRX080 JWL constants and modeling the cylinder test using
the DYNA2D hydrocode gave the predictions for the cylinder wall motion in terms
of radial expansion with time (see Fig. 3.25) and cylinder wall velocity (see
Fig. 3.26).
134 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

3.11 FOX-7 Formulation

A mixture of FOX-7 with another explosive can enhance the detonation properties
of the mixture. A number of researchers have carried the formulation of FOX-7 and
noted that some properties can be changed significantly. Karlsson et al. [1] have
carried out detonation and sensitivity measurements of their formulation of FOX-7
with a composite called Lis-2. The impact and friction sensitivity of this formu-
lation and its components is summarized in Table 3.24. A plastic bound explosive
based on FOX-7 and an energetic binder was prepared and designated as LIS-2. The
energetic binder consisted of polyGLYN, Bu-NENA and H12MDI. Table 3.25
shows the composition of the formulation. This formulation showed no friction
sensitivity but it was more sensitive to impact than its respective components. The
formulation did not propagate to detonation during a detonation test in steel tubes
with a diameter of 25 mm, however the formulation did react violently during slow
heating (3.3 °C/h). It ignited at 220 °C and burned without damage to the test
container (bomb) or the surroundings.
Powala et al. [51] carried out Gap-test, sensitivity, and detonation velocity
measurements on PBX explosives of FOX-7, HMX, and RDX, and different
compositions of the explosives. In addition they carried out theoretical calculations
of detonation characteristics of mixtures of FOX-7 with HMX or RDX. The PBX
explosives contained 5% of PTFE. Table 3.26 shows part of their results.

Table 3.24 Impact and friction sensitivity of FOX-7 composition and its components [1]
Sample Drop heighta (cm) Min. load (N)
FOX-7 (recryst., 250–355 lm) 79 –
FOX-7 (recryst., <70 lm) 63 –
Binderb 159 –
LIS-2 (70% FOX-7) 40 >340
a
The highest drop height where no reaction occurs. Drop weight = 2 kg
b
The composition of the binder is shown in Table 3.25

Table 3.25 Composition of the formulation (LIS-2) [1]

Component Amount (weight)
FOX-7 (250–355 lm) 50%
FOX-7 (<70 lm) 20%
PolyGlyN 21%
Bu-NENA 5%
H12MDI (Desmodur-W) 4%
DBTDL Cat. Amounts
Cured for 24 h at 50 °C
3.12 Conclusion 135

Table 3.26 Detonation velocity of several FOX-7 formulation

95% explosives 100% 80% RDX 60% RDX 40% RDX 20% RDX 0% RDX
5% PTFE RDX 0% 20% 40% 60% 80% 100%
FOX-7 FOX-7 FOX-7 FOX-7 FOX-7 FOX-7
Detonation 8200 8290 8230 8200 8180 8200
velocity (m/s)
Density (g/cm3) 1.72 1.75 1.78 1.80 1.82 1.84
95% explosives 100% 80% RDX 60% RDX 40% RDX 20% RDX 0% RDX
10% PTFE RDX 0% 20% 40% 60% 80% 100%
FOX-7 FOX-7 FOX-7 FOX-7 FOX-7 FOX-7
Detonation 8500 8360 8300 8260 8150 8200
velocity (m/s)
Density (g/cm3) 1.82 1.82 1.82 1.83 1.84 1.85

3.12 Conclusion

FOX-7 has attracted a great deal of attention since its synthesis in 1998. Its eval-
uation is underway, however, various properties are scattered throughout the lit-
erature. A review of information available on DADE in the literature shows that its
detonation properties are similar to RDX, but it is less sensitive than RDX. Various
explosive properties suggests that a number of formulation is possible with FOX-7
to meet a variety of specialized applications. There is much more information
particularly in Chinese journals. The fact that FOX-7 is an ethene, and the two
electrons contribute to its reactivity should be useful in developing other insensitive
explosive of higher performance. In spite of the information available on its
synthesis and different formulations, there is a paucity of information on its
physicochemical and thermochemical properties.

References

1. Karlsson S, Östmark H, Eldsäter C, Carlsson T, Bergman H, Wallin S, Pettersson A (2002)

Detonation and sensitivity properties of FOX-7 and formulations containing FOX-7. Swedish
Defence Research Agency Report, Revised
2. Crawford MJ, Evers J, Goebel M, Klapoetke TM, Mayer P, Oehlinger G, Welch JM (2007)
c-FOX-7: structure of a high energy density material immediately prior to decomposition.
Propellants, Explos, Pyrotech 32:478–495
3. Evers J, Klapoetke TM, Mayer P, Oehlinger G, Welch J (2006) a- and b-FOX-7, polymorphs
of a high energy density material, studied by X-ray single crystal and powder investigations in
the temperature range from 200 to 423 K. Inorg Chem 45(13):4996–5007. Also The three
ambient pressure polymorphs of FOX-7, New Trends in Research of Energetic Materials,
2007, 368-375, Pardubice, Czech Republic, April 25–27, 2007
4. Fan XZ, Li JZ, Liu ZR (2007) Thermal behavior of 1,1-diamino-2,2-dinitroethylene. J Phys
Chem A 111:13291–13295
136 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

5. Anniyappan M, Talawar MB, Gore GM, Venugopalan S, Gandhe BR (2006) Synthesis,

characterization and thermolysis of 1,1-diamino-2,2-dinitroethylene (FOX-7) and its salts.
J Hazard Mater 137(2):812–819
6. Lochert IJ (2001) FOX-7- A new insensitive explosive. Weapons Systems Divisio
Aeronautical and Maritime Research Laboratory, DSTO-TR-1238, Australia
7. Latypov NV, Bergman J, Langlet A, Wellmar U, Bemm U (1998) Synthesis and reactions of
1,1-Diamino-2,2-dinitroethylene. Tetrahedron 54:11525–11536
8. Latypov NV, Johansson M, Holmgren E, Sizova EV, Sizov VV, Bellamy AJ (2007) On the
Synthesis of 1,1-Diamino-2,2-dinitroethene (FOX-7) by Nitration of 4,6-Dihydroxy-2-
methylpyrimidine. Org Process Res Dev 11(1):56–59
9. Jalovy Z, Marecek P, Dudek K, Weidlich T (2001) Synthesis and properties of
1,1-Diamino-2,2-dinitroethene, New Trends in Research of Energetic Materials. In Ed S
Zeman Proceeding Seminar, 4th, Pardubice, Czech Republic, April 11–12, pp 151–161
10. Wahigren K, ed (2004) FOI Weapons and Protection Division, Annual Report, p 11
11. Ostmark H, Bergman H, Bemm U, Goede P, Holmgren E, Johansson M, Langlet A,
Latypov NV, Pettersson A, Pettersson M-L, Wingborg N, Vorde C, Stenmark H, Karlsson L,
Hihkio M (2001) 2,2-dinitro-ethene-1,1-diamine (FOX-7) - properties, analysis and scale-up
Int Annu Conf ICT 32nd(Energetic Materials):26/1–26/21 12
12. Cai HQ, Shu YJ, Yu WF, Li JS, Cheng BB (2004) Study on synthesis of FOX-7 and its
reaction mechanism. ActaChim Sinica 62(3):295–301
13. Cai HQ, Shu YJ, Yu WF, Zeng GY (2004) Cheng BB Research development of
1,1-diamino-2, 2 dinitroethylene. HannengCailiao 12:124–128
14. Cai HQ, Shu YJ, Huang H, Cheng BB (2004) Li JS Study on Reactions of 2-
(Dinitromethylene)-4,5 imidazolidinedione. J Org Chem 69:4369–4374
15. Cai HQ, Shu YJ, Cheng BB, Bi-Bo (2005) Improved method for synthesis of FOX–7.
YingyongHuaxue 22(1):95–98
16. Trzcinski WA, Cudzilo S, Chylek Z, Szymanczyk L (2008) Detonation properties of
1,1-diamino-2,2-dinitroethene (DADNE). J Hazard Mater 157(2–3):605–612. doi:10.1016/
jjhazmat200801026
17. Chylek Z, Pietrzyk S (2007) Effect of water on preparation of 1,1-diamino-2,2-dinitroethene
(FOX-7). Biuletyn Wojskowej Akademii Technicznej 56(2):297–305
18. Dewey MA (2007) Synthesis, evaluation, and formulation studies on new oxidizers as
alternatives to ammonium perchlorate in DoD missile propulsion Applications, ATK Launch
Systems, SERDP Project WP1403, 23 April 2007
19. Clausen JL, Clough S, Gray M, Gwinn P (2007) Experimental screening assessment of
perchlorate replacements, ERDC/CRREL TR-07-12, August 2007
20. Zhou C, Zhou Y, Huang X (2005) Wang X Synthesis and properties of
1,1-diamino-2,2-dinitroethylene. HuozhayaoXuebao 28(2):65–67
21. Bladek J, Pietrzyk S, Cudzilo S, Chylek Z (2009) Application of thin layer chromatography
for monitoring of FOX–7 synthesis, propellants, explosives. Pyrotechnics 34(4):321–325
22. Orzechowski A, Powała D, Florczak B, Maranda A, Nowaczewski J (2006) Optimization of
crystallization of 1,1-Diamino-2-2dinitroethylene, Proc New Trends in Research of Energetic
Materials, Pardubice, Czech Republic 2006, Apr 19–21, 2006, 693–700
23. Goh EM, Cho JR, Kim JK (2005) Safe and convenient pilot scale process of 1,1–Diamino–
2,2-dinitroethylene, American Chemical Society, p IEC-025, 230th ACS National Meeting,
Washington, DC, Aug 28–Sept 1
24. Chung KH, Goh EM, Cho JR (2005) Synthetic modification and scale-up process for 1,1–
diamino–2,2-dinitroethene (FOX-7). In: International Annual Conference ICT 36th (Energetic
Materials), 52/1–52/13
25. Goh EM, Kim HS (2010) The scale up process improvement of 1,1-Diamino-2,2-
dinitroethane (DADNE) New Trends in Research of Energetic Materials. In: Proceeding
10th Seminar, Pardubice, Czech Republic, Apr 21–23, 2010, 495–500
26. Bellamy AJ (2007) FOX-7 (1,1-diamino-2,2-dinitroethene) Struct Bonding (Berlin, Ger) 125
(High Energy Density Materials):1–33. doi:10.1007/430_2006_054
References 137

27. Teipel U, Fuhr I, Hartlieb K, Kjellstroem A, Eldsaeter C (2004) Crystallization of

1,1-diamino-2,2-dinitro-ethylene (FOX-7). In: International Annual Conference ICT 35th:51/
1–51/11
28. Fuhr I, Mikonsaari I (2004) Production and characterization of insensitive explosive. In:
Proceedings of the 2004 Insensitive Munitions and Energetic Materials Symposium, San
Francisco, USA, November 14–17, 2004
29. Daniel MA, Davies PJ, Locher IJ (2010) FOX-7 for Insensitive Boosters. Weapons Systems
Division, Defence Science and Technology Organisation. Australia, DSTO-TR-2449
30. Welch J (2008) Low sensitivity energetic materials. PhD Dissertation,
Ludwig-Maximilians-UniversitätMünchen
31. Bemm U, Ostmark H (1998) 1, 1 - Diamino - 2, 2 - dinitroethylene: a novel energetic material
with infinite layers in two dimensions. Acta Cryst Sect C C54:1997–1999
32. Zhao J, Liu H (2008) High-pressure behavior of crystalline FOX-7 bydensity functional
theory calculations. Compu Mater Sci 42:698–703
33. Xu KZ, Chang CR, Song JR, Zhao FQ, Ma HX, Lu XQ, Hu RZ (2008) Preparation, crystal
structure and theoretical calculation (FOX-7). Chinese of J Chem 26(3):495–499
34. Calculated using Advanced Chemistry Development (ACD/Labs) Software V819 for Solaris
(1994–2008 ACD/Labs) Science Finder
35. Kim CK, Cho SG, Kim CK, Park H-Y, Zhang H, Lee HW (2008) Prediction of densities for
solid energetic molecules with molecular surface electrostatic potentials. J Comput Chem
29:1818–1824
36. Xu K, Song J, Zhao F, Ma H, Gao H, Chang C, Ren Y, Hu R (2008) Thermal behavior,
specific heat capacity and adiabatic time-to-explosion of G(FOX-7). J Hazard Mater 158(2–
3):333–339. doi:10.1016/jjhazmat200801077
37. Zerilli FJ, Kuklja MM (2007) Ab-Initio equation of state of a organic molecular crystal:
1,1-Diamino-2,2-dinitroethylene. J Phys Chem A 111:1721–1725
38. Peiris SM, Wong CP, Zerilli FJ (2004) Equation of state and structural changes in
diaminodinitroethylene under compression. J Chem Phys 120(17):8060–8066
39. Meents A, Dittrich B, Johnas SKJ, Thome V, Weckert EF (2008) Charge-density studies of
energetic materials: CL-20 and FOX-7 Acta Crystallogr. Sect B: Struct Sci 64(1):42–49.
doi:10.1107/S0108768107055292
40. Meents A, Dittrich B, Johnas SKJ, Thome V, Weckert EF (2008) Charge-density studies of
energetic materials: CL-20 and FOX-7 Acta Crystallogr. Sect B: Struct Sci 64(4):519. doi:10.
1107/S0108768108017497
41. Sun X-Q, Ju X-H, Xu X-J, Fan X-W (2007) J Chinese Chem Soc 54:1451–1456
42. Xing XL, Xue L, Zhao FQ, Gao HX, Hu RZ (2009) Thermochemical properties of
1,1-diamino–2,2–dinitroethylene (FOX-7) in dimethyl sulfoxide (DMSO). Thermochim Acta
491(1–2):35–38
43. Majano G, Mintova S, Bein T, Klapotke TM (2007) Confined detection of
high-energy-density materials. J Phys Chem C111:6694–6699
44. Ottis J, Benova B (2007) Determination of FOX - 7 purity by UV spectroscopy, New Trends
in Research of Energetic Materials, Proc 10thSeminar, Pardubice, Czech Republic, Apr 25–27,
2007, (Pt 2), 831-835, 2007
45. Dorsett H (2000) Computational Studies of FOX-7, A New Insensitive Explosive. Weapons
Systems Divisions, Aeronautical and Maritime Research Laboratory, Australia,
DSTO-TR-1054
46. Sinditskii VP, Levshenkov AI, Egorshev VY, Serushkin VV (2003) Study on combustion and
thermal decomposition of 1,1-diamino-2,2-dinitroethylene (FOX-7) Proc Int Pyrotech Semin
30th(Europyro 2003, Volume 1):299–311
47. Civis M, Civis S, Sovova K, Dryahina K, Spanel P, Kyncl M (2011) Laser ablation of FOX-7:
proposed mechanism of decomposition. Anal Chem (Washington, DC, US) 83(3):1069–1077.
doi:10.1021/ac1028769
138 3 FOX-7 (1,1-Diamino-2,2-Dinitroethylene)

48. Sorescu DC, Boatz JA, Thompson DL (2003) First principles calculations of the adsorption of
nitromethane and 1,1-Diamino-2,2-dinitroethylene (FOX-7) Molecules on the Al(111)
Surface. In: Proceedings of the 2003 User Group Conference, IEEE, 2003
49. Chen ZE, Li ZY, Yao N, Lei, Wang D (2010) Safety property of FOX-7 and HTPB
propellants. Chin J Energ Mater 18:316–319
50. Cullis IG, Townsley R (2011) The potential of FOX-7 explosive in insensitive munition
design J Appl Mech 78(5):051012/1–051012/8
51. Powala D, Orzechowski A, Paplinski A, Maranda (2009) Some properties of PBX containing
FOX-7. In: Proceeding New Trends in Research of Energetic Materials, Pardubice, Czech
Republic 2009, Apr 1–3, 2009, 781–786, 2009

Additional Scholarly Articles for further Reading

52. Artemenko AG et al (2011) QSAR analysis of the toxicity of nitroaromatics in Tetrahymena

pyriformis: structural factors and possible modes of action. SAR QSAR Environ Res
22(5–6):575–601. doi:10.1080/1062936X.2011.569950
53. Artsob H et al (1986) Arbovirus infections in several Ontario mammals, 1975–1980. Can J
Vet Res 50(1):42–46
54. Bellamy AJ, Latypov NV, Goede P (2002) Transamination reactions of 1,1-diamino-2,2-
dinitroethene (FOX-7). J Chem Res, Synop (6):257, 641–661. doi:10.3184/03082340210
3172103
55. Borges I Jr (2014) Electronic and ionization spectra of 1,1-diamino-2,2-dinitroethylene,
FOX-7. J Mol Model 20(3):2095
56. Buszewski B, Michel M, Cudzilo S, Chylek Z (2009) High performance liquid chromatog-
raphy of 1,1-diamino-2,2-dinitroethene and some intermediate products of its synthesis.
J Hazard Mater 164(2–3):1051–1058. doi:10.1016/j.jhazmat.2008.09.018
57. Cheng K-F, Liu M-H, Chen C, Hong Y-S (2010) Computational optimum conditions for
FOX-7 synthesis–A comparative synthesis route. J Mol Struct: THEOCHEM 957(1–3):6–14.
doi:10.1016/j.theochem.2010.06.02
58. Chtragadda K, Vargeese AA (2017) A kinetics investigation on the nitro-nitrite rearrangement
mediated thermal decomposition of high temperature monoclinic phase of 1,1-Diamino-2,2-
Dinitroethylene (c-Fox-7). J Chem Sci 129:281. doi:10.1007/s12039-016-1220-z
59. de Klerk WPC, Popescu C, van der Heijden AEDM (2003) Study on the decomposition
kinetics of FOX-7 and HNF. J Therm Anal Calorim 72(3):955–966
60. Dreger ZA, Stash AI, Yu Z, Chen Z,Tao Y, Gupta YM (2016) High-pressure crystal
structures of an insensitive energetic crystal: 1,1-Diamino-2,2-dinitroethene. J Phys Chem C
120:1218–1224
61. Dubovik AV, Kozak GD, Aleshkina EA (2007) Theoretical estimation of explosion hazard of
NTO, FOX-7, TNAZ, and CL-20. University of Pardubice, pp 484–495
62. Ek S, Eldsaeter C, Goede P, Holmgren E, Tryman R, Latypov N (2005) Synthesis and
characterisation of 2,2-dinitro-1,3-propanediol-based plasticisers. Cent Eur J Energ Mater 2
(4):33–45
63. Evers J, Klapoetke TM, Mayer P, Oehlinger G, Welch J (2006) a- and b-FOX-7, polymorphs
of a high energy density material, studied by X-ray single crystal and powder investigations in
the temperature range from 200 to 423 K. Inorg Chem 45(13):4996–5007. doi:10.1021/
ic052150m
64. Florczak B (2008) A comparison of properties of aluminized composite propellants
containing HMX and FOX-7. Cent Eur J Energ Mater 5(3–4):103–111
65. Garg S, Gao H, Parrish DA, JnM Shreeve (2011) FOX-7 (1,1-Diamino-2,2-dinitroethene):
Trapped by Copper and Amines. Inorg Chem 50(1):390–395. doi:10.1021/ic102136r
66. Ghanta S (2016) Theoretically predicted Fox-7 based new high energy density molecules.
J Mol Struct 1118:28–33
Additional Scholarly Articles for further Reading 139

67. Ghule VD, Deswal S, Devi A, Kumar TR (2016) Computer-Aided Design of Energetic Tris
(tetrazolyl)amine Derivatives and Salts. Ind Eng Chem Res 55(4):875–881. doi:10.1021/acs.
iecr.5b04587
68. Herrmann M, Foerter-Barth U, Kempa PB (2009) Size/strain diffraction peak broadening of
the energetic materials FOX-7, RDX and ADN. Cent Eur J Energ Mater 6(2):183–193
69. Herve G, Jacob G, Latypov N (2005) The reactivity of 1,1-diamino-2,2-dinitroethene
(FOX-7). Tetrahedron 61(28):6743–6748. doi:10.1016/j.tet.2005.05.010
70. Huang B, et al (2010) Fabrication of FOX-7 quasi-three-dimensional grids of
one-dimensional nanostructures via a spray freeze-drying technique and size-dependence of
thermal properties. J Hazard Mater 184(1–3):561–566. doi:10.1016/j.jhazmat.2010.08.072
71. Jones DEG, Vachon MCR, Wang R, Kwok QSM (2004) Preliminary studies on the thermal
properties of FOX-7. In: Proceeding NATAS Annu Conf Therm Anal Appl 32nd:105.17.703/
1–105.17.703/15
72. Kempa PB, Herrmann M (2006) Temperature resolved X-ray diffraction for the investigation
of the phase transitions of FOX-7. Part Part Syst Charact 22(6):418–422. doi:10.1002/ppsc.
200501006
73. Landerville AC, Conroy MW, Budzevich MM, Lin Y, White CT, Oleynik II (2010)
Equations of state for energetic materials from density functional theory with van der Waals,
thermal, and zero-point energy corrections. Appl Phys Lett 97(25):251908/1–251908/3
doi:10.1063/1.3526754
74. Liu M-H, Cheng K-F, Chen C, Hong Y-S (2011) Computational study of FOX-7 synthesis in
a solvated reaction system. Int J Quantum Chem 111(9):1859–1869. doi:10.1002/qua.22472
75. Lochert IJ (2001) DSTO advances in the evaluation of FOX-7. In: Proceeding International
Pyrotechnics Seminar, vol 28, pp479–489
76. Luo J, et al. (2010) Syntheses and thermal behaviors of Rb(FOX-7)H2O and Cs(FOX-7)
H2O. Bull Korean Chem Soc 31(10):2867–2872. doi:10.5012/bkcs.2010.31.10.2867
77. Mandal AK, Pandey RK, Asthana SN, Kulkarni A, Kulkarni BD (2011) Modeling and
simulation of micro reactor with nitration of 2-methyl-4,6-dihydroxy-pyrimidine. Sci Technol
Energ Mater 72(1–2):9–20
78. Meents A, Dittrich B, Johnas SKJ, Thome V, Weckert EF (2008) Charge-density studies of
energetic materials: CL-20 and FOX-7. Acta Crystallogr, Sect B: Struct Sci 64(4):519. doi:10.
1107/S0108768108017497
79. Muthurajan H, Sivabalan R, Talawar MB, Venugopalan S, Gandhe BR (2006) Computer code
for the optimization of performance parameters of mixed explosive formulations. J Hazard
Mater 136(3):475–481. doi:10.1016/j.jhazmat.2006.01.066
80. Sorescu DC, Boatz JA, Thompson DL (2001) Classical and Quantum-Mechanical Studies of
Crystalline FOX-7 (1,1-Diamino-2,2-dinitroethylene). J Phys Chem A 105(20):5010–5021
doi:10.1021/jp010289m
81. Teipel U (2006) Product design of particulate energetic materials. Mater Sci Technol 22
(4):414–421. doi:10.1179/174328406X91113
82. Trzciński W, Belaada A (2016) 1,1-Diamino-2,2-dinitroethene (DADNE, FOX-7) –
Properties and Formulations (a Review). Central Eur J Energ Mater 13(2):527–544
Chapter 4
2,4 Dinitroanisole (DNAN)

Abstract DNAN was historically used as an explosive in warheads containing

Amatol 40 and is currently being investigated as a replacement for
2,4,6-Trinitrotoluene (TNT) in melt-cast insensitive munitions (IM) formulations.
Alternatives with suitable chemical and physical properties have been sought.
2,4-Dinitroanisole (DNAN) is a promising alternative that prima facie appears to
possess adequate properties and, by virtue of reduced sensitivity, may enable the
development of a new class of low sensitivity melt-cast formulations for use in
Insensitive Munitions (IM). This chapter provides an overview of DNAN including
its synthesis, characterization, and basic properties. In addition, the sensitivity and
explosive properties of various DNAN-based formulations (containing RDX and/or
NTO) are discussed.

4.1 Introduction

Dinitroanisole [DNAN] finds applications in various fields such as synthesis of

dyes, insecticide, and explosive formulations. It is a less sensitive explosive and can
be handled and transported with less stringent conditions. Because of these prop-
erties, DNAN is being tested by the Military Industry as a replacement for
2,4,6-trinitrotoluene (TNT) in explosive formulations. For example, Picatinny
Arsenal, USA is developing a range of DNAN based explosive formulations typ-
ically referred to as the “PAX explosives”. DNAN appears to promise a new class
of low sensitive melt-cast formulations. It was during World War II that DNAN was
used along with ammonium nitrate and RDX as an explosive by name Amatol 40.
The recent interest in DNAN stems from the fact that it can be used as an ingredient
in less-sensitive melt-cast formulations than TNT, and it is classified as a Class 4.1
flammable solid. Because of this classification it is subject to less stringent inter-
national transportation requirements than Class 1 materials. DNAN is a stable
compound and has a much higher melting point compared to TNT. It is cheaper to
manufacture compared to TNT and is also less toxic. It is soluble in ethanol, ether,

© US Government (outside the USA) 2018 141

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7_4
142 4 2,4 Dinitroanisole (DNAN)

acetone, and benzene, and highly soluble in pyridine. Recently DNAN has been
used with oxidizers for incendiary and armor-piercing munitions [1].

4.2 Synthesis

The synthesis of DNAN has evolved over the years. Although DNAN can be
prepared by a number of methods starting with different raw materials, some the
processes need harsh experimental conditions and, involves toxic raw materials,
and generates hazardous wastes. However, current routes use less harsh conditions,
and addresses environmental concerns. The main synthesis methods use
chlorobenzene, phenol, 1-chloro-2,4-dinitrobenzene (DNCB), and anisole as the
starting raw materials.
The reaction path when chlorobenzene is used as the starting raw material is
shown in Fig. 4.1. In this process, chlorobenze is first nitrated using a mixture of
sulfuric and nitric acid at 313 K forming DNCB.
DNCB next reacts with sodium hydroxide in the presence of methanol (CH3OH)
under ambient conditions producing DNAN (Fig. 4.2). The reaction involves
simple nucleophilic aromatic substitution of the highly labile chloro substituent
with a methoxide anion. However, under the experimental conditions, CH3OH and
NaOH also produce hydroxide nucleophile leading to formation of other
chloro-derivatives. As a result, both the yield and the purity of the product are low.
Davies and Provatas [2] raised a similar concern for this route for production of
DNAN.
Direct nitration of phenolic compounds is typically highly exothermic and dif-
ficult to control and therefore is not a preferable route. Slater-Blanc et al. [3]
suggested several alternate paths to avoid the direct nitration path. Following
nitration of phenol, the product 1-hydroxyl-2,4-dinitrobenzene undergoes methy-
lation to pro-dice DNAN. The reaction path is shown in Fig 4.3.
Another route for preparing DNAN is the nitration of anisole directly. The
reaction pathway is shown in Fig. 4.4. One of the disadvantages of this route is the
formation of both 2,4- and 2,6-dinitroanisole. DNAN has also been prodiced by
nitration of p-nitro- and o-nitroanisole.
Researchers have pursued variation of one of these methods for the preparation
of DNAN. Barnett et al. [4] synthesized nitroanisoles by boiling 1-chloro-2,
4-dinitrobenzene with sodium methoxide in methanol to study the reaction rates.

Fig. 4.1 Nitration of

chlorobenzene to
1-chloro-2,4-dinitrobenzene
(DNCB) [4]
4.2 Synthesis 143

Fig. 4.2 Synthesis of DNAN from chlorobenzene [2]

Fig. 4.3 Synthesis of DNAN from phenol [3]

Fig. 4.4 DNAN from direct nitration of anisole [3]

The analysis of kinetics of the reaction showed that the specific reaction rate
constant, k, varied as a function of the percentage of sulfuric acid in the nitration
mixture. The log10k values varied from −3.8 to 1.0 over a concentration range of
55–72 mass% of sulfuric acid.
Dey et al. [5] carried out a detailed study for preparation of DNAN and studied
the effect of various parameters on the yield of DNAN. They used
2,4-dinitrochlorobenzene as the starting raw materials. Table 4.1 shows the effect of
various constituents on the yield of DNAN.
Davies and Provatas [2] provide a detailed description of the synthesis of DNAN
from DNCB. They used sodium hydroxide instead of sodium methoxide in the
synthesis of DNAN. The labile chlorine is methoxylated with methanol in the
presence of sodium. Holleman and Wilhelmy [6] also used the nitration of DCNB
route for the preparation of 2-4 and 2-6 dinitroanisoles, and used carbon disulfide
extraction process for separation.
A continuous process for the preparation of DNAN by the nitration of nitroa-
nisole has been described by Xu et al. [7]. The authors used 2-nitroanisole,
 144

Table 4.1 Effect of various parameters on the yield of DNAN when using 2,4-dinitrochlorobenzene as the starting material [5]
2,4-dinitrochlorobenzene NaOH 95% methyl alcohol Duration of heating 2,4-dinitroanisole (gms) (%) (mp) 2,4-dinitrophenol
20 6 150 6 13.7 70 68 27.7%
20 5 150 6 16.1 82.3 78–80 16.0%
20 4 150 6 18.8 96.1 86
160 32 1200 6 153.0 97.8 86
20 4 150 4 18.9 96.6 83
20 4 150 19.2 98.2 81
4 2,4 Dinitroanisole (DNAN)
4.2 Synthesis 145

Fig. 4.5 New dinitroanisole process (ATK process) [8]

4-nitroanisole, and their mixtures as raw materials. The reactions appear to have
been conducted at low pressures.
Alliant Techsystems [8] have the capability to make DNAN, CL-20, NTO, and
TEX. In this process, the starting material is 1-chloro-2,4-dinitro benzene (DNCB).
The process equipment is similar to that of TNT except for the solvent recovery
system. The production rate is 5–10 lb/h. A schematic diagram of the process is
shown in Fig. 4.5.
An interesting process using Phase Transfer Catalyst (PTC) is provided by Xia
et al. [9]. They used triethyl benzyl ammonium chloride as the PTC, and found a
reaction temperature of 329 K, mass ratio of catalyst to 2,4-dinitrochlorobenzene of
1:100 and a time of adding sodium hydroxide of 30 min as the best conditions. The
product was characterized by FT IR and HPLC methods.
The phenomenon of rate enhancement of a reaction between chemical species
located in different phases (immiscible liquids or solid and liquid) by addition of a
small quantity of an agent (called the ‘phase-transfer catalyst’) that extracts one of
the reactants, most commonly an anion, across the interface into the other phase so
that reaction can proceed. These catalysts are salts of ‘onium ions’ (e.g.
tetraalkylammonium salts) or agents that complex inorganic cations (e.g. crown
ethers). The catalyst cation is not consumed in the reaction although an anion
exchange does occur [10].

4.3 Structure

Two stable polymorphic forms of DNAN exist; 2-4, Dinitroanisole and 2-6,
Dinitroanisole. However, only 2-4, Dinitroanisole exhibits explosive properties.
Nyburg et al. [11], and Malinovskii et al. [12] have shown that 2-4, Dinitroanisole
exhibits a monoclinic structure. They have determined the crystal unit cell param-
eters, and provide information on bond angles and bond distances. Xue et al. [13]
146 4 2,4 Dinitroanisole (DNAN)

Table 4.2 Structural Parameters Values

parameters of 2-4,
dinitroanisole [11] Monoclinic, P21/n
a 8.772 (2)
b 12.645 (2)
c 15.429 (4) Å
b 81.89 (2)°
V 1694 Å3
Z 8
Dx 1.56 g/cm3
k (MoKa1) 0.7093 Å
l 1.26 cm−1

found a polymorphic modification of 2-4, Dinitroanisole with similar bond lengths

but some different torsional bond angles. They found that both modifications crys-
tallize in P21/n, but have different molecular packing. The data provided by Nyburg
et al. [11] are tabulated in Table 4.2.
Detailed information on bond angels and bond lengths are proved by Nyburg
et al. [11].

4.3.1 Spectral Data

The NMR spectrum for DNAN can be obtained from Wiley Subscription Services
Inc. [14] and is given in Fig. 4.6. The NMR spectrum is useful in checking the
purity of the substance.
The spectrum was taken using a Varian HA-60 in Chloroform-d (865-49-6) and
Tetramethylsilane (75-76-3) was used as the standard.
The IR spectrum was obtained from the Integrated Spectral Database System of
Organic Compounds, National Institute of Advanced Industrial Science and
Technology (Japan). The spectrum is shown in Fig. 4.7.

Fig. 4.6 NMR spectrum [14]

4.4 Physical and Chemical Properties 147

Fig. 4.7 IR absorption

spectrum [15]

4.4 Physical and Chemical Properties

Various chemical and physical properties of DNAN are listed in Table 4.3.

4.4.1 Solubility in Various Media

Boddu et al. [21] determined solubility of DNAN both in water and in the presence
of different concentrations of electrolytes. They also reported octanol-water parti-
tion coefficient and Henry’s law constant as a function of temperature. Their data
are presented in Tables 4.4. The DNAN used for this study was received from the
Ordance Systems, Kingsport, Tennessee, U.S.A. The concentration of DNAN in
different media was determined by HPLC with an UV detector at 254 nm. Extra
precautions were taken to avoid recrystallization when measuring the concentration.
Their apparatus for the determination of Henry’s law constants is shown in Fig. 4.8
and the data are tabulated in Table 4.4.
Tables 4.5 and 4.6 show data on solubility and octanol-water partition
coefficients.
QSPR model is extensively used to predict the solubility of military, pharma-
ceutical, and various other types of molecules. Boddu et al. [21, 22] used QSPR
model and the model predictions are compared with the results from EPI Suite.
The EPI suite predicts properties at 298.15 K. The EPI predictions are much dif-
ferent from the experimental data of Boddu et al. [22]
Potoff [23] has made model predictions based on Lennard-Jones 6-12 potential
with a columbic term for partial charges. Potoff states “the vapor liquid coexistence
curves, vapor pressures, boiling points and critical points were determined for a
148 4 2,4 Dinitroanisole (DNAN)

Table 4.3 Some properties of 2,4-dinitroanisole

Properties Values References
Synonyms DNAN; Anisole, 2,4-dinitro; 1-Methoxy-2,4-dinitrobenzene;
2,4-Dinitroanisol; 2,4-Dinitrophenyl methyl ether;
Dinitroanisole; Benzene, 1-methoxy-2,4-dinitro-
CAS number 119-27-7
Structural NO 2
formula
OMe

O2 N
Force field
analysis

Empirical C7H6N2O5
formula
Molecular mass g mol−1, 198.13
Density g/mL, 1.336 [CRC]
Molar volume cm3mol−1, 137 ± 3.0 at 293 K and 760 Torr [16]
Boiling point 479.15 K at 12 mm Hg [17]
588 K [18]
592.77 K [19]
Melting point 367.65 K [17]
359.9 K [18]
Flash point 180.5 ± 24.3 °C [16]
Critical 806 K [18]
temperature
Critical pressure 39.9 bar [18]
Dipole moment 3.83 Debye [21]
Acentric factor 0.858 [22]
Vapor pressure 0.000145 mm Hg and [18]
0.000138 mm Hg [16]
0.0000895 @ 298.15 K [17]
(continued)
4.4 Physical and Chemical Properties 149

Table 4.3 (continued)

Properties Values References
Enthalpy of 19.91 kJ/mol [19]
fusion
Velocity of 5320 m/s
detonation
Detonation 9.5 GPa
pressure
Temperature (K) 298.15 308.15 318.15
Log Kow 1.612 ± 0.014 1.549 ± 0.013 1.472 ± 0.025
Log Kow 1.38 1.70 1.92 [18]
Koc 169 at pH 1 and 298.15 K [16]
Vapor pressure 8.59E-5 Torr @ 25 °C, [16,
0.000138 mm Hg @ 25 °C 17]
Enthalpy of 57.21 ± 3.0 kJmol−1 [16]
vaporization
Aqueous solubility 0.14 0.159 g L-1 @ [18]
298.15 K
Bioconcentration 9.1 g L-1 @ 25 °C 4.14 °C [16,
factor (BCF) 20]
Dermal permeability 0.74 lg cm−2 hr−1 [2]
coefficient (Kp)

Table 4.4 Henry’s law constant (kH) as a function of temperature [21]

Temperature (K) 298.15 308.15 318.15
m3 Pa mol−1 (kH) 1.366 1.397 1.442

F
Gas

Gly-

Fig. 4.8 Experimental setup for the determination of Henry’s Law constant [21]
150 4 2,4 Dinitroanisole (DNAN)

Table 4.5 Aqueous solubility of DNAN (S, mg/L) in the presence of NaCl and CaCl2 salts at
different temperatures
Vol.% of salt solution Temperature (K)
298.15 308.15 318.15
0 276.2 ± 2.5 399.2 ± 4.0 560.0 ± 5.0
1% NaCl 267.1 ± 2.5 388.6 ± 3.0 527.2 ± 5.0
5% NaCl 233.5 ± 2.5 320.1 ± 2.5 437.2 ± 4.0
10% NaCl 190.7 ± 2.5 240.0 ± 2.5 321.4 ± 2.5
1% CaCl2 268.1 ± 2.5 388.8 ± 3.0 537.5 ± 5.0
5% CaCl2 249.0 ± 2.5 333.5 ± 3.0 463.5 ± 4.0
10% CaCl2 224.2 ± 2.5 276.7 ± 2.5 378.7 ± 3.0

Table 4.6 Octanol-water partition coefficients at different temperatures [22]

Temperature (K) 298.15 308.15 318.15
Log Kow 1.612 ± 0.014 1.549 ± 0.013 1.472 ± 0.025

Fig. 4.9 Co-Existence plot for DNAN. IC model (diamond); 4C model (triangle); 6C model
(circle); 10C model (square) [23]

series of force fields for DNAN. These force fields are denoted IC, 4C, 6C and 10 °C,
corresponding to the original partial charges derived from a CHELPG analysis of
HF/6-31 g + (d,p) ab initio calculations and 4, 6 and 10% reductions from these
values, respectively”. Figures 4.9 and 4.10, reproduced from Potoff’s report, show
the two-phase coexistence curve and vapor pressure data.
4.4 Physical and Chemical Properties 151

Fig. 4.10 Vapor pressure

plot for DNAN. IC model
(diamond); 4C model
(triangle); 6C model (circle);
10C model (square) [23]

4.4.2 Vapor Pressure

Highsmith and Johnston [24] in their work on synthesis of DNAN carefully fol-
lowed the time-temperature-pressure variation. They also computed the vapor
pressure of DNAN using a ChemCad model and their values shown graphically is
reproduced in Fig. 4.11. Potoff [23] values are in the range of 555–900 K where as
Highsmith and Johnston [24] values range from 300 to 423 K.

Fig. 4.11 Temperature-vapor pressure calculated [24]

152 4 2,4 Dinitroanisole (DNAN)

Table 4.7 Solubility of RDX in DNAN [2]

Temperature (K) 373 383 393
Solubility (g/100 g) 11 17 20

4.5 Detonation Characteristics

The performance of DNAN is about 10% less compared to TNT [2] but it is highly
insensitive. Its ignition temperature is about 347 °C compared to 306 °C for TNT.
The velocity of detonation and other detonation characteristics are included.

4.6 Decomposition

Desvergnes [25] studied the hydrolysis of DNAN and found that it formed
2,4-dinitrophenol and methanol
C6H3CH3O(NO2)2 + H2O ! C6H3OH(NO2)2 + CH3OH.
However in a recent study, Bausinger and Preuss [26] did not observe such a
hydrolysis and conclude that DNAN is stable. This allowed them to carry out
analysis based on liquid chromatography.
Boddu et al. [27] have studied degradation of DNAN on nanoparticles of
magnesium and zinc oxide as catalysts. The have identified that degradation occurs
through ring cleavage, hydroxylation, amination and denitration. The transforma-
tion products were identified through HPLC, LC-MS, FTIR and 1H-NMR studies.
The transformation products are shown in Fig. 4.12. The approximate composition
of the products are also shown in Fig. 4.12.
Zhao et al. [28] have also identified 2,4-diaminoanisole from their hydrogenation
studies of DNAN on palladium catalysts. These studies indicate that degradation
and transformation products can be controlled using the catalyst and redox
conditions.

4.7 Biodegradation/Biotransformations

Biodegradation studies are important for treatment of wastewaters generated from

manufacture and also to understand the fate of DNAN in soils and slurries. Both
aerobic and anaerobic degradation studies have been reported. Perreault et al. [29]
have reported aerobic transformation of soils and slurries supplemented with carbon
and nitrogen sources. They found that DNAN was completely transformed in
34 days while complete biotransformation (co-meblism) in soils is observed in
8 days by Bacillus Sp. (strain Bacillus 1 G). HPLC and LC-MS analysis of
4.7 Biodegradation/Biotransformations 153

Fig. 4.12 Degradation of 2,4 dinitroanisole on MgO and ZnO nanostructures [27]

transformation products show the formation of 2-amino-4-nitroanisole as the major

end product following the regioselective reduction of the ortho-nitro group. The
authors have identified various intermediate compounds arylnitroso and arylhy-
droxylamino derivatives. Secondary reaction products involving these intermediates
formed azoxy- and azo-dimers. Acetylated and demethylated products were also
observed (Fig. 4.13). Platten et al. [30] have studied biotransformation of DNAN in
aqueous systems using anaerobic fluidized-bed bioreactors. They have used ethanol
as the electron donor. They also report that DNAN transformed into diaminoni-
trosol, and formation of azocompounds after exposure to air.
Figure 4.14 shows the dimers formation.

4.8 Detection

Schechter and Haller [31] discuss a calorimetric procedure for detection and esti-
mation of DNAN which is rapid and accurate. Further this method gives a linear
calibration curve. A HPLC method has been described by Chow et al. [32] in a
recent paper. They analyzed samples containing 0.02–1000 ppm of DNAN in the
154 4 2,4 Dinitroanisole (DNAN)

Fig. 4.13 Proposed degradation routes of 2,4-DNAN with Baxillus 13 G. path a Primary
transformation routes of DNAN by Bacillus 13G; path b Production of azoxy- and azo-
compounds (4 and 5, respectively) from compound 1 and 2; path c proposed secondary
transformation routes of compound 2 to produce acetylated compounds (compounds in brackets
were not detected) [30]

presence of 16 other explosives. Chow et al. [32], evaluated and modified the U.S.
EPA Method 8330 the analysis of DNAN and MNA by HPLC technique in various
aqueous media in the presence and absence of the 14 energetic compounds.
4.8 Detection 155

Fig. 4.14 Chemical structures of 2,4-dinitroanisole (DNAN) and N-methyl paranitro aniline
(MNA) and their transformation products, diaminoanisole, N-methyl-p-phenylenediamine, and
their dimers [30]

They the optimized method to separate all 14 energetic compounds from DNAN
and MNA using a tertiary mobile phase of water-methanol-acetonitrile (68:28:4) in
an isocratic run of 35 min.

4.9 Formulation Using DNAN

Davies and Provatas [2] further provide an extensive review of the characterization
and formulation of DNAN with other explosives such as RDX. Two DNAN/RDX
formulations, namely ARX- 4027 (60/40 RDX/DNAN + 0.25% MNA) incorpo-
rating RS-RDX (ARX-4027 M1) and non-RS-RDX (ARX-4027 M2) have been
studied. This has led to the study of the solubility of RDX in DNAN [2], and is
discussed later in this report. Davies and Provatas [2] have carried out extensive
study of these formulations. Table 4.7 shows the solubility of RDX in DNAN.
Wilson [33] provides density, velocity of detonation, and other useful infor-
mation on some formulations including PAX-21 and PAX-41. The data on some of
these formulations are shown in Table 4.8.
In addition to the above PAX formulations, several other formulations are tested
by the army. The PAX, OSX, and other formulations contain DNAN as one of the
components replacing TNT. Zhang and Dong [34] provide a review of
2,4-dinitroanisole(DNAN)-based melt-castable explosives, including its synthesis,
properties, thermal characteristics, and compatibility with other materials.
156 4 2,4 Dinitroanisole (DNAN)

Table 4.8 Comparison of DNAN formulations [33]

Material TMD VOD LSGT DSC MP Effluxviscosity Onset (°
(%) C)
(g.cm−3) Comp. B Cards Exotherm (sec) @96C
TNT 1.654 84 133 – –
COMP B 1.76329 100 207 80/215 –
PAX-21 1.72857 83 161 89/193 4.8–8.6
PAX-33 1.73614 89 144 88/207 8.7
PAX-34 1.76098 83 104 87/245 8.5
OSX-7 1.74835 95 118 92/215 15
OSX-CAN 1.59437 84 131 93/225 5.9
1043-03 1.76937 103 144 95/229 9.2
LGST large scale gap test

References

1. Nielson DB, Ashcroft BN, Doll DW (2005) Incendiary and armor-piercing munitions
containing metal fuels, oxidizer, and Class 1.1 explosives (USA). US Pat Appl Publ (2005),
US 2005199323 A1 20050915
2. Davies PJ, Provatas A (2006) Characterization of 2,4-Dinitroanisole: an ingredient for use in
low sensitivity melt cast formulations. Australian Government, Department of Defense
Report DSTO-TR-1904
3. Salter-Blanc AJ, Bylaska EJ, Johnston HJ, Tratnyek PG (2015) Predicting reduction rates of
energetic nitroaromatic compounds using calculated one-electron reduction potentials.
Environ Sci Technol 49(6):3778–3786. doi:10.1021/es505092s
4. Barnett JW, Moodie RB, Schofield K, Weston JB, Coombes RG, Golding JG, Tobin GD
(1977) Electrophilic aromatic substitution part 162 the nitration of anisole, o-methylanisole,
and p-methylanisole in aqueous sulphuric acid. J Chem Soc Perkin Trans 248–255
5. Dey BB, Govindachari TR, Udupa HK (1946) Preparation of 4-chloro-2-nitroanisole,
4-chloro-2-nitrophenetole, 2,4-dinitroanisole, and 2,4-dinitro–phenetole. J Sci Indus Res,
Sect B: Phys Sci 5B(3):37–40
6. Holleman F, Wilhelmy G (1902) Preparation of the dinitrophenols and dinitroanisoles, and
certain of their physical properties. Recl Trav Chim Pays-Bas 21:432–447
7. Xu W, Duan Y, Liu X (2006) Faming Zhuanli Shenqing Gongkai Shuomingshu. Chinese
Patent 1861564 and 1861565
8. Holt P, Johnston G, Sanderson AJ, Wesson P, Worthington J (2004) Development of an
efficient and green TNT manufacturing process. IM/EM Technical Symposium, San
Francisco, CA, 15–17 November
9. Xia X-Z, Xu Z-L, Li F, Zhao G-S (2010) Study on the synthesis of 2,4-dinitroanisole with
TEBA as phase transfer catalys. Huaxue Shijie 51(3):162–164
10. Muller P (1994) Glossary of terms used in physical organic chemistry (IUPAC
Recommendations 1994). Pure Appl Chem 66(5):1077–1184
11. Nyburg SC, Faerman CH, Prasad L, Palleros D, Nudelman N (1987) Structures of
2,4-dinitroanisole and 2,6-dinitroanisole. Acta Crystallogr C 43:686–689
12. Malinovskii ST, Fonar MS, Simonov YA, Dvorkin AA, Ganin EV, Luk’yanenko NG,
Musienko GS (1992) Crystal and molecular structures of the host-guest type of complex of
18-crown-6 with 24-dinitroanisole and 2–4-dinitroanisole in the free state. Kristallografiya
(Crystallogr Rep) 37:671–673
References 157

13. Xue G, Gong C-R, Chen H-Y (2007) Crystal structure of 2,4-dinitroanisole C7H6N2O5 Z.
Kristallogr 222:321–322
14. Greenberg D (2006) Spectral data were obtained from Wiley Subscription Services, Inc.
(US). Wiley STM Databases, Wiley Launches, Wiley Registry of Mass Spectral Data, 8th
edn
15. Yamaji T, Saito T, Hayamizu K, Yanagisawa M, Yamamoto O (2017) Integrated spectral
database system of organic compounds, National Institute of Advanced Industrial Science
and Technology, Spectrum ID: NIDA8188). (Japan) http://sdbs.db.aist.go.jp
16. Calculated using Advanced Chemistry Development (ACD/Labs) Software V904 for Solaris
(1994–2008 ACD/Labs)
17. Syracuse research corporation database
18. Toghiani RK, Toghiani H, Maloney SW, Boddu VM (2008) Prediction of physicochemical
properties of energetic materials. Fluid Phase Equilib 264:86–92
19. Chakka S, Boddu VM, Maloney SW, Damavarapu R, Paper Presented At the AIChE
Meeting
20. Mehrotra NK, Shukla JP, Saxena MC (1967) Relaxation times and dipole moments of some
substituted benzenes having hydroxyl, methoxy, or ethoxy groups. Indian J Pure Appl Phys
5(2):61–63
21. Boddu VM, Abburi K, Fredricksen AJ, Maloney SW, Damavarapu R (2009) Equilibrium
and column adsorption studies of 2,4-dinitroanisole (DNAN) on surface modified granular
activated carbons. Environ Technol 30(2):173–181
22. Boddu VM, Abburi K, Maloney SW, Damavarapu R (2008) Thermophysical properties of
an insensitive munitions compound, 2,4-dinitroanisole. J Chem Eng Data 53:1120–1125
23. Potoff J (2007) Prediction of environmental impact of high-energy materials with atomistic
computer simulations. Annual Report, Contract Number W9132–06-2-2027
24. Highsmith TK, Johnston HE (2004) Continuous process for preparing alkoxynitroarenes. US
Patent 0133046
25. Desvergnes L (1994) Sur quelques proprie´ te´ s physiques des de´ rive´ s nitre´ s. Monit
Scient 14(5 series):249–257
26. Bausinger T, Preuss J (2008) Stability of nitroaromatic specialty explosives in
reversed-phase liquid chromatographic systems. J Hazard Mater
27. Boddu VM, Abburi K, Maloney SW, Damavarapu R (2010) Physicochemical property
measurements on insensitive munitions compounds for environmental applications. CRC
Press, Boca Raton, pp 139–160
28. Zhao X, Chen X, Chen L (1997) Hydrogenation of 2,4–dinitroanisole in liquid phase. Jingxi
Huagong 14(5):41–43 (in Chinese)
29. Perreault NN, Manno D, Halasz A, Thiboutot S, Ampleman G, Hawai J (2012)
Biodegradation 23:287–295
30. Platten WE, Bailey D, Suidan MT, Maloney SW (2010) Chemosphere 81:11
31. Schechter S, Haller HL (1944) Colorimetric determination of 2,4-dinitroanisole. Ind Eng
Chem Anal Ed 16:325
32. Chow TM, Wilcoxon MR, Piwoni MD, Maloney SW (2009) Analysis of new generation
explosives in the presence of U.S. EPA method 8330 energetic compounds by
high-performance liquid chromatography. J Chromatogr Sci 47(1):40–43. doi:10.1093/
chromsci/47.1.40
33. Wilson AE (2006) BAE Systems. http://www.imemg.org/res/imemts2006_Wilson_3B.ppt.
pdf
34. Zhang G, Dong H (2010) Review on melt-castable explosives based on 2,4-dinitroanisole.
Chinese Journal of Energetic Materials Institute of Chemical Materials, CAEP, Mianyang,
China
158 4 2,4 Dinitroanisole (DNAN)

Additional Scholarly Articles for further Reading

35. Ahn SC, Cha DK, Kim BJ, Oh S-Y (2011) Detoxification of PAX-21 ammunitions
wastewater by zero-valent iron for microbial reduction of perchlorate. J Hazard Mater 192
(2):909–914. doi:10.1016/j.jhazmat.2011.05.104
36. Ahn SC, Hubbard B, Cha DK, Kim BJ (2014) Simultaneous removal of perchlorate and
energetic compounds in munitions wastewater by zero-valent iron and perchlorate-respiring
bacteria. J Environ Sci Health Part A Toxic/Hazard Subst Environ Eng 49(5):575–583.
doi:10.1080/10934529.2014.859455
37. Arnett CM, Rodriguez G, Maloney SW (2009) Analysis of bacterial community diversity in
anaerobic fluidized bed bioreactors treating 2,4-dinitroanisole (DNAN) and
n-methyl-4-nitroaniline (MNA) using 16S rRNA gene clone libraries. Microbes Environ
24(1):72–75
38. Bhatnagar N, Kamath G, Potoff JJ (2013) Prediction of 1-octanol-water and air-water
partition coefficients for nitro-aromatic compounds from molecular dynamics simulations.
Phys Chem Chem Phys 15(17):6467–6474. doi:10.1039/c3cp44284e
39. Boddu VM, Abburi K, Fredricksen AJ, Maloney SW, Damavarapu R (2009) Equilibrium
and column adsorption studies of 2,4-dinitroanisole (DNAN) on surface modified granular
activated carbons. Environ Technol 30(2):173–181. doi:10.1080/09593330802422993
40. Boddu VM, Maloney SW (2012) Physical properties of insensitive munitions compounds
for developing wastewater treatment technologies, vol 3. Air and Waste Management
Association, pp 1958–1965
41. Capela D et al (2001) Analysis of the chromosome sequence of the legume symbiont
Sinorhizobium meliloti strain 1021. Proc Natl Acad Sci USA 98(17):9877–9882. doi:10.
1073/pnas.161294398
42. Casjens S, Huang WM (1993) Linear chromosomal physical and genetic map of Borrelia
burgdorferi, the Lyme disease agent. Mol Microbiol 8(5):967–980. doi:10.1111/j.1365-
2958.1993.tb01641.x
43. Cayrou C, Turenne C, Behr MA, Drancourt M (2010) Genotyping of Mycobacterium avium
complex organisms using multispacer sequence typing. Microbiology 156(3):687–694.
doi:10.1099/mic.0.033522-0
44. Chakka S, Boddu VM, Maloney SW, Toghiani RK, Damavarapu R (2009) Vapor pressures
and melting points of select munitions compounds. American Institute of Chemical
Engineers, pp chakk1/1-chakk1/9
45. Chauhan S, Tyagi JS (2011) Analysis of transcription at the oriC locus in Mycobacterium
tuberculosis. Microbiol Res 166(6):508–514. doi:10.1016/j.micres.2010.10.005
46. Chiaramello AE, Zyskind JW (1990) Coupling of DNA replication to growth rate in
Escherichia coli: a possible role for guanosine tetraphosphate. J Bacteriol 172(4):2013–2019
47. Cho E, Ogasawara N, Ishikawa S (2008) The functional analysis of YabA, which interacts
with DnaA and regulates initiation of chromosome replication in Bacillus subtilis. Genes
Genet Syst 83(2):111–125. doi:10.1266/ggs.83.111
48. Choung K-K, Estiva E, Bremer H (1981) Genetic and physiological characterization of a
spontaneous mutant of Escherichia coli B/r with aberrant control of deoxyribonucleic acid
replication. J Bacteriol 145(3):1239–1248
49. Cirz RT, O’Neill BM, Hammond JA, Head SR, Romesberg FE (2006) Defining the
Pseudomonas aeruginosa SOS response and its role in the global response to the antibiotic
ciprofloxacin. J Bacteriol 188(20):7101–7110. doi:10.1128/JB.00807-06
50. Clark MA, Baumann L, Baumann P (1998) Sequence analysis of a 34.7-kb DNA segment
from the genome of Buchnera aphidicola (endosymbiont of aphids) containing groEL, dnaA,
the atp operon, gidA, and rho. Curr Microbiol 36(3):158–163. doi:10.1007/PL00006760
51. Costales-Nieves C, Boddu VM, Maloney SW, Chakka S, Damavarapu R, Viswanath DS
(2010) SPARC prediction of physical properties of explosive compounds. American
Institute of Chemical Engineers, pp a291/1-a291/17
Additional Scholarly Articles for further Reading 159

52. Coulouarn C, Aumasson R, Lamy-Bracq P, Bulot S (2014) Evaluation of melt-cast explosive

compositions based on TNT and DNAN NEXTER Munitions. Int Annu Conf ICT 45th
Energetic Materials: Particles, Processing, Applications): Coulouarn/1-Coulouarn/13, 13 pp
53. Cuddy MF, Poda AR, Chappell MA (2014) Estimations of Vapor Pressures by
Thermogravimetric Analysis of the Insensitive Munitions IMX-101, IMX-104, and
Individual Components. Propellants, Explos, Pyrotech 39(2):236–242. doi:10.1002/prep.
201300069
54. Dodard SG et al (2013) Ecotoxicological assessment of a high energetic and insensitive
munitions compound: 2,4-Dinitroanisole (DNAN). J Hazard Mater 262:143–150. doi:10.
1016/j.jhazmat.2013.08.043
55. Fischer D, Klapoetke TM, Stierstorfer J (2014) Oxalylhydrazinium nitrate and dinitrate—
efficiency meets performance. J Energ Mater 32(1):37–49. doi:10.1080/07370652.2012.
750697
56. Golius A, Isayev O, Gorb L, Hill FC, Leszczynski J (2014) Energetic compounds as
environmental contaminants: theoretical studies. American Chemical Society, p TOXI-118
57. Grau H, Gandzelko A, Samuels P (2014) Solubility determination of raw energetic materials
in molten 2,4-dinitroanisole. Propellants, Explos, Pyrotech 39(4):604–608. doi:10.1002/
prep.201300083
58. Hawari J et al (2015) Environmental fate of 2,4-dinitroanisole (DNAN) and its reduced
products. Chemosphere 119:16–23. doi:10.1016/j.chemosphere.2014.05.047
59. Hoyt N et al (2013) Biomarkers of oral exposure to 3-nitro-1,2,4-triazol-5-one (NTO) and
2,4-dinitroanisole (DNAN) in blood and urine of rhesus macaques (Macaca mulatta).
Biomarkers 18(7):587–594. doi:10.3109/1354750X.2013.829522
60. Kennedy AJ et al (2015) Inter- and intraspecies chemical sensitivity: A case study using
2,4-dinitroanisole. Environ Toxicol Chem 34(2):402–411. doi:10.1002/etc.2819
61. Kitcher E, Pavlov J, Koutsospyros A, Christodoulatos C, Braida W (2013) Reaction
mechanism of the reductive removal of NTO and DNAN from IM wastewater using
bimetals. American Chemical Society, p ENVR-238
62. Li Y, Hsieh W-P, Mahmudov R, Huang CP (2011) Treatment of ammunition wastewater
using ultrasonic Fenton (US-Fenton) process. American Institute of Chemical Engineers, pp
399a/1–399a/16
63. Liang J, Olivares C, Field JA, Sierra-Alvarez R (2013) Microbial toxicity of the insensitive
munitions compound, 2,4-dinitroanisole (DNAN), and its aromatic amine metabolites.
J Hazard Mater 262:281–287. doi:10.1016/j.jhazmat.2013.08.046
64. Linker BR et al (2015) Adsorption of novel insensitive munitions compounds at clay mineral
and metal oxide surfaces. Environ Chem 12(1):74–84. doi:10.1071/EN14065
65. Liu R, Zhang T, Liu Y, Yang L, Zhou Z (2013) Evaporation characteristics of low-melting
nitrocompounds by isothermal thermogravimetry. J Therm Anal Calorim 112(3):1523–1532.
doi:10.1007/s10973-012-2665-z
66. Liu R, Zhang T, Yang L, Zhou Z Researches on vapor pressure and thermal decomposition
of low-melting explosives. In, 2013. University of Pardubice, Institute of Energetic
Materials, p 441–449
67. Liu R, Zhang T, Zhou Z, Yang L (2014) Volatilization interference in thermal analysis and
kinetics of low-melting organic nitro compounds. RSC Adv 4(19):9810–9818. doi:10.1039/
c3ra47218c
68. Lopez-Canut V, Roca M, Bertran J, Moliner V, Tunon I (2011) Promiscuity in alkaline
phosphatase superfamily. Unraveling evolution through molecular simulations. J Am Chem
Soc 133(31):12050–12062. doi:10.1021/ja2017575
69. Lotufo GR, Biedenbach JM, Sims JG, Chappell P, Stanley JK, Gust KA (2015)
Bioaccumulation kinetics of the conventional energetics TNT and RDX relative to
insensitive munitions constituents DNAN and NTO in Rana pipiens tadpoles. Environ
Toxicol Chem 34(4):880–886. doi:10.1002/etc.2863
70. Mu R, Shi H, Yuan Y, Karnjanapiboonwong A, Burken JG, Ma Y (2012) Fast separation
and quantification method for nitroguanidine and 2,4-dinitroanisole by ultrafast liquid
160 4 2,4 Dinitroanisole (DNAN)

chromatography-tandem mass spectrometry. Anal Chem 84(7):3427–3432. doi:10.1021/

ac300306p
71. Mudryy R (2011) Solidification modeling of DNAN based explosive compositions. Int
Annu Conf ICT 42nd(Energetic Materials):111/1–111/11
72. Muscat D et al (2000) In-source decay of hyperbranched polyesteramides in matrix-assisted
laser desorption/ionization time-of-flight mass spectrometry. J Am Soc Mass Spectrom 11
(3):218–227. doi:10.1016/S1044-0305(99)00141-5
73. Niedzwiecka JB, Millerick KA, Galloway S, Schlautman MA, Finneran KT (2014)
Microbially mediated 2, 4-dinitroanisole (DNAN) degradation. American Chemical Society,
p ENVR-48
74. Olivares C, Liang J, Abrell L, Sierra-Alvarez R, Field JA (2013) Pathways of reductive
2,4-dinitroanisole (DNAN) biotransformation in sludge. Biotechnol Bioeng 110(6):1595–
1604. doi:10.1002/bit.24820
75. Platten WE III, Bailey D, Suidan MT, Maloney SW (2010) Biological transformation
pathways of 2,4-dinitro anisole and N-methyl paranitro aniline in anaerobic fluidized-bed
bioreactors. Chemosphere 81(9):1131–1136. doi:10.1016/j.chemosphere.2010.08.044
76. Platten WE, III, Bailey D, Suidan MT, Maloney SW (2013) Treatment of energetic
wastewater containing 2,4-dinitroanisole and N-methyl paranitro aniline. J Environ Eng 139
(1):104–109. doi:10.1061/(ASCE)EE.1943-7870.0000592
77. Provatas A, Wall C (2011) Thermal testing of 2,4-dinitroanisole (DNAN) as a TNT
replacement for melt-cast explosives. Int Annu Conf ICT 42nd(Energetic Materials):6/1–6/
12
78. Richard T, Weidhaas J (2014) Biodegradation of IMX-101 explosive formulation
constituents: 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and nitroguani-
dine. J Hazard Mater 280:372–379. doi:10.1016/j.jhazmat.2014.08.019
79. Richard T, Weidhaas J (2014) Dissolution, sorption, and phytoremediation of IMX-101
explosive formulation constituents: 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one
(NTO), and nitroguanidine. J Hazard Mater 280:561–569. doi:10.1016/j.jhazmat.2014.08.
042
80. Russell AL, Seiter JM, Coleman JG, Winstead B, Bednar AJ (2014) Analysis of munitions
constituents in IMX formulations by HPLC and HPLC-MS. Talanta 128:524–530. doi:10.
1016/j.talanta.2014.02.013
81. Saad R, Radovic-Hrapovic Z, Ahvazi B, Thiboutot S, Ampleman G, Hawari J (2012)
Sorption of 2,4-dinitroanisole (DNAN) on lignin. J Environ Sci 24(5):808–813. doi:10.1016/
S1001-0742(11)60863-2
82. Salter-Blanc AJ, Bylaska EJ, Johnston HJ, Tratnyek PG (2015) Predicting reduction rates of
energetic nitroaromatic compounds using calculated one-electron reduction potentials.
Environ Sci Technol 49(6):3778–3786. doi:10.1021/es505092s
83. Salter-Blanc AJ, Bylaska EJ, Ritchie JJ, Tratnyek PG (2013) Mechanisms and kinetics of
alkaline hydrolysis of the energetic nitroaromatic compounds 2,4,6-trinitrotoluene
(TNT) and 2,4-dinitroanisole (DNAN). Environ Sci Technol 47(13):6790–6798. doi:10.
1021/es304461t
84. Scott AM, Burns EA, Hill FC (2014) Theoretical study of adsorption of nitrogen-containing
environmental contaminants on kaolinite surfaces. J Mol Model 20(8):1–13. doi:10.1007/
s00894-014-2373-7
85. Scott AM, Burns EA, Hill FC (2014) Theoretical study of adsorption of nitrogen-containing
environmental contaminants on kaolinite surfaces. J Mol Model 20(8):2373
86. Scott AM, Burns EA, Lafferty BJ, Hill FC (2015) Theoretical predictions of thermodynamic
parameters of adsorption of nitrogen containing environmental contaminants on kaolinite.
J Mol Model 21(2):1–16. doi:10.1007/s00894-015-2577-5
87. Scott AM, Burns EA, Lafferty BJ, Hill FC (2015) Theoretical predictions of thermodynamic
parameters of adsorption of nitrogen containing environmental contaminants on kaolinite.
J Mol Model 21(2):21
Additional Scholarly Articles for further Reading 161

88. Shen J et al (2013) Pretreatment of 2,4-dinitroanisole (DNAN) producing wastewater using a

combined zero-valent iron (ZVI) reduction and Fenton oxidation process. J Hazard Mater
260:993–1000. doi:10.1016/j.jhazmat.2013.07.003
59. Sokkalingam N, Ketko MH, Potoff JJ (2010) Physical property prediction of energetic
materials from molecular dynamics simulation. CRC Press, Boca Raton, pp 37–62
90. Souza BS et al (2009) Hydrolysis of 8-quinolyl phosphate monoester: kinetic and theoretical
studies of the effect of lanthanide ions. J Org Chem 74(3):1042–1053. doi:10.1021/
jo801870v
91. Stanley JK, Lotufo GR, Biedenbach JM, Chappell P, Gust KA (2015) Toxicity of the
conventional energetics TNT and RDX relative to new insensitive munitions constituents
DNAN and NTO in Rana pipiens tadpoles. Environ Toxicol Chem 34(4):873–879. doi:10.
1002/etc.2890
92. Sviatenko L et al (2014) Comprehensive investigations of kinetics of alkaline hydrolysis of
2,4,6-trinitrotoluene, 2,4-dinitrotoluene, and 2,4-dinitroanisole. Environ Sci Technol 48
(17):10465–10474. doi:10.1021/es5026678
93. Taylor S, Park E, Bullion K, Dontsova K (2015) Dissolution of three insensitive munitions
formulations. Chemosphere 119:342–348. doi:10.1016/j.chemosphere.2014.06.050
94. Trzcinski WA, Cudzilo S, Dyjak S, Nita M (2012) A comparison of sensitivity and
performance characteristics of melt-pour explosives with TNT and DNAN binder.
University of Pardubice, Institute of Energetic Materials, pp 893–901
95. Tsendra O et al (2014) Adsorption of nitrogen-containing compounds on the (100) a-quartz
surface: Ab Initio cluster approach. J Phys Chem C 118(6):3023–3034. doi:10.1021/
jp406827h
96. Verbenko VN, Kuznetsova LV, Luchkina LA, Klopov NV (2009) Mutation in the cspH–
cspG gene cluster enhances expression of heat-shock proteins and SOS repair system of
Escherichia coli. Russ J Genet 45(9):1047–1054. doi:10.1134/S102279540909004X
97. Walsh MR et al (2013) Characterization of PAX-21 insensitive munition detonation
residues. Propellants, Explos, Pyrotech 38(3):399–409. doi:10.1002/prep.201200150
98. Walsh MR et al (2014) Energetic residues from the detonation of IMX-104 insensitive
munitions. Propellants, Explos, Pyrotech 39(2):243–250. doi:10.1002/prep.201300095
99. Walsh MR, Walsh ME, Ramsey CA, Brochu S, Thiboutot S, Ampleman G (2013)
Perchlorate contamination from the detonation of insensitive high-explosive rounds.
J Hazard Mater 262:228–233
100. Xiao L-B et al (2014) Thermochemical properties of 2,4-dinitroanisole in N-methyl
pyrrolidone and dimethyl sulfoxide. J Therm Anal Calorim 118(3):1755–1761. doi:10.1007/
s10973-014-4042-6
101. Xing X et al (2012) Specific heat capacity, thermal behavior, and thermal hazard of
2,4-dinitroanisole. Propellants, Explos, Pyrotech 37(2):179–182. doi:10.1002/prep.
201000077
102. Xu Z, Hao J, Braida W, Strickland D, Li F, Meng X (2011) Surface-enhanced Raman
scattering spectroscopy of explosive 2,4-dinitroanisole using modified silver nanoparticles.
Langmuir 27(22):13773–13779. doi:10.1021/la202560t
103. Zabihi-Mobarakeh H, Nezamzadeh-Ejhieh A (2015) Application of supported TiO2 onto
Iranian clinoptilolite nanoparticles in the photodegradation of mixture of aniline and
2,4-dinitroaniline aqueous solution. J Ind Eng Chem: Ahead of Print. doi:10.1016/j.jiec.
2014.12.003
Chapter 5
5-Nitro-2,4-Dihydro-3H-1,2,
4-Triazole-3-One (NTO)

Abstract NTO is a very attractive explosive due to its insensitivity, thermal and
mechanical stability. NTO can be used to prepare melt-cast explosives (NTO-TNT
mixture) as well as pressed explosives with thermoplastic binder and cast PBX
charges for Insensitive Munitions. In this chapter, various synthesis processes and
physico-chemical properties of NTO are discussed. A number of formulations along
with there explosive properties are presented and compared with neat NTO and
TNT. The toxicity, biodegradation, and detection techniques are also discussed in
this chapter.

5.1 Introduction

Both 5-Nitro-2,4-dihydro-3H-1,2,4-triazole-3-one and 3-Nitro-2,4-dihydro-

3H-1,2,4-triazole-5-one are abbreviated as NTO and are considered as a potential
insensitive replacement for RDX in various explosive formulations. 5-Nitro-2,
4-dihydro-3H-1,2,4-triazole-3-one and 3-Nitro-2,4-dihydro-3H-1,2,4-triazole-5-one
are isomers, and, therefore, have similar properties. NTO is a low sensitive material
and has been in use since 1980s. Its performance is slightly less than RDX, but
either similar or superior to other explosives. However, the high yields and the
availability of raw materials coupled with its excellent properties have made NTO a
preferred material compared to TATB, RDX and HMX. NTO is thermally stable
and exhibits low sensitivity to radiation damage and other stimuli. Therefore, it is
relatively easy to transport and store.

5.2 Synthesis

The first reported synthesis of NTO appears to be by Manchot and Noll [1], which
was followed by Chipen et al. [2]. Several synthesis routes have been developed
during 1980s. Synthesis of NTO is a two step process. In the first step triazol-3-one

© US Government (outside the USA) 2018 163

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7_5
164 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

(TO) is produced. In the second step TO undergoes nitration to produce NTO.

Attempts were made to produce TO by reacting acetone semicarbazone with formic
acid, semicarbazide hydrochloride (SC) with formic acid or with triethylorthofor-
mate [3]. However, the best method for synthesis of TO was found to be via
reaction of SC with formic acid.
Smith and Cliff [3] discussed various procedures for synthesis of NTO, and gave
details of a method adopted by Australian researchers. The simplest method appears
to be the condensation of SC with formic acid forming triazolone, followed by
nitration to TO forming NTO. Reactions are shown in Fig. 5.1.
As pointed out by Smith and Cliff [3], this reaction takes place at a very desirable
temperature of 338 K with yields approaching 80%. A detailed study of the kinetics
of nitration of 1,2,4-triazol-5-one using 70–100% nitric acid has been undertaken
by Zbarsky and Yudin [4]. It is interesting to note that the yield of NTO did not
depend on temperature in the range of 273–303 K and the reaction time, which was
independent of both the initial acid concentration in the range from 90 to 98%
HNO3 and the ratio of HNO3 to triazol-3-one (TO) in the range of 4–8 mol HNO3
per mole TO. They also reported that the yield dropped significantly in 98% HNO3
if the HNO3 to TO ratio was greater than 10. Mukundan et al. [5] followed the same
synthesis route and obtained pure NTO with 80% yield by crystallization from
water. Singh et al. [6] used the same reaction scheme but used 70% nitric acid for
nitration of TO to NTO.
The Defence Science & Technology Organisation Aeronautical and Maritime
Research Laboratory of Australia [7] used a similar scheme for preparation of NTO.
In their one-pot synthesis route, formic acid and SC mixed at ambient temperature

Fig. 5.1 Reaction scheme for the synthesis of NTO

5.2 Synthesis 165

in the ratio of 8:3 (formic acid:SC). The intermediate compound was obtained by
stirring the mixture at 338 K. The nitration was carried out using a mixture of neat
nitric acid and 98% sulfuric acid (5:1 ratio). The final product NTO was obtained by
recrystallization from hot water with a 77% yield.
Li [8] also employed the one-pot synthesis route for preparation of NTO. In his
process, cyclocondensation of semicarbazide with formic acid followed by nitration
provided an yield of 76.8% NTO. Kim et al. described [9] the preparation of NTO
by mixing 1,2,4-triazol-5-one with a mixture of 98% sulfuric acid and 70% nitric
acid in a reactor at 298 K., and then raising the temperature to 308–318 K. The
temperature was maintained in this range to generate a crystal nucleus of
3-nitro-1,2,4-triazol-5-one and the reaction was completed by heating the reaction
mixture to 333–343 K.
Spears et al. [7] reviewed the preparation of NTO by various researchers who
used different ratios of semicarbazide, formic acid, nitric acid, and mixtures of
sulfuric and nitric acid under different experimental conditions. The yields varied
from 36 to 75% based on semicarbazide. These reaction schemes for the preparation
of NTO from TO summarized by Spears et al. [7] are given in Fig. 5.2.

Fig. 5.2 Methods for synthesis of NTO from TO [7, 13]

166 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

The nanosize particles offer lower sensitivity to various stimuli and can enhance
performance of energetic materials. Yang et al. [14] prepared NTO nano particles
using spray freezing technique from 90% pure neat NTO. Several techniques
including scanning electron and atomic force microscopy, X-ray diffraction, ther-
mogravimetric analysis, and differential and scanning calorimetry were used to
characterize the particles. The results show that NTO particles have an elongated
shape with a size of 70–90 nm. The SEM obtained by the authors is shown in
Fig. 5.3, and the thermogravimetric and DSC results in Fig. 5.4. The DSC data
showed the decomposition of nanoparticles in the temperature range of 513–543 K
that is 16 K lower than the microsize particles. The TGA data also showed that the
mass loss of nanoparticles started at a temperature 40 K lower than microparticles,
suggesting that nanoparticles are more sensitive than micro-size particles.
Wang et al. [15] employed a reverse microemulsion of solvent evaporation
method to prepare nanoparticles of NTO. An n-alkanol was used as a co-surfactant.
The mass ratio between surfactant and co-surfactant was 7:1 and the water content
of the solution was 24%. The experiment was carried out at 298–303 K under a
vacuum between −0.6 and −0.85 MPa. The particle size of NTO produced by this
method was in the range of 10–30 nm.
Several authors have reviewed the literature for the synthesis of NTO. Ma et al.
[16], along with the review of the synthesis process, also discussed various prop-
erties of NTO. These included crystal structure, thermal behaviors, toxicity and
various compounds of NTO with alkali, alkaline earth, transition metals and rare

Fig. 5.3 Scanning electron micrograph of nano-NTO (with permission from [14])
5.2 Synthesis 167

Fig. 5.4 Thermal analysis results of micro-NTO and nano-NTO. (1 DSC curve of nano-NTO; 2
DSC curve of micro-NTO; 3 TG curve of nano-NTO; 4 TG curve of micro-NTO) (with permission
from [14])

earth metals. Smith and Cliff [3] reviewed NTO based explosive formulations. They
also discussed various chemical and physical properties of NTO, and explosive
characteristics.

5.3 Structure

Crystalline NTO exists in two polymorph forms—a and b, with a being the
dominant polymorph and more stable. The different forms are obtained by using
different crystallization techniques.
Lee and Gilardi [17] prepared a-NTO by slow cooling of a hot solution of NTO
in water, followed by refrigeration. The crystals appear as long needles. For
preparation of b-NTO, recrystallization from methanol or a mixed ethanol/
dichloromethane solvent was employed. They noted that b-NTO prepared this way
remained stable for six month after which it decomposed. As noted by Lee and
Gilardi [17], b-NTO can also be prepared by cooling from a hot aqueous solution of
NTO, but large enough quantities could not be obtained by this method. They
studied the XRD patterns of both a and b polymorphs of NTO and provided the
lattice parameters. The lattice parameters are shown in Table 5.1 and the XRD
pattern in Fig. 5.5. Bolotina et al. [18] also studied the crystal structure of the
metastable a form at 298 K, and that of b-NTO as a function of temperature from
100 to 298 K [19]. Their results are compared in the same Table 5.1. Both the
research groups obtained similar results.
168 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Fig. 5.5 XRD pattern of

NTO [20]

Table 5.1 Lattice parameters of a and b polymorphs of NTO [18]

Crystal polymorph a b
Space group P1 P21/C
Unit cell Triclinic, 8 molecules/cell Monoclinic, 4 molecules/cell
a (Å) 5.12 9.236
b (Å) 10.30 5.513
c (Å) 17.9 9.107
a (º) 106.7
b (º) 97.7 100.77
c (º) 90.2
Density (g/cm3) 1.92 1.878

The work of Bolotina et al. [19] with b-form revealed some interesting infor-
mation. Although the b-form is solid from 100 to 298 K, the density of the b-form
varied from 1.926 at 100 K to 1.876 at 298 K.

5.4 Properties

Various physical and chemical properties of NTO are summarized in Table 5.2.
A detailed discussion of some of these properties is provided in the following
sections.

5.4.1 Heat Capacity and Entropy

Osmont et al. [26] computed the ideal gas heat capacity and entropy using B3LYP/
6-31G(d,p)//B3LYP/6-31G(d,p) technique based on the density function theory.
5.4 Properties 169

Table 5.2 Chemical and physical properties of NTO

Common chemical formula 5-Nitro-2,4-dihydro-3H-1,2,4-triazole-3-one
Other names 5-oxy-3-nitro-1,2,4-triazol-5-(ONTA);
5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO)
CAS no. 932-64-9 [NTO 3, 5]
Empirical formula C2H2N4O3
Structural formula O

H
H
N N

N
O2 N
Molecular mass 130
Density (gcm−3) 1.93 [21]; 2.46 [22];1.911 [23]
Molar volume (cm3mol−1) 52.7 ± 7.0 [22]
Boiling point (K) 568 [23]
Melting point (K) 539.35 [23] 543 [21]; 546 [24] 547.9 [24]
Auto-ignition temperature (K) 538.2 [24]
Critical temperature (K) 829 [23]
Critical pressure 86.0 [23]
Acentric factor 0.798 [23]
Log Kow 0.82; −1.19 [23]
Koc 1.0 to 4.24 @ pH 10 to 1 [22]
pKa 3.67 [1]; 3.78 [4] 4.7 ± 020 [22]
−2.09 ± 0.20 [18] Basic
Vapor pressure log P = −1.375 ± 0.656 [22]
Liquid: ln P = 14.82 − 9914.4/T pressure in MPa
[24]
Solid: lnP = −12984.4/T + 20.48 [24]
Enthalpy of formation (kJmol−1) −59.83 [24]; −117.21 [21]; −100.7 [25];
−30.927 kcal mol−1 [7]
Enthalpy of formation (gas phase), −0.9 [22]; −3.2 and −5.7 [7]
(kcal/mol)
Enthalpy of combustion (kJmol−1) −943.4 to −995.7 [20]
Enthalpy of vaporization (kJmol−1) 82.4 [20]
Enthalpy of sublimation (kJmol−1) 110.5 [23]
Enthalpy of fusion (kJmol−1) 28.0 [20]; 20.17 [19]; 27 [23]; 92.8 [24]
Enthalpy of explosion (kJ/mol) 4100; 409.2 [25]
Specific energy (kJ/mol) 122.9 [25]
Heat capacity (J g−1 k−1) 1.46 [24]
LD50 rats and mice (g/kg) 5
Velocity of detonation (ms−1) 8564 [2]
Aqueous solubility (g/l) 7.56; 9.97 @ 25 °C [1]; 49 [26]; in acetone 18 g/l;
in DMSO 625 g/l [26]
170 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Table 5.3 Ideal gas heat capacity and entropy [26]

Heat capacity
Temperature (K) Cp (cal mol−1 K−1) Temperature (K) Cp (cal mol−1 K−1)
300 28.1 2000 58.1
400 34.2 2500 59.2
500 39.1 3000 59.9
600 42.9 3500 60.3
800 48.1 4000 60.6
1000 51.4 4500 60.8
1500 55.9 5000 61.0
Entropy
Temperature (K) S (cal mol−1 K−1) Temperature (K) S (cal mol−1 K−1)
300 85.2 2000 172.4
400 94.2 2500 185.5
500 102.4 3000 196.3
600 109.9 3500 205.6
800 123.0 4000 213.7
1000 134.1 4500 220.8
1500 156.0 5000 227.3

The harmonic oscillator rigid rotator approximation was used in these calculations.
They found that the contribution due to harmonic molecular motions, in particular
internal rotations, is negligible. The values of the heat capacity and entropy cal-
culated at various temperatures are given in Table 5.3.
Li et al. [27] proposed the following equation for calculation of specific heat
capacity of NTO in the temperature range of 283–353 K.

CP ¼ 0:2806 þ 2:7103  103 T ð5:1Þ

They used the standard molar heat capacity of NTO as 141.53 J/mol/K at
298.15 K and then using the Cp–temperature data, thermodynamic functions (en-
thalpy, entropy and Gibbs free energy) of NTO between 283 and 353 K, relative to
the standard temperature 298.15 K, the heat capacities were determined.

5.4.2 Solubility

NTO is soluble in a number of solvent including water, acetone, and acetonitrile.

The solubility data of NTO in various solvent compiled by Smith and Cliff [3] is
given in Table 5.4.
5.4 Properties 171

Table 5.4 Solubility in different solvents [3]

Solvent Temperature (°C) Solubility (g/100 ml)
Water 4.85 0.72
18.95 1.28
43.3 2.60
100 *10
Acetone 18.95 1.68
Ethyl acetate 18.95 0.28
Dichloromethane 18.95 <0.02

Table 5.5 Experimental mole fraction solubility x of NTO in water [28]

Mole fraction (x) Temperature (K) Mole fraction (x) Temperature (K)
0.001 383 284.65 0.012 308 351.85
0.002 762 307.05 0.013 657 356.05
0.004 137 319.65 0.015 002 358.45
0.005 508 327.95 0.016 344 361.95
0.006 875 334.85 0.017 682 364.25
0.008 239 340.55 0.019 016 366.75
0.009 599 345.45 0.020 347 367.55
0.010 956 349.65

Kim et al. [28] measured the density and solubility of NTO in water over a range
of temperature. The purity of NTO is stated to be better than 99.93 mol% and the
accuracy of mass measurements was better than ±0.0001 g, and that of mole
fractions was better than ±2  10−4. Both the solubility and density of NTO was
reported as the mole fraction of NTO in water. Their data on solubility and density
of NTO in water are shown in Tables 5.5 and 5.6.
Kim et al. [28] also correlated the solubility data to an exponential equation and
is given below:

x ¼ 1:429  107 e0:0322 ð5:2Þ

where, x is the solubility, and T is temperature in K.

The suggested correlation for density calculation is as follows:

q ¼ 1166:74 þ 427:75 x  0:5508T þ 5:9576 xT ð5:3Þ

where q is in (kg/m3), T is in K and x is the mole fraction. The data predicted by

these two correlations are compared with the experimental data in Figs. 5.6 and 5.7.
Zbarsky and Yudin [4] studied the solubility of NTO in water and water-nitric
acid mixtures. They measured the solubility during both cooling cycle (leading to
crystallization of NTO from the solution) and heating cycle (disappearance of the
172 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Table 5.6 Experimental densities for xNTO+ (1 − x)H2O [28]

102 x T (K) q (kg/m3) 102 x T (K) q (kg/m3)
0.2762 308.15 1003.3 0.5508 363.15 981.1
0.2762 313.35 1000.8 0.5508 368.15 978.5
0.2762 318.15 997.9 0.8239 333.15 1003.2
0.2762 323.15 995.2 0.8239 338.15 1000.8
0.2762 328.15 992.5 0.8239 343.15 998.3
0.2762 333.15 989. 8 0.8239 348.15 995.8
0.2762 338.15 987.0 0.8239 353.15 993.7
0.2762 343.15 984.1 0.8239 358.15 990.9
0.2762 348.15 981.6 0.8239 363.15 988.3
0.2762 353.15 979.1 0.8239 368.15 985.8
0.2762 358.15 976.4 1.0956 343.15 1003.9
0.2762 363.15 973.7 1.0956 348.15 1002.1
0.2762 368.15 971.0 1.0956 353.15 999.9
0.5508 328.15 999.4 1.0956 358.15 997.6
0.5508 333.15 996.4 1.0956 363.15 995.2
0.5508 338.15 993.8 1.0956 368.15 992.8
0.5508 343.15 990.6 1.3657 353.15 1006.5
0.5508 348.15 988.0 1.3657 358.15 1004.2
0.5508 353.15 985.9 1.3657 363.15 1001.9
0.5508 358.15 984.0 1.3657 368.15 999.6

Fig. 5.6 Mole fraction of

NTO (in natural log scale) as
a function of reciprocal of
temperature [28]
5.4 Properties 173

Fig. 5.7 Density of NTO

aqueous solutions as a
function of mole fraction x:
(filled circle) x = 0.002 762,
(filled square) x = 0.005 508,
(filled up triangle) x = 0.008
249, (filled down triangle)
x = 0.010 956, (filled
diamond) x = 0.013 657 [28]

Fig. 5.8 Solubility of NTO

in different concentrations of
nitric acid. Asterisk: 33.3%
HNO3; white diamond: 51.8%
HNO3; white circle: 61.0%
HNO3; white triangle: 69.1%
HNO3; filled circle: 80.5%
HNO3; filled diamond: water.
With permission from [4]

solid crystal from the solution). They correlated the mole fraction of NTO in the
solution according to the Shreader equation and evaluated the enthalpy of disso-
lutions during cooling and heating. Figures 5.8 and 5.9 show the solubility data at
different temperatures and concentrations of nitric acid. The results indicate that the
solubility increases with temperature as expected but is independent of
concentration.
174 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Fig. 5.9 Solubility of NTO

in nitric acid at different
temperatures. White triangle:
0 °C; white circle: 40 °C;
filled circle: 70 °C. With
permission from [4]

A number of researchers have used variations of the density function theories for
estimation of various properties of NTO. These include estimation of thermody-
namic properties [29], study of dimer and their energetics [30], study of NTO-water
interactions [31], study of NTO-ammonia interactions [32], and determination of
structural parameters.

5.4.3 Vapor Pressure of NTO

Sinditskii et al. [24] reported a limited number of experimental vapor pressure data
of NTO. They also calculated the NTO vapor pressure above the liquid and solid
phases from the heat of sublimation and taking into account the equality of the
vapor pressure above the liquid and solid phases at the melting point. Their
experimental and predicted vapor pressure data are given in Fig. 5.10. They pro-
posed following expressions for estimation of the vapor pressure.
The expression for calculating vapor pressure above the liquid is given by:

9914:4
ln P ¼ 14:82  ð5:4Þ
T

The expression for calculating vapor pressure above the solid is given by:

12984:4
ln P ¼ 20:48  ð5:5Þ
T
5.4 Properties 175

Fig. 5.10 Vapor pressure as a function of reciprocal temperature: 1 (points and line)—NTO
surface temperature, 2 (line)—vapor pressure above solid NTO, calculated from [8], 3 (points)—
initial vapor pressures of NTO in glass Bourdon gauge in experiments on NTO decomposition.
With permission from [24]

The calculated vapor pressure data from these two expressions are also given in
Fig. 5.10 for comparison.

5.5 Decomposition and Destruction

NTO can be destructed thermally, chemically by reacting it with other compounds,

photochemically, and through biological degradation. Generally, the thermal
decomposition process depends on temperature and pressure. However, other fac-
tors, such as phase change during decomposition, can alter the reaction path ways.
As a result, there are significant disagreements among researchers on the decom-
position reaction pathways and consequently on decomposition reaction rates.
Singh et al. [6] provided an excellent review of the thermolysis and mechanism of
NTO degradation. These decomposition pathways may be described as follows:
1. First step involving the thermal decomposition of NTO in which the C–NO2
bond breaks. This can happen by direct thermal activation [33, 34] or catalysis
by H atom transfer and loss of HONO [35].
176 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

2. Decomposition by producing CO2 and N2O [36, 37].

3. Decomposition by producing CO2 and N2 as gaseous products [38].
4. Decomposition by producing small amount of NO2 and HONO [38].
5. No production of NO2 or HONO [39].
Rothgery et al. [33] studied the thermal decomposition of NTO using DSC,
TGA-MS, and ARC. Based on the analysis of the decomposition products, they
suggested the following decomposition reaction:

1 1 1
C2 H2 N4 O3 ðsÞ ! C2 H3 OðsÞ þ H2 OðlÞ þ CO2 ðgÞ
6 6 3
1 3 4 1 7
þ N2 OðgÞ þ COðgÞ þ N2 ðgÞ þ NOðgÞ þ H2 ðgÞ
3 2 3 6 12
ð5:6Þ

Prabhakaran et al. [37] also studied the thermal decomposition of NTO using
TGA, DTA, IR, DSC, XRD and hot stage microscopy. The gaseous product
evolved during the decomposition was analyzed by IR. The compounds that were
identified in the gas phase included CO2, NO2, NO and N2O in larger amounts.
However, small amounts of CO and HCN were also detected.
Meredith et al. [40] reviewed the decomposition pathways that are proposed by
several researchers. Ostmark et al. [41, 42] suggested that the decomposition is
initiated through the loss of NO2 group, whereas Oxley et al. [35] noted that HONO
group was lost first (Figs. 5.11 and 5.12).

Fig. 5.11 NTO decomposition path suggested by Ostmark et al. [41]

Fig. 5.12 NTO decomposition path suggested by Oxley et al. [35]

5.5 Decomposition and Destruction 177

The decomposition pathways suggested by Beardall et al. [43] involved ring

opening as shown in Fig. 5.13.
A migration of nitro group followed by breakdown of the triazole ring, as shown
in Fig. 5.14, was the proposed decomposition pathway by Oxley et al. [44].
Menapace et al. [45] studied thermochemical and photochemical decomposition
of NTO and per deuterio NTO (NTO-d2) using electron paramagnetic resonance
(EPR) and high performance liquid chromatography (HPLC). They identified
several intermediates. The EPR data during photochemical decomposition of NTO
(NTO-d2)/acetone (acetone-d6) solutions at room temperature showed the presence
of NTO hydroxy nitroxide radicals. The NTO nitro group abstracts hydrogen atoms
from other NTO species and/or acetone forming these radicals. The reaction
pathway for the above concept in which NO2 group on NTO removes hydrogen
atoms from other NTO species and/or from acetone is shown in Fig. 5.15.
The decomposition of NTO can be accomplished from its aqueous and methanol
solutions. Oxley et al. [35] prepared solutions containing 4 wt% NTO in water and
in methanol and observed decompositions of NTO to be first order (up to 70%
conversion) in the temperature range of 240–280 °C. The decomposition rates were
generally faster than those of neat NTO. However, 50 mg of solid NTO decom-
posed four times faster than those of 100 mg NTO in water or in methanol solution.
The concentration of NTO in water or in methanol had negligible effect on
exhibited the decomposition rate at 260 °C. They also reported higher

Fig. 5.13 Decomposition of NTO through ring opening [43]

Fig. 5.14 Migration of NO2 group during decomposition of NTO [44]

178 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Fig. 5.15 Thermo and photochemical destruction of NTO

decomposition rate in the presence of either NO2, NH3, nitric acid, 50 wt%
ammonium nitrate or TO.
Interestingly, Zbarsky and Yudin [4] noted that NTO can also be decomposed in
100% nitric acid. They noted that at HNO3 concentrations of 98–100%, the
decomposition rate of N-NTO was higher than the rate of NTO formation.

5.5.1 Laser Induced Decomposition

In this method, solid samples of NTO were decomposed using 7 ns pulses from a
Nd:YAG laser (Quantel 660-50) applied normal to the surface of the pellet at
266 nm wavelength. The gaseous products released during decomposition are
detected using 118 nm single-photon ionization in a time-of-flight mass spec-
trometer [46]. The decomposition products are given in Table 5.7.

Table 5.7 Identification of products following laser-induced decomposition of NTO [46]

Observed (m/z) Proposed product
56 from 84?
71 CN3OH
83–85 C2N3OHx, x = 1–3
100 C2N3O2H2
101 C2N3O2H3
114 C2N4O2H2
130 NTO, C2N4O3H2
5.6 Nitration Kinetics 179

Fig. 5.16 Rate constant for

NTO formation at 25 °C
during nitration reaction.
Filled circle: from N-NTO;
white circle: from TO. With
permission from [4]

Table 5.8 Parameters of the Arrhenius equation for triazol-3-one nitration and NTO decompo-
sition. [4]
Reaction HNO3(%) A (s−1) E (kJ/mol)
Nitration 77.9 1.06e13 86.0
Nitration 89.27 1.13e12 76.5
Nitration 100 2.02e10 66.8
Destruction 100 6.89e12 78.5

5.6 Nitration Kinetics

Zbarsky and Yudin [4] studied the kinetics of nitration of N-NTO and TO to NTO.
The reaction followed first-order reaction in both the cases, and was found to be
dependent on both the concentration and temperature. Figure 5.16 shows the
dependence of rate constant on the concentration of HNO3 at 25 °C, and the
Arrhenius parameters are shown in Table 5.8. The Arrhenius equation is written as
follows:

E
ln k ¼ ln A  ð5:7Þ
RT

5.7 Decomposition Kinetic Rates

A number of studies focused on determining the decomposition rate of NTO. Most

of the researchers agreed on a first-order reaction rate. Kondrikov et al. [47] studied
thermal decomposition of NTO/3-5 in the temperature range of 473–533 K.
According to them, the overall decomposition reaction includes two distinct stages:
180 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Table 5.9 Arrhenius parameters reported by various researchers for first order decomposition rate
equation [47]
E (kcal/mol) ln A (S−1) T (°C) Method References
40.7 26.9 100–137 NO Chemiluminescence [49]
44.8 38.3 229–246 ITGA, Avrami-Erofeev Equation [37]
49.3 47.6 195–210 IR [37]
50.2 44.5 229–246 ITGAa [37]
78.1 67.0 220–280 HPLC [50]
87.5 ± 1.8 77.8b 225–245 HPLC [45]
120.4 112.1 266–280 DSC [51]
a
TGA data in Ref. [37] recalculated using second order rate model in Ref. [45]
b
Calculated from data given in Ref. [45]

the fast first-order decomposition and the subsequent autocatalytic reaction. Oxley
et al. [35] also reported a similar observation. The noted that the decomposition
reaction followed the first-order reaction up to 20% decomposition, and it was
autocatalytic after 50% conversion. The first order rate constants were calculated
using only the first 20% of the decomposition data. Arrhenius parameters reported
by various researchers for the first order reaction vary widely from each other. The
parameters are given in Table 5.9.
Vakul’skaya et al. [52] studied the tautomerism in their work on the
electro-chemical reduction of NTO. This study sheds light on the mechanism of
breakup of NTO and the radical formation. This study and their earlier studies [53,
54] should be useful in assessing the formation of compounds during NTO
degradation.
The manufacture of NTO contaminates various process streams during its
manufacturing and generates industrial wastes that need to be remediated before
discharging to the environment. Generally the recovery of NTO from these streams
is not economical due to its low concentration in the streams. The degradation of
NTO to less harmful chemicals is desirable. Besides thermal degradation, photo-
catalytic or biodegradation is a promising method. However it is important to assess
the products of such degradation as NTO involves the reduction of the nitro group,
which can be accompanied by the formation of toxic intermediates such as primary
amines and hydroxylamines.

5.8 Photocatalytic Degradation

Campion et al. [55] noted complete destruction of 150 mg/L of NTO in 3 h when
the solution was irradiated at 290 nm in the presence of 0.4 g/L of TiO2. They did
not observe significant photo-degradation of NTO in the absence of the catalyst.
They also applied Fenton reaction for degradation of NTO. In this reaction, a
5.8 Photocatalytic Degradation 181

Fig. 5.17 Mechanism for degradation of NTO by hydroxyl radical (OH.) as proposed by
Campion et al. [55]

mixture of a ferrous salt and hydrogen peroxide is used to degrade NTO. The
reaction mechanism hypothesized by Campion et al. [55] is shown in Fig. 5.17. The
Fenton reaction converted NTO to CO2, nitrates and probably ammonium ions. No
harmful intermediates were detected. A mixture of 1% H2O2 and 80 mg/L of FeSO4
degraded 150 mg/L NTO in 5 min.

5.9 Biodegradation of NTO

Selected microorganisms can degrade NTO from industrial waste streams. Campion
et al. [56] used a Bacillus licheniformis strain, isolated from the contaminated
solutions, to biodegradation NTO from a 15 g/l solution. The biodegradation process
proceeded through the nitro-reduction of NTO, followed by the ring cleavage of the
formed primary amine 5-amino-1,2,4-triazol-3-one (ATO). The final biodegraded
products included carbon dioxide (40%), urea and a polar compound, assumed to be
hydroxyurea. The assumed biodegradation path is shown in Fig. 5.18.
Sarlauskas et al. [57] studied the enzymatic reduction of NTO and ANTA rel-
evant to their cytotoxicity. Three mechanisms were studied that included oxyhe-
moglobin oxidation and single- and two-electron reduction by flavoenzymes. The

Fig. 5.18 Mechanism for biodegradation of NTO

182 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

direct oxidation converted oxyhemoglobin into methemoglobin. The single-electron

reduction involved flavoenzymes dehydrogenases-electrontransferases NADPH:
cytochrome P-450 reductase (P-450R) and ferredoxin: NADP+reductase
(FNR) that facilitated the free radical formation of nitroaromatic compounds and
their redox cycling. The two-electron reduction was carried out using rat NAD
(P)H: quinone oxidoreductase (DT-diaphorase, NQO1) and Enterobacter
cloacae NAD(P)H-: nitroreductase (NR). These enzymes reduce nitroaromatics
to the corresponding hydroxylamines.

5.10 Spectroscopic Analysis of NTO

The IR and Raman spectra are important tools for analysis and identification of
chemical compounds. Hiyoshi et al. [58] have obtained the IR and Raman spectra
and their assignments for NTO. These spectra are shown in Fig. 5.19 and wave-
lengths at which the peaks are observed are given in Table 5.10.
They also recorded Raman and IR spectra for NTO labeled with isotopes 15N,
13
C, and deuterium (D). The Ab initio calculations showed a close agreement
between the predicted values and experimental data.
Lewis et al. [59] obtained Stokes the Raman Spectra of NTO with 785 and
830 nm excitation. They used commercial samples obtained from the Federal

Fig. 5.19 IR and Raman spectra of NTO. a Raman spectrum was taken at 532 nm (*1 mW),
with resolution of 2–5 cm−1. b IR spectrum with a resolution of 1 cm−1 [58]
5.10 Spectroscopic Analysis of NTO 183

Table 5.10 Wave number of NTO for Raman and IR shifts for Fig. 5.19
Peak locations during Raman Peak locations in IR spectrum
shift (cm−1) (cm−1)
146 1009 sh 682 1340
192 1018 723 1355 sh
227 1104 731 1473
243 1190 750 sh 1541
347 1255 755 1546 sh
418 1286 762 sh 1590 vw
473 1332 787 1600
585 1360 829 1674 sh
600 1475 948 1691
691 1545 1006 1712
729 1548 sh 1018 3198
742 sh 1702 1109 3242
751 3192 1188
830 3241 1280
sh shoulder, vw very weak
All frequencies in cm−1

Bureau of Investigation to explore the suitability of this method for a rugged,

portable spectrometer that can be employed in the field. Based on their findings they
concluded that the Fourier transform (FT)-Raman is the preferred method for
fluorescence-free analysis of explosive materials in the laboratory, and 830 nm
excitation should be used for a field-portable instrument. The Raman spectra
obtained for several explosives including NTO at various excitations are given in
Fig. 5.20. It may be noted there are significant difference in these spectra that may
be utilized to distinguish NTO from other explosives. For NTO, the excitation at
785 and 830 nm did not make any difference between the two spectra.

5.11 Detonation Characteristics

Various detonation properties of NTO are provided in the following tables along
with the methods used for their determination.

5.11.1 Vacuum Stability Test

The vacuum stability test data showed NTO is fairly stable up to a temperature of
150 °C. The experiments were carried out in the temperature range of 100–150 °C
by a number of researchers. The maximum amount of gas evolved in this tem-
perature range was reported to be 1.45 cm3/g. The data are given in Table 5.11.
184 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Fig. 5.20 Raman spectra of HMX, NTO, and TCNB over the spectral range 200–2200 cm−1:
a HMX, 785 nm; b HMX, 830 nm; c NTO, 785 nm; d NTO, 830 nm; e TCNB, 785 nm and
f TCNB, 830 nm [59]

Table 5.11 Vacuum stability test data

Material Temperature (°C) Duration (h) Gas evolved (cm3/g) References
NTO 100 48 0.2 [60–63]
NTO 100 193 1.45 [61]
NTO 110 20 0.06 [65]
NTO 120 40 0.0 [7]
NTO 120 48 0.3 [60–62]
NTO 130 193 1.45 [64]
NTO 150 193 1.7 [64]
NTO 150 200 Stable [66, 67]

5.11.2 Impact Sensitiveness

The impact sensitiveness of NTO is shown in Table 5.12. The data indicates that
NTO is less sensitive compare to other explosives such as RDX, HMX, and PETN.
The sensitivity of NTO for impact is the subject of a study by Agrawal et al. [68]
who used high-speed photographic technique.
5.11 Detonation Characteristics 185

Table 5.12 Results from impact sensitivity tests

Test method Result References
Julius Peter apparatus results (J) 22 [64]
Rotter impact (Figure of sensitivitya) 80–90 [7]
Rotter impact (Figure of sensitivityb) 316 [63, 69]
US drop impact type 12 (cm) >280 [60–62, 70]
US drop impact type 12B (cm) 293 [60, 61, 71]
US impact sensitivity H50 (cm) 92 [72, 73]
30 kg Hammer, Non-reaction height (m) >4 [64, 74, 75]
a
RDX Reference of [80] used
b
RDX Reference of [100] used

Table 5.13 BAM friction sensitivity test results

Researchers Test Data References
SNPE data (N) >353 [74, 75]
South Africa data (N) >353 [63, 69]
SNPE data (N) >353 [64]

5.11.3 Friction Sensitivity Tests

The tests were carried out using BAM Friction test protocols by two laboratories.
Both of them reported similar values. The BAM friction test data for NTO showed
it to be less sensitive to friction compared to PETN, RDX, and HMX and similar to
TNT and TATB. The data for NTO is shown in Table 5.13.

5.11.4 Electrostatic Discharge Sensitivity

The sensitivity of NTO to electrostatic discharge has been measured in several

laboratories. The data are given in Table 5.14, which indicate that NTO is com-
parable to RDX and TNT.

5.11.5 Thermal Sensitivity

Ignition temperature is an important factor for explosives as it determines the

storage and handling of the materials. NTO was found to ignite at a much higher
temperature than PETN, RDX, and HMX. It is almost the same as TNT, but it is
more sensitive than TATB. The temperature of ignition of NTO measured by
various groups is given in Table 5.15.
186 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Table 5.14 Electrostatic sensitivity test results

Research groups Test results References
Australian data (J) >4.5 [3]
South Africa data (J) 15 [63, 69]
SNPE data (J) >0.726 [76, 77]
Czech data (J) [96] 8.98 [78]
US data (3 mil, J) 0.91 [60–62]
US data (10 ml, J) 3.40 [60, 64]

Table 5.15 Ignition temperature

Research groups Temperature Values (°C) References
SNPE Temperature of ignition 280 [64, 74, 75]
MRL Temperature of ignition 258 [7]
Henkin critical temperature 237 [60–62, 71]
Henkin critical temperature 216 [79]

5.11.6 Shock Sensitivity

Becuwe and Delclos [64] measured the shock sensitivity of NTO using a Large
Scale Gap Test. They used a number of 0.19 mm polymethylmethacrylate attenu-
ation discs to determine the shock sensitivity of NTO and several other explosives.
The shock sensitivity of NTO was 260. The results indicated that NTO is less
sensitive compared to PETN, RDX, and HMX and more sensitive than TATB.

5.12 Detonation Velocity

The detonation velocity report by various groups for NTO is given in Table 5.16.
The data showed that the detonation velocity of NTO was less than that of RDX and
HMX, but it was higher than TATB, whereas it has a similar detonation velocity as
PETN.

Table 5.16 Detonation velocity of NTO

Research group Detonation velocity (m/s) References
French data 8510 [64, 74, 75]
Czech data 8590 [80]
American data 8560 [72]
5.12 Detonation Velocity 187

Doherty and Simpson [72] also used the CHETA software to predict the deto-
nation velocity, whereas Becuwe and Delclos [75] used the Kamlet and Jacobs
method [81]. Both the groups reported good agreement with the experimental data.

5.13 Detonation Pressure

Plate dent tests were used to determine the detonation pressure of NTO [60–62].
Tests were conducted with NTO charges of different Theoretical Maximum Density
(TMD). The BKW equation of state was used for prediction of detonation pres-
sures. The experimental and calculated detonation pressures for these charges are
given in Table 5.17.

5.14 Formulations

A low sensitive mixture with high detonation properties is highly desirable. The
low sensitivity of NTO to various mechanical stimuli makes it an ideal material for
explosive formulation with other high performance explosives such an RDX, HMX,
and TNT. A number of NTO based formulations have been proposed by various
groups. They are summarized in Table 5.18. Following the formulation of the
explosives, their detonation properties were measured and also predicted using
known software such as CHETA. These detonation properties are listed in
Tables 5.19 and 5.20.
Based on both experimental and estimated data it appears that NTO based
explosive formulation has potential to meet the needs of the ADF and Insensitive
Munitions. Also, these formulations can improve storage, handling, and trans-
portation of them. However, large scale charges should be tested to confirm their
performance and response to various stimuli.

Table 5.17 Detonation pressure for NTO at various charge densities. Both measured and
calculated values from BKW equation of state are reported [60–62]
Charge density (g/cm3) Charge diameter (cm) Pressure (GPa)
Measure Calculated
1.93 (100% TMD) – – 34.9
1.781 (92.2% TMD) 4.13 27.8 28.4
1.853 (96% TMD) 4.13 26.0 31.6
1.782 (92.3% TMD) 2.54 24.0 28.4
1.855 (96.1% TMD) 2.54 Failed 31.6
1.759 (91.1% TMD) 1.27 25.0 27.1
1.824 (94.5% TMD) 1.27 Failed –
Table 5.18 Composition of various formulations using NTO
188

Designation NTO TNT RDX HMX AP Aluminum Additives Energetic Plasticizer Binder References
TNTO 50 50 – – [82]
TNTO/D2 52 42 – 6 (D2 Wax) [82]
TNTO/OD2 52 42 – 6 (OD2 Wax) [82]
TNTO O 38 40 16 (Aluminium) 6 (D2 Wax) [82]
TNTO I 42 34 19 (Aluminium) 5 (D2Wax) [82]
TNTO II 42 32 19 (Aluminium) 7 (D2 Wax) [82]
TNTO III 42 30 19 (Aluminium) 9 (D2Wax) [82]
AFX-644 (TNTO IV) 40 30 20 (Aluminium) 10 (D2Wax) [82]
AFX-645 48 32 12 (Aluminium) 8 (1-800 Ganex) [83]
GD-1 65 35 – – [84, 85]
GD-2 35 35 30 (HMX) – [84, 85]
South African 1 40 60 – – [63, 69]
South African 2 25 50 25 (RDX) – [63, 69]
B 2214 72 – 12 – – 16 (HTPB) [64, 86–92]
B 2225 # # – - – 14.5 (HTPB) [76]
B 2233 31 – 6 28 10 15 (HTPB) [93]
B 2245 8 12 – 43 25 12 (HTPB) [87]
B 2248 46 – 42 - – 12 (HTPB) [87, 92, 94]
B 3017 74 – – - – 26 (Energetic) [90, 94]
B 3021 50 25 – - – 25 (Energetic) [87, 90, 94, 95]
PBXW-121 63 10 – - 15 12 (HTPB) [96]
PBXW-122 47 5 – 20 15 13 (HTPB) [97, 98]
PBXW-124 27 20 – 20 20 13 (HTPB) [98]
PBXW-125 22 20 – 20 26 12 (HTPB) [98]
(continued)
5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)
Table 5.18 (continued)
5.14

Designation NTO TNT RDX HMX AP Aluminum Additives Energetic Plasticizer Binder References
PBXW-126 22 20 – 20 26 12 (Polyurethane) [98, 99]
CPX 412 50 30 – 10 (K10) 10 (PolyNIMMO) [100]
CPX 413 45 35 – 10 (K10) 10 (PolyNIMMO) [92, 100, 101]
Formulations

CPX 450 40 20 20 (Aluminium) 10 (K10) 10 (PolyNIMMO) [102]

CPX 455 40 20 20 (Aluminium) 10 (K10) 10 (PolyNIMMO) [102]
CPX 458 30 30 20 (Aluminium) 10 (K10) 10 (PolyNIMMO) [102]
CPX 459 20 40 20 (Aluminium) 10 (K10) 10 (PolyNIMMO) [102]
CPX 460 27.5 27.5 25 (Aluminium) 10 (K10) 10 (PolyNIMMO) [102]
GD-3 12 12 – – 16 (HTPB) [84, 85]
GD-5 43 43 – 10 (BDNPA/F) 7 (PGA) [84, 85]
HX 310 47 47 10 NG – 18 (HTPB) [92]
CHN-037 – – 24 (GAP) [103]
GD-9 47.5 47.5 2.5 (Cariflex 1101) [84, 85]
GD-10 48.8 48.8 2.4 (Cariflex 1101) [84, 85]
GD-11 48 48 4 (Cariflex 1101) [84, 85]
GD-12 48 48 4 (Cariflex 1101) [84, 85]
GD-13 48 48 2/2 (Hy Temp/DOA) [84, 85]
GD-14 48 48 4 (Estane) [84, 85]
French 1 55.5 37 7/0.5 (KelF/Graphite) [74, 86]
189
Table 5.19 Modification using surfactants
190

Formulation Density Velocity of Critical Volume of gas H50% BAM Electrostatic Impact References
(g/cm3) detonation diameter evolved (cm3/ (cm) friction discharge (J) sensitivity
(m/s) (mm) g) (N) (F of I)
TNTO 1.74 7340 16 0.09 91.5 41.2 0.062 [82, 83, 104]
TNTO/D2 1.54 6470 <25 0.29 >200.5 53.0 0.062 [82, 83, 104]
TNTO/OD2 1.61 6900 <25 – >200.5 – – [82, 83, 104]
TNTO O 0.21 >200.5 41.2 0.040 [82, 83, 104]
TNTO I 1.76 6670 25–51 – >200.5 – – [82, 83, 104]
TNTO II 1.74 6840 32–35 0.35 >200.5 53.0 0.040 [82, 83, 104]
TNTO III >200.5 – – [82, 83, 104]
AFX-644 1.70 6960 41–43 0.37 >200.5 60.8 0.040 [82, 83, 104]
GD-1 1.750 7510 – – – [84, 85]
GD-2 1.761 7870 – – – [84, 85]
South Africa >353 170 276 [63, 69]
Sample: NTO/TNT
(40/60)
South Africa >353 170 186 [63, 69]
Sample: NTO/
RDX/TNT
(25/25/50)
B 2214 1.63 7495 35 [64, 87, 89, 90, 92]
(confined)
65
(unconfined)
B 2245 1.81 5150 – [87]
B 2248 1.70 8130 11 [92]
B 3017 1.75 7780 10–15 [88, 90]
5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

(continued)
Table 5.19 (continued)
5.14

Formulation Density Velocity of Critical Volume of gas H50% BAM Electrostatic Impact References
(g/cm3) detonation diameter evolved (cm3/ (cm) friction discharge (J) sensitivity
(m/s) (mm) g) (N) (F of I)
B 3021 1.77 8100 <10 [88, 90]
Formulations

GD-3 – 6838 – [84, 85]

GD-5 – 8035 – [84, 85]
HX 310 1.57 7750 <10 [92]
CPX 412 1.66 7200 – [100]
CPX 413 1.74 8150 10 [92, 100]
CPX 450 1.85 7762 – [102]
CPX 458 1.85 7676 – [102]
CPX 459 1.86 7761 – [102]
CPX 460 1.88 6420 – [102]
GD-9 8280 192 0.320 [84, 85]
GD-10 8352 192 0.180 [84, 85]
GD-11 8187 – – [84, 85]
GD-12 8174 252 – [84, 85]
GD-13 8275 252 – [84, 85]
GD-14 8268 213 – [84, 85]
191
Table 5.20 Materials, friction sensitivity tests
192

Type of tests Materials References

NTO PETN HMX RDX TNT TATB
Impact sensitivity tests
Julius Peter apparatus CSI test (J) 22 – 5 4.5 30 – [12]
Rotter impact (Figure of insensitivity) 80–90 40 60 80 106–115 – [3]
Rotter impact (Figure of insensitivity) 316 – – 100 221 – [84, 86]
US drop impact type 12 (cm) >280 12 26 22 148 >320 [9–11, 91]
US drop impact type 12B (cm) 293 16–32 28–38 41 – – [9, 10, 92]
US impact sensitivity H50 (cm) 92 13–16 32 28 80 >177 [89, 90]
30 kg Hammer: non reaction height (m) >4 0.5 0.5 1 >4 >4 [12, 93, 94]
BAM friction sensitivity tests
SNPE data >353 125 175 133 *353 >353 [93, 94]
South African data (N) >353 – – 247 >353 – [84, 86]
SNPE data >353 – 100 113–174 300 – [12]
Electrostatic discharge sensitivity
Australian data >4.5 4.5 – 3
South African data (J) 15 0.225 0.138 [85, 86]
SNPE data (J) >0.726 – – [5, 6]
Czech data (J) 8.98 2.49 6.85 [96]
US data (3 mil, J) 0.91 0.22 – [9, 11]
US data (10 mil, J) 3.40 0.55 – [9, 11]
Thermal sensitivity ignition tests
Ignition temp (SNPE), C 280 190 270 220 290 350 [12, 93, 94]
Ignition temp (MRL), C 258 149 – 216 240 – [3]
Henkin critical temp, C 237 175 210 219.6 261 – [9–11, 92]
Henkin critical temp, C 216 – – – – – [62]
5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

(continued)
Table 5.20 (continued)
5.14

Type of tests Materials References

NTO PETN HMX RDX TNT TATB
Shock sensitivity test
SNPE results (No. of discs) 260 330 305 310 190 [12, 93, 94]
Formulations

Detonation velocity
French data (m/s) 8510 8500 9100 8850 8000 [12, 93, 94]
Czech data (m/s) 8590 8930 9130 8890 – [96]
American data (m/s) 8560 – 9300 8930 8100 [89]
193
194 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Trzcinski and Szymanczyk [105] determined detonation characteristics of sev-

eral mixtures containing NTO with TNT, RDX, and HMX. Their comparison of the
experimental data with CHEETAH predictions reveals good agreement. Results
show that as the percentage of NTO increases, detonation velocities decrease, and
with lower percentage TNT detonation velocity increases.

5.15 Toxicity

The synthesis of NTO involves release of significant amount of NTO into the
atmosphere as wastewater that generally contains 10–15 g/L of NTO. Therefore,
understanding of NTO’s toxicological effect is of great interest. London and Smith
[106] at Los Alamos National Laboratories conducted the following tests to provide
a preliminary assessment of its toxicity: (1) acute oral toxicity, (2) primary skin
irritation, (3) skin sensitization, and (4) eye (conjunctival) instillation. The fol-
lowing conclusions were made from the preliminary tests. The LD50 values for
NTO for mice and rats when administered orally are found to be are greater than
5 g/kg that is considered to be slightly toxic or practically non-toxic in both species.
It is a mild irritant to rabbit skin. NTO does not induce sensitization in the intra-
dermal guinea pig assay and the rabbit eye test is considered negative; however,
transient conjunctival and corneal irritation did result from the NTO exposure in
several animals and one developed a chronic anterior uveitis.
Sarlauskas et al. [107] studied the mechanisms of toxicity of NTO following
their reactions with the single-electron transferring flavoenzymes NADPH: cyto-
chrome P-450 reductase and ferredoxin: NADP+reductase, two-electron transfer-
ring flavoenzymes mammalian NAD(P)H: quinone oxidoreductase
(DT-diaphorase), and Enterobacter cloacae NAD(P)H: nitroreductase, and their
reactions with oxyhemoglobin. The results show NTO to be mildly toxic.
Reddy et al. [108] investigated the genotoxicity of NTO, using several geno-
toxicity tests, including the Ames test, Chinese Hamster Ovary (CHO) cell chro-
mosome aberration test, L5178Y TK+/− mouse lymphoma mutagenesis test and rat
micronucleus test. These studies reveal that NTO was not genotoxic in either in vitro
or in vivo tests and suggest a low risk of genetic hazards associated with exposure.

5.16 Detection

The general technique for detecting NTO appears to be through the detection of
decomposition products. This procedure was adopted by Tabrizchi and Ilbeigi
[109], and by Garland et al. [46]. An ion mobility spectrometer (IMS) was used by
Tabrizchi and Ilbeigi [109] to detect and identify NTO from the gas phase. In
Fig. 5.21 the positive ion mobility spectrum of NTO is shown along with the
background spectrum and the NO2 spectrum. Although the decomposition products
of NTO in the temperature range of 180–250 °C contain CO2, CO, NO2, NO,
5.16 Detection 195

Fig. 5.21 Detection of decomposition products by an ion mobility spectrometer [46]

Fig. 5.22 Mass spectrum of

the products from laser
induced decomposition of
NTO in a time-of-flight mass
spectrometer. Laser fluence:
380 mJ/cm2; Delay between
the decomposition and
ionization lasers: 55 ls

HONO, H2O, N2, CH2O, and N2O, only NO, NO2, and HONO increased the NO+
peak. This NO+ peak may be used to identify NTO.
As discussed earlier, Garland et al. [46] studied laser-induced decomposition of
NTO. The decomposition products are given earlier in Table 5.7. Following
decomposition, they used a Time-of-Flight mass spectrometry to detect the
decomposition products. The spectrum is shown in Fig. 5.22. The large peak at
130 m/z is for NTO/C2N4O3H2 which can be used to detect NTO directly.
196 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Oehrle [110] outlines a capillary electrophoretic method for the analysis of NTO
in presence of several other explosives. Oehrle [110] claims capillary elec-
trophoresis (CE) is better than HPLC technique particularly in the presence of
explosives other than TNT. CE is found to have high resolution and speed in the
analysis of both neutral compounds and ions whereas HPLC methods for analyzing
NTO mixtures give reasonable results for NTO and TNT. Figure 5.23 shows the
number compounds that could be analyzed by CE.
Mass spectra of NTO can be used to detect NTO as it showed distinct pattern
during thermal decomposition. The spectrum is shown in Fig. 5.24. According to

Fig. 5.23 Electropherogram of NTO in the presence of 14 other nitramine and nitroaromatic
explosives. Peaks: 1 = HMX (10 mg/l); 2 = RDX (10 mg/l); 3 = TNB (10 mg/l); 4 = DNB
(10 mg/l); 5 = NB (10 mg/l); 6 = TNT (l0 mg/l); 7 = Tetryl (10 mg/l); 8 = NTO (15 mg/l);
9 = 2,4 DNT (10 mg/l); 10 = 2,6-DNT; 11 = 3-NT; 12 = 4-NT; 13 = 3-NT; 14 = 2-Am-4,6-
DNT [10 mg/l]; and 15 = 4-Am-2,6-DNT (10 mg/l)

Fig. 5.24 Fragmentation of NTO during mass spectrometry

5.16 Detection 197

Fig. 5.25 Fragmentation of NTO during mass spectrometry

Ostmark, three distinct zone was observed: the molecular ion (m/z 130) for
undecomposed NTO, the azole ring (m/z 83, 84, and 85), and the azole ring
fragmentation (m/z 41, 42, 43, and 44). The fragmentation pattern is given in
Fig. 5.25. The fragmentation pattern can be used to detect NTO from its mixtures.

5.17 Conclusion

NTO has attracted attention as a possible replacement for RDX and similar ener-
getic materials in various military propellants and explosives. Large scale pro-
duction of NTO will lead to environmental concerns, but economical degradation
methods are not available. In addition there are no cost effective detection tech-
niques. Both detection and degradation need various physical and chemical prop-
erties which are lacking.

References

1. von M Manchot, Noll R (1905) Ueber Derivate des Triazols (On the derivatives of triazols).
Justus Liebigs Annalen de Chemie 343:1–27
2. Chipen GI, Bokalder RP, Grinshtein VY (1966) 1, 2, 4-triazol-3-one and its nitro and amino
derivatives. Chem Heterocycl Compds 2(1):110–116
3. Smith MW, Cliff MD (1999) NTO-based formulations: a technology review.
DSTO-TR-0796
198 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

4. Zbarsky VL, Yudin NV (2005) Kinetics of the synthesis of NTO in nitric acid. Propellants
Explos Pyrotech 30(4):298–302
5. Mukundan T, Purandare GN, Nair JK, Pansare SM, Sinha RK, Singh H (2002) Explosive
nitrotriazolone formulates. Defence Sci J 52(2):127–133
6. Singh G, Kapoor IPS, Tiwari SK, Felix PS (2001) Studies on energetic compounds part 16
chemistry and decomposition mechanisms of 5-nitro-2,4dihydro-3H-1,2,4-triazole-3-one
(NTO). J Hazard Mater B 81:67–82
7. Spears RJ, Louve CN, Wolfson MG (1989) A preliminary assessment of NTO as an
insensitive high explosive. MRL-TR-89-19 DSTO
8. Li J (1998) One-pot synthesis of 3-nitro-1,2,4-triazol-5-one. Beijing Ligong Dexue Xuebao
18(4):518–519
9. Kim HS, Goh EM, Park BS (2003) Preparation method of 3-nitro-1,2,4-triazol-5-one by a
process minimizing heat generation during crystallization. US Patent 6583293
10. Chipen GI, Bokalder RP, Grinshtein VYa (1966) 1,2,4-triazol-3-one and its nitro and amino
derivatives. Chem Heterocycl Compd 2(1):79–83
11. Lee K-Y, Coburn MD (1985) 3-nitro-1,2,4-triazol-5-one, a less sensitive explosive. Los
Alamos National Laboratory Report No LA-10302-MS
12. Kroger CF, Miethchen R, Frank H, Soemer M, Pilz S (1969) 1, 2, 4-triazoles. 17. nitration
and bromination of 1, 2, 4-triazolones. chemische berichte 102(3):755
13. Katritzky R, Ogretir C (1982) The kinetic nitration and basicity of 1,2,4-triazol-5-ones. Chim
Acta Tureica 10:137–146
14. Yang G, Nie F, Li J, Guo Q, Qiao Z (2007) Preparation and characterization of nano-NTO
explosive. J Energ Mater 25:35–47
15. Wang D, Zhang J, Wang J, Wang B (2007) Preparation of nanometer NTO by W/O
microemulsion. Huogongpin 14(1):9–11
16. Ma H, Song J, Hu R (2006) A review on 3-nitro-1, 2, 4-triazol-5-one and its salts.
Huozhayao Xuebao 29(6):9–15
17. Lee KY, Gilardi R (1993) Structure and properties of energetic materials. Material Research
Society, Pittsberg, PA, p 237; Lee KY, Gilardi R (1993) Mater Res Soc Symp Proc 296:237
18. Bolotina N, Kirschbaum K, Pinkerton AA, Alan A (2005) Energetic materials: a-NTO
crystallizes as a four component triclinic twin. Acta Crystallogr Struct Sci B 61(5):577–584
19. Bolotina NB, Zhurova EA, Pinkerton AA (2003) crystal structure. J Appl Cryst 36:280–285
20. Yi J-H, Zhao F-Q, Gao H-X, Xu S-Y, Wang M-C, Hu R-Z (2008) Preparation,
characterization, non-isothermal reaction kinetics, thermodynamic properties, and safety
performances of high nitrogen compound: Hydrazine 3-nitro-1,2,4-triazol-5-one complex.
J Hazard Mater 153:261–268
21. Badgujar DM, Talawar MB, Asthana SN, Mahulikar PP (2008) Advances in science and
technology of modern energetic materials: an overview. J Hazard Mater 151:289–305
22. Calculated using Advanced Chemistry Development (ACD/Labs) Software V814 for Solaris
1994–2008 (ACD/Labs)
23. Toghiani RK, Toghiani H, Maloney SW, Boddu VM (2008) Prediction of physicochemical
properties of energetic materials. Fluid Phase Equilib 264(1–2):86–92
24. Sinditskii VP, Smirnov SP, Yu EV (2007) Thermal decomposition of NTO: an explanation
of the high activation energy. Propellants, Explos, Pyrotech 32(4):277–287
25. Volk F, Bathelt H (2002) Performance parameters of explosives: equilibrium and
non-equilibrium reactions. Propellants, Explos, Pyrotech 27:136–141
26. Osmont A, Catoire L, Gökalp I, Yang V (2007) Ab initio quantum chemical predictions of
enthalpies of formation, heat capacities, and entropies of gas-phase energetic compounds.
Combust Flame 151:262–273
27. Li ZN, Ma HX, Song JR, Zhao FQ, Xu KZ, Hu RZ (2008) Specific heat capacity,
thermodynamic properties and adiabatic time-to-explosion of NTO. Chin J Explos
Propellants No 3
References 199

28. Kim KJ, Kim MJ, Lee JM, Kim SH, Kim HS, Park BS (1998) Solubility, density, and
metastable zone width of the 3-nitro-1,2,4-triazol-5-one + water system. J Chem Eng Data
43:65–68
29. Liu MH, Chen C, Hong YS, Liu CW (2005) Polyparametric modification equation for
estimating thermodynamic properties of energetic nitro compounds. Theor Chem Acc 113
(1):35–41
30. Xiao HM, Ju XH, Xu LN, Fang GY (2004) A density-functional theory investigation of
3-nitro-1,2,4-triazole-5-one dimers and crystal. J Chem Phys 121:12523–12531
31. Fang GY, Xu LN, Hu XG, Li XH, Xiao HM, Ju XH, Gong XD (2005) Density functional
theory study of the interaction between 3-nitro-1, 2, 4-triazol-5-one and water. J Theor
Comput Chem 4(3):849–856
32. Fang GY, Xu LN, Hu XG, Li XH (2005) Density functional theory study of the interaction
between 3-nitro-1, 2, 4-triazol-5-one and ammonia. Int J Quantum Chem 105(2):148–153
33. Rothgery EF, Audette DE, Wedlich RC, Csejka DA (1991) The study of the thermal
decomposition of 3-nitro-1,2,4-triazol-5-one (NTO) by DSC, TGA-MS, and ARC.
Thermochim Acta 185(2):235–243
34. Brill TB, Brush PJ, Patil DG (1993) Thermal decomposition of energetic materials 58.
Chemistry of ammonium nitrate and ammonium dinitramide near the burning surface
temperature. Combust Flame 92(1–2):178–186
35. Oxley JC, Smith JL, Zhou Z, McKenney RL (1995) Thermal decomposition studies on NTO
and NTO/TNT. J Phys Chem 99:10383–10391
36. Garland NL, Ladouceur HD, Nelson HH (1997) Laser-induced decomposition of NTO.
J Phys Chem A 101:8508–8512
37. Prabhakaran KV, Naidu SR, Kurian EM (1994) XRD, spectroscopic and thermal analysis
studies on 3-nitro-l,2,4-triazol-5-one. Thermochim Acta 241:199–212
38. Ostmark H, Bergman H, Aquist G, Langlet A, Persson B Decomposition of NTO: some
initial observations. In: Proceedings of the 16th international pyrotechnics seminar,
Jönköping, Sweden, p 874
39. Williams GK, Palopoli SF, Brill TB (1994) Thermal decomposition of energetic materials
65. Conversion of insensitive explosives (NTO, ANTA) and related compounds to
polymeric melon-like cyclic azine burn-rate suppressants. Combust Flame 98:197
40. Meredith C, Russell TP, Mowrey RC, McDonald JR (1998) Decomposition of
5-nitro-2,3-dihydro-3H-1,2,4-triazol-3-one (NTO): energetics associated with several pro-
posed initiation routes. J Phys Chem A 102:471–477
41. Ostmark H (Nov 1991) Thermal decomposition of NTO FOA. Report D-2017823 National
Defense Research Establishment: Sundbyberg, Sweden
42. Ostmark H, Bergman H, Åqvist G (1993) The chemistry of 3-mtro-1,2,4-triazol-5-one
(NTO): thermal decomposition. Thermochim Acta 213(1):165–175
43. Beardall DJ, Botcher TR, Wight CA (1996) Explosive thermal decomposition mechanism of
NTO. Mater Res Soc Symp Proc 418:379–384
44. Oxley JC, Smith JL, Yeager KE, Rogers E, Dong XX (1996) NTO decomposition studies.
In: Brill TB, Russell TP, Tao WC, Wardle RB (eds) MRS decomposition, combustion, &
detonation chemistry of energetic materials 418:135. https://doi.org/10.1557/PROC-418-135
45. Menapace JA, Marlin JE, Bruss DR, Dascher RV (1991) Photochemical and thermochemical
decomposition of 3-nitro-1,2,4-triazol-5-one and predeuterio-3-nitro-1,2,4-triazol-5-one in
neat and mixed systems. J Phys Chem 95(14):5509–5517
46. Garland NL, Ladouceur HD, Nelson HH (1997) Laser-induced decomposition of NTO.
J Phys Chem A 101:8508–8512
47. Kondrikov BN, Smirnov P, Minakin AV, Doherty RM (2004) Chemical kinetics of the
thermal decomposition of NTO. Propellants, Explos, Pyrotech 29(1):27–33
48. Brill TB, Gongwer PE, Williams GK (1994) Thermal decomposition of energetic materials
66 kinetic compensation effects in HMX, RDX, NTO. J Phys Chem 98:12242–12247
200 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

49. Ostmark H, Bergman H, Aqrist G, Langlet A, Persson B (June 1991) Decomposition of

NTO: some initial observations. In: Sixteenth international pyrotechnics seminar, Jonkijping,
Sweden, pp 874–886
50. Oxley JC, Zhou Z, Smith JL, McKenney RL (March 21–24 1994) Thermal decomposition
studies on NTO and NTO/TNT. In: Proceedings of the ADPA international symposium on
energetic materials technology international symposium on energetic materials technology,
meeting #450, Florida, USA, 21–24 March, American Defense Preparedness Association,
pp 155–165
51. Yi X, Hu R, Wang X, Fu X, Zhu C (1991) Thermal behaviour of 3-nitro-1,2,4-triazol-5-one
and its salts. Thermochim Acta 189:283–296
52. Vakul’skaya TI, Titova, IA, Dolgushin, GV, Loppyrev, VA (2005) Free radicals in various
C-amination reactions of 1-methyl-4-nitropyrazole. Magnetic Resonance in Chemistry
43:1023–1027
53. Vakul’skaya TI, Rakhmatulina TN, Pevzner MS, Kofman TP, Lopyrev VA (1987) EPR and
polarography of nitroazoles. 6. 3-Nitro-1,2,4-triazoles. Chem Heterocycl Comp 23(3):287–291
54. Lopyrev VA, Larina LI, Sosonkin IM, Vakul’skaya TI, Kalb GL, Shibanova EF (1985) EPR
and polarography of nitroazoles. 5. First step in the electrochemical reduction of
2-substituted 5(6)-nitrobenzimidazole using a rotating platinum ring-disk electrode. Chem
Heterocycl Comp 21:688 (Translated from Khim. Geterotsikl Soedin 21(6):827–832 (June
1985); Chemosphere 38(7):1561–1570)
55. Campion LL, Giannotti C, Ouazzani J (1999) Photocatalytic degradation of
5-nitro-1,2,4-triazol-3-one NTO in aqueous solution of TiO2. Comparison with Fenton
oxidation. Chemosphere 38(7):1561–1570
56. Campion LL, Vandais A, Ouazzani J (1999) Microbial remediation of NTO in aqueous
industrial wastes FEMS. Microbiol Lett 176:197–203
57. Sarlauskas J, Nemeikaite-Ceniene A, Anusevicius Z, Miseviciene L, Maroziene A,
Markevicius A, Cenas N, Naturforsch Z (2004) Enzymatic redox properties of novel
nitrotriazole explosives implications for their toxicity. 59(5–6):399–404
58. Hiyoshi RI, Kohno Y, Nakamura J (2004) Vibrational assignment of energetic material
5-Nitro-2,4-dihydro-1,2,4-triazol-3-one (NTO) with labeled isomers. J Phys Chem A
108:5915–5920
59. Lewis ML, Lewis IR, Griffiths PR (2005) Raman spectrometry of explosives with a
no-moving-parts fiber coupled spectrometer: a comparison of excitation wavelength. Vib
Spectrosc 38:17–28
60. Lee K-Y, Coburn MD (1985) 3-nitro-l,2,4-triazol-5-one, a less sensitive explosive.
LA-10302-MS Los Alamos National Laboratory Los Alamos, USA
61. Lee K-Y, Coburn MD (1988) 3-nitro-l,2,4-triazol-5-one, a less sensitive explosive. US
Patent 4,733,610
62. Lee K-Y, Chapman LB, Coburn MD (1987) 3-nitro-l,2,4 triazol-5-one, a less sensitive
explosive. J Energ Mater 5:27–33
63. Barnard PW, Fouche FC, Bezuidenhout HC (1997) Less sensitive TNT based formulations.
In: Australasian explosive ordnance symposium (Parari ’97) 3rd Canberra, Australia, 12–14
64. Becuwe A, Delclos A (1993) Low-sensitivity explosive compounds for low vulnerability
warheads. Propellants, Explos, Pyrotech 18:1–10
65. Marecek P, Pokornä J, Vävra P (1998) A study of some insensitive explosives. In:
International conference of ICT 29th Karlsruhe Federal Republic of Germany 30 June–3
July, Fraunhofer-Institut Für Chemische Technologie Berghausen, Bundesrepublik,
Deutschland 52(l):52(5)
66. Graham KJ, Williams EM, Lynch RD, Floyd TG, Struck SR (1994) Reducing the sensitivity
of high-performance warhead fills. In: Insensitive munitions technology symposium,
meeting #471, Virginia, USA 6–9 June, American Defense Preparedness Association,
pp 541–563
67. Sanderson AJ (1997) A draft sheet for 3-nitro-l,2,4-triazol-5-one. The NIMIC Coordinated
Characterisation Program
References 201

68. Agrawal JP, Walley SM, Field JE (1998) A high-speed photographic study of the impact
initiation of hexanitro hexaaza isowurtzitane and nitrotriazolone. Combus Flame 112:62–72
69. Fouche FC, van Schalkwyk GC (1996) TNT-based insensitive munitions. In: International
conference of ICT 27th Karlsruhe Federal Republic of Germany, 25–28 June,
Fraunhofer-Institut Für Chemische Technologie Berghausen, Bundesrepublik, Deutschland
69(1):69(12)
70. Hall TN, Holden JR (1988) Navy explosives handbook explosive effects and properties, part
III properties of explosives and explosive compositions. NSWC MP 88-116 White Oak
Laboratory Naval Surface Warfare Centre, Maryland, USA
71. Popolato A, Forsberg HC, Gritzo LA (1957). In: Popolato A (ed) Handbook of properties of
some explosives of interest to GMX-division. May 24, 1957 (CRD)
72. Doherty RM, Simpson RL (1997) A comparative evaluation of several insensitive high
explosives. In: International conference of ICT 28th Karlsruhe Federal Republic of
Germany, 24–27 June, Fraunhofer-Institut Für Chemische Technologie Berghausen,
Bundesrepublik, Deutschland 32(l):32(23)
73. Dobratz BM (1981) LLNL explosives handbook properties of chemical explosives and
explosive simulants. Lawrence Livermore National Laboratory, California, USA
74. Becuwe A, Delclos A (1987) L’Oxynitrotriazole et son Utilisation et tant Qu’Explosif
Insensible. In: International conference of ICT 18th Karlsruhe Federal Republic of Germany,
1–3 July, Fraunhofer-Institut Für Chemische Technologie Berghausen, Bundesrepublik,
Deutschland 27(1):27(14)
75. Becuwe A, Delclos A (1987) Oxynitrotriazole and it’s use as insensitive explosive. In:
Jing D (ed) International symposium on pyrotechnics and explosives 1st Beijing China 12–
15 Oct, China Academic Publishers Beijing China 255–261
76. Sanderson AJ (1994) A programme and data for the characterisation of new ingredients for
energetic materials. The NIMIC Coordinated Characterisation Programme 110:57–62
77. Sanderson AJ (1997) A draft sheet for 3-nitro-l,2,4-triazol-5-one. The NIMIC Coordinated
Characterisation Program
78. Zeman V, Zeman S (1997) Relationship between the electric spark sensitivity and detonation
velocities of some polynitro compounds. In: International conference of ICT 28th Karlsruhe
Federal Republic of Germany, 24–27 June, Fraunhofer-Institut Für Chemische Technologie
Berghausen, Bundesrepublik, Deutschland 67(1):67(10)
79. Aubert SA, Corley JD, Glenn JG (1993) Development of TNTO composite explosives.
WL-TR-92-7073 Wright Laboratory Eglin Air Force Base, Florida, USA
80. Zeman V, Zeman S (1997) Relationship between the electric spark sensitivity and detonation
velocities of some polynitro compounds. In: International conference of ICT 28th Karlsruhe
Federal Republic of Germany, 24–27 June, Fraunhofer-Institut Für Chemische Technologie
Berghausen, Bundesrepublik, Deutschland 67(1):67(10)
81. Kamlet MJ, Jacobs SJ (1968) Chemistry of detonations I a simple method for calculating
detonation properties of C-H-N-O explosives. J Chem Phys 48(1):23–35
82. Aubert SA, Corley JD, Glenn JG (1993) Development of TNTO composite explosives.
WL-TR-92-7073 Wright Laboratory, Eglin Air Force Base, Florida, USA
83. Corley JD, Stewart AC (1995) Fuzed insensitive general purpose bomb containing
AFX-645. Final Report WL-TR-95-7019 Wright Laboratory, Eglin Air Force Base, Florida,
USA
84. Hammer JO, Skjold E, Kildal SK, Gjersoe R, Mathieu J, Berger B, Mäder P, Bircher HR
(1997) Formulation of NTO based compositions. In: Insensitive munitions and energetic
materials technology symposium event #854, Florida, USA, 6–9 Oct, National Defense
Industrial Association
85. Bircher HR, Mathieu J, Berger B, Mäder P, Skjold E, Kildal SK, Gjersoe R, Hammer JO
(1997) Vulnerability and performance of NTO based high explosives. In: Insensitive
munitions and energetic materials technology symposium event #854, Florida, USA, 6–9
Oct, National Defense Industrial Association
202 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

86. Becuwe A, Isler J (1997) Extremely insensitive detonating substances (EIDS) for 16
munitions applications. In: Insensitive munitions and energetic materials technology
symposium event #854, Florida, USA 6–9 Oct, National Defense Industrial Association
87. Becuwe A, Delclos A, Isler J (1995) EIDS high explosives for 16 munitions. In:
International symposium on energetic materials technology meeting #680, Arizona, USA,
24–27 Sept, American Defense Preparedness Association,pp 119–124
88. Becuwe A, Delclos A, Donzel G, Golfier M (1997) Improvements in NTO based PBXs a
new powerful and insensitive class of PBX. In: Insensitive munitions and energetic materials
technology symposium event #854, Florida, USA, 6–9 Oct, National Defense Industrial
Association
89. Becuwe A, Delclos A (1989) Use of oxynitrotriazole to prepare an insensitive high
explosive. In: Symposium (international) on detonation 9th HI Oregon, USA, 28 Aug–l
Sept, pp 871–876
90. Becuwe A, Delclos A, Donzel G, Golfier M (1998) Improvements in NTO based PBXs. In:
International conference of ICT 29th Karlsruhe Federal Republic of Germany, 30 June–3
July, Fraunhofer-Institut Für Chemische Technologie Berghausen, Bundesrepublik,
Deutschland 95(l):95(5)
91. Quidot M, Hamaide S, Groux J, Gimenez P, Isler JC (1993) Fragment impact initiation of
cast PBXs in relation with shock sensitivity tests. In: International detonation symposium
10th Massachusetts, USA, 12–16, July Office of Naval Research, Virginia, USA, pp 113–
121
92. Lamy P, Leiber C-O, Cumming AS, Zimmer M (1996) Air senior national representative
long term technology project on insensitive high explosives (IHEs) studies of high energy
insensitive high explosives. In: International conference of ICT 27th Karlsruhe Federal
Republic of Germany, 25–28ÜI June, Fraunhofer-Institut Für Chemische Technologie
Berghausen, Bundesrepublik, Deutschland 1(1):1(14)
93. Nouguez B (1994) Dual formulation warheads: a mature technology. In: Insensitive
munitions technology symposium meeting #471, Virginia, USA, 6–9 June, American
Defense Preparedness Association, pp 280–287
94. Becuwe A, Delclos A, Donzel G, Golfier M (1997) Improvements in NTO based PBXs a
new powerful and insensitive class of PBX. In: Insensitive munitions and energetic materials
technology symposium event #854, Florida, USA, 6–9 Oct, National Defense Industrial
Association
95. Kayser V, Boussufe R, Kihm JF, Deneuville P, Pascal S (1994) Use of cast PBX in
insensitive high performance shaped charges. In: Insensitive munitions technology
symposium meeting #471, Virginia, USA, 6–9 June, American Defense Preparedness
Association, pp 574–584
96. Spear RJ, Dagley IJ, Whitty P (1994) Options for future RAAF GP bombs meeting IM and/
or HD 16 criteria. DSTO-CIC-0001 Aeronautical and Maritime Research Laboratory,
Melbourne, Australia
97. Senn MR, Newman KE, Wise TE, Jones WS (1990) Chemicals and processing assessment
of candidate explosives for the advanced bomb family. IHTR-1370 Naval Ordnance Station
Indian Head, USA
98. Wilson LT, Reedal DR, Simpson BM (1997) Comparison of PBXW-126 and PBXC-129 for
use in large fragmenting warheads. In: Insensitive munitions and energetic materials
technology symposium event #854, Florida, USA, 6–9 Oct, National Defense Industrial
Association
99. Murphy MJ, Simpson RL, Urtiew PA, Souers PC, Garcia F, Garza RG (1995) Reactive flow
model development for PBXW-126 using modern nonlinear optimisation methods. In:
Schmidt SC, Tao WC (eds) Conference of the American physical society topical group on
shock compression of condensed matter, American Institute of physics conference
proceedings 370 Washington, USA, 13–18 Aug, AIP Press, New York, USA, pp 417–420
100. Cumming AS, Gaulter SE, Leach CJ (1994) The formulation of an insensitive high
explosive based on HMX, NTO and PolyNIMMO. In: Insensitive munitions technology
References 203

symposium meeting #471, Virginia, USA, 6–9 June, American Defense Preparedness
Association, pp 376–382
101. Cumming AS (1997) Part 1—focus area reports. Technical panel WTP-4 energetic materials
and propulsion technology. Volume III, UK, 14–18 April, The Technical Cooperation
Program, pp 97–99
102. Leach CJ, Garaty BJ, Cox KJ (1997) Progress in aluminised IHE. The Technical
Cooperation Program Technical panel W-4 energetic materials and propulsion technology.
In: 22nd meeting, United Kingdom, 14–18 April, pp 1–8
103. Mclntosh G (1997) Effect of 245 GHz microwave radiation on diverse explosives.
DREV-TM-9702 Defence Research Establishment Valcartier, Quebec, Canada
104. Aubert SA (1994) Characterisation of the hydrodynamic performance properties of NTO and
TNTO composite explosives. WL-TR-94-7037 Wright Laboratory, Eglin Air Force Base,
Florida, USA
105. Trzcinski WA, Szymanczyk L (2005) Detonation properties of low-sensitivity NTO-based
explosives. Energ Mater 23:151–168
106. London JE, Smith DM (1985) A toxicological study of NTO. Report No LA-10533-MS
UC-48
107. Sarlauskas J, Nemeilaite-Ceniene A, Anusevicius Z, Miseviciene L, Maroziene A,
Markevicius A, Cenas N (2004) Enzymatic redox properties of novel nitrotriazole
explosives implications for their toxicity. Z Naturforsch 59c:399–404
108. Reddy G, Song J, Kirby P, Lenta EM, Crousea LCB, Johnson MS (2011) Genotoxicity
assessment of an energetic propellant compound, 3-nitro-1,2,4-triazol-5-one (NTO).
Mutation Res 719:35–40
109. Tabrizchi M, Lbeigi VI (2010) Detection of explosives by positive corona discharge ion
mobility spectrometry. J Hazard Mater 176:692–696
110. Oehrle SA (1997) Analysis of 3-nitro- 1,2,4-triazole-5-one (NTO) in explosive mixtures by
capillary electrophoresis. Propellants Explos Pyrotech 22:1–3

Additional Scholarly Articles for Further Reading

111. Amandurdyeva AD, Saraev VV, Kuz’mina NE, Golod EL (2004) Adamantylazoles: VIII.
Acid-catalyzed adamantylation of 1,2,4-triazol-5-ones. Russ J Gen Chem 74(8):1277–1281.
doi:10.1007/s11176-005-0151-z
112. Andes FS, III (1974) Identification of kinetic performance losses of NTO/MMH. Air Force
Rocket Propulsion Laboratory, 45 pp
113. Asahi H, Inabe T (1994) Charge-transfer complexes of 1,4,5,8-naphthalenetetrones and
1,4,9,10-anthracenetetrones. Novel acceptors for electrically conducting materials. Chem
Mater 6(10):1875–1879. doi:10.1021/cm00046a050
114. Asahi H, Inabe T (1995) Novel conductive charge-transfer complexes of
1,4,5,8-naphthalenetetrone (NTO) and 1,4,9,10-anthracenetetrone (ATO). Synth Met 70
(1–3):1117–1118. doi:10.1016/0379-6779(94)02780-3
115. Bak A, Maranda A, Nowaczewski J, Szerszen M (2006) Some properties of high explosive
mixtures of low sensitivity to external stimuli. Cent Eur J Energ Mater 3(3):53–64
116. Barnes MW, Deppert TM, Taylor RD (1996) Gas-generating compositions using
dicyanamide salts as fuel. US5544687A
117. Beard BC, Sharma J (1993) Early decomposition chemistry of NTO, (3-nitro-1,2,4-triazol-
5-one). J Energ Mater 11(4–5):325–343. doi:10.1080/07370659308019715
118. Becuwe A, Delclos A, Isler J (1995) EIDS high explosives for 1.6 munitions. American
Defense Preparedness Association, pp 119–124
119. Bhatnagar N, Kamath G, Potoff JJ (2013) Prediction of 1-octanol-water and air-water
partition coefficients for nitro-aromatic compounds from molecular dynamics simulations.
Phys Chem Chem Phys 15(17):6467–6474. doi:10.1039/c3cp44284e
204 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

120. Boddu VM, Maloney SW (2012) Physical properties of insensitive munitions compounds
for developing wastewater treatment technologies, vol 3. Air & Waste Management
Association, pp 1958–1965
121. Bolotina N, Kirschbaum K, Pinkerton AA (2005) Energetic materials: a-NTO crystallizes as
a four-component triclinic twin. Acta Crystallogr, Sect B: Struct Sci B 61(5):577–584.
doi:10.1107/S0108768105022792
122. Bolotina NB, Zhurova EA, Pinkerton AA (2003) Energetic materials: variable-temperature
crystal structure of b-NTO. J Appl Crystallogr 36(2):280–285. doi:10.1107/
S002188980300092X
123. Borro-Escribano B, Martinez-Alpuente I, Blanco AD, Torrente J, Fernandez-Manjon B,
Matesanz R (2013) Application of game-like simulations in the Spanish Transplant National
Organization. Transplant Proc 45(10):3564–3565
124. Botcher TR, Beardall DJ, Wight CA, Fan L, Burkey TJ (1996) Thermal decomposition
mechanism of NTO. J Phys Chem 100(21):8802–8806. doi:10.1021/JP952984Y
125. Brill TB, Zhang TL, Tappan BC (2000) Thermal decomposition of energetic materials 74.
Volatile metal isocyanates from flash pyrolysis metal-NTO and metal-picrate salts and an
application hypothesis. Combust Flame 121(4):662–670. doi:10.1016/S0010-2180(99)
00172-8
126. Can Z, Uezer A, Tekdemir Y, Ercag E, Tuerker L, Apak R (2012) Spectrophotometric and
chromatographic determination of insensitive energetic materials: HNS and NTO, in the
presence of sensitive nitro-explosives. Talanta 90:69–76. doi:10.1016/j.talanta.2011.12.077
127. Catoire L, Chaumeix N, Paillard C (2004) Chemical kinetic model for
monomethylhydrazine/nitrogen tetroxide gas-phase combustion and hypergolic ignition.
J Propul Power 20(1):87–92. doi:10.2514/1.9234
128. Chakka S, Boddu VM, Maloney SW, Damavarapu R (2008) Prediction of physicochemical
properties of energetic materials via EPI suite. American Institute of Chemical Engineers, pp
437/1–437/10
129. Chakka S, Boddu VM, Maloney SW, Toghiani RK, Damavarapu R (2009) Vapor pressures
and melting points of select munitions compounds. American Institute of Chemical
Engineers, pp chakk1/1–chakk1/9
130. Chang C-R et al (2008) Molecular structure, theoretical calculation and thermal behavior of
DAG (NTO). Chin J Chem 26(9):1549–1554. doi:10.1002/cjoc.200890280
131. Chang CW, Wong YM, Chang TC, Chen C (1997) AM1 study of ammonium
3-nitro-1,2,4-triazole-5-onate (ANTO). Propellants, Explos, Pyrotech 22(4):240–241
132. Ciezak JA, Trevino SF (2005) Theoretical and experimental study of the inelastic neutron
scattering spectra of b-5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one. J Mol Struct:
THEOCHEM 732(1–3):211–218. doi:10.1016/j.theochem.2005.07.022
133. Ciller JA, Serna FJ, Quintana JR (1992) Thermal characterization of mixtures of
nitrotriazolone with HMX and RDX. J Energ Mater 10(4–5):251–265. doi:10.1080/
07370659208018925
134. Coburn MD, Lee KY (1990) Picryl derivatives of 5-nitro-2,4-dihydro-3H-1,2,
4-triazol-3-one. J Heterocycl Chem 27(3):575–577. doi:10.1002/jhet.5570270318
135. Cortial S, Chaignon P, Sergent D, Dezard S, Ouazzani J (2012) Dehydrogenation, oxidative
denitration and ring contraction of N, N-dimethyl-5-nitrouracil by a Bacillus nitroreductase
Nfr-A1. J Mol Catal B Enzym 76:1–8. doi:10.1016/j.molcatb.2011.11.014
136. Cronin MP, Day AI, Wallace L (2007) Electrochemical remediation produces a new
high-nitrogen compound from NTO wastewaters. J Hazard Mater 149(2):527–531. doi:10.
1016/j.jhazmat.2007.08.007
137. Crouse LCB, Lent EM, Leach GJ (2015) Oral toxicity of 3-nitro-1,2,4-triazol-5-one in rats.
Int J Toxicol 34(1):55–66. doi:10.1177/1091581814567177
138. Cuddy MF, Poda AR, Chappell MA (2014) Estimations of vapor pressures by
thermogravimetric analysis of the insensitive munitions IMX-101, IMX-104, and individual
components. Propellants, Explos, Pyrotech 39(2):236–242. doi:10.1002/prep.201300069
Additional Scholarly Articles for Further Reading 205

139. Cudzilo S, Trzcinski WA (2001) A study on detonation characteristics of pressed NTO.

J Energ Mater 19(1):1–21. doi:10.1080/07370650108219390
140. Cumming AS (1995) Characteristics of novel United Kingdom energetic materials.
American Defense Preparedness Association, pp 69–74
141. Daimon Y, Terashima H, Koshi M (2014) Chemical kinetics of hypergolic ignition in N2H4/
N2O4-NO2 gas mixtures. J Propul Power 30(3):707–716. doi:10.2514/1.B35004
142. Dauerman L, Fraser W (1970) Preignition products from propellants at simulated high
altitude conditions (Comment). Combust Sci Technol 2(4):177–178. doi:10.1080/
00102207008952246
143. De Paz JLG, Ciller J (1993) On the use of AM1 and PM3 methods on energetic compounds.
Propellants, Explos, Pyrotech 18(1):33–40. doi:10.1002/prep.19930180107
144. Deguchi K, Kanno K, Miyagawa H (1976) Application of the natural transition orbital
(NTO) method to excited states. Chem Phys Lett 39(1):169–173. doi:10.1016/0009-2614
(76)85222-0
145. Delpeyroux D, Charrue P, Simonetti P (1998) Calculation of the energetic performances of
explosives: prediction of the heat of formation. High Temp - High Pressures 30(5):625–628.
doi:10.1068/htec351
146. Dlott DD, Hambir S, Franken J (1998) The new wave in shock waves. J Phys Chem B 102
(12):2121–2130. doi:10.1021/JP973404V
147. Ebrahimbeiki Chimeh A, Montazer M, Rashidi A (2013) Conductive and photoactive
properties of polyethylene terephthalate fabrics treated with nano TiO2/nano carbon blacks.
Carbon 64:559. doi:10.1016/j.carbon.2013.07.080
148. Elijosiute E, Jankunaite D, Eicher-Lorka O (2015) TD-DFT study of the electronic
absorption spectra of iron(III) monoisothiocyanate. Polyhedron 90:41–46. doi:10.1016/j.
poly.2015.01.034
149. Ellis GJ, Bezuidenhout HC (1999) Determination of the detonation energy and some of the
energetic characteristics of various NTO-based formulations. In: International Annual
Conference ICT 30th:63/1–63/10
150. Fan L, Dass C, Burkey TJ (1996) Synthesis and thermal decomposition of 15 N-labeled
NTO. J Labelled Compd Radiopharm 38(1):87–94. doi:10.1002/(SICI)1099-1344(199601)
38:1<87:AID-JLCR819>3.0.CO;2-I
151. Fang G, Xu L, Hu X, Li X (2008) DFT study of the interaction between
3-nitro-1,2,4-triazole-5-one and hydrogen fluoride. J Hazard Mater 160(1):51–55. doi:10.
1016/j.jhazmat.2008.02.082
152. Festoff BW (ed) (1990) NATO ASI series. Series A, life sciences, vol 191: serine proteases
and their serpin inhibitors in the nervous system: regulation in development and in
degenerative and malignant disease. In: Proceedings of a NTO advanced research workshop
on regulation of extravascular fibrinolysis in nervous system development and disease, Held
2–8 July 1989, Plenum Press, Marater, Italy
153. Finch A, Gardner PJ, Head AJ, Majdi HS (1991) The enthalpies of formation of
1,2,4-triazol-5-one and 3-nitro-1,2,4-triazol-5-one. J Chem Thermodyn 23(12):1169–1173.
doi:10.1016/S0021-9614(05)80150-8
154. Finch A, Gardner PJ, Head AJ, Majdi HS (1993) The standard enthalpies of formation of the
ammonium and silver salts of 3-nitro-1,2,4-triazol-5-one. Thermochim Acta 213(1–2):17–
22. doi:10.1016/0040-6031(93)80003-S
155. Franken J, Hambir SA, Dlott DD (1998) Ultrafast spectroscopy of laser-driven shock waves
in molecular materials. Mol Cryst Liq Cryst Sci Technol, Sect A 314:25–36. doi:10.1080/
10587259808042453
156. Grau H, Gandzelko A, Samuels P (2014) Solubility determination of raw energetic materials
in molten 2,4-dinitroanisole. Propellants, Explos, Pyrotech 39(4):604–608. doi:10.1002/
prep.201300083
157. Guillemin JP, Menard Y, Brunet L, Bonnefoy O, Thomas G (2008) Development of a new
mixing rheometer for studying rheological behaviour of concentrated energetic suspensions.
J Non-Newtonian Fluid Mech 151(1–3):136–144. doi:10.1016/j.jnnfm.2007.12.007
206 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

158. Guillemin J-P, Brunet L, Bonnefoy O, Thomas G (2007) A flow time model for melt-cast
insensitive explosive process. Propellants, Explos, Pyrotech 32(3):261–266. doi:10.1002/
prep.200700028
159. Hahma A (1995) On the combustion of Al under detonation; experimental and theoretical
studies. American Defense Preparedness Association, pp 153–159
160. Halcy M, Kuperman RG, Checkai RT (2009) Aquatic toxicity of 3-nitro-1,2,4-triazol-5-one.
DIR, ECBC, pp 2, 7–27
161. Harding JT, Fry V, Tuffias RH, Kaplan RB (1987) Oxidation resistance of CVD (chemical
vapor deposition) coatings. Ultramet, 29 pp
162. Hare DE et al (1996) Ultrafast dynamics of shock waves and shocked energetic materials.
Mater Res Soc Symp Proc 418(Decomposition, Combustion, and Detonation Chemistry of
Energetic Materials):337–348
163. Hayashi R, Kowhakul W, Susa A, Koshi M (2009) Detection of explosives using a vacuum
ultraviolet ionization time-of-flight mass spectrometry (VUV-TOFMS). Sci Technol Energ
Mater 70(3):62–67
164. He B, Nie W, Feng S, Su L, Zhuang F (2013) Effects of NTO oxidizer temperature and
pressure on hypergolic ignition delay and life time of UDMH organic gel droplet.
Propellants, Explos, Pyrotech 38(5):665–684. doi:10.1002/prep.201200160
165. He B, Nie W, He H (2012) Unsteady combustion model of no metalized organic gel fuel
droplet. Energy Fuels 26(11):6627–6639. doi:10.1021/ef300990d
166. Hidding B, Pfitzner M, Bruno C, Simone D (2008) Silanes/H2O2: a high-performance
synthetic bipropellant for chemical space propulsion. J Propul Power 24(1):150–153. doi:10.
2514/1.30346
167. Hiyoshi RI, Brill TB (2002) Thermal decomposition of energetic materials 83. Comparison
of the pyrolysis of energetic materials in air versus argon. Propellants, Explos, Pyrotech 27
(1):23–30. doi:10.1002/1521-4087(200203)27:1<23::AID-PREP23>3.0.CO;2-B
168. Hiyoshi RI et al (2006) Effect of pressure on the vibrational structure of insensitive energetic
material 5-nitro-2,4-dihydro-1,2,4-triazole-3-one. J Phys Chem A 110(32):9816–9827.
doi:10.1021/jp063142+
169. Hoyt N et al (2013) Biomarkers of oral exposure to 3-nitro-1,2,4-triazol-5-one (NTO) and
2,4-dinitroanisole (DNAN) in blood and urine of rhesus macaques (Macaca mulatta).
Biomarkers 18(7):587–594. doi:10.3109/1354750X.2013.829522
170. Irfan I, Sawangjaroen N, Bhat AR, Azam A (2010) New dioxazole derivatives: synthesis and
effects on the growth of Entamoeba histolytica and Giardia intestinalis. Eur J Med Chem 45
(4):1648–1653. doi:10.1016/j.ejmech.2009.12.051
171. Ishikawa Y, McQuaid MJ (2007) Reactions of NO2 with CH3NHNH and CH3NNH2: a
direct molecular dynamics study. J Mol Struct: THEOCHEM 818(1–3):119–124. doi:10.
1016/j.theochem.2007.05.014
172. Jadhav HS, Talawar MB, Dhavale DD, Asthana SN, Krishnamurthy VN (2005) Synthesis,
characterization and thermolysis of 2,4-dihydro -2,4,5-trinitro-3H-1,2,4-triazol-3-one
(DTNTO): a new derivative of 3-nitro-1,2,4-triazol-5-one (NTO). Indian J Eng Mater Sci
12(5):467–471
173. Jokela K, Kalsch I (2004) Decontamination of MMH- and NTO/MON-propellant tanks. Eur
Space Agency, [Spec Publ] SP SP-555(Space Propulsion 2004):157–161
174. Joo Y-H, Gao H, Zhang Y, JnM Shreeve (2010) Inorganic or organic azide-containing
hypergolic ionic liquids. Inorg Chem 49(7):3282–3288. doi:10.1021/ic902224t
175. Jung J-W, Kim K-J (2011) Effect of supersaturation on the morphology of coated surface in
coating by solution crystallization. Ind Eng Chem Res 50(6):3475–3482. doi:10.1021/
ie102099a
176. Keshavarz MH, Pouretedal HR, Semnani A (2007) Novel correlation for predicting impact
sensitivity of nitroheterocyclic energetic molecules. J Hazard Mater 141(3):803–807. doi:10.
1016/j.jhazmat.2006.07.046
Additional Scholarly Articles for Further Reading 207

177. Keshavarz MH, Sadeghi H (2009) A new approach to predict the condensed phase heat of
formation in acyclic and cyclic nitramines, nitrate esters and nitroaliphatic energetic
compounds. J Hazard Mater 171(1–3):140–146. doi:10.1016/j.jhazmat.2009.05.118
178. Kim KJ (2000) Spherulitic crystallization of 3-nitro-1,2,4-triazol-5-one in
water + N-methyl-2-pyrrolidone. J Cryst Growth 208(1–4):569–578. doi:10.1016/S0022-
0248(99)00408-X
179. Kim K-J, Kim H-S (2008) Agglomeration of NTO on the surface of HMX particles in
water-NMP solvent. Cryst Res Technol 43(1):87–92. doi:10.1002/crat.200710946
180. Kim K-J, Kim M-J, Lee J-M, Kim S-H, Kim H-S, Park B-S (1998) Experimental solubility
and density for 3-nitro-1,2,4-triazol-5-one + C1 to C7 1-alkanols. Fluid Phase Equilib 146
(1, 2):261–268. doi:10.1016/S0378-3812(98)00182-4
181. Kim YH, Lee K, Koo KK, Shul YG, Haam S (2002) Comparison study of mixing effect on
batch cooling crystallization of 3-nitro-1,2,4-triazol-5-one (NTO) using mechanical stirrer
and ultrasound irradiation. Cryst Res Technol 37(9):928–944. doi:10.1002/1521-4079
(200209)37:9<928:AID-CRAT928>3.0.CO;2-R
182. Knowles PJ (1972) Helium absorption into nitrogen tetroxide (NTO) and Aerozine-50
(A-50). J Spacecr Rockets 9(9):708–709. doi:10.2514/3.61782
183. Kohno Y, Takahashi O, Saito K (2001) Theoretical study of initial decomposition process of
NTO dimer. Phys Chem Chem Phys 3(14):2742–2746. doi:10.1039/b101745o
184. Krause G (2012) Volume-dependent self-ignition temperatures for explosive materials.
Propellants, Explos, Pyrotech 37(1):107–115. doi:10.1002/prep.201100007
185. Krzmarzick MJ, et al. (2015) Biotransformation and Degradation of the Insensitive
Munitions Compound, 3-nitro-1,2,4-triazol-5-one (NTO), by Soil Bacterial Communities.
Environ Sci Technol. Ahead of Print. doi:10.1021/acs.est.5b00511
186. Kulkarni PB, Purandare GN, Nair JK, Talawar MB, Mukundan T, Asthana SN (2005)
Synthesis, characterization, thermolysis and performance evaluation studies on alkali metal
salts of TABA and NTO. J Hazard Mater 119(1–3):53–61. doi:10.1016/j.jhazmat.2004.12.014
187. Kulkarni PB et al (2005) Studies on salts of 3-nitro-1,2,4-triazol-5-one (NTO) and
2,4,6-trinitroanilino benzoic acid (TABA): potential energetic ballistic modifiers. J Hazard
Mater 123(1–3):54–60. doi:10.1016/j.jhazmat.2005.04.010
188. Le Campion L, Adeline MT, Ouazzani J (1997) Separation of NTO related
1,2,4-triazole-3-one derivatives by a high performance liquid chromatography and capillary
electrophoresis. Propellants, Explos, Pyrotech 22(4):233–237. doi:10.1002/prep.
19970220410
189. Le Campion L, Delaforge M, Noel JP, Ouazzani J (1998) Metabolism of 14C-labeled
5-nitro-1,2,4-triazol-3-one (NTO): comparison between rat liver microsomes and bacterial
metabolic pathways. J Mol Catal B Enzym 5(1–4):395–402. doi:10.1016/S1381-1177(98)
00103-9
190. Le Campion L, Giannotti C, Ouazzani J (1999) Photocatalytic degradation of
5-nitro-1,2,4-triazol-3-one (NTO) in aqueous suspension of TiO2 comparison with Fenton
oxidation. Chemosphere 38(7):1561–1570. doi:10.1016/S0045-6535(98)00376-2
191. Lee JS, Jaw KS (2006) Thermal decomposition properties and compatibility of CL-20, NTO
with silicone rubber. J Therm Anal Calorim 85(2):463–467. doi:10.1007/s10973-005-7325-0
192. Li D, Haneda H, Hishita S, Ohashi N (2005) Visible-light-active nitrogen-containing TiO2
photocatalysts prepared by spray pyrolysis. Res Chem Intermed 31(4–6):331–341. doi:10.
1163/1568567053956653
193. Lin H, Zhu S-G, Zhang L, Peng X-H, Chen P-Y, Li H-Z (2013) Intermolecular interactions,
thermodynamic properties, crystal structure, and detonation performance of HMX/NTO
cocrystal explosive. Int J Quantum Chem 113(10):1591–1599. doi:10.1002/qua.24369
194. Linker BR et al (2015) Adsorption of novel insensitive munitions compounds at clay mineral
and metal oxide surfaces. Environ Chem 12(1):74–84. doi:10.1071/EN14065
195. Liu Z, Wu Q, Zhu W, Xiao H (2015) Vacancy-induced initial decomposition of condensed
phase NTO via bimolecular hydrogen transfer mechanisms at high pressure: a DFT-D study.
Phys Chem Chem Phys 17(16):10568–10578
208 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

196. Long GT, Brems BA, Wight CA (2002) Thermal activation of the high explosive NTO:
sublimation, decomposition, and autocatalysis. J Phys Chem B 106(15):4022–4026. doi:10.
1021/jp012894v
197. Ma H et al (2009) Preparation, non-isothermal decomposition kinetics, heat capacity and
adiabatic time-to-explosion of NTODNAZ. J Hazard Mater 169(1–3):1068–1073. doi:10.
1016/j.jhazmat.2009.04.057
198. McMillen DF, Erlich DC, He C, Becker CH, Shockey DA (1997) Fracture-induced and
thermal decomposition of NTO using laser ionization mass spectrometry. Combust Flame
111(3):133–160. doi:10.1016/S0010-2180(97)00100-4
199. Muthurajan H, Sivabalan R, Talawar MB, Asthana SN (2004) Computer simulation for
prediction of performance and thermodynamic parameters of high energy materials. J Hazard
Mater 112(1–2):17–33. doi:10.1016/j.jhazmat.2004.04.012
200. Najafi M, Samangani AK (2011) Non-isothermal kinetic study of the thermal decomposition
of melamine 3-nitro-1,2,4-triazol-5-one salt. Propellants, Explos, Pyrotech 36(6):487–492.
doi:10.1002/prep.201000153
201. Nandi AK, Singh SK, Kunjir GM, Singh J, Mandal AK, Pandey RK (2013) Assay of the
intensive high explosive 3-nitro-1,2,4-triazol-5-one (NTO) by acid-base titration. Cent Eur J
Energ Mater 10(1):113–122
202. Nazari A, Montazer M, Dehghani-Zahedani M (2013) Nano TiO2 as a new tool for
mothproofing of wool: protection of wool against Anthrenus verbasci. Ind Eng Chem Res 52
(3):1365–1371. doi:10.1021/ie302187c
203. Nouguez B, Mahe B, Vignaud PO (2009) Cast PBX related technologies for IM shells and
warheads. Sci Technol Energ Mater 70(6):135–139
204. Oestmark H, Bergman H, Aqvist G (1993) The chemistry of 3-nitro-1,2,4-triazol-5-one
(NTO): thermal decomposition. Thermochim Acta 213(1–2):165–175. doi:10.1016/0040-
6031(93)80014-2
205. Osmont A, Catoire L, Klapotke TM, Vaghjiani GL, Swihart MT (2008) Thermochemistry of
species potentially formed during NTO/MMH hypergolic ignition. Propellants, Explos,
Pyrotech 33(3):209–212. doi:10.1002/prep.200700213
206. Oxley JC, Smith JL, Rogers E, Dong XX (1997) NTO decomposition products tracked with
15 N labels. J Phys Chem A 101(19):3531–3536. doi:10.1021/JP9640078
207. Oxley JC, Smith JL, Yeager KE (1995) Synthesis of 15 N-labeled isomers of
5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO). J Energ Mater 13(1&2):93–105. doi:10.
1080/07370659508019345
208. Oxley JC, Smith JL, Zhou Z, McKenney RL (1995) Thermal decomposition studies on
NTO. International Annual Conference ICT 26th(Pyrotechnics):28/1–28/15
209. Oxley JC, Smith JL, Zhou Z, McKenney RL (1995) Thermal decomposition studies on NTO
and NTO/TNT. J Phys Chem 99(25):10383–10391. doi:10.1021/j100025a047
210. Piotrowski T, Fraczak M, Buczkowski D, Paplinski A, Maranda A (2006) The ranking of
explosives by use of material indices as proposed in the Temclev-Ex method. Cent Eur J
Energ Mater 3(1–2):3–17
211. Powala D, Orzechowski A, Maranda A, Nowaczewski J, Lorek A (2004) Researches on new
crystalline form of some insensitive high explosives in PBX. Cent Eur J Energ Mater 1
(1):63–73
212. Prabhakaran KV, Naidu SR, Kurian EM (1994) XRD, spectroscopic and thermal analysis
studies on 3-nitro-1,2,4-triazol-5-one. Thermochim Acta 241(1–2):199–212. doi:10.1016/
0040-6031(94)87018-7
213. Quinn MJ Jr, Bannon DI, Jackovitz AM, Hanna TL, Shiflett AA, Johnson MS (2014)
Assessment of 3-nitro-1,2,4-triazol-5-one as a potential endocrine disrupting chemical in rats
using the Hershberger and uterotrophic bioassays. Int J Toxicol 33(5):367–372. doi:10.1177/
1091581814548729
214. Russell AL, Seiter JM, Coleman JG, Winstead B, Bednar AJ (2014) Analysis of munitions
constituents in IMX formulations by HPLC and HPLC-MS. Talanta 128:524–530. doi:10.
1016/j.talanta.2014.02.013
Additional Scholarly Articles for Further Reading 209

215. Salvador CAV, Costa FS (2006) Vaporization lengths of hydrazine fuels burning with NTO.
J Propul Power 22(6):1362–1372. doi:10.2514/1.18348
216. Sarangapani R, Ramavat V, Reddy S, Subramanian P, Sikder AK (2015) Rheology studies
of NTO-TNT based melt-cast dispersions and influence of particle-dispersant interactions.
Powder Technol 273:118–124. doi:10.1016/j.powtec.2014.12.013
217. Sarangapani R, Ramavat V, Reddy TS, Patil RS, Gore GM, Sikder AK (2014) Effect of
particle size and shape of NTO on micromeritic characteristics and its explosive
formulations. Powder Technol 253:276–283. doi:10.1016/j.powtec.2013.11.029
218. Schoenman L (1995) 4000°F materials for low-thrust rocket engines. J Propul Power 11
(6):1261–1267. doi:10.2514/3.23967
219. Schwarzenbach D, Kirschbaum K, Pinkerton AA (2006) Order-disorder twinning model and
stacking faults in alpha-NTO. Acta Crystallogr B 62(Pt 5):944–948
220. Schwarzenbach D, Kirschbaum K, Pinkerton AA (2006) Order-disorder twinning model and
stacking faults in a-NTO. Acta Crystallogr, Sect B: Struct Sci B 62(5):944–948. doi:10.
1107/S0108768106024761
221. Scott AM, Burns EA, Hill FC (2014) Theoretical study of adsorption of nitrogen-containing
environmental contaminants on kaolinite surfaces. J Mol Model 20(8):1–13. doi:10.1007/
s00894-014-2373-7
222. Scott AM, Burns EA, Lafferty BJ, Hill FC (2015) Theoretical predictions of thermodynamic
parameters of adsorption of nitrogen containing environmental contaminants on kaolinite.
J Mol Model 21(2):21
223. Shekhar H (2012) Studies on empirical approaches for estimation of detonation velocity of
high explosives. Cent Eur J Energ Mater 9(1):39–48
224. Shukla MK, Hill F (2014) Dissociative adsorption of
5-nitro-2,4-dihydro-3h-1,2,4-triazol-3-one (NTO) on aluminum-terminated (0001) surface
of a-alumina as predicted from plane-wave density functional theory. J Phys Chem C 118
(1):310–319. doi:10.1021/jp408661h
225. Sinditskii VP et al (2009) Evaluation of decomposition kinetics of energetic materials in the
combustion wave. Thermochim Acta 496(1–2):1–12. doi:10.1016/j.tca.2009.07.004
226. Singh G, Felix SP (2003) Studies of energetic compounds, part 29: effect of NTO and its
salts on the combustion and condensed phase thermolysis of composite solid propellants,
HTPB-AP. Combust Flame 132(3):422–432. doi:10.1016/S0010-2180(02)00479-0
227. Singh G, Felix SP (2003) Studies on energetic compounds. Part 32: crystal structure,
thermolysis and applications of NTO and its salts. J Mol Struct 649(1–2):71–83. doi:10.
1016/S0022-2860(02)00717-2
228. Singh G, Kapoor IPS, Felix SP, Agrawal JP (2002) Studies on energetic compounds part 23:
preparation, thermal and explosive characteristics of transition metal salts of
5-nitro-2,4-dihydro-3H-1,2,4-triazole-3-one (NTO). Propellants, Explos, Pyrotech 27
(1):16–22. doi:10.1002/1521-4087(200203)27:1<16:AID-PREP16>3.0.CO;2-W
229. Singh G, Kapoor IPS, Mannan SM, Tiwari SK (1998) Studies on energetic compounds Part
7 thermolysis of ring-substituted arylammonium salts of 3-nitro-1,2,4-triazole-5-one (NTO).
J Energ Mater 16(2 & 3):101–118. doi:10.1080/07370659808217507
230. Singh G, Kapoor IPS, Mannan SM, Tiwari SK (1998) Studies on energetic compounds. Part
6. Synthesis of ring-substituted arylammonium salts of 3-nitro-1,2,4-triazol-5-one(NTO).
J Energ Mater 16(1):31–43. doi: 10.1080/07370659808216092
231. Singh G, Kapoor IPS, Tiwari SK (2000) Studies on energetic compounds (part 18):
preparation and kinetics of thermolysis of alkaline earth metal salts of
5-nitro-2,4-dihydro-3H-1,2,4-triazole-3-one (NTO). Indian J Chem Technol 7(5):236–241
232. Singh G, Kapoor IPS, Tiwari SK, Felix SP, Ninan KN, Varghese TL (2002) Studies on
energetic compounds. Part 15: transition metal salts of NTO as potential energetic ballistic
modifiers for composite solid propellants. J Energ Mater 20(4):309–327. doi:10.1080/
07370650208244826
210 5 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

233. Singh G, Kapoor IPS, Tiwari SK, Prem FS (2000) Studies on energetic compounds. Part 12.
Preparation and thermolysis of transition metal salts of 5-nitro-2,4-dihydro-3H-1,
2,4-triazol-3-one (NTO). Indian J Eng Mater Sci 7(3):167–171
234. Singh G, Prem Felix S (2002) Studies on energetic compounds 25. An overview of
preparation, thermolysis and applications of the salts of 5-nitro-2,4-dihydro-3H-1,2,
4-triazol-3-one (NTO). J Hazard Mater 90(1):1–17. doi:10.1016/S0304-3894(01)00349-1
235. Singh G, Prem Felix S (2003) Studies on energetic compounds Part 36: evaluation of
transition metal salts of NTO as burning rate modifiers for HTPB-AN composite solid
propellants. Combust Flame 135(1–2):145–150. doi:10.1016/S0010-2180(03)00156-1
236. Stanley JK, Lotufo GR, Biedenbach JM, Chappell P, Gust KA (2015) Toxicity of the
conventional energetics TNT and RDX relative to new insensitive munitions constituents
DNAN and NTO in Rana pipiens tadpoles. Environ Toxicol Chem 34(4):873–879. doi:10.
1002/etc.2890
237. Sutton NV, Dubb HE, Bell RE, Lysyj I, Neale BC (1965) Chemical analysis of corrosive
oxidizers. II. Instrumental analysis of nitrogen tetroxide. Advan Chem Set 54:231–236
238. Teipel U, Krober H, Krause HH (2001) Formation of energetic materials using supercritical
fluids. Propellants, Explos, Pyrotech 26(4):168–173. doi:10.1002/1521-4087(200110)26:
4<168:AID-PREP168>3.0.CO;2-X
239. Tuerker L, Atalar T (2006) Quantum chemical study on 5-nitro-2,4-dihydro-3H-1,2,
4-triazol-3-one (NTO) and some of its constitutional isomers. J Hazard Mater 137(3):1333–
1344. doi:10.1016/j.jhazmat.2006.05.015
240. Tuerker L, Bayar CC (2012) NTO-picryl constitutional isomers-A DFT study. J Energ Mater
30(1):72–96. doi:10.1080/07370652.2010.543005
241. Underwood CJ, Wall C, Provatas A, Wallace L (2012) New high nitrogen compounds
azoxytriazolone (AZTO) and azotriazolone (azoTO) as insensitive energetic materials.
New J Chem 36(12):2613–2617. doi:10.1039/c2nj40800g
242. Van der Heijden AEDM (1998) Crystallization and characterization of energetic materials.
Curr Top Cryst Growth Res 4:99–114
243. Vaullerin M, Espagnacq A, Blaise B (1998) Reparametrization of the BKW equation of state
for the triazoles and comparison of the detonation properties of HMX, TNMA, and NTO by
means of ab-initio and semiempirical calculations. Propellants, Explos, Pyrotech 23(2):73–
76. doi:10.1002/(SICI)1521-4087(199804)23:2<73:AID-PREP73>3.0.CO;2-M
244. Vaullerin M, Espagnacq A, Morin-Allory L (1998) Prediction of explosives impact
sensitivity. Propellants, Explos, Pyrotech 23(5):237–239. doi:10.1002/(SICI)1521-4087
(199811)<237:AID-PREP237>3.0.CO;2-#
245. Wallace L, Cronin MP, Day AI, Buck DP (2009) Electrochemical method applicable to
treatment of wastewater from nitrotriazolone production. Environ Sci Technol 43(6):1993–
1998. doi:10.1021/es8028878
246. Walsh MR et al (2014) Energetic residues from the detonation of IMX-104 insensitive
munitions. Propellants, Explos, Pyrotech 39(2):243–250. doi:10.1002/prep.201300095
247. Walsh MR et al (2013) Characterization of PAX-21 insensitive munition detonation
residues. Propellants, Explos, Pyrotech 38(3):399–409. doi:10.1002/prep.201200150
248. Williams GK, Brill TB (1995) Thermal decomposition of energetic materials. 68.
Decomposition and sublimation kinetics of NTO and evaluation of prior kinetic data.
J Phys Chem 99(33):12536–12539. doi:10.1021/j100033a027
249. Xie Y, Hu R, Wang X, Fu X, Zhu C (1991) Thermal behavior of 3-nitro-1,2,4-triazol-5-one
and its salts. Thermochim Acta 189(2):283–296
250. Xie Y, Hu R, Yang C, Feng G, Zhou J (1992) Studies on the critical temperature of thermal
explosion for 3-nitro-1,2,4-triazol-5-one (NTO) and its salts. Propellants, Explos, Pyrotech
17(6):298–302
251. Yang G, Nie F (2006) Preparation and characterization of core/shell structure of HMX/NTO
composite particles. Sci Technol Energ Mater 67(2):77–81
Additional Scholarly Articles for Further Reading 211

252. Yau AD, Byrd EFC, Rice BM (2009) An investigation of KS-DFT electron densities used in
atoms-in-molecules studies of energetic molecules. J Phys Chem A 113(21):6166–6171.
doi:10.1021/jp9010845
253. Ye S, Tonokura K, Koshi M (2003) Energy transfer rates and impact sensitivities of
crystalline explosives. Combust Flame 132(1/2):240–246. doi:10.1016/S0010-2180(02)
00461-3
254. Yim W-L, Z-f Liu (2001) Application of Ab initio molecular dynamics for a priori
elucidation of the mechanism in unimolecular decomposition: the case of
5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO). J Am Chem Soc 123(10):2243–2250.
doi:10.1021/ja0019023
255. Yun S-S, Kim J-K, Kim C-H (2006) Lanthanide complexes of some high energetic
compounds, crystal structures and thermal properties of 3-nitro-1,2,4-triazole-5-one
(NTO) complexes. J Alloys Compd 408–412:945–951. doi:10.1016/j.jallcom.2004.11.087
256. Zbarsky V, Basal A, Yudin N, Zhilin VF (2003) Study on solubility of 2,4-dihydro-3H-1,2,
4-triazol-3-one and 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one in diluted acid. International
Annual Conference ICT 34th:139/1–139/8
257. Zeman S (1997) Kinetic compensation effect and thermolysis mechanisms of organic
polynitroso and polynitro compounds. Thermochim Acta 290(2):199–217. doi:10.1016/
S0040-6031(96)03078-X
258. Zeman S (2003) New aspects of impact reactivity of polynitro compounds. Part IV.
Allocation of polynitro compounds on the basis of their impact sensitivities. Propellants,
Explos, Pyrotech 28(6):308–313. doi:10.1002/prep.200300021
259. Zhang TL, Hu RZ, Li FP (1994) Structural characterization and thermal decomposition
mechanisms of alkaline earth metal (Mg, Ca, Sr, and Ba) salts of 3-nitro-1,2,4-triazol-5-one.
Thermochim Acta 244(1–2):185–194
260. Zhu W et al (2015) Shaping single-crystalline trimetallic Pt-Pd-Rh nanocrystals toward
high-efficiency C-C splitting of ethanol in conversion to CO2. ACS Catal 5(3):1995–2008.
doi:10.1021/cs5018419
261. Zhurova EA, Pinkerton AA (2001) Chemical bonding in energetic materials: beta-NTO.
Acta Crystallogr B 57(Pt 3):359–365
262. Zhurova EA, Pinkerton AA (2001) Chemical bonding in energetic materials: b-NTO. Acta
Crystallogr, Sect B: Struct Sci B 57(3):359–365. doi:10.1107/S0108768100020048
263. Zhurova EA, Tsirelson VG, Stash AI, Yakovlev MV, Pinkerton AA (2004) Electronic
energy distributions in energetic materials: NTO and the biguanidinium dinitramides. J Phys
Chem B 108(52):20173–20179. doi:10.1021/jp0470997
Chapter 6
Hexanitrostilbene (HNS)

Abstract This chapter summarizes the properties of 2, 2′, 4, 4, 6, 6′ hexanitros-

tilbene (HNS) relative to more common thermally stable explosives. The very fine
crystalline HNS material, purified by extraction of impurities, is designated as
HNS-I. HNS-II is a larger particle-size, higher bulk-density, free-flowing material
obtained by recrystallization of HNS-I.

6.1 Introduction

2, 2′, 4, 4, 6, 6′ hexanitrostilbene, HNS, [also known as JD-X] is a heat resistant

explosive and has been used extensively in space applications. It was used on the
Apollo spaceship program for stage operation. It is less sensitive compared to other
compounds such as tetryl. It is used in military applications for detonating fuses.
HNS exists in two polymorphs HNS I and HNS II. HNS I appears as thin fluffy
plates where as HNS II exists in orthorhombic crystalline form. There are minor
differences in the properties of these two polymorphs, but the yield of HNS II is too
small to be of commercial use. Another form HNS IV has been by produced from
HNS II [1]. While HNS I and II are used in mild detonating fuses, HNS IV is used
as an initiator. HNS has been used in the manufacture of new booster explosives [2]
such as LX-15 (RX-26-AS) for some time. It is a heat-resistant explosive with a low
vapor pressure, high vacuum stability and a melting point between 316 and 321 °C.
Neyer [1] has reported the explosive properties of HNS-IV. The USA military
standard MIL-E-82903 is very specific of how HNS IV is made from HNS I. It
states “HNS-IV shall be crash precipitated from HNS-II which was recrystallized
from HNS-I conforming to WS 5003. HNS-II must be prepared by recrystallization
from an organic solvent system (i.e., Dimethylformamide—DMF certified) by the
process approved by the contracting agency. HNS-IV shall be a superfine particle
size material with a surface area of 5.0–25.0 square meters per gram (m/g). HNS-I
is a high explosive synthesized by a “one-step” process from trinitrotoluene
(TNT).”

© US Government (outside the USA) 2018 213

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7_6
214 6 Hexanitrostilbene (HNS)

6.2 Synthesis

Shipp [3] is credited for synthesizing HNS first by reacting tri-nitrobenzyl bromide
with alcoholic potash. Although Reich et al. [4] used a similar synthesis route
before Shipp, it was found out that the compound Reich et al. synthesized was 2, 2′,
4, 4, 6, 6′ hexanitrobibenzyl. Shipp confirmed the product to be HNS by performing
spectral and elemental analysis. The reaction path used by Shipp is shown below
(Fig. 6.1). Shipp reported an over-all yield of 40–45%.
Shipp and Kaplan [5] modified the original process of Shipp and also discussed
the reaction mechanisms. The modified reaction scheme is shown in Fig. 6.2.
Shipp [6] was issued a patent based on the above synthesis route. In this process
HNS is prepared by reacting 2,4,6-trinitrotoluene (TNT) with a 5% aqueous sodium
hypochlorite solution in the presence of tetrahydrofuran (THF) and methanol
(MeOH) as solvents. TNT is chlorinated producing trinitrobenzyl chloride, which
subsequently reacts with NaOH producing a mixture of HNS and HNBiB that
precipitates out as crystals. However, Kayser [7] noted that a combined yield of
HNS and HNBiB is less than 50% with the remainder of the material forming a
red-tar fraction. Approximately 98% of the HNS can be recovered in the crystalline
form from the product stream. However, several by-products and unreacted TNT
have been found trapped within the HNS crystals. The byproducts include HNBiB,
Anil, PiOH, PiCHOH, PiCH2Cl, chloropicrin, PiCOOH, PiCl, PiCHO, TNB, and
unreacted TNT.
Several attempts have been made to develop simple methods employing com-
paratively cheaper and less toxic solvents to get better yields of HNS. Similar
experiments with different concentrations of sodium hypochlorite at different pH
and solvent systems were attempted. The overall reaction schemes are shown

Piperidine
CHO + Pi CH3
Benzene
=
CH CHPi

HO 2
NO2 Cl NO2

HNO3 1. Pyridine
H2SO4
O2N =
CH CHPi
2. POCl3
O2N CH = CHPi

HO
NO2
NO2
3
4 NO2

NaI
PiCH = CHPi Pi = O2N
MeCOEt
HOAc 1

NO2

Fig. 6.1 Reaction path chemical structure of HNS [3]

6.2 Synthesis 215

Fig. 6.2 Shipp process 2, 2′, 4, 4, 6, 6′ hexanitrostilbene stilbene yield [5]

below. Synthesis routes for HNS have been surveyed by Singh and Singh [8] and
shown in Fig. 6.3.
Sodium hypochlorite, calcium hypochlorite or potasium hypochlorite in con-
centrations varying from 5 to 12% were used in the synthesis of HNS and 42%
yield was obtained. Procedures for the preparation of 2,4,6 trinitrobenzyl chloride
with 85% yield and 2, 2′, 4, 4′, 6, 6′ hexanitrobibenzyl with 79% yield were
reported. Later on three modifications of Shipp process were reported.

Fig. 6.3 Synthesis of Hexanitrostilbene overall reaction can be depicted TBRL (Terminal
Ballistics Research Laboratory) process [8]
216 6 Hexanitrostilbene (HNS)

6.2.1 UK Laboratory HNS Process

This report [9] describes the separation, characterization, and analysis of the
products which the Shipp hexanitrostilbene (HNS) process yields. In this process,
trinitrotoluene (TNT), dissolved in a mixture of tetrahydrofuran (THF) and
methanol (MeOH), is reacted with commercial bleach (NaOCl) to form HNS
(Fig. 6.4). Hexanitrostilbene has been tested in silver and aluminum detonating
cords. These cords were loaded with the explosive precipitated both from organic
solvents and acid solvents at two different density ranges (detonation velocities).
Thermal stability is reflected as changes in detonation velocity as a function of
temperature and time of exposure.

6.2.2 Kompolthy Process

Kompolthy et al. [10], [Hungarian Pat. T/9639 No. VE-719 (CO6 f 9/04, Fig. 6.5)],
developed a new procedure based on the air oxidation of TNT. They also observed
that the preparation of HNS from TNT could be done in two steps as follows. Shipp
and Kaplan [5] showed that TNT could be converted to HNBB or HNS using sodium
hypochlorite under varied conditions, but they did not demonstrate any procedure for
converting HNBB to HNS. Shipp and Kaplan obtained a 79% yield of HNBB from
TNT. Kompolthy et al. obtained an 82% yield of HNBB and reported yields of
76–91% of HNS from HNBB using dimethylformamide or dimethylsulfoxide as
solvents in a reaction mixture containing methanol, potassium hydroxide, copper
sulfate and pyridine. This Kompolthy et al. work has been repeated by others but
yields of only 25–40% of HNS have been obtained. There is, therefore, a need for a
process for the production of HNS in high reproducible yields.
In the synthesis of HNS, the yield depends on the concentration of the alkali and
there appears to be an optimum concentration. Some modifications have been made
to these processes in the UK [9] and Kompolthy et al. [11, 12]. Several other
processes, including continuous processes, have been described both in open and
patented literature. HNS is made industrially using the Schipp and Kaplan process
[5]. Singh and Malhotra [13] have surveyed the literature on HNS up to 1983.

Fig. 6.4 U. K. Laboratory

HNS Process [9]
6.2 Synthesis 217

Fig. 6.5 Kompolthy-Hungarian process [10]

Sleadd et al. [14] and Morris et al. [15] disclosed processes for the production of
HNS which essentially consisted of oxidative coupling of TNT in the presence of air,
methanolic potassium hydroxide solution, a polar aprotic solvent and optionally a
catalyst consisting of anhydrous copper sulphate or cobalt naphthenate (Fig. 6.6). The
first unequivocal synthesis of HNS was disclosed in U.S. Pat. No. 3,505,413 [3].

Fig. 6.6 Synthesis of HNS [14, 15]

218 6 Hexanitrostilbene (HNS)

Several modifications in starting materials, catalysts, and process parameters

have been used, and these as tabulated by Morris et al. [15] are shown below along
with original references.
• Shipp [6]: NaOCl, THF, MeOH
• Kompolthy et al. [10]: Co/Cu complex, O2, Base, Polar Aprotic Solvent (PAS)
• Duffin et al. [16]: Carboxylate base, O2, PAS
• Duffin et al. [17]: CuCl2, Carboxylate base, PAS
• Kompolthy et al. [12]: HNBB, O2, Copper complex, Base, PAS
• Gilbert [19]: HNBB, O2, Copper complex, Base, PAS
• Sollott [20]: TNBCl, THF, Methanol, Base.
• Duffin et al. [18]: HNBB, Carboxylate base, O2, PAS.
Morris et al. [21] carriedout improvements for scale-up of HNS. This is a two
step process consisting of:
1. Vary Shipp conditions to maximize HNBB—No THF, higher temperature,
added base
2. Use Gilbert process to convert HNBB to HNS—DMSO, copper amine complex
and air as the oxidant.
Bellamy [22] reaction scheme is shown in (Fig. 6.7). One can envisage that HNS
is formed by self-condensation of TNBCl (reaction between TNBCl and its con-
jugate base B), via R-chlorohexanitrobibenzyl, whilst HNBB is formed by cross
condensation of TNBCl with the conjugate base of TNT (A), the mode of addition
generating conditions which favor one or the other of these two products. In less
controlled mixing regimes both products are likely to be formed. In the batch
synthesis of HNS, the reaction occurs in essentially two stages.
Golding and Hayes [23] used Schipp synthesis and studied the effects of time,
temperature, pH, solvent composition and mode of TNT addition on the yield of
HNS. They found the reaction to be highly susceptible to variations in process
conditions, particularly the type of base and water concentrations. A British patent by
Golding et al. [24] describes the synthesis of HNS by the oxidation of TNT using
curic (II) and Co (III) salts. Various solvents including DMF, pyridine,
N-methylpyrrolidone, hexamethylphosphoramide, dioxane, N,N-dimethylacetamide,
DMSO, HMPA, di-Me propylene urea, dimethylethylene urea were used. Gilbert
[19] used different oxidizing agents in particular copper (II) compounds, halogenating
agents, quinones, and air or oxygen, in the synthesis of HNS. The reactions were
carried out in basic medium with a proper solvent.
Bellamy [25] scaled up the synthesis of HNS from 2.5 to 25 g of TNT reactant.
The author used the same reaction time but varied the diameter of the stirrer by a
factor of two. The variation of the ratio of NaOCl to TNT (0.5–1.2) and the
concentration of reactants were also investigated. Various conditions for the
after-reaction period (2 h) were explored on the basis of the author’s work with a
batch reactor, including (i) no pH control, (ii) pH control using aq. H2SO4 and
NaOH solutions, and (iii) pH control using aq. RNH3Cl and RNH2 solutions. Under
6.2 Synthesis 219

Fig. 6.7 Synthesis of HNS NO 2 NO 2

by Bellamy [22]
HO-
O2N CH3 O2N CH2

NO 2 NO 2
A
TNT
NaOCl

NO 2 NO 2

HO-
O2N CHCl O2N CH2Cl

NO 2 NO 2
B TNBCl
NO 2 O2N

TNBCl + B O2N CHCl CH2 NO 2

- Cl -

NO 2 O2N

HO- HCl

NO 2 O2N

O2N CH CH NO 2

NO 2 O 2N

HNS
NO 2 O2N

TNBCl + A O2N CH2 CH2 NO 2

-Cl-

NO 2 O2N

HNBB

most of the conditions investigated the author reports better yields and selectivity.
The intermediate in the Schipp synthesis is a-chloro-2,2′,4,4′,6,6′-hexanitrobibenzyl.
An NMR of this compound has been presented by Bellamy [25]. Lu [26] describe a
two-step process starting with TNT via an intermediate hexylnitrobibenzyl and fur-
ther oxidation. They claim good conversion of TNT and yield of HNS. The effects of
solvents in their synthesis has been described in a separate communication [27].
Orechowski et al. [28] have paid particular attention to obtain cubic crystals in
their attempt to synthesize HNS. Various parameters affecting the formation and
growth of crystals were investigated. They used tetrahydrofurane as the solvent and
N,N,N,-tertbutylamineammonium chloride as the phase transfer catalyst.
A combination of solvents and 100% fuming nitric acid was used for
220 6 Hexanitrostilbene (HNS)

crystallization, and the crystal density was 1.74 g/cm3. Prior to this study, Dacons
[29] studied the crystallization of HNS. A continuous method for the preparation of
HNS from TNT and crystallization using nitric acid is the subject of a study by
Emeury [30]. It is reported that this method yielded crystals of 6.2 m diameter
melting at 317 °C, and had a detonation velocity of 6900 ms−1 when used with 5%
poly (tetra fluoro-ethylene). A patent filed for the U.K. Defense Department
describes a process for the production of HNS by catalytic oxidation of TNT using
a cupric or a cobalt salt [31]. Yet another method of synthesis is the conversion of
4,6-trinitrobenzyl chloride to 2,2′,4,4′,6,6′-hexanitrostilbene by nitrogen bases such
as amines instead of sodium hydroxide [20]. Higher yields are reported in this route.
An interesting place where HNS IV is made is at Perkin Elmer Optoelectronics [1].

6.3 Structure

Gerard and Hardy [32] reported that HNS is monoclinic with space group P21/c,
with a = 22.326(7), b = 5.5706(9), c = 14.667(2) Å, and b = 110.04(1)°; Dm (exptl.)
= 1.74(1) and Dx(calcd.) = 1.745(1) g/cm3 for Z = 4 final R = 0.051 for 2345
reflections. The atomic coordinates are given. Two different molecules have a
symmetry center either in 2(d) o ri n2 (c). Their benzene planes are parallel
and 1.298 and 1.428 Å apart, respectively. The NO2 groups are twisted in at
5.51–48.64° with respect to the C-rings. The molecules are tilted with regard to the
axes and make a herringbone pattern. Molecular stacking gives the shortest inter-
molecular distances. A structural comparison between HNS and TNT is made.
Chang et al. [33] state that TNT and HNS are monoclinic, space group P21/c,
with a 21.230(5) and 22.083(6), b 6.081(2) and 5.554(1), c 14.958(5) and 14.634(3)
Å., and b =110.12(2) and 108.45(2)°; Z = 4, resp. The structures were solved by
direct methods and refined by block-diagonal full-matrix least-squares to R = 0.037
and 0.050, resp. The thermal-expansion coefficients are given. The bond lengths
and angles are described.
Wang et al. [34] have performed theoretical computations on the electronic
structure of HNS and its derivatives. They also correlated detonation velocities,
molecular volumes, densities detonation pressures, and bond dissociation energies
of HNS and its derivatives with various factors such as oxygen balance, number of
nitro groups, and other parameters.
A recent paper by Shu et al. [35] has dealt with the crystal structure and thermal
expansion of HNS in the temperature range of 303–513 K. They also computed the
theoretical densities of HNS in this temperature range, and present XRD patters.
The lattice parameters followed linear relations with temperature, and the density
followed the relation

q ¼ 1:7509  2:8032  104 T

6.3 Structure 221

Table 6.1 Lattice parameters of HNS [35]

T a (Å) b (Å) c (Å) b (°) Volume Density (g/ Rwpa
(°C) (Å3) cm3) (%)
30 22.3472 5.5753 14.6698 110.05 1716.98 1.7418 8.44
60 22.3927 5.5851 14.6740 110.00 1724.51 1.7342 8.21
90 22.4400 5.5961 14.6798 109.96 1732.67 1.7260 8.33
120 22.4915 5.6076 14.6864 109.92 1741.49 1.7172 8.68
150 22.5382 5.6174 14.6889 109.88 1748.94 1.7099 9.07
180 22.5931 5.6300 14.6947 109.83 1758.29 1.7008 9.55
210 22.6501 5.6431 14.7015 109.79 1768.10 1.6914 10.29
240 22.7062 5.6542 14.7025 109.74 1776.61 1.6833 11.08
210 22.6465 5.6422 14.6987 109.79 1767.19 1.6923 10.23
180 22.5928 5.6308 14.6954 109.83 1758.58 1.7006 9.68
150 22.5403 5.6190 14.6891 109.87 1749.63 1.7093 9.03
120 22.4833 5.6059 14.6796 109.91 1739.58 1.7191 8.80
90 22.4370 5.5960 14.6740 109.95 1731.85 1.7268 8.39
60 22.3901 5.5855 14.6684 110.00 1723.83 1.7348 8.34
30 22.3450 5.5757 14.6640 110.043 1716.34 1.7424 8.21

The data on crystal parameters, according to Shu et al. are shown in Table 6.1.
The authors give the initial parameters used to generate the Rietveld refinement data
shown in Table 6.1.
The XRD patterns shown in Fig. 6.8 indicate no phase changes but mere
expansion.
Table 6.2 lists some thermochemical properties of HNS.

Fig. 6.8 XRD patterns phase changes of HNS at various temperatures [35]
222 6 Hexanitrostilbene (HNS)

Table 6.2 Some properties of HNS

HNS Hexanitrodiphenylethylene, 1,2bis-(2,4,6-trinitrophenyl)-ethylene, 1,1′-
(1,2-ethenediyl)bis-(2,4,6-trinitrobenzene)
CA name Benzene, 1,1′-(1,2-ethenediyl)bis[2,4,6-trinitro-
CAS No. 20062-22-0
Empirical C14H6N6O12
formula
Structural formula NO2 NO2

CH CH

O2N NO2 O2N NO2

Molecular mass (g mole−1) 450.15
Density (g cm−3) 1.74 @ 25 °C [36,
1.847 @ 20 °C 37]
Molar volume (cm3 mol−1) 243.6  3.0, 293.15 K and 760 Torr [37]
Boiling point (°C) 578  50 [37]
Melting point (°C) 316; 317 [23]
Flash point (°C) 275.4  22.9 [37]
Crystal: Orthorhombic; Unit cell: a = 22.13, b = 5.57,
c = 14.67 Å
Kow 112 [21]
Koc 86 [17]; 383 [37]
logP 2.218  0.744, Temp: 25 °C [37]
Vapor pressure Pa (20 °C) 1.33  10−7
Vapor pressure equation log10 P ¼ 14:19  4:576T
43 010
with T in K and P in Torr
Henry’s law constant 2.7  10−9 atm m3/mL [38]
Aqueous solubility mg/L [20/25 °C] 0.22 [38]
Molar solubility (4.9  10−7 pH 1 [37]
mol/L) @ 25 °C
Enthalpy of combustion −1535.34  1.08 [39]
(k cal/mol)
Enthalpy of formation −13.89 [39]
(s) (k cal/mol)
Enthalpy of formation 29.2 [39,
(g) (K cal/mol) 69.0 40]
Enthalpy of sublimation 43.01 [41]
(K cal/mol)
Enthalpy of vaporization 19.9 [37]
(K cal/mol)
Enthalpy of detonation (K cal/ 494.9 [42]
mol)
Heat capacity Cp in [43]
(continued)
6.4 Polymorphism 223

[cal/(g °C)] Cp = 0.201 + (1.27  10−3) T − (2.36  10−6) T2

47 < T < 220; T in °C
Diffusion in air (m2/s) [20 °C] 4.5  10−6 [38]
Diffusion in water (m2/s) [20 ° 3.9  10−10 [38]
C]
Koc 383 @ pH 10 and 25 °C [37]
Bioconcenration 28.6 for pH 1 to 10 @ 25 °C [37]

6.4 Polymorphism

HNS exists in four forms—HNS I, HNS II, HNS III and HNS IV. However the
properties of I and II do not differ very much, and the yields of HNS II are low.
HNS I, HNS II, and HNS IV are the most useful forms. Singh and Malhotra [13]
have compared the properties, and some of the properties are shown in Table 6.3.
The vapor pressure of HNS measured by Rosen and Dickinson [41] are tabulated
in Table 6.4. They used the Langmuir method to collect the data, and fitted the data
to Clausius-Clapeyron type relation

43; 010
Log10 P ¼ 14:19 
4:576T

where T is in K, and P in Torr.

Table 6.3 Comparison of properties of HNS I and II [13]

HNS I HNS II
Shape of the crystal Plate like Dense orthorhombic
Melting point (K) 589.15 592.15
Bulk density (g/cm3) 0.32–0.45 0.45–1.0
DSC on set of exotherm (K) 588.15 598.15
Velocity of detonation (m/sec) [density = 1.70] 7000 7000
Autoignition point (K) 598.15 598.15
Enthalpy of combustion (k J g/mole) 6500 6500
Impact sensitivity 50% height, cm NOL-ERL 44 61

Table 6.4 Vapor pressure as Temperature (°C) VP( 10−7), Torr

a function of temperature [36]
161.4 0.396
166.4 0.592
177.3 2.15
185.8 4.97
206.3 39.4
224 6 Hexanitrostilbene (HNS)

Table 6.5 Solubility [9] of Solvent 30 40 60

HNS (g/100 ml of solvents) at
various temperatures in °C Nitrobenzene 0.059 0.072 0.094
Ethyl-methylketone 0.035 0.052 0.061
Acetone 0.064 0.075 0.131
Methanol 0.003 0.006 0.008
Dimethylformarnide 1.312 1.703 2.198
Acetonitrile 0.043 0.064 0.084
Cyclohexanone 0.118 0.156 0.206

Solubility of energetic materials such as HNS is necessary for purification by

crystallization. Singh and Malhotra [13] provide the solubility values listed in
Table 6.5.
Williams and Kuklenz [44] have determined temperature-dependent solubility of
HNS in ten solvents and solvent blends using the Tyndall effect. The solubilities of
HNS at 25 °C were used to determine the three-component Hansen solubility
parameters [HSP] (dD = 18.6, dP = 13.5, dH = 6.1 MPa1/2) and the radius of the
solubility sphere (R0 = 5.8 MPa1/2). The HSP determined for HNS using
group-additivity (dD = 21.0, dP = 13.3, and dH = 8.6 MPa1/2) also correctly pre-
dicted the optimum solvents for this explosive. Table 6.6 shows the values of HSPs
for various solvents. Ideal gas heat capacity and entrory [30] are included in
(Table 6.7).

Table 6.6 Hansen Solubility Parameters (HSPs ) of HNS in various solvents

Solvent system dD/MPa1/2 dP/MPa1/2 dH (MPa1/2) g/100 mL RED
NMP 18.0 12.3 7.2 1.940 0.440
DMF 17.4 13.7 11.3 1.310 1.000
DMF (1) 17.4 13.7 11.3 1.237 1.000
DMSO 18.4 16.4 10.2 1.210 0.816
DMF (2) 17.4 13.7 11.3 1.126 1.000
NMP + 5% Water 17.9 12.5 9.0 0.569 0.631
4-Butyrolactone 19.0 16.6 7.4 0.541 0.498
Propylene carbonate 20.0 18.0 4.1 0.475 0.841
25% ACN + 75% DMF 16.9 14.8 10 0.452 0.943
NMP + 2.5% Water 17.9 12.4 8.1 0.261 0.523
Acetophenone 19.6 8.6 13 0.195 1.000
50% ACN + 50% DMF 16.4 15.9 8.7 0.175 1.000
Cyclohexanone 17.8 6.3 5.1 0.124 1.329
75% ACN + 25% DMF 15.8 16.9 7.4 0.069 1.152
1,2-dimethoxyethane 15.4 6.0 6.0 0.064 1.754
ACN 15.3 18.0 6.1 0.062 1.369
bis(2-methoxyethyl)ether 15.8 6.1 9.2 0.056 1.736
(continued)
6.4 Polymorphism 225

Table 6.6 (continued)

Solvent system dD/MPa1/2 dP/MPa1/2 dH (MPa1/2) g/100 mL RED
p-Dioxane 19.0 1.8 7.4 0.047 2.031
Methylethyl ketone 16.0 9.0 5.1 0.044 1.270
Ethyl acetate 15.8 5.3 7.2 0.037 1.773
ACN 15.3 18.0 6.1 0.035 1.369
Methyl formate 15.3 8.4 10.2 0.030 1.653
Ethyl formate 15.5 7.2 7.6 0.024 1.606
n-Propyl formate 15.5 7.1 8.6 0.017 1.652
2-Methoxy ethanol 16.2 9.2 16.4 0.014 2.089
Ethoxy benzene 18.4 4.5 4.0 0.011 1.614
1,2-Dichloroethane 19.0 7.4 4.1 0.007 1.135
Dichloromethane 18.2 6.3 6.1 0.006 1.289
Ethyl lactate 16.0 7.6 12.5 0.006 1.780
3-Methylphenol 18.0 5.1 12.9 0.004 1.880
2-Chloroethanol 16.9 8.8 17.2 0.003 2.142
Chlorobenzene 19.0 4.3 2.1 0.002 1.734
2-Ethoxy ethanol 16.2 9.2 14.3 0.002 1.813
2-Propanol 15.8 6.1 16.4 0.002 2.387
NMP + 10% Water 17.8 12.7 10.7 <0.001 0.882
Chloroform 17.8 3.1 5.7 0.001 1.838
Cyclohexanol 17.4 4.1 13.5 0.001 2.108
Ethanol 18.8 8.8 19.4 0.000 2.377
Methanol 15.1 12.3 22.3 0.000 2.991
Solute dD/MPa1/2 dP/MPa1/2 1/2
dH (MPa ) R0/MPa1/2
F
HNS 18.9 13.9 6.1 6.0 0.9824

Table 6.7 Ideal gas heat capacity and entropy [30]

T (K) 300 400 500 600 800 1000 1500
Cpo (cal mol−1 K−1) 101.7 124.2 142.4 156.6 176.2 188.5 204.5
T (K) 2000 2500 3000 3500 4000 4500 5000
Cpo (cal mol−1 K−1) 211.6 215.3 217.4 218.7 219.6 220.2 220.7
T (K) 300 400 500 600 800 1000 1500
So (cal mol−1 K−1) 195.7 228.1 257.9 285.2 333.2 373.9
453.9
T (K) 2000 2500 3000 3500 4000 4500 5000
So (cal mol−1 K−1) 513.8 561.4 600.9 634.5 663.8 689.7
712.9
226 6 Hexanitrostilbene (HNS)

Fig. 6.9 Raman spectra of

the HNS containing
explosives in nitro-aromatic
Group A recorded with
1064-nm laser excitation over
the Raman shift range
300 ± 3600 cm2 (a) HNS 1
HNBiB, (b) HNS II, and
(c) HNS Super® ne

6.5 Spectra

Lewis et al. [45] used Fourier Transform Raman spectroscopy to measure the
spectra of several nitro-containing explosives including HNS. Figure 6.9 shows
their results collected using a 1064 nm laser excitation. Of the two HNS com-
pounds, HNS Superfine composed of particle sizes of less than 1 lm, and HNS II is
composed of particle sizes of 100 ± 300 lm. These different particle sizes lead to
changes in melting points. The spectra of these compounds appear to be similar
with slight band shifts.

6.6 Sensitivity

The sensitivity of HNS depends on the density as expected. Clement and Rudolf
[46] have carried out gap tests on HNS with density varying from 165 to 1.70
gcm−3. They were able to achieve these densities by making pellets at different
pressures varying from 2 to 4.3 kbar.

References

1. Neyer BT, Cox L, Stoutenborough T, Tomasoski R (2003) HNS-IV explosive properties and
characterization tests. 39th AIAA/ASME/-SAE/ASEE Joint Propulsion Conference and
Exhibit AIAA-2003-5138, Huntsville AL July 20–24, 2003
2. Golopol HA, Fields DB, Moody GL (1977) A new booster explosive. LX-15, Rev. 1, NTIS
Report UCRL-52175, March 18, 1977
3. Shipp KG (1964) Reactions of a-substituted polynitrotoluenes. i. synthesis of 2,2′,4,4′,6,6′-
hexanitrostilbene. J Org Chem 29(9):2620–2623
References 227

4. Reich S, Wetter O, Widmer M (1912) Über das 2.4.6-trinitro-benzylbromid und seine

derivate. Ber Dtsch Chem Ges 45(3):3055–3061
5. Shipp KG, Kaplan LA (1966) Reactions of a-substituted polynitrotoluenes. ii. the generation
and reactions of 2,4,6-trinitrobenzyl anion. J Org Chem 31:857–861
6. Shipp KG (1970) Hexanitrostilbene. US Pat 3 505 413 A
7. Kayser EG (1983) An investigation of the Shipp hexanitrostilbene (HNS) process. J Energy
Mater 1(4):325–348
8. Singh B, Singh H (1982) Synthesis of 2,2′,4,4′,6,6′-hexanitrostilbene. Def Sci J 31(4):305–
308
9. Kilmer EE (1979) Hexanitrostilbene—survey of processes of synthesis and sources of
procurement. Proc Symp Explos Pyrotech 10th: Paper No 6–7 pp
10. Kompolthy T, Bencz G, Deres J, Hajos L (1975) A Process for the preparation of
2,2′,4,4′,6,6′-hexanitrostilbene. 28 April 1975. Hung. Teljes, HU 9639 19750428
11. Kompolthy T, Bencz G, Deres J, Hajos L (1975) Process for production 2,2′,4,4′,6,6′-
hexanitrostilbene. Hungarian Patent HU167394, 28 Oct 1975
12. Kompolthy T, Deres J, Hajos LL (1976) 2,2′,4,4′,6,6′-hexanitrostilbene. Chem Abstr
84:58886
13. Singh B, Malhotra RK (1983) Hexanitrostilbene and its properties. Def Sci J 33(2):165–176
14. Sleadd B, Greer P, Mueller G, Owens J (2007) Process improvement studies for scale-up of
hns at holston army ammunition plant. NDIA insensitive munitions & energetic materials
technology symposium 2007, BAE SYSTEMS OSI, Holston Army Ammunition Plant
15. Morris J, Clark G, Price D (2009) Process improvement studies for scale-up of hns at holston
army ammunition plant. BAE SYSTEMS OSI, Holston Army Ammunition Plant
16. Duffin HC, Golding P, Jaweera-Bandar AM (1986) Production of hexanitrostilbene (HNS).
US 4626606 A Dec 2, 1986
17. Duffin HC, Golding P, Wells CHJ (1998) A Parametric study of the synthesis of 4, 4H, 5, 5H,
7, 7H-Hexanitro-1, 1H-Binaphthyl. Propellants Explosives, …, 217.148.94.129
18. Duffin HC, Golding P, Jaweera-Bandara AM (1985) Production of hexanitrostilbene (hns).
Secr Defence Brit, February 13, 1985: EP0132990-A2 (2 worldwide citation)
19. Gilbert EE (1980) The preparation of hexanitrostilbene from hexanitrobibenzyl. Propellants
Explos 5(6):168–172
20. Sollott GP (1982) Conversion of 2,4,6-trinitrobenzyl chloride to 2,2′,4,4′,6,6′-hexanitros-
tilbene by nitrogen bases. J Org Chem 47(12):2471–2474
21. Morris J, Price D, Tucker N, Dye T, Kelly T (2015) BAE systems energetics pilot plant.
Insensitive munitions & energetic material technology symposium 2015, BAE Systems
Ordnance Systems Inc. Holston Army Ammunition Plant, Kingsport TN, USA
22. Bellamy AJ (2010) Synthesis of Hexanitrostilbene (HNS) using a kenics static mixer. Org
Process Res Dev 14(3):632–639
23. Golding P, Hayes GF (1979) Studies on the synthesis of 2,2′,4,4′,6,6′-hexanitrostilbene.
Propellants Explos 4(6):115–120
24. Golding P, Jayaweera-Bandara AM, Duffin HC, Charles H (1988) Production of hexanitros-
tilbene (HNS) from trinitrotoluene oxidation by transition metal compound. EP 1988-904587
25. Bellamy AJ (2010) Identification of a-chloro-2,2′,4,4′,6,6′-hexanitrobibenzyl as an impurity
in hexanitrostilbene. J Energ Mater 28(1):1–16
26. Lu M, Sun R, Lu C, Hui J (1994) New method for synthesis of hexanitrostilbene. Nanjing
Ligong Daxue Xuebao 5:8–11
27. Lu M (1994) Solvent effect on the reaction in two-step synthesis of hexanitrostilbene.
Hanneng Cailiao 2(2):31–35
28. Orzechowski A, Powala D, Maranda A, Pawlowski W (2005) Crystallization of hexanitros-
tilben. New trends in research of energetic materials Proceedings 8th Seminar Pardubice
Czech Republic, 2005 Apr 19–21, 2:687–694
228 6 Hexanitrostilbene (HNS)

29. Dacons JC (1981) Recrystallization of hexanitrostilbene from nitric acid and water. US Patent
4260837
30. Emeury JML (1980) Hexanitrostilbene for pyrotechnic applications. Eur Space Agency. [Spec
Publ] ESA SP, (ESA SP-144 Explos Pyrotech-Appl Spat) 63–68
31. Golding P, Jayaweera-Bandara A, Duffin H (1988) Production of hexanitrostilbene (HNS).
US 5023386 A, Brit UK Pat 2205312 16 pp
32. Gerard F, Hardy A (1988) Structure of 2,2′,4,4′,6,6′-hexanitrostilbene, HNS, a comparison
with 2,4,6-trinitrotoluene, TNT. Acta Crystallo graphica Section C: Crystal Structure
Communications C 44(7):1283–1287
33. Chang HC, Tang CP, Chen YJ, Chang CL (1987) Molecular structures of 2,4,6-trinitrotoluene
(TNT) and 2,2′,4,4′,6,6′-hexanitrostilbene (HNS). Internationale
Jahrestagung-Fraunhofer-Institut fuer Treib- und Explosiv- stoffe 18th (Technol Energ
Mater) 51/1-51/13
34. Wang G-X, C-h Shi, X-d Gong, H-m Xiao (2009) Theoretical investigation on structures,
densities, detonation properties, and the pyrolysis mechanism of the derivatives of HNS.
J Phys Chem A 113(7):1318–1326
35. Shu X, Tian Y, Song G, Zhang H, Kang B, Zhang C, Liu Y, Liu X, Sun J (2011) Thermal
expansion and theoretical density of 2,2′,4,4′,6,6′-hexanitrostilbene. J Mater Sci 46(8):2536–
2540
36. Meyer R, Kohler J, Homburg A (2002) Explosives. 5th ed Wiley–VCH
37. Calculated using Advanced Chemistry Development (ACD/Labs) Software V904 for Solaris
(1994–2008) (ACD/Labs)
38. Environment Agency (2000) Collation of. toxicological data and development of guideline
values for expansion substances. R&D Project Record P5-036/01, Bristol, 2000
39. Martantz S, Armstrong GT (1968) Heats of combustion of trans-stilbene and
trans-2,2′,4,4′,6,6′-hexanitrostilbene (HNS). J Chem Eng Data 13:118–121
40. Osmont A, Catoire L, Gökalp I, Yang V (2007) Ab initio quantum chemical predictions of
enthalpies of formation, heat capacities, and entropies of gas-phase energetic compounds.
Combust Flame 151:262–273
41. Rosen JM, Dickinson C (1969) Vapor pressures and heats of sublimation of some high
melting organic explosives. J Chem Eng Data 14:120–124
42. Ornellas DL (1982) Calorimetric determinations of the heat and products of detonation for
explosives: October 1961 to April 1982. Rep UCRL-52821, LLNL, USA
43. Department Of The Army Technical Manual (1984) Military Explosives, TM 9-1300-214
Department of Army, September 1984
44. Williams DL, Kuklenz KD (2009) A determination of the hansen solubility parameters of
hexanitrostilbene (HNS). Propellants, Explos, Pyrotech 34(5):452–457
45. Lewis IR, Daniel NW Jr, Griffiths PR (1997) Interpretation of raman spectra of
nitro-containing explosive materials: Part I: Group frequency and structural class
membership. Appl Spectros 51:1854–1867
46. Clement D, Rudolf K (2006 Apr 19–21) Hexanitrostilbene—density dependent sensitivity.
New Trends in Research of Energetic Materials Proc 9th Seminar Pardubice Czech Republic
540–543

Additional Scholarly Articles for Further Reading

47. Achuthan CP, Samudre SS, Gharia JS (1984) Hexanitrostilbene—a heat-resistant explosive.
J Sci Ind Res 43(4):197–199
48. Aziz A, Cartwright M, Hill CJ (1996) Thermal stability of the crystallization nucleant:
2,4,6-trinitrotoluene, TNT, and 2,2′,4,4′,6,6′-hexanitrostilbene. HNS. J Therm Anal 47
(6):1617–1628. doi:10.1007/BF01980908
Additional Scholarly Articles for Further Reading 229

49. Bellamy AJ, Brzoska E (2003) Contamination of explosive materials with

N-methylpyrrolidin-2-one (NMP). J Energ Mater 21(1):43–55. doi:10.1080/
07370650305583
50. Bellamy AJ, Price TP, Mahon MF, Drake R, Mansell J (2005) Crystal structure of the 1:1
adduct of hexanitrostilbene and dioxane. J Energ Mater 23(1):33–41. doi:10.1080/
07370650590920278
51. Can Z, Uezer A, Tekdemir Y, Ercag E, Tuerker L, Apak R (2012) Spectrophotometric and
chromatographic determination of insensitive energetic materials: HNS and NTO, in the
presence of sensitive nitro-explosives. Talanta 90:69–76. doi:10.1016/j.talanta.2011.12.077
52. Cartwright M, Collett GC (1993) Effect of additives on the nucleation of TNT. J Energy
Mater 11(3):167–193. doi:10.1080/07370659308227809
53. Cartwright M, Hill CJ (1995) Thermal investigation of the crystallization nucleant formed
between 2,4,6-trinitrotoluene, (TNT) and 2,2′,4,4′,6,6′-hexanitrostilbene (HNS). J Therm Anal
44(5):1021–1036. doi:10.1007/BF02547530
54. Casetta B, Garofolo F (1994) Characterization of explosives by liquid chromatography/mass
spectrometry and liquid chromatography/tandem mass spectrometry using electrospray
ionization and parent-ion scanning techniques. Org Mass Spectrom 29(10):517–525. doi:10.
1002/oms.1210291002
55. Chen L-Z, Zhou F-R, Wang J-L (2014) Solubilities of 2,4,6-Trinitrotoluene in Methanol and
Binary Mixtures of Methanol + Water from 293.15 to 333.15 K. J Solution Chem 43
(12):2163–2169. doi:10.1007/s10953-014-0263-3
56. Clement D, Rudolf KP (2007) The shock initiation threshold of HNS as a function of its
density. Propellants, Explos, Pyrotech 32(4):322–325. doi:10.1002/prep.200700035
57. da Silva G, Iha K, Cardoso AM, Mattos EC, Dutra RdCL (2010) Study of the thermal
decomposition of 2,2′,4,4′,6,6′-hexanitrostilbene. J Aerosp Technol Manage 2(1):41–46
58. Du Z, Zhang R, Fu D, Tong H, Li F (2012) Study on cook-off test of HNS at constant
temperatures. Procedia Eng 45:580–583. doi:10.1016/j.proeng.2012.08.207
59. Fourmigue M, Boubekeur K, Batail P, Renouard J, Jacob G (1998) Light-induced detonant
materials: charge-transfer complexes of tetrathiafulvalene (TTF) with hexanitrostilbene
(HNS) and tetraazidoquinone (TAZQ) and their associated C-HO hydrogen-bonded
networks. New J Chem 22(8):845–850. doi:10.1039/a709257a
60. Gallo AE, Tench N (1984) Commissioning of a production plant for hexanitrostilbene.
J Hazard Mater 9(1):5–11. doi:10.1016/0304-3894(84)80002-3
61. Golding P, Hayes GF (1983) A parametric study of the synthesis of 2,2′,4,4′,6,6′-
hexanitrostilbene from trinitrotoluene and sodium hypochlorite. Propellants, Explos,
Pyrotech 8(2):35–39. doi:10.1002/prep.19830080202
62. Huang P, Shi W (2011) Study on terahertz time-domain spectroscopy of HNS by sample
measure and quantum chemistry calculation. Propellants, Explos, Pyrotech 36(6):513–518.
doi:10.1002/prep.201010041
63. Kaur J, Arya VP, Kaur G, Gupta YP, Verma MM, Lata P (2010) Determination of solvent
contamination and characterization of ultrafine HNS particles after solvent recrystallization.
Propellants, Explos, Pyrotech 35(5):487–493. doi:10.1002/prep.200800094
64. Kaur J, Arya VP, Kaur G, Lata P (2013) Evaluation of the thermomechanical and explosive
properties of bimodal and hybrid polymer bonded explosive (PBX) compositions based on
HNS and HMX. Cent Eur J Energy Mater 10(3):371–391
65. Kilmer EE (1968) Heat-resistant explosives for space applications. J Spacecraft Rockets 5
(10):1216–1219. doi:10.2514/3.29452
66. Kony M, Dagley IJ, Whelan DJ (1992) Deuterium isotope effects on the rates of thermal
decomposition of 2,2′,4,4′,6,6′-hexanitrostilbene in the condensed phase. J Phys Chem 96
(20):8001–8006. doi:10.1021/j100199a034
67. Lee J-S, Hsu C-K, Chang C-L (2002) A study on the thermal decomposition behaviors of
PETN, RDX, HNS and HMX. Thermochim Acta 392–393:173–176. doi:10.1016/S0040-
6031(02)00099-0
230 6 Hexanitrostilbene (HNS)

68. Liu G-h, Ye Z, Li H, Che R, Cui L (2012) Biological treatment of hexanitrostilbene

(HNS) produced wastewater using an anaerobic-aerobic immobilized microbial system. Chem
Eng J (Amsterdam, Neth) 213:118–124. doi:10.1016/j.cej.2012.09.115
69. Liu R, Zhang T, Zhou Z, Yang L, Yu W (2015) Nanoscale Effect on Thermal Decomposition
of 2,2′,4,4′,6,6′-hexanitrostilbene by Dynamic Pressure Measuring Thermal Analysis. J Energ
Mater 33(1):34–50. doi:10.1080/07370652.2013.877103
70. Lu T, Yao K, Mao Y, Xu J, Wang P, Lu M (2013) A Novel and Efficient Synthesis of
Hexanitrostilbene by N-Hydroxyphthalimide/FeCl2-Catalyzed Aerobic Dehydrogenation of
Hexanitrobibenzyl. J Energ Mater 31(3):217–223. doi:10.1080/07370652.2012.710870
71. Lu T-t, Lu M (2012) Efficient 2,2,6,6-tetramethylpiperidine-1-oxyl/iron catalyzed aerobic
dehydrogenation of hexanitrobibenzyl to hexanitrostilbene. J Chin Chem Soc (Weinheim,
Ger) 59(7):899–903. doi:10.1002/jccs.201100473
72. Minier LM, Oxley JC (1990) Thermolysis of nitroarenes: 2,2′,4,4′,6,6′-hexanitrostilbene.
Thermochim Acta 166:241–249. doi:10.1016/0040-6031(90)80185-2
73. Mohan VK, Field JE (1984) Impact initiation of hexanitrostilbene. Combust Flame 56
(3):269–277. doi:10.1016/0010-2180(84)90061-0
74. Oxley JC, Smith JL, Yue J, Moran J (2004) Hypergolic reactions of TNT. Proc NATAS Annu
Conf Therm Anal Appl 32nd:113.17.583/1–113.17.583/7
75. Parry MA, Thorpe BW (1979) The role of HNS (2,2′,4,4′,6,6′-hexanitrostilbene) in the grain
modification of TNT. J Cryst Growth 47(4):541–550. doi:10.1016/0022-0248(79)90137-4
76. Philp DK, Thorpe BW (1976) Nucleation of 2,4,6-trinitrotoluene by 2,2′,4,4′,6,6′-
hexanitrostilbene. J Cryst Growth 35(2):133–138
77. Qian W, Shu Y, Li H, Ma Q (2014) The effect of HNS on the reinforcement of TNT crystal: a
molecular simulation study. J Mol Model 20(10):1–7. doi:10.1007/s00894-014-2461-8
78. Rieckmann T, Volker S, Lichtblau L, Schirra R (2001) Investigation on the thermal stability
of hexanitrostilbene by thermal analysis and multivariate regression. Chem Eng Sci 56
(4):1327–1335. doi:10.1016/S0009-2509(00)00355-9
79. Rieckmann T, Volker S, Lichtblau L, Schirra R (2001) Thermal decomposition of
hexanitrostilbene at low temperatures. J Anal Appl Pyrolysis 58–59:569–587. doi:10.1016/
S0165-2370(00)00177-7
80. Selig W, Schroyer B, Silveira VG, Smathers ER (1972) Charge transfer complexes of
2,2′,4,4′,6,6′ hexanitrostilbene (HNS). Explosivstoffe 20(11–12):204–218
81. Setchell RE (1984) Grain-size effects on the shock sensitivity of hexanitrostilbene
(HNS) explosive. Combust Flame 56(3):343–345
82. Setchell RE, Taylor PA (1988) A refined equation of state for unreacted hexanitrostilbene.
J Energy Mater 6(3–4):157–199. doi:10.1080/07370658808012553
83. Shui M et al. (2013) Photothermal decomposition of HNS at 532 nm. Opt (Munich, Ger) 124
(23):6115–6118. doi:10.1016/j.ijleo.2013.04.089
84. Sitzmann ME, Foti SC (1975) Solubilities of explosives. Dimethylformamide as general
solvent for explosives. J Chem Eng Data 20(1):53–55. doi:10.1021/je60064a032
85. Sun Y et al (2013) Laser-induced decomposition of 2,2′,4,4′,6,6′-hexanitrostilbene at 263, 527
and 1053 nm. Asian J Chem 25(8):4247–4250. doi:10.14233/ajchem.2013.13914
86. Sun Y, Xu T, Shu Y, Zhong F (2013) UV-induced photodecomposition of 2, 2′, 4, 4′, 6, 6′-
hexanitrostilbene (HNS). Mater Sci-Pol 31(3):306–311. doi:10.2478/s13536-013-0105-9
87. Taylor RE, Groot H, Donaldson AB (1983) Thermal diffusivity of hexanitrostilbene
(HNS) high explosive. Therm Conduct 16:251–260
88. Teipel U, Mikonsaari I (2002) Size reduction of particulate energetic material. Propellants,
Explos, Pyrotech 27(3):168–174. doi:10.1002/1521-4087(200206)27:3<168:AID-
PREP168>3.0.CO;2-D
89. Wang G, Gong X, Xiao H (2013) A theoretical study on the vibrational spectra and
thermodynamic properties for the derivatives of HNS with -CH3, -N3, and -NF2 groups. Adv
Mater Res (Durnten-Zurich, Switz) 742:202–208. doi:10.4028/www.scientific.net/AMR.742.
202
Additional Scholarly Articles for Further Reading 231

90. Wang G-X, Gong X-D, Liu Y, Xiao H-M (2013) A theoretical study on the infrared spectra,
thermodynamic functions, and detonation parameters for the -CN, -NC, -NNO2, and -ONO2
derivatives of HNS. J Theor Comput Chem 12(1):1250095/1–1250095/14. doi:10.1142/
S0219633612500952
91. Wang J et al (2009) Prefilming twin-fluid nozzle assisted precipitation method for preparing
nanocrystalline HNS and its characterization. J Hazard Mater 162(2–3):842–847. doi:10.
1016/j.jhazmat.2008.05.107
92. Waschl J, Richardson D (1991) Effect of specific surface area on the sensitivity of
hexanitrostilbene to flyer plate impact. J Energy Mater 9(4):269–282. doi:10.1080/
07370659108018628
93. Waschl JA (1996) Temperature effects on the performance of a complete explosive device.
J Energy Mater 14(3 & 4):153–171. doi:10.1080/07370659608216062
94. Zengguo F, Boren C (1994) Studies on reactions of polynitrostilbenes with sodium azide.
J Energy Mater 12(4):237–247. doi:10.1080/07370659408018653
95. Zhu W, Shi C, Xiao H (2009) Density functional theory study of high-pressure behavior of
crystalline hexanitrostilbene. J Mol Struct: THEOCHEM 910(1–3):148–153. doi:10.1016/j.
theochem.2009.06.029
Chapter 7
N-Methy-4-Nitroaniline (MNA)

Abstract N-Methyl-4-nitroaniline (MNA) is used as an additive to lower the

melting temperature of energetic materials in the synthesis of insensitive explosives.
This chemical is commonly used as an intermediate in the synthesis of dyes,
antioxidants, pharmaceuticals and gasoline, in gum inhibitors, poultry medicines,
and as a corrosion inhibitor.

7.1 Introduction

N-Methyl-4-nitroaniline is a stabilizer which enhances the service life of

double-base and minimum smoke propellants. The use of MNA as a stabilizer has
been discussed Provatas and Davies [1]. They considered RDX/MNA and DNAN/
MNA fortheir vacuum thermal stability tests, and obtained temperature of ignition
for these mixtures. They also provide the DSC of pure components and mixtures.
Some defence standards for MNA have been issued by the Ministry of Defence UK
[2]. Padmanabhan et al. [3] carried out methylation of several aromatic amines, and
obtained 20% yields of MNA. The spectral characteristics of n(NH) absorption
bands of ‘free’ N-methyl-4-nitroaniline with various proton acceptors were deter-
mined within the temperature range 285–350 K [4].
In Table 7.1, proton acceptors are specified along with enthalpy, entropy, and
equilibrium constants for the complex. a is the slope of the enthalpy-spectral shift
relation.

7.2 Solvents

The effect of solvent mixtures on the electronic spectra of MNA has been studied by
Seifried and Bekárek [5]. Table 7.2 shows the wave numbers for the stated mixture
of solvents. In Table 7.2, wave numbers are in (cm−1. 103). Extensive data are
reported in the paper.

© US Government (outside the USA) 2018 233

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7_7
234 7 N-Methy-4-Nitroaniline (MNA)

Table 7.1 Thermodynamic properties of MNA complexes [4]

Proton a −ΔHcalc −ΔHexp ΔS K298
Acceptor (kcal mole−1) (kcal mole−1) (cal mole−1 K−1) (dm3 mol−1)
CH3CN 6.2 4.0 4.1 12.3 2.1
THF 3.9 4.5 13.1 3.0
DMF 6.8 7.1 18.8 12.1
DMSO 7.7 8.5 22.5 21.4
HMPA 9.6 9.3 23.9 39.1

Table 7.2 Effect of solvents on electronic spectra of MNA [5]

Hexane + acetone
vol.% 0 20 40 60 80 100
Wave No. 24.75 23.98 23.81 23.70 23.64 23.41
Cyclohexanol + ethanol
vol.% 0 20 40 60 80 100
Wave No. 29.22 26.74 26.46 26.32 26.25 26.09

7.3 Physical Properties

Two publications, Toghiani et al. [6] and Boddu et al. [7], provide information on
thermophysical properties of MNA. Toghiani et al. used estimation procedures to
evaluate physical properties where as Boddu et al. provide experimental data on
aqueous solubility (Sw), octanol–water partition coefficient (Kow), and Henry’s law
constant (KH). Their data along with other data are shown in Table 7.3.

7.4 Solubility

The experimental aqueous solubility data of Boddu et al. [7] as a function of

temperature in different media are presented in Table 7.4.
The predicted solubility data of Togiani et al. [6] is shown in Fig. 7.1.
A comparison of the experimental data of Boddu et al. [7] with the predicted data of
Toghiani et al. [6] shows that they differ by orders of magnitude, and points to the
fact that the predicted data have to be carefully analyzed before they are used for
any purpose.

7.5 Spectrum

The IR absorption spectrum is shown in Fig. 7.2, and NMR in Fig. 7.3.
7.5 Spectrum 235

Table 7.3 Some properties of N-Methy-4-nitroaniline

Name N-Methy-4-nitroaniline
Other names: Aniline, N-methyl-p-nitro- (6CI,7CI,8CI); 4-
(Methylamino)nitrobenzene; 4-Nitro-N-methylaniline;
Methyl(4-nitrophenyl)amine; N-Methyl-4-nitroaniline;
N-Methyl-4-nitrobenzenamine; N-Methyl-p-nitraniline;
N-Methyl-p-nitroaniline; N-Monomethyl-p-nitroaniline;
NSC 5390; p-(Methylamino)nitrobenzene;
p-Nitro-N-methylaniline
CAS Number: 100-15-2
Structural formula: C2N

NHMe
Empirical Formula: C7 H8N2O2
Molecular Mass (g mole−1) 152.15
Density (g/cm3) 1.26
Molar Volume, cm3/mol @ 298.15 K and 760 Torr 120.7 ± 3.0
Boiling point (K) 527; 563.75 [6],
[8]
Melting point 423.15 [6]
Flash point (K) 402.65 ± 22.6 [8]
Critical temperature (K) 748 [6]
Critical pressure (bar) 41.7 [6]
Acentric factor 0.659 [6]
Log Kow 2.04; 1.47; 1.574; 0.807 [6]
2.1028 ± 0.0209 @ [7]
298.15 K
1.9846 ± 0.0305 @ [7]
308.15 K
1.9377 ± 0.0146 @ [7]
318.15 K
Enthalpy of fusion (kJmol−1) 18.85 [6]
Enthalpy of vaporization (kJmol−1) 53.00 ± 3.0 [8]
Vapor pressure, Torr @ 298.15 K 2.05  10−3 [8]
Aqueous solubility, mg l−1 @ 298.15 K 1.17; 0.347 [6]
971.3 (Ideal solubility) [6]
Henry’s Law Constant:
(continued)
236 7 N-Methy-4-Nitroaniline (MNA)

Table 7.3 (continued)

Name N-Methy-4-nitroaniline
KH (M3 Pa mol−1) 0.6100 @ 298.15 K [7]
0.5566@ 308.15 K [7]
0.5160@ 318.15 K [7]
KH (dimentionless g/aq) 2.46  10−4 @ [7]
298.15 K
2.25  10−4 @ [7]
308.15 K
2.08  10−4 @ [7]
318.15 K
pKa (Most Basic @ 298.15 K) 0.56 ± 0.12 [8]
Koc in the pH range of 1–10 @ 298.15 K 225–306 [8]
Bioconcentration factor @ pH 1.0–10 15.3–20.9 [8]

Table 7.4 Aqueous solubility in presence of NaCl and CaCl2 salts at different temperatures [7]
Medium Solubility (mg/L)
298.15 K 308.15 K 318.15 K
Water 85.42 ± 0.85 111.51 ± 1.12 141.93 ± 1.42
1% NaCl 79.49 ± 0.80 96.65 ± 0.97 128.17 ± 1.28
5% NaCl 63.69 ± 0.64 75.51 ± 0.76 113.96 ± 1.14
10% NaCl 49.56 ± 0.50 58.22 ± 0.58 76.28 ± 0.76
1% CaCl2 82.82 ± 0.83 104.99 ± 1.05 134.81 ± 1.35
5% CaCl2 72.30 ± 0.72 95.03 ± 0.95 117.29 ± 1.17
10% CaCl2 60.62 ± 0.61 85.84 ± 0.86 101.28 ± 1.01
7.5 Spectrum 237

Fig. 7.1 Solubility as a function of temperature [6]

Fig. 7.2 IR Spectra of MNA (Source: Integrated Spectral Database System of Organic
Compounds, data were obtained from the National Institute of Advanced Industrial Science and
Technology, Japan)
238 7 N-Methy-4-Nitroaniline (MNA)

Fig. 7.3 NMR spectrum. Source: Spectral data were obtained from Wiley Subscription Services,
Inc. (US)

References

1. Provatas A, Davies PJ (1998) DNAN—A Replacement for TNT in Melt-Cast Formulations.

Australian Melt-cast Research and Development, Explosives & Pyrotechnics Group,
Weapons Systems Division, Defence Science and Technology Organisation, EDINBURGH
SA
2. Ministry of Defence (1990) N-METHYL-4-NITROANILINE. UK 68–37 Issue 2, 23 March
1990
3. Padmanabhan S, Laxma RN, Durant GJ (1997) A convenient one pot procedure for
N-methylation of aromatic amines using trimethyl orthoformate. Synth Commun 27(4):691–
699
4. Borisenkoa VE, Yu A, Zavjalovaa TG, Tretjakovaa ZS, Kozlovaa A, Koll J (2004)
Thermodynamic properties of the hydrogen bonded complexes between N-substituted anilines
and proton acceptors. Molecular Liquids 109:125–135
5. Seifried R, Bekárek V (1998) Solvent effect of mixed solvents on the electronic spectra of
N-methyl-2-nitroaniline and N-methyl-4-nitroaniline. Acta Universitatis Palackianae
Olomucensis FACULTAS RERUM NATURALIUM 1998 CHEMICA 37
6. Toghiani RK, Toghiani H, Maloney SW, Boddu VM (2008) Prediction of physicochemical
properties of energetic materials. Fluid Phase Equilib 264:86–92
7. Boddu VM, Krishnaiah A, Maloney SW, Damavarapu R (2008) Physicochemical properties of
an insensitive munitions compound, N-methyl-4-nitroaniline (MNA). J Hazardous Materials
155:288–294
8. Calculated using Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris
(1994–2008 ACD/Labs)
Additional Scholarly Articles for Further Reading 239

Additional Scholarly Articles for Further Reading

9. Abraham MH, Duce PP, Morris JJ, Taylor PJ (1987) Hydrogen bonding Part 2 Equilibrium
constants and enthalpies of complexation for 72 monomeric hydrogen-bond acids with
N-methylpyrrolidinone in 1,1,1-trichloroethane. J Chem Soc, Faraday Trans 1 83(9):2867–81
doi:10.1039/f19878302867
10. Ahmed A, Sandler SI (2012) Solvation free energies and hydration structure of
N-methyl-p-nitroaniline. J Chem Phys 136(15):154505
11. Bailey RT, Cruickshank FR, Pavlides P, Pugh D, Sherwood JN (1991) Organic materials for
nonlinear optics: interrelationships between molecular properties, crystal structure, and optical
properties. J Phys D Appl Phys 24(2):135–145. doi:10.1088/0022-3727/24/2/009
12. Basque P, Ritcey AM (1994) Langmuir-Blodgett films from a cellulose derivative containing
N-methyl-4-nitroaniline. Polym Mater Sci Eng 71:488–489
13. Benchabane M (1993) Gas evolution analysis III Chemical compatibility study of GAP based
propellant by the DVST. J Energ Mater 11(2):119–34. doi:10.1080/07370659308018643
14. Boddu VM, Maloney SW (2012) Physical properties of insensitive munitions compounds for
developing wastewater treatment technologies. In: Air & Waste Management Association, vol
3. p 1958–1965
15. Buncel E, Rajagopal S (1989) Solvatochromic studies of novel azo merocyanine dyes. The
p*azo scale of solvent polarity. J Org Chem 54(4):798–809. doi:10.1021/jo00265a017
16. Damman P, Vallee R, Dosiere M, Toussaere E, Zyss J (2001) Oriented crystallization of NLO
organic materials. Synth Met 124(1):227–232. doi:10.1016/S0379-6779(01)00459-3
17. Dezern JF (1988) Synthesis and characterization of BTDA-based poly(amide imides).
J Polym Sci Part A: Polym Chem 26(8):2157–2169. doi:10.1002/pola.1988.080260813
18. Drago RS (1992) Extension of the unified scale of solvent polarities to acceptor probes:
concerns about b-p* parameters. J Org Chem 57(24):6547–6552. doi:10.1021/jo00050a033
19. Eilmes A (2014) Solvatochromic probe in molecular solvents: implicit versus explicit solvent
model. Theor Chem Acc 133(9):1–13. doi:10.1007/s00214-014-1538-x
20. Elliot MS, Smith FJ, Fraser AM (2000) Synthetic procedures yielding targeted nitro and
nitroso derivatives of the propellant stabilisers diphenylamine, N-methyl-4-nitroaniline, and
N, N’-diethyl-N, N’-diphenylurea. Propellants Explos Pyrotech 25(1):31–36. doi:10.1002/
(SICI)1521-4087(200001)25:1<31:AID-PREP31>3.0.CO;2-Z
21. Ferguson G, Glidewell C, Low JN, Skakle JMS, Wardell JL (2001) Hydrogen bonding in
C-methylated nitroanilines: the three-dimensional framework structure of
2-methyl-4-nitroaniline. Acta Crystallogr, Sect C: Cryst Struct Commun C 57(3):315–316.
doi:10.1107/S0108270100019405
22. Fife TH, Bembi R (1993) Metal ion promoted hydroxide ion and water catalyzed hydrolysis
of amides. Effects of the acyl group and the leaving group. J Am Chem Soc 115(24):11358–
11363. doi:10.1021/ja00077a039
23. Gajda K, Daszkiewicz Z, Kozubek E, Ejsmont K, Zarychta B (2014) Theoretical multipolar
atom model transfer in nitro-derivatives of n-methylaniline. Cryst Growth Des 14(11):5737–
5748. doi:10.1021/cg500984p
24. Garofalo A et al (2010) Design, synthesis, and dna-binding of n-alkyl(anilino)quinazoline
derivatives. J Med Chem 53(22):8089–8103. doi:10.1021/jm1009605
25. Hayashi S (1999) Differential broadening caused by dipolar interaction with 1H in 13C
MAS NMR signals split by residual dipolar interaction with 14N. Magn Reson Chem 37
(11):843–851
26. Hayata K, Yanagawa K, Koshiba M (1990) Field analysis of the Cherenkov doubling of
infrared coherent radiation utilizing an organic crystal core bounded by a glass capillary.
J Appl Phys 68(12):6033–6043. doi:10.1063/1.346915
27. Kanoun MB, Botek E, Champagne B (2010) Electrostatic modeling of the linear optical
susceptibilities of 2-methyl-4-nitroaniline, m-nitroaniline, 3-methyl-4-nitropyridine N-oxide
240 7 N-Methy-4-Nitroaniline (MNA)

and 2-carboxylic acid-4-nitropyridine-1-oxide crystals. Chem Phys Lett 487(4–6):256–262.

doi:10.1016/j.cplett.2010.01.021
28. Kanoun MB, Champagne B (2011) Calculating the second-order nonlinear optical
susceptibilities of 3-methyl-4-nitropyridine N-oxide, 2-carboxylic
acid-4-nitropyridine-1-oxide, 2-methyl-4-nitroaniline, and m-nitroaniline crystals. Int J
Quantum Chem 111(4):880–890. doi:10.1002/qua.22852
29. Keswani CL, Weber DJ (1967) Thin-layer chromatography of substituted nitroanilines and
related compounds. J Chromatogr 30(1):130–135. doi:10.1016/S0021-9673(00)84121-7
30. Khan F, Pal D, Ghosh A, Cameotra SS (2013) Degradation of 2,4-dinitroanisole (DNAN) by
metabolic cooperative activity of Pseudomonas sp. strain FK357and Rhodococcus imtechen-
sis strain RKJ300. Chemosphere 93(11):2883–2888. doi:10.1016/j.chemosphere.2013.09.005
31. Ko C-J et al (2013) Nitroanilines enhancing the holographic data storage characteristics of the
9,10-phenanthrenequinone-doped poly(methyl methacrylate) photopolymer. J Appl Polym
Sci 127(1):643–650. doi:10.1002/app.37835
32. Kobeissi M, Yazbeck O, Chreim Y (2014) A convenient one-pot synthesis of polysubstituted
pyrroles from N-protected succinimides. Tetrahedron Lett 55(15):2523–2526. doi:10.1016/j.
tetlet.2014.03.021
33. Kodiyath R et al (2013) Assemblies of silver nanocubes for highly sensitive SERS chemical
vapor detection. J Mater Chem A 1(8):2777–2788. doi:10.1039/c2ta00867j
34. Kumar VMMJ, Shameer H, Jayadevaiah KV, Jayachandran E, Sreenivasa GM (2009)
Synthesis, characterization and biological evaluation of thiazolidinone derivatives as potential
antimicrobial agents. J Chem Pharm Sci 2(2):128–131
35. Lebegue N, Gallet S, Flouquet N, Carato P, Giraudet S, Berthelot P (2004) Synthesis of
4-methoxybenzylamino derivatives of dibenzothiadiazepine dioxide. Heterocycles 63
(11):2457–2463. doi:10.3987/COM-04-10095
36. Longo M, Cavallaro A (1996) Determination of aromatic amines at trace levels by
derivatization with heptafluorobutyric anhydride and gas chromatography - electron-capture
negative-ion chemical ionization mass spectrometry. J Chromatogr A 753(1):91–100
37. Nesterov VN, Timofeeva TV, Borbulevych OY, Antipin MY, Clark RD (2000) A
combinatorial chemistry approach to new materials for non-linear optics. I. Five schiff bases.
Acta Crystallogr, Sect C: Cryst Struct Commun C56(8):971–975. doi:10.1107/
S0108270100002845
38. Nunes N, Elvas-Leitao R, Martins F (2014) UV-Vis spectroscopic study of preferential
solvation and intermolecular interactions in methanol/1-propanol/acetonitrile by means of
solvatochromic probes. Spectrochim Acta, Part A 124:470–479. doi:10.1016/j.saa.2014.01.
021
39. Ojo IAO, Ajayi I, Akingbohungbe AE, Adereti A (2006) The synthesis and assessment of
some benzyl anilinomethyl sulfides as insecticides. Int J Chem (Calcutta, India) 16(1):21–28
40. Patel KD, Patel CN, Patel GM (2014) Synthesis and antidiabetic activity of novel
4-substituted-N-[phenyl(2,4,5-triphenyl-1H-imidazol-1-yl)methyl]benzenamine. Inventi
Impact: Med Chem(4):142–145, 4 pp
41. Pavlat P, Hlavac J, Bekarek V (1998) Solvent effect on electronic and vibrational spectra of
N-methyl-2-nitroaniline and N-methyl-4-nitroaniline. Chem Pap 52(4):226–229
42. Pavlat P, Hlavac J, Bekarek V (1997) Solvent effect on electronic and vibrational spectra of
N-methyl-2-nitroaniline and N-methyl-4-nitroaniline. In: Vydavatelstvo STU, p 111–112
43. Platten WE 3rd, Bailey D, Suidan MT, Maloney SW (2010) Biological transformation
pathways of 2,4-dinitro anisole and N-methyl paranitro aniline in anaerobic fluidized-bed
bioreactors. Chemosphere 81(9):1131–1136
44. Sena VLM, Srivastava RM, de Simone CA, da Cruz Goncalves SM, Silva RO, Pereira MA
(2007) Conventional and microwave-assisted reaction of N-(hydroxymethyl)phthalimide with
arylamines: synthesis of N-[(arylamino)methyl] phthalimide derivatives. J Braz Chem Soc 18
(6):1224–1234
45. Smiataczowa K, Maj K, Widernik T, Nesterowicz M (1998) Basicity of
N-arylglucopyranosylamines in methanol. Pol J Chem 72(3):587–594
Additional Scholarly Articles for Further Reading 241

46. Sophy KB, Shedge SV, Pal S (2008) Noniterative Density Functional Response Approach:
Application to Nonlinear Optical Properties of p-Nitroaniline and Its Methyl-Substituted
Derivatives. J Phys Chem A 112(44):11266–11272
47. Steinmetz FP et al (2014) Methods for assigning confidence to toxicity data with multiple
values—Identifying experimental outliers. Sci Total Environ 482–483:358–365
48. Stephens J, Gebre T, Batra AK, Aggarwal MD, Lal RB (2003) Microhardness studies on
organic crystals. J Mater Sci Lett 22(3):179–180
49. Tayebee R, Rezaei Seresht E, Jafari F, Rabiei S (2013) Simple Methodology for the Aerobic
N-Methylation of Substituted Anilines Catalyzed by Zirconium Oxychloride Octahydrate,
ZrOCl2
8H2O. Ind Eng Chem Res 52(32):11001–11006
50. Turker L (2013) Detonation velocity—a molecular aspect. Adv Chem Model 4:223–236
51. Vijay Kumar MMJ et al (2009) N-substituted-thiazolidinones: synthesis and characterization
of new novel anti-inflammatory agents. Int J Pharm Sci 1(1):42–54
52. Vijay Kumar MMJ, Jayadevaiah KV, Nagaraja TS, Shameer H, Jayachandran E,
Sreenivasa GM (2009) Synthesis, characterization and anthelmintic activity of novel
N-substituted thiazolidinones. J Chem Pharm Sci 2(4):277–280
53. Watanabe T, Yamamoto H, Hosomi T, Miyata S (1991) New molecular design for
noncentrosymmetric crystal structures: lambda shape molecules for frequency doubling.
NATO ASI Ser, Ser E 194(Org. Mol. Nonlinear Opt. Photonics):151–9
54. Yonehara H, Kang W-B, Kawara T, Pac C (1994) Synthesis and second-harmonic generation
properties of 2-(4-nitroanilino)-1,3,5-triazine derivatives. J Mater Chem 4(10):1571–1577
55. Zheng X et al (2007) Analgesic agents without gastric damage: Design and synthesis of
structurally simple benzenesulfonanilide-type cyclooxygenase-1-selective inhibitors. Bioorg
Med Chem 15(2):1014–1021
56. Zhou J, Chen S (1998) Manufacture of N-methyl-4-nitroaniline as explosive stability
detecting standard. Huozhayao Xuebao 21(3):30–35
Chapter 8
1-Azido-2-Nitro-2-Azapropane (ANAP)

Abstract Thermodynamic and explosive properties of 1-azido-2-nitro-2-

azapropane (ANAP) have been determined in a combined computational ab ini-
tio and EXPLO5 (Becker—Kistiakowsky—Wilson equation of state, BKW EOS)
study. The enthalpy of formation of ANAP in the liquid phase, heat of detonation,
detonation pressure and detonation velocity of ANAP were calculated. ANAP
compounds were characterized using vibrational (IR and Raman) and multinuclear
NMR spectroscopy, elemental analysis and low-temperature single crystal X-ray
diffraction. ANAP represents a covalently bound liquid energetic material which
contains both a nitramine unit and an azide group in the molecule.

8.1 Introduction

1-azido-2-nitro-2-azapropane, ANAP, is a colorless liquid which is stable but

explodes in the presence of a flame. It has friction sensitivity of 120 N and an
impact sensitivity of 1 J.

8.2 Synthesis

Klapotke et al. [1] describe a two-step synthesis of ANAP. In the first step,
trimethyl-hexahydro-triazine was converted into 1-chloro-2-nitro-2-azapropane
which is treated with sodium azide to yield ANAP.
U.S. Patent 3883374 [2] describes a method of preparation of ANAP. The patent
gives the following details which are reproduced. Two hundred and fifty mL of
redistilled dioxane and 62.4 g of trioxylmethylene were placed in a 1 L three
necked flask having a gas inlet tube, a mechanical stirrer, a thermometer and a
drying tube. Dry HCl gas was passed into the mixture until it was almost clear.

© US Government (outside the USA) 2018 243

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7_8
244 8 1-Azido-2-Nitro-2-Azapropane (ANAP)

The addition of HCl was stopped and the temperature of the reaction mixture
was allowed to drop to 35 °C before 39.6 g of dry, powdered methyl nitramine has
added. The rate of addition was such that the temperature did not rise above 40 °C.
After the addition was complete, the passage of HCl was resumed and continued for
3 h. The reaction mixture was allowed to stand for 13 h at ambient temperature.
The solvent was then removed on a rotary evaporator. The product was a
greenish-yellow oil.
15.7 g of the oil was dissolved in 100 mL of acetone in a beaker and the beaker
was immersed in an ice-salt bath. A solution of 25.2 g of sodium azide in 75 mL of
water was added with mechanical stirring. The reaction mixture was blanketed with
dry nitrogen during this operation and the temperature was maintained below 10 °C.
After standing 64 h the reaction mixture was extracted with ether and the extract
was dried over MgSO4. The ether was evaporated leaving a greenish-yellow pro-
duct in an amount equivalent to an 80% yield. Distillation under reduced pressure
gave a clear liquid [3, 4]. Table 8.1 lists the structure and other names of ANAP
while Table 8.2 lists some physical properties of ANAP.

Table 8.1 Structure and other names of ANAP

Name ANAP
CAS No. 55680-29-0
NO2

Me N CH2 N3
Empirical formula C2H5N5O2
CA index name Methanamine, 1-azido-N-methyl-N-nitro-
Other names 2-Nitrazapropyl azide

Table 8.2 Physical properties of 1-azido-2-nitro-2-azapropane (ANAP)

Molecular mass 131.11
Crystal system Orthorhombic [2]
Boiling/Decomposition temperature (K) 433–453 [1]
Enthalpy of vaporization (kJ mol−1) 39.7 ± 0.8
Density (g cm−3) 1.493 [2]
Refractive index, nm 1.4828 Wave length: 589.3
Enthalpy of formation (kJ mol−1) (l) ΔHof = ANAP(l) = +297.1 [2]
Enthalpy of detonation (Qv) (kJ kg−1) −6088 [2]
Detonation pressure (P) (GPa) 23.8 [2]
Detonation temperature (K) 4092 [2]
Detonation velocity (D) (ms−1) 8033 [2]
References 245

References

1. Klapotke TM, Steemann FX, Suceska M (2008) Computed thermodynamic and explosive
properties of 1-Azido-2-nitro-2-azapropane (ANAP). Propellants, Explos, Pyrotech 33
(3):213–218
2. Rosher R (1975) Double-base propellant containing organic azide. The United States of
America as represented by the Secretary of the Navy (Washington DC) US 3883374
3. Boese R, Klapotke TM, Meyer P, Verma V (2006) Synthesis and characterization of
1-Azido-2-Nitro-2-Azapropane and 1-Nitrotetrazolato-2-Nitro-2-Azapropane. Propellants,
Explos, Pyrotech 31(4):263–268
4. Klapotke TM, Mayer P, Schulz A, Weigand1 JJ (2005) 5-Diamino-4-methyltetrazolium
dinitramide. 2032 9 J. Am Chem Soc 127:2032–2033

Additional Scholarly Articles for Further Reading

5. Dorofeeva OV, Ryzhova ON, Suntsova MA (2013) Accurate prediction of enthalpies of

formation of organic azides by combining g4 theory calculations with an isodesmic reaction
scheme. J Phys Chem A 117(31):6835–6845. doi:10.1021/jp404484q
6. Heeb G, et al. (2007) New energetic materials for nitrocellulose based propellants. Int Annu
Conf ICT 38th:101/1-101/13
7. Pjatakov NF, Shlyapochnikov VA, Cherskaya NO, Vjyunova IB (1995) Intermolecular
interactions of nitramines. Proc Int Pyrotech Semin 21st:698–712
8. Rosher R (1975) Organic azides. US3873579A
9. Stepanov RS, Kruglyakova LA (1999) Thermal decomposition of polyfunctional azido
compounds. Int Annu Conf ICT 30th:47/1-47/8
10. Stepanov RS, Kruglyakova LA, Astachov AM (2007) Thermal decomposition of high energy
compound azidonitramines. Cent Eur J Energ Mater 4(1–2):151–156
11. Unterhalt B, Leiblein F (1979) Nitramines, XII: N-Fluoromethyl- and N-azidomethyl-
N-alkylnitramines. Arch Pharm (Weinheim, Ger) 312(2):159–64
Chapter 9
1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene
(TATB)

Abstract This chapter reviews the research and development work on 1, 3,

5-Triamino-2, 4, 6-trinitrobenzene (TATB), and TATB-based formulations.
Syntheses, analytical methods, thermophysical properties, performance, formula-
tions, and toxicological and safety of TATB are included in this chapter.

9.1 Introduction

There has been a renewed interest in the synthesis and characterization of new
energetic materials during the past two to three decades. This is due in part to find
materials of better performance but also to reduce the loss of lives and property due
to accidental explosions that could occur during the different stages of explosive
preparation, manufacture, formulations, load assemble and package operations, and
use.
Military is focused to minimize the collateral damage to all sites other than the
targeted sites. Determining the fate of these chemicals in the environment is also as
important. Detecting hidden explosives requires extremely accurate data on vapor
pressure for development of sensors.
Accurate predictive methods for testing and fielding of new energetic materials
to minimize the cost and time associated with an experimental program are
required. In the present collecion of properties, it has become evident that models
currently used to predict properties are far from satisfactory. For example, pre-
diction of crystal density paves the way in predicting detonation velocities.
Enthalpies of formation and sublimation are critical in assessing the potential
energy release and performance in a gun or a warhead.
Studying syntheses pathways, reaction mechanisms and products, exhaust plume
signature, etc. require accurate physicochemical properties.
Among the various insensitive high explosives 1, 3, 5-Triamino-2, 4,
6-trinitrobenzene, commonly known as TATB, is an attractive insensitive explosive
as it satisfies the safety requirements at high temperatures and its resistance to

© US Government (outside the USA) 2018 247

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7_9
248 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

accidental initiation and explosion. In addition it readily forms eutectics with other
explosives such as 1,3,5,7-tetranitro-1,3,5,7-tetra azacyclooctane (HMX), trinitro-
toluene (TNT), and several others. This paper should be viewed as a companion
review to the excellent review by Dobratz [1]. TATB is perhaps the most
thermo-resistant insensitive explosive known to date. Although TATB contains an
amino group, it is much more stable compared to a nitro compound such as
trinitrobenzene.
The potential of TATB as an insensitive explosive was realized during the
1960s. TATB is used in modern nuclear warheads in the military and deep oil well
explorations in the civilian community, and as a reagent in the manufacture of
liquid crystal displays. It is used extensively in the USA. In recent years it is the
preferred conventional secondary high explosive in nuclear weapons [2].
Dobratz [1] cites Jackson and Wing as the earliest workers to mention TATB in
1888, although it was left to Flurscheim and Holmes [3] to synthesize pure TATB
by ammoniation of pentanitroaniline. Many processes yield TATB with a small
percentage of chlorine but recent attempts to make chlorine-free TATB have been
documented. TATB exhibits both in monoclinic and triclinic crystal structures and
is classified as a heat resistant explosive.

9.2 Synthesis and Manufacture

The current industrial method is to nitrate 1, 3, 5-trichlorobenzene to give 1, 3,

5-trichloro-2, 4, 6-trinitrobenzene. Nitration is carried out at 423 K using a mixture
of nitric and sulfuric acids. It is reacted with ammonia in a toluene medium to yield
the product. One method of synthesis of TATB has been described in Fig. 9.1. The
current cost of TATB prohibits its use for civilian applications but new routes for its
synthesis could reduce the cost of production. One such route is patented by
Mitchell et al. [4] who used picramide as the starting material. Bellamy et al. [5]
have described a new route starting with 1, 3, 5-trihydroxy benzene for the syn-
thesis of TATB. Although the direct nitration of 1, 3, 5-trihydroxy benzene can be
carried out, Bellamy et al. have suggested a number of modifications. The authors
give details of the above syntheses methods, claim improved yields and report other
starting materials. They also show their synthesis of TATB by vicarious nucle-
ophilic substitutions. In all the syntheses methods, the low solubility of TATB has
posed a problem.
Thiokol Corporation has set up a pilot-plant for the production of TATB as
described by Dressen et al. [6]. This process is based on the synthetic route pro-
posed by Bellamy et al. [5]. The overall process yield was 81%. The syntheses
routes are shown in Figs. 9.1 and 9.2. A similar synthesis method as shown in
Fig. 9.3 was followed by researchers at Pantex to reduced chlorine contamination.
Aniline was used as a starting material to synthesize 1, 3, 5-trichlorobenzene by
Urbansky and Vasudeva [7] in their attempts to synthesize TATB. TNT was the
9.2 Synthesis and Manufacture 249

Fig. 9.1 Synthesis of TATB using 1, 3, 5-trichlorobenzene. Reproduced from Ref. [5]

Fig. 9.2 New synthesis of TATB. Reproduced from Ref. [5]

starting material for Atkins et al. [8] to form 2,3,4,5,6-pentanitroaniline using H2S
and NH4OH, which was converted to TATB after adding NH3, toluene, and CCl4.
High purity TATB was synthesized by Ott and Benzinger [9] by ammonolysis of
3,5-dichloro-2,4,6-trinitroanisole in toluene at room temperature.
Recently Yang et al. [10] have prepared nano particles by amination of TCTNB
[1, 3, 5-trichloro-2, 4, 6-trinitrobenzene] in toluene medium. The surface area of the
particles was 22 m2/g and pore diameter 1.7 nm. X-ray Diffraction (XRD) patterns
of nano and micron sized TATB are shown in Fig. 9.4. XRD studies showed that
the particles are about 60 nm in size. The size of these particles may be small for
250 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

Fig. 9.3 Modified synthesis of TATB. Reproduced from Ref. [5]

d = 3.144

cps

25.0

20.0

15.0

10.0

b
0.0
5.0
a
x 10^3
10 20 30 40 50 60
2Θ

Fig. 9.4 XRD diagram of nano TATB (a) and micron TATB (b). Reproduced from Ref. [10]
9.2 Synthesis and Manufacture 251

certain formulations, and by changing the experimental parameters it is possible to

obtain larger particles. Nevertheless, nano particles would give higher surface
energy and higher detonation energy.
Pagoria et al. [11] and Agrawal [12] provide excellent reviews of the synthesis of
several energetic explosive materials. These two reviews complement one another
in discussing the current state of knowledge in the synthesis of explosive and
propellant materials.

9.3 Structure

TATB has a simple ring structure with long C–C bonds and short C–N bonds with
six fractured hydrogen bonds. Agrawal [12] states that there is strong evidence of
inter-and intramolecular hydrogen bonds. These strong hydrogen bonds induce a
strong dipole-dipole van der Waals-Keesom force and affect properties such as
boiling and melting points which are evident in TATB. X-ray diffraction studies
have indicated two molecules per unit cell and extensive O–N and N–H hydrogen
bonding, and a layered structure. This gives rise to polarity and dispersion forces,
and affects solvation and physical properties.
TATB is a planar molecule with a triclinic centrosymmetric lattice. Based on the
structures shown in Fig. 9.5, Huang et al. [13] evaluated the vibrational frequen-
cies, and the assignments are shown in Table 9.1. Except for the weak bands all
other bands have been verified in the experimental spectrum.
A more detailed assignment of vibrational frequencies has been carried out by
Liu et al. [14]. The simulated infrared spectra agree well with the experimental data
shown in Fig. 9.6.
These two studies indicate that there is a conformational change in TATB from
crystalline phase to gas phase possibly due to intermolecular hydrogen bonding.
The assignments made by Liu et al. [14] agree more closely with experimental data.
Kolb and Rizzo [15] used the same structure in their evaluation of thermal
expansion of TATB crystal.
TATB undergoes structural changes on heating as observed by Son et al. [16].
This is similar in nature to what one observes with HMX where a phase change
occurs from b to d. Son et al. observed second harmonic generation both in
transmission through a thin layer of powdered crystal and in reflection from the
surface of a pressed polycrystalline pellet. The results were also confirmed by XRD.
The Differential Scanning Calorimetry (DSC) thermogram [17] in Fig. 9.7
shows that TATB exothermic decomposing temperature lies between 360 and 390 °C
indicating its excellent thermal stability and heat resistance. This shows how some of
the properties of nitro explosives can be improved with the introduction of other
groups such as amino groups as in the case of TATB. The products of decomposition
of TATB appear to be HCN, CO2, NO2, and H2O with approximate activation energy
of 150 kJ/mol [18]. It is likely that C=C homolysis occurs in the form of ring scission
leading to these products.
252 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

Fig. 9.5 The equilibrium geometry of TATB [13]

Table 9.1 Summary of Symmetrical N–H stretching 3220.9

assignment of vibrational
Unsymmetrical N–H stretching 3322.5
modes (cm−1) [13]
Unsymmetrical N–O stretching 1571.3
Symmetrical N–O stretching 1235.6
C–N stretching [Amino group] 1613.1; 779.56
C–N’ stretching [Nitro group] 1321.5
Skeletal stretching [Ring] 1448.4; 1181.2; 1031.4
Weak bands 932.54; 539.32; 741.48

9.4 Crystal Properties

Crystal density is important information used to predict the performance of known

and unknown energetic materials. The experimental lattice parameters [19] are:
a (Ao) = 9.01; b = 9.028; c = 6.812; a = 108.58 deg; b = 91.82; c = 119.97;
space group: P1. The crystal structure of TATB has been calculated based on Ab
Initio method by Byrd and Rice [20]. Among the different methods used by the
authors, it appears that the Perdew-Wang 91 theory gives better estimates of vol-
umes with pressure in comparison with experimental data. A crucial point in such
predictions is the inclusion of dispersion forces in the model as they play an
important role.
9.4 Crystal Properties 253

100.0

80.0

447.9 6
1321.5
1031.4
60.0
Transmittance

779.56
730.31
40.0
3220.9

1448.4
1571.3

702.5 5
3322.5

20.0

1613.1
0.00

1181.2
1235.6
4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
Wave number (cm )

Fig. 9.6 Experimental IR spectrum of TATB [14]

Fig. 9.7 DSC profile of

TATB. [17]

Kolb and Rizzo [15] have carried out X-ray crystallographic studies from 214 to
377 K to monitor the cell constants of triclinic and monoclinic forms of TATB. The
calculated cell volumes are shown in Table 9.2. The authors have carried out linear
regression analysis on the data and found the anisotropic volume coefficient of
thermal expansion to be 30.4
10−5 K−1. The unit cell constants are also tabulated
in their paper.
254 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

Table 9.2 Experimental cell Triclinic form C-Centered monoclinic

volume for TATB as a form
function of temperature [15]
Temp (°C) Vol (A3) Temp (°C) Vol (A3)
−59 ± 3 434.5 −57 ± 1 875.2
−45 ± 3 436.2 −47 ± 2 874.1
−36 ± 1 436.3 −34 ± 2 877.3
−26 ± 1 437.4 −23 ± 2 878.5
−13 ± 3 438.7 −12 ± 1 880.2
11 ± 2 441.6 1 ± 1 883.0
23 ± 1 442.9 12 ± 1 885.5
35 ± 1 447.0 23 ± 1 889.8
44 ± 1 446.7 35 ± 1 895.1
54 ± 1 447.7 45 ± 1 896.7
65 ± 1 449.5 57 ± 2 899.1
76 ± 1 451.9 67 ± 1 901.4
83 ± 1 453.4 76 ± 1 903.0
94 ± 1 454.7 86 ± 1 908.3
104 ± 1 456.2 95 ± 1 910.9

9.5 Physical and Thermodynamic Properties

Table 9.3 provides a list of the general physical properties of TATB [21–28]. This
list reveals the disagreement in the values of some of the properties and the need for
more accurate values.

9.6 Thermodynamic Properties

Rosen and Dickinson [23] measured vapor pressures and enthalpies of sublimation
of high melting explosives including TATB. These authors have made careful
measurements of temperatures and pressures but failed to mention the purity of
TATB used. The impurities in TATB include amino- and chloro-compounds of
dinitrobenzene. The vapor pressure of TATB reported in the literature [23, 26, 29]
is summarized in Table 9.4.
The least squares fit of the vapor pressures to the Antoine type equation is given
by
 
60261:2
Log10 P ¼ 14:6777 
6:87372
T
9.6 Thermodynamic Properties 255

Table 9.3 Physical properties of TATB

CAS number 3058-38-6
Empirical formula C6H6N6O6
Molecular mass (Daltons) 258.1
Enthalpy of formation (kJ/kg) −541.4 [21]
Enthalpy of explosion [H2O] (kJ/kg) 3062 [21]
Enthalpy of sublimation (kJ/mol) 180.3 [22]
168.2 [23]
168.1 [24]
Crystal density (g/cm3) 1.93 [21]
Melting point (K), Melts above 573 K but decomposes 623.15 [21]
above 712 [25]
Decomposition temperature (K) 594–599 [25]
623.15 [26]
Enthalpy of fusion (kJ/mol) 43.0 [25]
Critical temperature (K) 913 [25]
Critical pressure (bar) 56.5 [25]
Acentric factor 1.802 [25]
Aqueous solubility @ 25°C: 0.16 [25]
0.197
2.5
Log Kow −1.5 [25]
−0.44
4.74
Volume coefficient of thermal expansion [crystal] 30.4
10−5 K−1 [214– [15]
377 K]
Crystal heat capacity at 293 K J/g °C 1.38 [28]
1.09 [27]
Thermal conductivity (J/cms °C) 8.0
10−3 [28]

Table 9.4 Vapor pressure of t (°C) P
107 torr References

TATB
129.3 0.740 [23]
136.2 1.88 [23]
150.0 9.82 [23]
161.4 32.25 [23]
166.4 45.8 [23]
177.3 167.0 [23]
177.3 167.0 [26]
175.0 240.0 [29]
200.0 2100.0 [29]
256 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

where T is in K and is different from the fit given by Rosen and Dickenson. Vapor
pressure data are very important in predicting the properties of any substance and
also in its detection. This table shows the need to generate accurate vapor pressure
data. As reported by Agrawal [12, 30] the boiling point of TATB is not well
defined, and it is insoluble in most of the solvents except sulfuric acid. It starts
decomposing close to the melting point.
Osmont et al. [31] have carried out theoretical evaluation of standard state
enthalpy of formation at 298.15 K, and heat capacities and entropy in the tem-
perature range of 300–5000 K for various energetic compounds. Their value of
enthalpy of formation is −0.7 kcal/mol−1. Ideal gas heat capacity data are shown in
Table 9.5, and entropy values in Table 9.6.

9.7 Solubility

Talawar et al. [17] have tabulated the solubility of TATB in different solvents at
room temperature. The values are tabulated in Table 9.7. These are calculated
values but the authors do not mention the method of calculation. They also doc-
ument the DSC and Thermogravimetric Analysis (TGA) profiles, and mechanical
properties of TATB/Polymer-Bonded Explosive (PBX) formulations.
Selig [32] has discussed methods of measuring solubility of extremely low
soluble materials and measured the solubility of TATB in various solvents. Selig
[32] reports the solubility of TATB in sulfuric acid-water mixtures as reproduced in
Table 9.8.
During their study on recrystallization, Foltz et al. [33, 34] measured the solu-
bility of TATB in dimethyl sulfoxide (DMSO). The measurements were carried out
gravimetrically. The values at 294.35 and 418.65 K were 0.47 and 6.80 g/L,
respectively. The authors also use larger particles from approximately 60 to 220 lm

Table 9.5 Calculated Cp0 (cal mol−1 K−1) in the temperature range of 300–1500 K [31]
Temp (K) 300 400 500 600 800 1000 1500
Heat capacity (cal mol−1 K−1) 60.3 74.8 86.1 94.9 106.9 114.7 125.4
Temp (K) 2000 2500 3000 3500 4000 4500 5000
Heat capacity (cal mol−1 K−1) 130.5 133.3 134.9 136.0 136.7 137.1 137.5

Table 9.6 Calculated S0 (cal mol−1 K−1) in the temperature range of 300–1500 K [31]
Temp (K) 300 400 500 600 800 1000 1500
Entropy (cal mol−1 K−1) 129.8 149.2 167.2 183.7 212.8 237.6 286.4
Temp (K) 2000 2500 3000 3500 4000 4500 5000
Entropy (cal mol−1 K−1) 323.3 352.8 377.2 398.1 416.3 432.5 446.9
9.7 Solubility 257

Table 9.7 Solubility of Solvent Solubility (ppm)

TATB in various solvents at
298.15 K [17] Methanesulfonic acid 820
Hexamethylphosphortriamide 150
Ethanesulfonic acid 120
DMSO 70
Hexafluroacetone sesquihydrate 68
N-Methyl-2-pyrrolidone 58
N,N-Dimethylacetamide 33
DMF 27
Tetramethylurea 26
Dimethyl methylphosphonate 22
N,N-Dimethyl propionamide 16
Conc. Nitric acid 14
3-Methylsulfone 13
Pyridine 12
Trimethylphosphate 11
Acetone 3
Acetonitrile, Acetic anhydride 1
Trifluoroacetic acid, Acetic acid 1

Table 9.8 Solubility of H2SO4:H2O Acid (vol. %) (g TATB/100 mL)

TATB in sulfuric acid:water
mixtures [32] 1:1 50 >0.02
2:1 66.7 <0.02
4:1 80 −0.24
5.67:1 85 −0.32
7:1 87.5 >1.28
9:1 90 −3.84
Concentrated 100 >24.0

for use in different formulations. The enthalpy of detonation of TATB is calculated

to be 3.267 against an experimental value of 3.062 kJ/g [35].

9.8 Performance

Kennedy et al. [36] describe methods of preparing TATB in the range of 1.2–6 lm
and dent profiles in detonation-spreading spot-size tests. The density of the different
particles tested varied from 1.693 to 1.810 g/cm3. The results indicate that particle
morphology and crystal structure influence the sensitivity of TATB. Similar tests
have also been conducted by Tran et al. [37]. Some detonation characteristics of
TATB, based on watershock measurements, are listed in Table 9.9 [38].
258 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

Table 9.9 Detonation characteristics [38]

Density (g/cm3) Detonation Vel. (m/s) Detonation Pr. (kBar) Detonation energy (cal/gm)
1.80 7,658 259.4 829
1.50 6,555 174.6 808

Table 9.10 Comparison of SDA.FOR algorithm with Mader values [39, 40]
Density PCJ (Mbar) TCJ (K) DCJ (m/s)
g/cm3 BKW SDA BKW SDA BKW SDA
TATB 1.895 0.326 0.325 1887 1890 8411 8365

Mader [39] used the Becker-Kistiakowsky-Wilson (BKW) equation of state

model to calculate the detonation velocity of TATB as a function of density. His
calculations using 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) parameters and
assuming carbon as either graphite or diamond do not show good agreement with
experimental data.
Based on the Chapman-Jouguet theory, Borg et al. [40] wrote a code -SDA.
FOR- to perform chemical equilibrium calculations for detonation of explosives,
and compared their results with the values obtained by Mader for TATB.
Table 9.10 shows the comparison. They also show some results for other explo-
sives and other models.
Becuwe and Delclos [41] compare the sensitivities of nitrotriazolene (NTO),
TATB, RDX, HMX and pentaerythritol tetranitrate (PETN), and show that TATB
undergoes spontaneous ignition at a higher temperature compared to other explo-
sives. According to Chevalier et al., [42] the velocity of detonation is higher for
HMX compared to TATB but the axial curvature is higher for TATB for any given
diameter. They have measured the velocity of detonation for different compositions
of TATB.

9.9 TATB Formulations

TATB is combined with other explosives and polymers to produce formulations

with varying properties such as densities, velocities of detonation, and impact
sensitivity. These formulations make the explosive less sensitive to shock and at the
same time impart desirable properties. Hallam [43], and Kolb and Pruneda [44]
have discussed the bonding of TATB with Kel-F 800 and the effect of solvents, and
found that different polymers did not change the character of the TATB surface
energies. Pruneda et al. [45] have discussed the combination of TATB with Kel-F
800 using various solvents in order to increase the binding of TATB with the
polymer. The performance of TATB + HMX bonded with Kel-F 800 polymer is
shown in Table 9.11. The review by Rainwater et al. [46] is recommended.
9.10 Conclusions 259

Table 9.11 TATB/HMX based PBXs and their properties

Composition TATB HMX Kel-F 800 Density VOD Impact sensitivity
Mass% Mass% Mass% g/cm3 m/s cm
PBX-9502 95 0 5 1.895 7706 –
X-0344 71.25 23.75 5 1.894 8046 –
PBX-9501 0 95 5 1.832 8802 –
– 0 90 10 1.869 – <30

9.10 Conclusions

This paper together with the papers referenced herein provides a survey of the
properties of TATB and its formulations. The values of the properties listed in this
paper reveal that there are discrepancies in the reported values, and the prediction
models are far from satisfactory. There is a need to collect accurate experimental
data and develop better models. This would be useful not only in the case of TATB
but for all insensitive explosives.

References

1. Dobratz BM (1995) The insensitive high explosive triaminotrinitrobenzene (TATB).

Development and Characterization-1888 to 1994 Report LA-13104-H, Los Alamos National
Laboratory, Los Alamos NM, USA
2. Agrawal JP, Hodgson RD (2007) Organic chemistry of explosives. Wiley, Hoboken NJ
3. Flurscheim B, Holmes EL (1929) CCCXCIX Pentanitroaniline. J Chem Soc (London) 304 L
Hexaminobenzene 334
4. Mitchell AR, Pagoria PF, Schmidt RD (1997) US Patent No 5,569,783, 29 Oct 1996;
5,633,406, 27 May 1997; 6,069,277, 30 May 2000
5. Bellamy AJ, Ward SJ, Golding P (2002) Synthesis of ammonium diaminopicrate (ADAP), a
new secondary explosive. Propellants Explos Pyrotech 27(2):59–61
6. Druce RL, Souers PC, Chow C, Roeske F Jr, Vitello P, Hrousis C (2005) Detonation in
TATB hemispheres. Propellants Explos Pyrotech 30(2):95–100. doi:10.1002/prep.
200400089
7. Urbansky T, Vasudeva SK (1978) Heat resistant explosives. J Scientific Ind Res 37:221–280
8. Atkins RL, Hollins RA, Wilson WS (1986) Synthesis of polynitro compounds
hexa-substituted benzenes. J Org Chem 51:3261–3266
9. Ott RG, Benzinger TM (1991) Preparation of 1,3,5-trizmino-2,4,6-trinitrobenzene.
J Energetic Mater 5:343 US Patent No 4,997,987
10. Yang G, Nie F, Huang H, Zhao L, Pang W (2006) Preparation and characterization of
nano-TATB explosive. Propellants Explos Pyrotech 31:390
11. Pagoria PF, Lee GS, Mitchell AR, Schmidt RD (2002) A review of energetic materials
synthesis. Thermochim Acta 384:187
12. Agrawal JP (1998) Recent trends in high-energy materials. Progr Energy Combustion Sci
24:1–30
13. Huang Z, Chen B, Gao G (2005) IR vibrational assignments for TATB from the density
functional B3LYP/6-31G(d) method. J Mol Struct 752:87
260 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

14. Liu H, Zhao J, Ji G, Wei D, Gong Z (2006) Vibrational properties of molecule and crystal of
TATB: A comparative density functional study. Phys Lett A 358:63
15. Kolb JR, Rizzo HF (1979) Growth of 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) I
anisotropic thermal txpansion. Propellants Explos Pyrotech 4:10
16. Son SF, Asay BW, Henson BF, Sander RK, Ali AN, Zielinski PM, Phillips DS,
Schwarz RB, Skidmore CB (1999) Dynamic observation of a thermally activated structure
change in 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) by second harmonic generation.
J Phys Chem B 103(26):5434–5440. doi:10.1021/JP983307H
17. Talawar MB, Agarwal AP, Anniyappan M, Gore GM, Asthana SN, Venugopalan S (2006)
Method for preparation of fine TATB (2–5 lm) and its evaluation in plastic bonded
explosive (PBX) formulations. J Hazard Mater 137(3):1848–1852. doi:10.1016/j.jhazmat.
2006.05.031
18. Makashir PS, Kurian EM (1996) Spectroscopic and thermal studies on the decomposition of
1,3,5-triamino-2,4,6-trinitrobenzene. J Therm Anal 46:225
19. Cady HH, Larson AC (1965) The crystal structure of 1,3,5-triamino-2,4,6-trinitrobenzene.
Acta Crystallogr 18(3):485–496. doi:10.1107/S0365110X6500107X
20. Byrd EFC, Rice BM (2009) Improved prediction of heats of formation of energetic materials
using quantum mechanical calculations. [Erratum to document cited in CA144:256621].
J Phys Chem A 113(19):5813. doi:10.1021/jp806520b
21. Meyer R, Kohler J, Homburg A (2002) Explosives, 5th edn. Wiley-VCH, Weinheim
Germany, p 344
22. Garza RG (1979) A thermogravimetric study of TATB and two TATB-based explosives.
Report UCRL-82723 Lawrence Livermore National Laboratory, Livermore CA, USA
23. Rosen JM, Dickinson C (1969) Vapor pressures and heats of sublimation of some
high-melting organic explosives. J Chem Eng Data 14(1):120–124. doi:10.1021/
je60040a044
24. Stephenson RM, Malanowski S (1987) Handbook of the thermodynamics of organic
compounds. Elsevier, New York
25. Toghiani RK, Toghiani H, Maloney SW, Boddu VM (2008) Prediction of physicochemical
properties of energetic materials. Fluid Ph Eq 64:86
26. Solovyev VP, Selezenev AA, Aleinikov AY, Lashkov VN, Postnikov AY (2007)
Calculation and experimental determination of the HE dependence specific heat versus
temperature. In University of Pardubice, pp 299–306
27. Jones DA, Parker RP (1994) Simulation of cookoff results in a small scale test. Report
DSTO-TR-0090 DSTO Aeronautical and Maritime Research Laboratory, Melbourne,
Australia
28. Beard BC, Sharma J (1993) Surface chemical characterization methods applied to energetic
materials. Mater Res Soc Symp Proc 296(Structure and Properties of Energetic
Materials):257–268 (Boston MA 1992) DH Liebenberg, RW Armstrong, JJ Gilman
(eds) Materials Research Society, Pittsburgh PA
29. F Nie, G Yang, G Zheng, Z Qiao, H Huang (2007) Proc NTREM Conference, Pardubice.
p 452, April 25–27
30. Agrawal JP (2005) Some new high energy materials and their formulations for specialized
spplications. Propellants Explos Pyrotech 30:316
31. Osmont A, Catoire L, Gökalp I, Yang V (2007) Ab initio quantum chemical predictions of
enthalpies of formation, heat capacities, and entropies of gas-phase energetic compounds.
Combust Flame 151:262
32. Selig W (1977) How to Estimate the Solubility of an Insoluble Compound:
1,3,5-Triamino-2,4,6-Trinitrobenzene (TATB). Report UCID-17412-Rev. 1, 1977.
Estimation of the Solubility of 1,3,5-Triamino-2,4,6-Trinitrobenzene (TATB) in Various
Solvents, Report UCID-17412, 1977, Lawrence Livermore National Laboratory,
Livermore CA, USA
References 261

33. Foltz MF, Ornellas DL, Pagoria PF, Mitchell AR (1996) Recrystallization and solubility of
1,3,5-triamino-2,4,6-trinitrobenzene in dimethyl sulfoxide. J Mater Sci 31(7):1893–1901.
doi:10.1007/BF00372205
34. Foltz MF, Maienschein JL, Green LG (1996) Particle size control of
1,3,5-triamino-2,4,6-trinitrobenzene by recrystallization from DMSO. J Mater Sci 31
(7):1741–1750. doi:10.1007/BF00372187
35. Keshavarz MH (2007) Quick estimation of heats of detonation of aromatic energetic
compounds from structural parameters. J Hazard Mater 143:549
36. Kennedy JE, Lee KY, Spontarelli T, Stine JR (1998) Los Alamos, Report LA-UR-98-2525
37. Tran TD, Pagoria PF, Hoffman DMN, Cunningham B, Simpson RL, Lee RS, Cutting JL
(2002) http://www.intdetsymporg/detsymp2002/PaperSubmit/FinalManuscript/pdf/Tran-
238pdf
38. Department of Army (1984 September) Military explosives, TM 9-1300-214, pp 8–72
39. Mader CL (2008) Numerical modeling of explosive and propellants. CRC Press, New York
NY
40. Borg RAJ, Kemister G, Jones DA (1995 October) DSTO-TR-0226. Aeronautical and
Maritime Research Laboratory, Melbourne, Australia
41. Becuwe A, Delclos A (1993) Low-sensitivity explosive compounds for low vulnerability
warheads. Propellants Explos Pyrotech 18(1):1–10. doi:10.1002/prep.19930180102
42. Chevalier JM, Carion N, Protat JC, Redasse JC (1993) Propagation phenomena on the
detonation wave front. Phys Rev Lett 71(5):712–714. doi:10.1103/PhysRevLett.71.712
43. Hallam JS (1976) TATB formulation study. Univ California, UCID-17087, p 28
44. Kolb JR, Pruneda CO (1979) Surface chemistry and energy of untreated and thermally
treated TATB and plastic-bonded TATB composites. Lawrence Livermore National
Laboratory, UCRL-82623 CONF-790632-9
45. Pruneda CO, Bower JK, Kolb JR (1980) Polymeric coatings effect on energy and sensitivity
of high explosives. Org Coat Plast Chem 42:588–594
46. Rainwater KA, Lightfoot JM, Richardson RB (1988) Literature review of the lifetime of
DOE materials: aging of plastic bonded explosives and the explosives and polymers
contained therein. Report ANRCP-1998-12, Amarillo National Resource Center for
Plutonium, San Antonio TX, USA

Additional Scholarly Articles for Further Reading

47. Adriaanse C (2010) Security: colorful response to TATP explosives. Chem Ind 21:9
(London, UK)
48. Al-Jalili TAR, Shah HN (1988) Protoheme, a dispensable growth factor for Bacteroides
fragilis grown by batch and continuous culture in a basal medium. Curr Microbiol 17(1):13–
18
49. Almog J, Klein A, Tamiri T, Shloosh Y, Abramovich-Bar S (2005) A field diagnostic test for
the improvised explosive urea nitrate. J Forensic Sci 50(3):582–586
50. Amani M, Chu Y, Waterman KL, Hurley CM, Platek MJ, Gregory OJ (2012) Detection of
triacetone triperoxide (TATP) using a thermodynamic based gas sensor. Sens Actuators B
162(1):7–13
51. Andrews G, Lewis D, Notey J, Kelly R, Muddiman D (2010) Part I: characterization of the
extracellular proteome of the extreme thermophile Caldicellulosiruptor saccharolyticus by
GeLC-MS2. Anal Bioanal Chem 398(1):377–389
52. Armitt D, Zimmermann P, Ellis-Steinborner S (2008) Gas chromatography/mass spectrom-
etry analysis of triacetone triperoxide (TATP) degradation products. Rapid Commun Mass
Spectrom 22(7):950–958
262 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

53. Ball R (2013) Thermal oscillations in the decomposition of organic peroxides: identification
of a hazard, utilization, and suppression. Ind Eng Chem Res 52(2):922–933. doi:10.1021/
ie301070d
54. Banerjee S, Mohapatra SK, Misra M, Mishra IB (2009) The detection of improvised
nonmilitary peroxide based explosives using a titania nanotube array sensor.
Nanotechnology 20(7):075502
55. Bellamy AJ (1999) Triacetone triperoxide: its chemical destruction. J Forensic Sci 44
(3):603–608
56. Benson SJ, Lennard CJ, Maynard P, Hill DM, Andrew AS, Roux C (2009) Forensic analysis
of explosives using isotope ratio mass spectrometry (IRMS)—preliminary study on TATP
and PETN. Sci Justice 49(2):81–86
57. Brady JE, Smith JL, Hart CE, Oxley J (2012) Estimating ambient vapor pressures of low
volatility explosives by rising-temperature thermogravimetry. Propellants Explos Pyrotech
37(2):215–222. doi:10.1002/prep.201100077
58. Brady JJ, Judge EJ, Levis RJ (2010) Identification of explosives and explosive formulations
using laser electrospray mass spectrometry. Rapid Commun Mass Spectrom 24(11):1659–
1664
59. Brauer B, Dubnikova F, Zeiri Y, Kosloff R, Gerber RB (2008) Vibrational spectroscopy of
triacetone triperoxide (TATP): anharmonic fundamentals, overtones and combination bands.
Spectrochim Acta A Mol Biomol Spectrosc 71(4):1438–1445
60. Brauer CS, Barber J, Weatherall JC, Smith BT, Tomlinson-Phillips J, Wooten A (2011)
Characterization of peroxide-based explosives using Raman spectroscopy: isotopic analysis
and DFT calculations of triacetone triperoxide (TATP). Proc SPIE 8019:80190H/1-80190H/
6 (Sensors, and command, control, communications, and intelligence (C3I) technologies for
homeland security and homeland defense X)
61. Brautigam CA, Deka RK, Schuck P, Tomchick DR, Norgard MV (2012) Structural and
thermodynamic characterization of the interaction between two periplasmic Treponema
pallidum lipoproteins that are components of a TPR-protein-associated TRAP transporter
(TPAT). J Mol Biol 420(1–2):70–86
62. Bry A, Frenois C, Nony S, Forzy A, Hairault L (2009) Sampling importance for the
detection of explosives vapors by laboratory techniques. Actual Chim 334:28–35
63. Bulatov V, Reany O, Grinko R, Schechter I, Keinan E (2013) Time-resolved, laser initiated
detonation of TATP supports the previously predicted non-redox mechanism. Phys Chem
Chem Phys 15(16):6041–6048
64. Bulatov V, Reany O, Grinko R, Schechter I, Keinan E (2013) Time-resolved, laser initiated
detonation of TATP supports the previously predicted non-redox mechanism. Phys Chem
Chem Phys 15(16):6041–6048
65. Buttigieg GA, Knight AK, Denson S, Pommier C, Bonner Denton M (2003)
Characterization of the explosive triacetone triperoxide and detection by ion mobility
spectrometry. Forensic Sci Int 135(1):53–59
66. Cagan A, Schmidt H, Rodriguez JE, Eiceman GA (2010) Fast gas
chromatography-differential mobility spectrometry of explosives from TATP to Tetryl
without gas atmosphere modifiers. Int J Ion Mobility Spectrom 13(3–4):157–165
67. Capua E, Cao R, Sukenik CN, Naaman R (2009) Detection of triacetone triperoxide (TATP)
with an array of sensors based on non-specific interactions. Sens Actuators B 140(1):122–
127
68. Cerna J, Bernes S, Canizo A, Eyler N (2009) 3,3,6,6,9,9-Hexaethyl-1,2,4,5,7,8-
hexaoxacyclononane at 296 K. Acta Crystallogr Sect C: Cryst Struct Commun 65(11):
o562–o564
69. Chen J, Wu W, McNeil AJ (2012) Detecting a peroxide-based explosive via molecular
gelation. Chem Commun (Camb) 48(58):7310–7312
70. Chen N-C, Wu S-H, Wang C-H, Tsai C-L, Huang Y-T, Shih H-M (2014) Thermal hazard
assessment of triacetone triperoxide (TATP) using differential scanning calo-rimetry (DSC).
J Appl Fire Sci 23(4):423–434. doi:10.2190/AF.23.4.d
Additional Scholarly Articles for Further Reading 263

71. Chou H-H, Shih H-H, Cheng C-H (2010) Triptycene derivatives as high-Tg host materials
for various electrophosphorescent devices. J Mater Chem 20(4):798–805. doi:10.1039/
B918188A
72. Climent E et al (2013) Selective, sensitive, and rapid analysis with lateral-flow assays based
on antibody-gated dye-delivery systems: the example of triacetone triperoxide. Chemistry 19
(13):4117–4122
73. Contini AE, Bellamy AJ, Ahad LN (2012) Taming the beast: measurement of the enthalpies
of combustion and formation of triacetone triperoxide (TATP) and diacetone diperoxide
(DADP) by oxygen bomb calorimetry. Propellants Explos Pyrotech 37(3):320–328. doi:10.
1002/prep.201100100
74. Cooper JK, Grant CD, Zhang JZ (2013) Experimental and TD-DFT study of optical
absorption of six explosive molecules: RDX, HMX, PETN, TNT, TATP, and HMTD.
J Phys Chem A 117(29):6043–6051
75. Corfield R (2006) Was TATP lethal liquid? Chem Ind 16:4 (London, UK)
76. Costales-Nieves C, Boddu VM, Maloney SW, Chakka S, Damavarapu R, Viswanath DS
(2010) SPARC prediction of physical properties of explosive compounds. In American
institute of chemical engineers, pp a291/1–a291/17
77. Cotte-Rodriguez I, Chen H, Cooks RG (2006) Rapid trace detection of triacetone triperoxide
(TATP) by complexation reactions during desorption electrospray ionization. Chem
Commun (Camb) 9:953–955
78. Cotte-Rodriguez I, Hernandez-Soto H, Chen H, Cooks RG (2008) In situ trace detection of
peroxide explosives by desorption electrospray ionization and desorption atmospheric
pressure chemical ionization. Anal Chem 80(5):1512–1519 (Washington, DC, US) doi:10.
1021/ac7020085
79. Crowson A, Cawthorne R (2012) Quality assurance testing of an explosives trace analysis
laboratory–further improvements to include peroxide explosives. Sci Justice 52(4):217–225
80. Damour PL, Freedman A, Wormhoudt J (2010) Knudsen effusion measurement of organic
peroxide vapor pressures. Propellants Explos Pyrotech 35(6):514–520. doi:10.1002/prep.
200900083
81. DeCamp DL, Lim S, Colman RF (1988) Reaction of pyruvate kinase with the new
nucleotide affinity labels 8-[(4-bromo-2,3-dioxobutyl)thio]adenosine 5’-diphosphate and 5’-
triphosphate. Biochemistry 27(20):7651–7658. doi:10.1021/bi00420a012
82. DeGreeff L, Rogers DA, Katilie C, Johnson K, Rose-Pehrsson S (2015) Technical note:
headspace analysis of explosive compounds using a novel sampling chamber. Forensic Sci
Int 248:55–60
83. Denekamp C, Gottlieb L, Tamiri T, Tsoglin A, Shilav R, Kapon M (2005) Two separable
conformers of TATP and analogues exist at room temperature. Org Lett 7(12):2461–2464
84. Dobrokhotov V et al (2012) Toward the nanospring-based artificial olfactory system for
trace-detection of flammable and explosive vapors. Sens Actuators B 168:138–148
85. Dubnikova F et al (2005) Decomposition of triacetone triperoxide is an entropic explosion.
J Am Chem Soc 127(4):1146–1159. doi:10.1021/ja0464903
86. Dubnikova F, Kosloff R, Oxley JC, Smith JL, Zeiri Y (2011) Role of metal ions in the
destruction of TATP: theoretical considerations. J Phys Chem A 115(38):10565–10575
87. Dubnikova F, Kosloff R, Zeiri Y, Karpas Z (2002) Novel approach to the detection of
triacetone triperoxide (TATP): its structure and its complexes with ions. J Phys Chem A 106
(19):4951–4956
88. Dunayevskiy I, Tsekoun A, Prasanna M, Go R, Patel CKN (2007) High-sensitivity detection
of triacetone triperoxide (TATP) and its precursor acetone. Appl Opt 46(25):6397–6404
89. Efremenko I, Zach R, Zeiri Y (2007) Adsorption of explosive molecules on human hair
surfaces. J Phys Chem C 111(32):11903–11911
90. Egorshev VY, Sinditskii VP, Smirnov SP (2013) A comparative study on two explosive
acetone peroxides. Thermochim Acta 574:154–161
264 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

91. Eren S, Uezer A, Can Z, Kapudan T, Ercag E, Apak R (2010) Determination of

peroxide-based explosives with copper(II)-neocuproine assay combined with a molecular
spectroscopic sensor. Analyst 135(8):2085–2091 (Cambridge, UK)
92. Espinosa-Fuentes EA, Pacheco-Londono LC, Barreto-Caban MA, Hernandez-Rivera SP
(2012) Novel uncatalyzed synthesis and characterization of diacetone diperoxide.
Propellants Explos Pyrotech 37(4):413–421. doi:10.1002/prep.201000130
93. Evans HK, Tulleners FAJ, Sanchez BL, Rasmussen CA (1986) An unusual explosive,
triacetonetriperoxide (TATP). J Forensic Sci 31(3):1119–1125
94. Ewing RG, Waltman MJ, Atkinson DA (2011) Characterization of triacetone triperoxide by
ion mobility spectrometry and mass spectrometry following atmospheric pressure chemical
ionization. Anal Chem 83(12):4838–4844 (Washington DC, US)
95. Ezoe R, Imasaka T, Imasaka T (2015) Determination of triacetone triperoxide using
ultraviolet femtosecond multiphoton ionization time-of-flight mass spectrometry. Anal Chim
Acta 853:508–513
96. Fan W, Young M, Canino J, Smith J, Oxley J, Almirall JR (2012) Fast detection of
triacetone triperoxide (TATP) from headspace using planar solid-phase microextraction
(PSPME) coupled to an IMS detector. Anal Bioanal Chem 403(2):401–408
97. Fang X, Ahmad SR (2009) Detection of explosive vapour using surface-enhanced Raman
spectroscopy. Appl Phys B: Lasers Opt 97(3):723–726
98. Felix-Rivera H, Ramirez-Cedeno ML, Sanchez-Cuprill RA, Hernandez-Rivera SP (2011)
Triacetone triperoxide thermogravimetric study of vapor pressure and enthalpy of
sublimation in 303–338 K temperature range. Thermochim Acta 514(1–2):37–43
99. Fialkov AB, Moragn M, Amirav A (2011) A low thermal mass fast gas chromatograph and
its implementation in fast gas chromatography mass spectrometry with supersonic molecular
beams. J Chromatogr A 1218(52):9375–9383
100. Fidler Albo RL et al (2010) Degradation of triacetone triperoxide (TATP) using
mechanically alloyed Mg/Pd. Propellants Explos Pyrotech 35(2):100–104
101. Fitzgerald M, Bilusich D (2011) Sulfuric, hydrochloric, and nitric acid-catalyzed triacetone
triperoxide (TATP) reaction mixtures: an aging study. J Forensic Sci 56(5):1143–1149
102. Fitzgerald M, Bilusich D (2012) The identification of chlorinated acetones in analyses of
aged triacetone triperoxide (TATP). J Forensic Sci 57(5):1299–1302
103. Fujiyama-Novak JH, Gaddam CK, Das D, Vander Wal RL, Ward B (2013) Detection of
explosives by plasma optical emission spectroscopy. Sens Actuators B 176:985–993
104. Gaft M, Nagli L (2008) UV gated Raman spectroscopy for standoff detection of explosives.
Opt Mater 30(11):1739–1746 (Amsterdam, The Netherlands)
105. Gerber M, Walsh G, Hopmeier M (2014) Sensitivity of TATP to a TASER electrical output.
J Forensic Sci 59(6):1638–1641
106. Germain ME, Knapp MJ (2008) Turn-on fluorescence detection of H2O2 and TATP. Inorg
Chem 47(21):9748–9750
107. Girotti S et al (2011) A quantitative chemiluminescent assay for analysis of peroxide-based
explosives. Anal Bioanal Chem 400(2):313–320
108. Giubileo G, Colao F, Puiu A (2012) Identification of standard explosive traces by infrared
laser spectroscopy: PCA on LPAS data. Laser Phys 22(6):1033–1037
109. Giubileo G, Puiu A (2010) Photoacoustic spectroscopy of standard explosives in the MIR
region. Nucl Instrum Methods Phys Res, Sect A 623(2):771–777
110. Gu H, et al. (2010) Geometry-independent neutral desorption device for the sensitive
EESI-MS detection of explosives on various surfaces. Analyst 135(4):779–788 (Cambridge,
UK) doi:10.1039/b921579d
111. Haroune N, Crowson A, Campbell B (2011) Characterisation of triacetone triperoxide
(TATP) conformers using LC-NMR. Sci Justice 51(2):50–56
112. Hilton CK, Krueger CA, Midey AJ, Osgood M, Wu J, Wu C (2010) Improved analysis of
explosives samples with electrospray ionization-high resolution ion mobility spectrometry
(ESI-HRIMS). Int J Mass Spectrom 298(1–3):64–71
Additional Scholarly Articles for Further Reading 265

113. Hiyoshi RI, Nakamura J, Brill TB (2007) Thermal decomposition of organic peroxides
TATP and HMTD by T-jump/FTIR spectroscopy. Propellants Explos Pyrotech 32(2):127–
134
114. Huestis DL, Mullen C, Coggiola MJ, Oser H (2008) Laser-ionization mass spectrometry of
explosives and chemical warfare simulants. Sel Top Electron Syst 48:417–423 (Spectral
sensing research for water monitoring applications and science and technology for chemical,
biological and radiological defense)
115. Huestis DL, Mullen C, Coggiola MJ, Oser H (2008) Laser-ionization mass spectrometry of
explosives and chemical warfare simulants. Int J High Speed Electron Syst 18(1):159–165
116. Jensen L, Mortensen PM, Trane R, Harris P, Berg RW (2009) Reaction kinetics of acetone
peroxide formation and structure investigations using Raman spectroscopy and X-ray
diffraction. Appl Spectrosc 63(1):92–97
117. Jian F, Qiao Y, Yu H, Zhuang R (2007) Hydrogen peroxide biosensor based on the
electrochemistry of the myoglobin-TATP composite film. Anal Lett 40(14):2664–2672.
doi:10.1080/00032710701588572
118. Junqueira JRC, de AWR, Salles MO, Paixao TRLC (2013) Flow injection analysis of picric
acid explosive using a copper electrode as electrochemical detector. Talanta 104:162–168
119. Katz G, Zybin S, Goddard WA III, Zeiri Y, Kosloff R (2014) Direct MD simulations of
terahertz absorption and 2D spectroscopy applied to explosive crystals. J Phys Chem Lett 5
(5):772–776. doi:10.1021/jz402801m
120. Kessel R (1991) An end to TATP in the UK. Hastings Cent Rep 21(6):3
121. Kozole J et al (2012) Characterizing the gas phase ion chemistry of an ion trap mobility
spectrometry based explosive trace detector using a tandem mass spectrometer. Talanta
99:799–810
122. Kozole J, Levine LA, Tomlinson-Phillips J, Stairs JR (2015) Gas phase ion chemistry of an
ion mobility spectrometry based explosive trace detector elucidated by tandem mass
spectrometry. Talanta 140:10–19. doi:10.1016/j.talanta.2015.03.001
123. Krishna BV, Misra VN, Mukherjee PS, Sharma P (2002) Microstructure and properties of
flame sprayed tungsten carbide coatings. Int J Refract Met Hard Mater 20(5–6):355–374.
doi:10.1016/S0263-4368(02)00073-2
124. Kuzmin VV, Solov’ev MYe, Tuzkov YB, Kozak GD (2008) Forensic investigation of some
peroxides explosives. Cent Eur J Energ Mater 5(3–4):77–85
125. Latendresse CA, Fernandes SC, You S, Zhang HQ, Euler WB (2013) A fluorometric sensing
array for the detection of military explosives and IED materials. Anal Methods 5(20):5457–
5463. doi:10.1039/c3ay40293b
126. Lazic V, Palucci A, Jovicevic S, Carpanese M (2011) Detection of explosives in traces by
laser induced breakdown spectroscopy: differences from organic interferents and conditions
for a correct classification. Spectrochim Acta Part B 66(8):644–655. doi:10.1016/j.sab.2011.
07.003
127. Lazic V, Palucci A, Jovicevic S, Poggi C, Buono E (2009) Analysis of explosive and other
organic residues by laser induced breakdown spectroscopy. Spectrochim Acta Part B 64B
(10):1028–1039. doi:10.1016/j.sab.2009.07.035
128. Li X, Zhang Z, Tao L (2013) A novel array of chemiluminescence sensors for sensitive,
rapid and high-throughput detection of explosive triacetone triperoxide at the scene. Biosens
Bioelectron 47:356–360. doi:10.1016/j.bios.2013.03.002
129. Li X, Zhang Z, Tao L (2013) A novel microarray chemiluminescence method based on
chromium oxide nanoparticles catalysis for indirect determination of the explosive triacetone
triperoxide at the scene. Analyst 138(5):1596–1600 (Cambridge, UK) doi:10.1039/
c3an00084b
130. Lin H, Suslick KS (2010) A colorimetric sensor array for detection of triacetone triperoxide
vapor. J Am Chem Soc 132(44):15519–15521
131. Lu D, Cagan A, Munoz RAA, Tangkuaram T, Wang J (2006) Highly sensitive
electrochemical detection of trace liquid peroxide explosives at a Prussian-blue
‘artificial-peroxidase’ modified electrode. Analyst 131(12):1279–1281
266 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

132. Lubczyk D, Grill M, Baumgarten M, Waldvogel SR, Muellen K (2012) Scaffold-optimized

dendrimers for the detection of the triacetone triperoxide explosive using quartz crystal
microbalances. ChemPlusChem 77(2):102–105
133. Lubczyk D, Siering C, Loergen J, Shifrina ZB, Muellen K, Waldvogel SR (2010) Simple
and sensitive online detection of triacetone triperoxide explosive. Sens Actuators B 143
(2):561–566
134. MacCrehan W, Moore S, Hancock D (2011) Development of SRM 2907 trace terrorist
explosives simulants for the detection of semtex and triacetone triperoxide. Anal Chem 83
(23):9054–9059 (Washington DC, US) doi:10.1021/ac201967m
135. MacCrehan W, Moore S, Schantz M (2012) Reproducible vapor-time profiles using
solid-phase microextraction with an externally sampled internal standard. J Chromatogr A
1244:28–36
136. Malashikhin S, Finney NS (2008) Fluorescent signaling based on sulfoxide profluorophores:
application to the visual detection of the explosive TATP. J Am Chem Soc 130(39):12846–
12847
137. Mamo SK, Gonzalez-Rodriguez J (2014) Development of a molecularly imprinted
polymer-based sensor for the electrochemical determination of triacetone triperoxide
(TATP). Sensors 14(12):23269–23282. doi:10.3390/s141223269
138. Marr AJ, Groves DM (2003) Ion mobility spectrometry of peroxide explosives TATP and
HMTD. Int J Ion Mobility Spectrom 6(2):59–62
139. Matyas R (2013) Triacetonetriperoxide—a notorious explosive. Chem Listy 107(4):277–282
140. Matyas R, Chylkova J (2013) Study of TATP: method for determination of residual acids in
TATP. Forensic Sci Int 228(1–3):170–173. doi:10.1016/j.forsciint.2013.01.007
141. Matyas R, Jirasko R, Lycka A, Pachman J (2011) Study of TATP: formation of new
chloroderivates of triacetone triperoxide. Propellants Explos Pyrotech 36(3):219–224.
doi:10.1002/prep.201000158
142. Matyas R, Pachman J (2007) Thermal stability of triacetone triperoxide. Sci Technol Energ
Mater 68(4):111–116
143. Matyas R, Pachman J (2010) Study of TATP: influence of reaction conditions on product
composition. Propellants Explos Pyrotech 35(1):31–37. doi:10.1002/prep.200800044
144. Matyas R, Pachman J, Ang H-G (2008) Study of TATP: spontaneous transformation of
TATP to DADP. Propellants Explos Pyrotech 33(2):89–91. doi:10.1002/prep.200700247
145. Matyas R, Pachman J, Ang H-G (2009) Study of TATP: spontaneous transformation of
TATP to DADP—Full Paper. Propellants Explos Pyrotech 34(6):484–488. doi:10.1002/
prep.200800043
146. Matyas R, Selesovsky J (2009) Power of TATP based explosives. J Hazard Mater 165(1–
3):95–99. doi:10.1016/j.jhazmat.2008.09.063
147. Matyas R, Selesovsky J, Musil T (2012) Study of TATP: mass loss and friction sensitivity
during ageing. Cent Eur J Energ Mater 9(3):251–260
148. Matyas R, Selesovsky J, Musil T (2013) Decreasing the friction sensitivity of TATP, DADP
and HMTD. Cent Eur J Energ Mater 10(2):263–275
149. Matyas R, Zeman S, Trzcinski W, Cudzilo S (2008) Detonation performance of TATP/
AN-based explosives. Propellants Explos Pyrotech 33(4):296–300. doi:10.1002/prep.
200700230
150. Mbah J, Knott D, Steward S (2014) Thermogravimetric study of vapor pressure of TATP
synthesized without recrystallization. Talanta 129:586–593. doi:10.1016/j.talanta.2014.06.
031
151. McGann WJ, Haigh P, Neves JL (2002) Expanding the capability of IMS explosive trace
detection. Int J Ion Mobility Spectrom 5(3):119–122
152. Mills A, Grosshans P, Snadden E (2009) Hydrogen peroxide vapor indicator. Sens
Actuators B 136(2):458–463. doi:10.1016/j.snb.2008.12.032
153. Mowlawi AA, Yazdani M (2009) Monte carlo simulation of soil moisture effects on
anti-tank landmines detection by neutron backscattering technique. Int J Mod Phys B 23
(32):5907–5913. doi:10.1142/S0217979209049735
Additional Scholarly Articles for Further Reading 267

154. Mullen C, Huestis D, Coggiola M, Oser H (2006) Laser photoionization of triacetone

triperoxide (TATP) by femtosecond and nanosecond laser pulses. Int J Mass Spectrom 252
(1):69–72. doi:10.1016/j.ijms.2006.01.018
155. Muller D, Levy A, Shelef R, Abramovich-Bar S, Sonenfeld D, Tamiri T (2004) Improved
method for the detection of TATP after explosion. J Forensic Sci 49(5):935–938
156. Munoz RAA, Lu D, Cagan A, Wang J (2007) “One-step” simplified electrochemical sensing
of TATP based on its acid treatment. Analyst 132(6):560–565
157. Odbadrakh K, Lewis JP, Nicholson DM (2010) Interaction of the explosive molecules RDX
and TATP with IRMOF-8. J Phys Chem C 114(17):7535–7540. doi:10.1021/jp906192g
158. Oestmark H, Wallin S, Ang HG (2012) Vapor pressure of explosives: a critical review.
Propellants Explos Pyrotech 37(1):12–23. doi:10.1002/prep.201100083
159. Oxley J et al (2008) Raman and infrared fingerprint spectroscopy of peroxide-based
explosives. Appl Spectrosc 62(8):906–915. doi:10.1366/000370208785284420
160. Oxley J, Smith J, Luo W (2006) Peroxide explosives: detection and destruction.
Proc NATAS Annu Conf Therm Anal Appl 34th:027.05.901/1-027.05.901/7
161. Oxley J, Smith JL, Brady J, Naik S (2010) Determination of urea nitrate and guanidine
nitrate vapor pressures by isothermal thermogravimetry. Propellants Explos Pyrotech 35
(3):278–283. doi:10.1002/prep.200800013
162. Oxley JC (2014) Explosive detection: how we got here and where are we going? Int J Energ
Mater Chem Propul 13(4):373–381. doi:10.1615/IntJEnergeticMaterialsChemProp.
2014011493
163. Oxley JC, Brady J, Wilson SA, Smith JL (2012) The risk of mixing dilute hydrogen
peroxide and acetone solutions. J Chem Health Saf 19(2):27–33. doi:10.1016/j.jchas.2011.
07.010
164. Oxley JC et al (2012) Accumulation of explosives in hair—part 3: binding site study.
J Forensic Sci 57(3):623–635. doi:10.1111/j.1556-4029.2011.02020.x
165. Oxley JC, Smith JL, Bowden PR, Rettinger RC (2013) Factors influencing triacetone
triperoxide (TATP) and diacetone diperoxide (DADP) formation: part I. Propellants Explos
Pyrotech 38(2):244–254. doi:10.1002/prep.201200116
166. Oxley JC, Smith JL, Bowden PR (2012) Rettinger RC Factors influencing triacetone
triperoxide (TATP) and diacetone diperoxide (DADP) formation. In North american thermal
analysis society, pp 65–77
167. Oxley JC, Smith JL, Brady JE, Steinkamp L (2014) Factors influencing destruction of
triacetone triperoxide (TATP). Propellants Explos Pyrotech 39(2):289–298. doi:10.1002/
prep.201300063
168. Oxley JC, Smith JL, Chen H (2002) Decomposition of a multi-peroxidic compound:
triacetone triperoxide (TATP). Propellants Explos Pyrotech 27(4):209–216. doi:10.1002/
1521-4087(200209)27:4<209:AID-PREP209>3.0.CO;2-J
169. Oxley JC, Smith JL, Huang J, Luo W (2009) Destruction of peroxide explosives. J Forensic
Sci 54(5):1029–1033. doi:10.1111/j.1556-4029.2009.01130.x
170. Oxley JC, Smith JL, Kirschenbaum L, Marimganti S, Bernier E (2005) Transfer of
explosives to hair. Proc NATAS Annu Conf Therm Anal Appl 33rd:094.36.892/
1-094.36.892/9
171. Oxley JC, Smith JL, Kirschenbaum L, Shinde KP, Marimganti S (2004) New source of
evidence: explosive traces in hair. Proc SPIE-Int Soc Opt Eng 5403:246–255 (Pt. 1, Sensors,
and command, control communications, and intelligence (C31) technologies for homeland
security and homeland defense III) doi:10.1117/12.548165
172. Oxley JC, Smith JL, Kirschenbaum LJ, Marimganti S (2007) Accumulation of explosives in
hair–part II: factors affecting sorption. J Forensic Sci 52(6):1291–1296
173. Oxley JC, Smith JL, Kirschenbaum LJ, Marimganti S, Vadlamannati S (2008) Detection of
explosives in hair using ion mobility spectrometry. J Forensic Sci 53(3):690–693. doi:10.
1111/j.1556-4029.2008.00719.x
174. Oxley JC, Smith JL, Kirschenbaum LJ, Marimganti S, Vadlamannati S (2008) Detection of
explosives in hair using ion mobility spectrometry. J Forensic Sci 53(3):690–693
268 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

175. Oxley JC, Smith JL, Kirschenbaum LJ, Shinde KP, Marimganti S (2005) Accumulation of
explosives in hair. J Forensic Sci 50(4):826–831. doi:10.1520/JFS2004545
176. Oxley JC, Smith JL, Luo W, Brady J (2009) Determining the vapor pressures of diacetone
diperoxide (DADP) and hexamethylene triperoxide diamine (HMTD). Propellants Explos
Pyrotech 34(6):539–543. doi:10.1002/prep.200800073
177. Oxley JC, Smith JL, Marimaganti K (2010) Developing small-scale tests to predict
explosivity. J Therm Anal Calorim 102(2):597–603. doi:10.1007/s10973-010-0983-6
178. Oxley JC, Smith JL, Resende E (2001) Determining explosivity part II: comparison of
small-scale cartridge tests to actual pipe bombs. J Forensic Sci 46(5):1070–1075
179. Oxley JC, Smith JL, Resende E, Pearce E, Chamberlain T (2003) Trends in explosive
contamination. J Forensic Sci 48(2):334–342
180. Oxley JC, Smith JL, Shinde K, Moran J (2005) Determination of the vapor density of
triacetone triperoxide (TATP) using a gas chromatography headspace technique. Propellants
Explos Pyrotech 30(2):127–130. doi:10.1002/prep.200400094
181. Oxley JC, Smith JL, Steinkamp L, Zhang G (2013) Factors influencing triacetone triperoxide
(TATP) and diacetone diperoxide (DADP) formation: part 2. Propellants Explos Pyrotech 38
(6):841–851. doi:10.1002/prep.201200215
182. Pacheco-Londono LC, Primera-Pedrozo OM, Hernandez-Rivera SP (2004) Experimental
and theoretical model of reactivity and vibrational detection modes of triacetone triperoxide
(TATP) and homologues. Proc SPIE-Int Soc Opt Eng 5617:190–201. doi:10.1117/12.
578603
183. Pachman J, Matyas R (2011) Study of TATP: stability of TATP solutions. Forensic Sci Int
207(1–3):212–214. doi:10.1016/j.forsciint.2010.10.010
184. Pal A, Clark CD, Sigman M, Killinger DK (2009) Differential absorption lidar CO2 laser
system for remote sensing of TATP related gases. Appl Opt 48(4):B145–B150. doi:10.1364/
AO.48.00B145
185. Parajuli S, Miao W (2013) Sensitive Determination of Triacetone Triperoxide Explosives
Using Electrogenerated Chemiluminescence. Anal Chem 85(16):8008–8015 (Washington
DC, US) doi:10.1021/ac401962b
186. Partridge A, Walker S, Armitt D (2010) Detection of impurities in organic peroxide
explosives from precursor chemicals. Aust J Chem 63(1):30–37. doi:10.1071/CH09481
187. Pena AJ, Pacheco-Londono L, Figueroa J, Rivera-Montalvo LA, Roman-Velazquez FR,
Hernandez-Rivera SP (2005) Characterization and differentiation of high energy cyclic
organic peroxides by GC/FT-IR, GC-MS, FT-IR, and Raman microscopy. Proc SPIE-Int Soc
Opt Eng 5778:347–358 (Pt. 1, Sensors, and command, control, communications, and
intelligence (C3I) technologies for homeland defense IV) doi:10.1117/12.604194
188. Pena-Quevedo AJ, Laramee JA, Durst HD, Hernandez-Rivera SP (2011) Cyclic organic
peroxides characterization by mass spectrometry and Raman spectroscopy. IEEE Sens J 11
(4):1053–1060. doi:10.1109/JSEN.2010.2057730
189. Peterson GR, Bassett WP, Weeks BL, Hope-Weeks LJ (2013) Phase pure triacetone
triperoxide: the influence of ionic strength, oxidant source, and acid catalyst. Cryst Growth
Des 13(6):2307–2311. doi:10.1021/cg301795j
190. Petrova T, Michalkova A, Leszczynski J (2010) Adsorption of RDX and TATP on
IRMOF-1: an ab initio study. Struct Chem 21(2):391–404. doi:10.1007/s11224-009-9542-9
191. Pettersson A, Johansson I, Wallin S, Nordberg M, Oestmark H (2009) Near real-time
standoff detection of explosives in a realistic outdoor environment at 55 m distance.
Propellants Explos Pyrotech 34(4):297–306. doi:10.1002/prep.200800055
192. Price MA, Ghee AH (2009) Modeling for detonation and energy release from peroxides and
non-ideal improvised explosives. Cent Eur J Energ Mater 6(3–4):239–254
193. Primera-Pedrozo OM, Pacheco-Londono LC, De la Torre-Quintana LF, Hernandez-Rivera
SP, Chamberlain RT, Lareau RT (2004) Use of fiber optic coupled FT-IR in detection of
explosives on surfaces. Proc SPIE-Int Soc Opt Eng 5403:237–245 (Pt. 1, Sensors, and
command, control communications, and intelligence (C31) technologies for homeland
security and homeland defense III) doi:10.1117/12.542812
Additional Scholarly Articles for Further Reading 269

194. Ramirez ML, Felix-Rivera H, Sanchez-Cuprill RA, Hernandez-Rivera SP (2010)

Thermal-spectroscopic characterization of acetone peroxide and acetone peroxide mixtures
with nitrocompounds. J Therm Anal Calorim 102(2):549–555. doi:10.1007/s10973-010-
0952-0
195. Rasanen R-M et al (2008) Determination of gas phase triacetone triperoxide with aspiration
ion mobility spectrometry and gas chromatography-mass spectrometry. Anal Chim Acta 623
(1):59–65. doi:10.1016/j.aca.2008.05.076
196. Ray RS, Sarma B, Mohanty S, Misra M (2014) Theoretical and experimental study of
sensing triacetone triperoxide (TATP) explosive through nanostructured TiO2 substrate.
Talanta 118:304–311. doi:10.1016/j.talanta.2013.09.057
197. Reany O, Kapon M, Botoshansky M, Keinan E (2009) Rich polymorphism in
triacetone-triperoxide. Cryst Growth Des 9(8):3661–3670. doi:10.1021/cg900390y
198. Romolo FS, Cassioli L, Grossi S, Cinelli G, Russo MV (2013) Surface-sampling and
analysis of TATP by swabbing and gas chromatography/mass spectrometry. Forensic Sci Int
224(1–3):96–100. doi:10.1016/j.forsciint.2012.11.005
199. Rowell F, Seviour J, Lim AY, Elumbaring-Salazar CG, Loke J, Ma J (2012) Detection of
nitro-organic and peroxide explosives in latent fingermarks by DART- and
SALDI-TOF-mass spectrometry. Forensic Sci Int 221(1–3):84–91
200. Ryniec R, Piszczek M, Szustakowski M (2010) Multicriterial analysis of explosives in the
THz range. Acta Phys Pol A 118(6):1235–1238
201. Salinas Y et al (2014) Chromo-fluorogenic detection of nitroaromatic explosives by using
silica mesoporous supports gated with tetrathiafulvalene derivatives. Chem—Eur J 20
(3):855–866. doi:10.1002/chem.201302461
202. Salinas Y et al (2014) Chromo-fluorogenic detection of nitroaromatic explosives by using
silica mesoporous supports gated with tetrathiafulvalene derivatives. Chemistry 20(3):855–
866
203. Santos JP et al. (2014) Nanocrystalline tin oxide nanofibers deposited by a novel focused
electrospinning method. Application to the detection of TATP precursors. Sensors 14
(12):24231–24243 doi:10.3390/s141224231
204. Schade W, Bohling C, Bauer C (2007) Laser optical sensors permit highly sensitive
detection of explosives. Phys J 6(4):25–30
205. Schulte-Ladbeck R, Edelmann A, Quintas G, Lendl B, Karst U (2006) Determination of
peroxide-based explosives using liquid chromatography with on-line infrared detection.
Anal Chem 78(23):8150–8155. doi:10.1021/ac0609834
206. Schulte-Ladbeck R, Karst U (2003) Determination of triacetonetriperoxide in ambient air.
Anal Chim Acta 482(2):183–188. doi:10.1016/S0003-2670(03)00212-5
207. Schulte-Ladbeck R, Kolla P, Karst U (2002) A field test for the detection of peroxide-based
explosives. Analyst 127(9):1152–1154 (Cambridge, UK) doi:10.1039/b206673b
208. Schulte-Ladbeck R, Kolla P, Karst U (2003) Trace analysis of peroxide-based explosives.
Anal Chem 75(4):731–735. doi:10.1021/ac020392n
209. Schulte-Ladbeck R, Vogel M, Karst U (2006) Recent methods for the determination of
peroxide-based explosives. Anal Bioanal Chem 386(3):559–565. doi:10.1007/s00216-006-
0579-y
210. Scott AM et al (2012) Molecular simulations of adsorption of RDX and TATP on IRMOF-1
(Be). J Mol Model 18(7):3363–3378. doi:10.1007/s00894-011-1338-3
211. Scott AM, Petrova T, Hill F, Leszczynski J (2012) Density functional theory study of
interactions of cyclotrimethylene trinitramine (RDX) and triacetone triperoxide (TATP) with
metal-organic framework (IRMOF-1(Be)). Struct Chem 23(4):1143–1154
212. Shaw A, Calhoun RL (2012) Electrogenerated chemiluminescence with ruthenium
trisbipyridine and TATP. ECS Trans 41:49–56 (27, Physical and analytical electrochemistry
(General session)–220th ECS meeting, 2011) doi:10.1149/1.3692523
213. Shen C, Li J, Han H, Wang H, Jiang H, Chu Y (2009) Triacetone triperoxide detection using
low reduced-field proton transfer reaction mass spectrometer. Int J Mass Spectrom 285(1–
2):100–103. doi:10.1016/j.ijms.2009.04.007
270 9 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB)

214. Sigman ME, Clark CD, Caiano T, Mullen R (2008) Analysis of triacetone triperoxide
(TATP) and TATP synthetic intermediates by electrospray ionization mass spectrometry.
Rapid Commun Mass Spectrom 22(2):84–90. doi:10.1002/rcm.3335
215. Sigman ME, Clark CD, Fidler R, Geiger CL, Clausen CA (2006) Analysis of triacetone
triperoxide by gas chromatography/mass spectrometry and gas chromatography/tandem
mass spectrometry by electron and chemical ionization. Rapid Commun Mass Spectrom 20
(19):2851–2857. doi:10.1002/rcm.2678
216. Sinditskii VP, Kolesov VI, Egorshev VY, Patrikeev DI, Dorofeeva OV (2014)
Thermochemistry of cyclic acetone peroxides. Thermochim Acta 585:10–15. doi:10.1016/
j.tca.2014.03.046
217. Song-im N, Benson S, Lennard C (2012) Establishing a universal swabbing and clean-up
protocol for the combined recovery of organic and inorganic explosive residues. Forensic Sci
Int 223(1–3):136–147. doi:10.1016/j.forsciint.2012.08.017
218. Song-im N, Benson S, Lennard C (2013) Stability of explosive residues in methanol/water
extracts, on alcohol wipes and on a glass surface. Forensic Sci Int 226(1–3):244–253
219. Stambouli A, El BA, Bouayoun T, Bellimam MA (2004) Headspace-GC/MS detection of
TATP traces in post-explosion debris. Forensic Sci Int 146(Suppl):S191–S194
220. Staples EJ (2004) Detecting chemical vapours from explosives using the zNose, an
ultra-high speed gas chromatograph. NATO Sci Ser, II 159:235–248 (Electronic noses &
sensors for the detection of explosives)
221. Tarvin M, McCord B, Mount K, Sherlach K, Miller ML (2010) Optimization of two
methods for the analysis of hydrogen peroxide: high performance liquid chromatography
with fluorescence detection and high performance liquid chromatography with electro-
chemical detection in direct current mode. J Chromatogr A 1217(48):7564–7572. doi:10.
1016/j.chroma.2010.10.022
222. Todd MW et al (2002) Application of mid-infrared cavity-ringdown spectroscopy to trace
explosives vapor detection using a broadly tunable (6–8 lm) optical parametric oscillator.
Appl Phys B: Lasers Opt 75(2–3):367–376. doi:10.1007/s00340-002-0991-8
223. Tomlinson-Phillips J, Wooten A, Kozole J, Deline J, Beresford P, Stairs J (2014)
Characterization of TATP gas phase product ion chemistry via isotope labeling experiments
using ion mobility spectrometry interfaced with a triple quadrupole mass spectrometer.
Talanta 127:152–162. doi:10.1016/j.talanta.2014.03.044
224. Tsaplev YB (2012) Decomposition of cyclic acetone peroxides in acid media. Kinet Catal 53
(5):521–524. doi:10.1134/S0023158412050163
225. van Duin A, Zybin S, Chenoweth K, Han S-P, Goddard WA, III (2005) Reactive force fields
based on quantum mechanics for applications to materials at extreme conditions. Lect Ser
Comput Comput Sci 4 B:1109–1113 (Advances in computational methods in sciences and
engineering)
226. van Duin ACT, Zeiri Y, Dubnikova F, Kosloff R, Goddard WA III (2005) Atomistic-scale
simulations of the initial chemical events in the thermal initiation of triacetonetriperoxide.
J Am Chem Soc 127(31):11053–11062. doi:10.1021/ja052067y
227. Viswanath DS, Reinig M, Ghosh TK, Boddu VM (2010) Vapor pressure of nitro compounds.
In vol Pt. 1. University of Pardubice, Institute of energetic materials, pp 306–309
228. Walter MA et al (2010) Triacetone triperoxide (TATP): hapten design and development of
antibodies. Langmuir 26(19):15418–15423. doi:10.1021/la1018339
229. Walter MA, Panne U, Weller MG (2011) A novel immunoreagent for the specific and
sensitive detection of the explosive triacetone triperoxide (TATP). Biosensors 1:93–106.
doi:10.3390/bios1030093
230. Widmer L, Watson S, Schlatter K, Crowson A (2002) Development of an LC/MS method
for the trace analysis of triacetone triperoxide (TATP). Analyst 127(12):1627–1632
(Cambridge, UK). doi:10.1039/b208350g
231. Wilkinson J, Konek CT, Moran JS, Witko EM, Korter TM (2009) Terahertz absorption
spectrum of triacetone triperoxide (TATP). Chem Phys Lett 478(4–6):172–174. doi:10.1016/
j.cplett.2009.07.079
Additional Scholarly Articles for Further Reading 271

232. Willer U, Schade W (2009) Photonic sensor devices for explosive detection. Anal Bioanal
Chem 395(2):275–282. doi:10.1007/s00216-009-2934-2
233. Wu S-H et al (2012) Thermal hazard analysis of triacetone triperoxide (TATP) by DSC and
GC/MS. J Loss Prev Process Ind 25(6):1069–1074
234. Wu S-H et al (2013) Effects of various fire-extinguishing reagents for thermal hazard of
triacetone triperoxide (TATP) by DSC/TG. J Therm Anal Calorim 113(2):991–995. doi:10.
1007/s10973-012-2788-2
235. Xie Y, Cheng IF (2010) Selective and rapid detection of triacetone triperoxide by
double-step chronoamperometry. Microchem J 94(2):166–170. doi:10.1016/j.microc.2009.
10.016
236. Xu M, Han J-M, Wang C, Yang X, Pei J, Zang L (2014) Fluorescence ratiometric sensor for
trace vapor detection of hydrogen peroxide. ACS Appl Mater Interfaces 6(11):8708–8714.
doi:10.1021/am501502v
237. Xu X, van dCAM, Kok EM, de BPCAM (2004) Trace analysis of peroxide explosives by
high performance liquid chromatography-atmospheric pressure chemical ionization-tandem
mass spectrometry (HPLC-APCI-MS/MS) for forensic applications. J Forensic Sci 49
(6):1230–1236
238. Yamaguchi S, Uchimura T, Imasaka T, Imasaka T (2009) Gas chromatography/
time-of-flight mass spectrometry of triacetone triperoxide based on femtosecond laser
ionization. Rapid Commun Mass Spectrom 23(19):3101–3106. doi:10.1002/rcm.4225
239. Zeman S, Bartei C (2008) Some properties of explosive mixtures containing peroxides.
J Hazard Mater 154(1–3):199–203. doi:10.1016/j.jhazmat.2007.10.013
240. Zeman S, Bartei C (2008) Some properties of explosive mixtures containing peroxides part
II. Relationships between detonation parameters and thermal reactivity of the mixtures with
triacetone triperoxide. J Hazard Mater 154(1–3):199–203
241. Zhang G (2010) A device for testing thermal impact sensitivity of high explosives.
Propellants Explos Pyrotech 35(5):440–445. doi:10.1002/prep.201000030
242. Zhang W-H, Zhang W-D, Chen L-Y (2010) Highly sensitive detection of explosive
triacetone triperoxide by an In2O3 sensor. Nanotechnology 21(31):315502
243. Zhukov IS, Kozak GD, Tsvigunov AN, Moroz NS (2010) Transformation of aluminum at
explosion of its mixtures with TATP and HMTD. In vol Pt. 2. University of Pardubice,
Institute of energetic materials, pp 822–824
244. Zuck A et al (2008) Explosive detection by microthermal analysis. J Energ Mater 26(3):
163–180
Chapter 10
Triacetone Triperoxide (TATP)

Abstract Information on thermophysical properties of energetic materials is lim-

ited and scattered in the literature. Although peroxides have been known as ener-
getic materials for a long time, triacetonetriperoxide has become prominent as a
homemade explosive in the recent years. The properties of TATP are extremely
important in its detection, and this chapter reviews the synthesis, properties,
for-mulations, detonation, and detection of triacetonetriperoxide.

10.1 Introduction

Improvised explosive devices have proved very fatal as has been evident in the Iraq
war, and the use of homemade explosives [HME] have proven to be more effective.
The HMEs, mostly peroxides, have eluded detection because of the low sensitivity
of the currently available sensors/detectors. Synthesis and characterization of new
energetic materials are receiving considerable interest to find materials that are safe
and show better performance. Among some of the common HMEs such as hex-
amethylene triperoxide, nitrourea, urea nitrate and others, TATP has become a
prominent one. In spite of the precautions taken during the manufacture of
explosives, there are always possibilities that accidental explosions can occur, more
so with extremely energetic materials such as TATP.
Triacetone triperoxide, TATP, is a simple but a powerful explosive. It has three
acetone molecules joined together by O–O linkages. It is a primary explosive, white
crystalline powder with an acid smell. It can be made easily and therefore the choice
explosive of terrorists including suicide bombers.
This substance was used in 2005 London bombings. TATP has an explosive
force equivalent to 50–80% of that of TNT. As TATP does not contain nitrogen, it
is likely to go through airport scanners without detection as most of the scanners are
calibrated for nitrogen containing chemicals. Reid, the shoe bomber, used TATP
along with a plastic explosive. He used TATP as a trigger by using a small thread of
TATP through 100 g of PETN [1]. The seven suspects who were arrested in
Vollsmose in Denmark in 2006 [2] and eight Al-Queda terrorists arrested in

© US Government (outside the USA) 2018 273

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7_10
274 10 Triacetone Triperroxide (TATP)

Copenhagen had access to homemade TATP. These two events happened in 2006
and 2007, respectively. In 2005 October, Hinrichs, a student at the Oklahoma
University, died near the football stadium after a backpack containing two to three
pounds of TATP exploded [3] due to his carelessness. Two contractors were
recently arrested by the Swedish police on suspicion that they were suspected of
sabotage of the Oskarshamn nuclear plant in southeastern Sweden. One of them
was carrying a small amount of TATP. These and many more incidents show the
explosive power of TATP, the relative ease with which it can be made, the
availability of chemicals for the synthesis of TATP, and the extreme difficulty in
detecting this compound as most of the detectors are calibrated for explosives
containing nitrogen. YouTube graphically illustrates the synthesis of
TATP. Although the civilian and military uses of TATP are limited, and the public
knowledge of peroxide explosives was very limited until recently, TATP has shot
into prominence for reasons mentioned earlier. Reports of the use of TATP by the
Mexican Drug Cartel during the past two to three years have been surfacing, and
TATP has been linked to the explosion of home-made bombs. The ease of
preparation of TATP has emboldened home grown terrorists, like Chad Wells, who
was arrested recently as reported in the Augusta Chronicle [4].
These events indicate the gravity of the situation, and the need to know as much
as possible about this chemical. Safe handling and disposal of these HMEs like
TATP require a good understanding and knowledge of the properties of these
compounds. To design and build sensitive and robust detection systems, it is
imperative to have accurate vapor pressure data besides other thermophysical
properties of these chemicals. Thermophysical properties are essential to develop
models to predict properties such as vapor pressure when experimental data are
lacking.
TATP is a white crystalline substance with an acid odor. It sublimes readily at
room temperature, and is extremely sensitive to impact, friction and electrostatic
discharge. It is extremely dangerous because of the constrained nature of the
molecule in a ring form in three dimensions. The problems of handling and extreme
sensitivity make it difficult to use TATP in military and civilian applications
although it is very easy to synthesize. It is reported that TATP in quantities less than
2 g burns but more than 2 g detonates when ignited. A TATP bomb can be made
with $100–$200 worth of chemicals, and simple equipment.
Denekamp et al. [5] have identified two stable conformal structures for TATP
based on experimental and theoretical evidence. Figure 10.1 shows the two con-
formal forms of TATP. These two forms are stable with energy of transition of
26.3 kcal/mole. The authors have carried out B3LYP/6-31G computations to arrive
at the crystal parameters. They note that this type of behavior is rare in cyclic
organic systems and attribute it to the overlap in the “flip-flop” transition state. It is
known that TATP contains the dimer of acetone peroxide [6] and a tetramer is also
observed [7].
The chemical name for TATP is 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,
8-Hexoxonane and is also known as peroxyacetone. Acetone peroxide most
10.1 Introduction 275

Δ E = 26.3 kcal mol-1

Fig. 10.1 Conformal Structures of TATP

commonly refers to the cyclic trimer TCAP (tri-cyclic acetone peroxide, or

tri-cyclo). The CAS Number is 17088-37-8.

10.2 Synthesis

TATP is prepared starting with hydrogen peroxide and acetone. As early as 1895,
Wolffenstein [8] discussed the effect of hydrogen peroxide concentration on ace-
tone. He showed that 10% peroxide can be used to synthesize TATP. Acid cat-
alyzed synthesis of TATP was first described in 1959 by Millas and Golubovic [9].
They added acetone (0.2 mol) at 273.15 K (0 °C) to a cold mixture of hydrogen
peroxide (50%, 0.2 mol) and sulfuric acid, kept the mixture at 273.15 K (0 °C) for
3 h, and then extracted it with pentane. This procedure uses large quantities of
sulfuric acid but is a fast and unsafe route to synthesize TATP. Dubnikova et al.
[10] used the same method as Millas and Golubovic but used smaller amounts of
sulfuric acid. This procedure improved the safety of the process. Mateo et al. [11]
prepared TATP by treating acetone at 271.15 K (−2 °C) with concentrated
hydrogen peroxide with sulfuric acid as the catalyst. They obtained 75% yield.
Pacheco-Londono et al. [12] used different ratios of acetone and H2O2 with different
inorganic acids as catalysts to make TATP. They used Density Functional Theory
to elucidate the mechanism of the reaction, and used B3LYP functional with the
6-31G basis set to carry out calculations of the electronic structure of the inter-
mediates and internal rotations and vibrations of TATP. A 1989 patent taken by
Costantini [13] and assigned to Rhone-Poulenc gives details of TATP synthesis and
destruction.
Jiang et al. [7] found SnCl4
5H2O and SnCl2
2H2O to be efficient catalysts for
the oxidation of acetone with 30% hydrogen peroxide at room temperature. This
method produced tetrameric acetone peroxide which was identified by molecular
weight determination, elemental analysis, FTIR, NMR and MS. Jensen et al. [14]
used Raman spectroscopy to study the synthesis of TATP. They studied the effect
of temperature and pH, and observed spectral changes during the course of the
reaction.
276 10 Triacetone Triperroxide (TATP)

10.3 Structure

TATP crystalline is a monoclinic solid with a P21/c space group and a coordination
number of 4. The lattice parameters are a = 13.925 Å, b = 10.790 Å, c = 7.970 Å,
and b = 91.64° [15]. It exists in a twisted boat chair form with O–O dis-
tance = 1.483 Å, C–O bond length of 1.422 Å, and the C–O–O angle 107.4°. The
C–O bond length is shorter than that found in other peroxides. Dubnikova et al. [10]
compared experimental bond lengths with values based on B3lYP calculations, and
their data are shown in Table 10.1. These values compare well with the values of
Groth [15]. As a part of a forensic investigation, Evans et al. [16] provide chemical
ionization and electron impact mass spectra, infrared spectrum, and some physical
properties of TATP.

10.4 Detection

The synthesis of TATP mentioned above reveals that it can be made easily from
readily available raw materials. This has made TATP a choice explosive for terrorist
activities. In order to provide safety and protect human lives, it is essential to have
extremely sensitive techniques to detect TATP. In recent years a great deal of
attention has been paid to the detection of TATP. There was no reliable method to
detect TATP until 2003 [17]. Since 2003, the number of papers published in the
open literature on the detection of TATP has exceeded 100. The absence of nitro,
amino, or aromatic groups makes it difficult to detect TATP. The explosive nature
of TATP makes it difficult to even analyze the material, and therefore special care
has to be taken to prepare a sample. Many national laboratories in the United States
are involved in the detection of TATP [18].
Several methods including IR and Raman spectroscopy, ion mobility spec-
trometry, 1H and 13C NMR, HPLC, GC/MS, chemical ionization coupled to tandem
mass spectrometry, and laser photo-acoustic and photoionization techniques have

Table 10.1 Comparison Bond length/angle Expt. Calc.

experimental and calculated
bond lengths and bond angles O–C 1.419, 1.418, 1.417 1.422
[10] O–C 1.422 1.421
O–O 1.466, 1.471, 1.473 1.458
C–C 1.512, 1.514, 1.516 1.528
C–C 1.505, 1.510 1.529
<O–C–O 112.2, 112.5, 112.8 112.9
<O–C–C 102.7, 103.2, 107.8 102.9
<O–C–C 112.1, 112.5, 112.8 112.3
<O–O–C 107.6, 112.8 108.6
<C–C–C 113.0, 114.2 113.6
10.4 Detection 277

been used to detect and analyze TATP. Utilizing the quantum cascade laser pho-
toacoustic spectroscopy technique, Dunayevskiy et al. [19] were able to detect
TATP to 18 ppb levels. However this level of sensitivity may not be enough to
detect TATP from a distance of 5 to 10 m when someone is carrying this explosive.
Because of the difficulties in handling TATP, Dunayevskiy et al. [19] describe a
simple apparatus for preparation and collection of TATP for analysis. Mullen et al.
[20] describe a laser ionization time-of-flight mass spectrometric technique to study
its potential for detection of TATP. In addition to the laser ionization time-of-flight
mass spectrum, the authors also present UV spectra of both TATP and H2O2 and
compare with the available literature spectra.
Canines are commonly employed to detect various substances such as drugs and
conventional explosives, however, canines are being trained to detect TATP as
more incidents have taken place using TATP. It appears that trials reveal that
canines can detect 200 lg of TATP [21] although the present method used for
training canines is not too satisfactory. Muller et al. [22] report that they were able
to detect 6.4 ng using a GC/MS system. They used Amberlite XAD7 as the
adsorbent and acetonitrile as the eluent. They also report the presence of TATP in
several post-explosion areas in and around Jerusalem, Israel.
Based on chemiluminescence principle, Scintrex Trace Systems [23] offers
E3500 for TATP detection. This is a hand held unit but the sensitivity of this system
is not mentioned. For portal detection of TATP, Synagen Guardian MS-ETD [24]
has designed and built the personal screening portal based on a technology from
Sandia National Laboratory. In this method, a puff of air dislodges trace amounts of
chemicals such as TATP which are analyzed by an MS- electron transfer dissoci-
ation technique. Another hand-held unit has been developed by Acro [25], an Israeli
small-scale company. It is a pen sized detector but its detection capability, cost, and
sensitivity are not revealed. It is a colorimetric method and requires about 25–50
micrograms of TATP. Figure 10.2 shows the sensitivity of the instrument based on
the information available on the company’s website. This sensor uses the peroxi-
dase enzyme method and is covered by a US Patent [26]. Nomadics [27] has several
patents on the detection of peroxides. In general the peroxide such as TATP is
decomposed and the released H2O2 is reacted further to finally yield CO2 which is
detected by light emission techniques.
A quantitative trace analysis of peroxide based explosives, hexamethylene-
triperoxidediamine (HMTD) and triacetone triperoxide (TATP) has been developed
by Ladbeck et al. [28] using fluorescence spectroscopy. The limit of detection was
2  10−6 mol l−1 for both TATP and HMTD. Sigman et al. [29] carried out the
analysis of TATP and the other products by electronspray mass spectrometry, and
were able to detect TATP at levels close to 60 ng. Compared to this level of detection,
the GC-MS method developed by Roman et al. [30] appears to be more sensitive
down to picogram levels. This method is claimed to be applicable to both TATP and
DADP to 50 pg levels. Ion mobility spectroscopy coupled with a triple quadrupole
mass spectrometer was used by Buttigieg [31] during the synthesis and analysis of
TATP. Sella and Shabat [32] developed a molecular probe to detect TATP. This
method is sensitive only at microgram levels, and may not be a practical tool.
278 10 Triacetone Triperroxide (TATP)

Fig. 10.2 Color sensitivity as a function of microgram TATP [25]

The detection systems described above have not been used as stand-off detection
systems. Gaft and Nagli [33] describe a UV Raman spectroscopic method for
standoff detection at distances close to 100 feet (30 m). The authors used a Schmidt–
Cassegrain telescope fiber-coupled to an Oriel MS260i spectrometer with a gated
ICCD detector along with a frequency- doubled Nd-YAG (532 nm, 20 mJ/pulse)
pulsed (8 ns, 13 Hz) laser system. In addition to TATP, they report to have studied
UN—urea–nitrate, TNT including by-products and mixtures, such as comp B
(mixture with RDX), DNT, RDX and mixtures such as C4, A5, ANFO—
ammonium-nitrate fuel-oil, PETN, HMX, and Semtex, a mixture of RDX and
PETN. This appears to pave the way for commercialization of stand-off detection
systems. They present typical Raman spectrum for each of these materials. Munoz
et al. [34] report an electrochemical method for the detection of TATP. This method
is carried out in liquid phase, and may not be useful as a practical detector. The
sensitivity appears to be at nanogram levels. In their recent paper, Banerjee et al. [35]
describe the use of titania nanotubes for the detection of TATP. The authors do not
discuss the sensitivity but it appears to be at the ppm levels. One plus point of this
research is that if the method could be made sensitive enough, it could be used in
hand-held detectors. Apblett et al. [36] report the use of molybdenum hydrogen
bronze nanoparticles for the detection of TATP and HMTD. As this is a calorimetric
method, the sensitivity of the method may not get to pictogram levels. The authors
discuss the possibility of this method as a method for in situ degradation of TATP.
Cotte-Rodriguez et al. [37] used both desorption electrospray ionization and des-
orption atmospheric pressure chemical ionization in their work on the detection of
TATP, HMTD, and other explosives. In this technique, the explosives were
10.4 Detection 279

complexed with certain dopants for analysis. The method is claimed to be fast and
reliable. Both TATP and HMTD were detected in the 1–5000 ng range.

10.5 Properties of TATP

The unstable nature of TATP and its explosive nature makes it difficult to determine
accurately the thermochemical and thermophysical properties, and literature search
revealed lack of data. Table 10.2 lists some of the common properties of TATP
from different sources [4, 38, 39].
Oxley et al. [40] measured the vapor pressure of TATP and their data are
tabulated in Table 10.3. Table 10.3 shows that the error between two measurements
sometimes is between 10 to 20% and shows the need for better methods and
accurate measurements.
The extremely unstable nature of the compound makes it difficult to measure
accurate values. The authors represent the vapor pressure-temperature data by the
relation.

5708
Log10 PðP on PaÞ ¼ 19:791 
T ðK Þ

where P is in Pascal, and T in K.

Table 10.2 Common properties of TATP

Empirical formula C9H18O6 CAS
No. 17088-37-8
Other names: 3,3,6,6,9,9-Hexamethyl-1,2,4,5,7,8-hexaoxacyclononane,
Molecular mass, g/mole 222.24
Crystal structure Monoclilnic with cell parameters [10]
a = 13.788 Å, b = 10.664 Å, c = 7.894 Å,
b = 91.77°, V = 1160.1 Å3
Density, g/mL 1.004 [38]
Molar volume, cm3mol−1 221.1 ± 3.0 [38]
Boiling point, K 370.15-433.15; 458.05 ± 30 (97–160 °C; [38]
184.9 ± 30 °C)
Melting point 367.15 (94 °C) [38]
365.15-366.15 (92–93 °C) [12]
Flash point 51.5 ± 24.4 [38]
Enthalpy of vaporization, 40.39 ± 3.0 [38]
kJ/mol 46.41 and 51.73 [39]
Koc 325 [38]
Velocity of detonation, 5300
m/s
Aqueous solubility, g/L 3.1 at 298.15 K (25 °C) [38]
Bioconcentration Factor 22.6 [38]
280 10 Triacetone Triperroxide (TATP)

Table 10.3 Vapor pressure of TATP [40]

T, K 285 285 295 295 298 298 305 305
VP, Pa 0.95 1.13 1.85 1.44 6.95 6.86 16.8 18.9
T, K 315 315 325 325 331 331
VP, Pa 46.1 51.2 98.4 101 720 596

10.6 TATP Decomposition

TATP decomposes around 150–160 °C. It also undergoes spontaneous transfor-

mation to DADP under certain conditions [41]. This decomposition depends on the
catalysts used, the ratio of reactants to catalyst, purity of chemicals used and
reaction conditions. The spectra of pure TATP have been recorded by Oxley et al.
[42] and their IR and Raman frequency assignments are shown in Table 10.4. In
addition they also present a comparative study of the vibrational spectra of several
peroxide compounds including HMTD, DADP, etc. Vibrational spectroscopy of
TATP is the subject of a presentation by Pacheco-Londono et al. [43]. In their
synthesis study, the authors used different acids as catalysts, and varied the ratio of
acetone to hydrogen peroxide. A recent study of the vibrational spectroscopy of
TATP was carried out by Brauer et al. [44]. They carried out experimental and
theoretical studies to analyze the overtones and anharmonic interactions.
The products of decomposition of TATP depend on the rate of heating as noticed
by Hiyoshi et al. [45]. Slow heating rates produced acetone whereas methane was
the product at higher heating rates. This could be because of the type of O–O
cleavage at different heating rates. Mullen et al. [46] in their study of laser ion-
ization time-of-flight mass spectroscopy found TATP decomposition products,
including acetyl ion C2H3O+, acetone ion C3H6O+, C3H7O+, C3H7O+2 , C3H6O+4 , and
C3H6O+5 . Matyas and Pachman [47] have carried out DTA measurements of TATP
in the presence of several inorganic acids. The decomposition rate was faster with
sulfuric acid compared to hydrochloric, nitric, or perchloric acids. Armitt et al. [48]
carried out a similar study to track the products of decomposition of TATP in the
presence of inorganic acids. The products and the rates of decomposition were
dependent on the type of acid. Part of this study is also reported elsewhere [49].

10.7 Formulations and Detonation Characteristics

The stability of TATP has prevented it to be used as a primary explosive although it

can be made easily from chemicals that are readily available and cheap. Hanson
[50] reports that TATP has 50–80% of the force of TNT, and creates a force of
nearly 1.5 tons per square inch. To get a perspective of the damage that could be
10.7 Formulations and Detonation Characteristics 281

Table 10.4 TATP calculated (at B3LYP/cc-pVDZ level of theory) harmonic frequencies (cm−1),
IR intensities (km/mole), Raman scattering activities (A4/AMU), and frequencies [42]
Frequency IR Raman Description
intensity activity
n1 99.2 0.7 0.4 O–O–C–Methyl torsional tangent
to ring
m2 100.1 0.6 0.4 O–O–C–Methyl torsional
m3 129.1 1.9 0.0 Collective O–O–C–Me torsional
m4 147.0 2.8 0.4 O–O–C–Methyl torsional and
Methyl twist
m5 147.6 3.2 0.5 O–O–C–Methyl torsional and
Methyl twist
Asynchronous
m13 236.4 0.4 2.5 C–O–O–C shear
m14 237.3 0.4 2.5 C–O–O–C shear
m16 296.3 0.3 0.0 Collective bending
m21 393.7 0.0 5.4 Ring breathing
m22 429.1 0.6 0.4 O–C–Methyl scissoring
m23 430.1 0.7 0.4 O–C–Methyl scissoring
m25 547.2 10.6 4.2 O–C–Methyl scissoring and
Methyl–C–
Methyl rocking
m26 547.4 10.4 4.2 O–C–Methyl scissoring and
Methyl–C–
Methyl
rocking
m27 557.1 0.0 22.8 Collective O–C–O scissoring
m28 572.9 13.0 0.0 Collective C–C–O scissoring
m29 623.8 6.6 2.5 O–C–O scissoring asynchronous
m30 624.1 6.6 2.5 O–C–O scissoring asynchronous
m31 792.1 28.6 0.3 O–C–O symmetrical stretching
and Methyl
–C–Me sym stretching
m32 792.6 28.6 0.3 O–C–O symmetrical stretching
and Methyl–
C–Methyl symmetrical stretching
m33 848.1 15.4 0.0 Collective O–C–O asymmetrical
stretching
m34 855.5 0.0 7.4 Collective O–C–O and Methyl–C–
Methyl
Symmetrical stretching
m35 891.2 24.7 10.1 O–C–O and Methyl–C–Methyl
asymmetric
Stretching Me–C–O symmetric stretching
m36 891.8 24.7 10.1 O–C–O and Methyl–C–Methyl
symmetric
(continued)
282 10 Triacetone Triperroxide (TATP)

Table 10.4 (continued)

Frequency IR Raman Description
intensity activity
Stretching Methyl–C–O asymmetric stretching
m37 903.6 3.1 32.1 O–O stretching asynchronous and
Methyl
Rocking asynchronous
m38 904.6 3.0 32.8 O–O stretching asynchronous and
Methyl
Rocking
synchronous
m39 906.6 0.1 19.9 O–O stretching synchronous
Methyl–C–
Methyl symmetrical stretching and Methyl rocking
synchronous
m43 956.3 17.9 13.3 Methyl–C–Methyl stretching O–
C–O
Symmetrical stretching
m44 957.1 16.1 12.8 Methyl–C–Methyl and O–C–O
symmetrical
Stretching
m45 962.7 0.0 66.2 Collective O–O and C–O
stretching
m48 1022.8 0.0 3.3 O–C–O symmetrical stretching
m49 1137.2 4.6 0.0 O–C–O asymmetric stretching
m50 1197.4 187.8 1.0 O–C–O and Methyl–C–Methyl
asymmetric
Stretching Methyl–C–O symmetrical stretching
m51 1197.6 192.6 1.0 O–C–O and Methyl–C–Methyl
asymmetric
Stretching, Methyl–C–O symmetric stretching
m52 1213.9 131.5 2.4 O–C–O and Methyl–C–Methyl
Symmetric stretching
m53 1214.0 131.4 2.4 O–C–O and Methyl–C–Methyl
symmetric stretching
m54 1220.9 0.0 9.8 Collective O–C–O and Methyl–C–
Methyl
Symmetric stretching
Table includes only the frequencies (all of them) that are concerned with O–O and C–O vibrations

done by such a force is to look at the force that support columns in buildings such
as the Oklahoma City A.P. Murrah building. The columns were designed to
withstand at least 3000 lb per square inch which is what TATP can create. In a
10.7 Formulations and Detonation Characteristics 283

Truzl test, Dubnikova et al. [10] found TATP to be 80% as effective as TNT, but its
volatility and unstable nature make it difficult to use for military and civilian
purposes. Matyas and Selesovsky [51] have presented the detonation characteristics
of various combinations of TATP, ammonium nitrate, water, uranium nitrate, fuel
oil, etc.
Mayatas et al. [52] have studied TATP formulation with ammonium nitrate
(AN) and water. They varied the mixture compositions from 21 to 31% TATP, 37
to 54% AN, and 19 to 32% water, and tested them for various properties including
detonation velocity. The results were compared with those of 2,4,6-trinitrotoluene
(TNT). The summary of their results are shown in Table 10.5. The compositions of
the four mixtures are pretty close to one another. An interesting observation that the
authors have made is the dependence of detonation velocity on charge diameter,
and the criticality of the charge diameter. The results of Table 10.5 indicate larger
charge diameters increase the detonation velocity and come closer to the detonation
velocity of TNT. It is not clear how they prepared their explosion emulsion
ammonium nitrate—ANE, but this low cost material has a detonation velocity
closer to TNT. Another publication by the authors [53] provides more data on
TATP+ ammonium nitrate and TATP+ urea nitrate.
Menning and Ostmark [54] measured the friction and impact sensitivity based on
the up and down method. The results of their tests are shown in Table 10.6. The
commercial samples used in these tests have been tested for purity by IR spec-
troscopy. The results of Table 10.6 are based on ten tests per sample. The authors
determined friction sensitivity using a Julius Peters (BAM) apparatus, and per-
forming the test by using an up-and-down method on both sides of the 50%
probability level.

Table 10.5 Experimental results on various explosive mixtures [52]

Explosive composition Internal charge Density Detonation velocity
TATP AN W diameter (mm) (gcm−3) (ms−1)
27 54 19 28 1.19 4110
26 54 20 46 1.16 4400
26 54 20 12.3 1.29 2520
26 54 20 16.5 1.29 2880
26 54 20 105 1.28 4810
21 53 26 25 1.14 4800
31 37 32 25 1.14 4470
TNT— 25 1.20 5480
test 1
TNT— 25 1.20 5460
test 2
ANFO 25 0.75 2180
ANE 25 1.06 5460
284 10 Triacetone Triperroxide (TATP)

Table 10.6 Friction and impact sensitivity of TATP based on up and down method [54]
Friction Impact
Sensitivity, Sensitivity, Temp/RH
Explosive Form BAM (kp/cm2) ERL (J) Std dev (J) ( °C/%)
TATP (FOI) Needle-like crystals <1.0 <1.2 − 21/74
TATP (FOI) Fine powder <0.5 <2.0 − 18/27
TATP (FOI) Fine powder <0.5 1.9 0.9 19/26
TATP (FOI) Crystals <0.5 <1.2 − 17/25
TATP (FOI) Fine powder <0.5 2.3 0.3 19/28

10.8 Destruction

Several methods including oxidation-reduction, and catalytic, have been explored

for the degradation and destruction of TATP. Fidler et al. [55] found 96% degra-
dation using an alloy of MgPd. They observed acetone to be the product of
decomposition. Bellamy [56] discusses a chemical reduction method for the safe
disposal of TATP. The risks involved in handling this sensitive explosive are shown
to be considerably reduced by dissolving it in toluene. Destruction of unwanted
samples of TATP could in principal be achieved in three ways (a) burning, prefer-
ably of a TATP solution, (b) thermal degradation, and (c) chemical destruction.

References

1. Fresco A, O’Neill S, Tendler S (July 15, 2005) Jamaican-born bomber from the suburbs of
Middle England. The Times, 15 July 2005, at www.timesonline.co.uk/article/0,22989–
1694965,00.html
2. Perry M, Berg M, Krukones J (2010) Danish ‘homegrown’ vollsmose group on 5 September
2006. sources of European History: Since 1900
3. NBC NEWS (2005) Bomb blast at University of Oklahoma. Bomb blast outside of sooner
football game. 2 Oct 2005
4. Sparks P (2009) Arrest warrant issued for man involving explosives. Augusta Chronicle, 20
Jan 2009
5. Denekamp C, Gottlieb L, Tamiri T, Tsoglin A, Shilav R, Kapon M (2005) Two separable
conformers of tatp and analogues exist at room temperature. Org Lett 7(12):2461–2464
6. Bayer VV (1900) Ueber die einwirkung des caro’schen reagens auf ketone. Chem Ber
33:858–864
7. Jiang H, Chu G, Gong H, Qiao QD (1999) Tin chloride catalyzed oxidation of acetone with
hydrogen peroxide to tetrameric acetone peroxide. J Chem Res 4:288–289
8. Wolffenstein (1895) Action of hydrogen peroxide on acetone and mesityl oxide. Berichte der
Deutschen Chemischen Gesellschaft 28:2265–2269
9. Milas NA, Golubovic A (1959) Studies in organic peroxides XXVI organic peroxides
derived from acetone and hydrogen peroxide. J Am Chem Soc 81:6461–6462
10. Dubnikova F, Kosloff R, Almog J, Zeiri Y, Boese R, Itzhaky H, Alt A, Keinan E (2005)
Decomposition of triacetone triperoxide is an entropic explosion. J Am Chem Soc 127
(4):1146–1159
References 285

11. Mateo M, Eyler GN, Alvarez EE, Canizo AI (1998) New method for the synthesis of cyclic
acetone triperoxide. Informacion Tecnologica 9(2):19–22
12. Pacheco-Londono LC PAJ, Primera-Pedrozo OM, Hernandez-Rivera SP, Mina N, Garcia R,
Chamberlain RT, Lareau RT (2004) An experimental and theoretical study of the synthesis
and vibrational spectroscopy of triacetone triperoxide (TATP). In: Proc SPIE-Int Soc Opt
Eng 5403(Pt 1, Sensors, and Command, Control Communications, and Intelligence (C31)
Technologies for Homeland Security and Homeland Defense III), pp 279–287
13. Costantini M (1989) Destruction of acetone peroxides. US Patent 5003109
14. Jensen L, Mortensen PM, Trane R, Harris P, Berg RW (2009) Reaction kinetics of acetone
peroxide formation and structure investigations using Raman spectroscopy and X-ray
diffraction. Appl Spectrosc 63(1):92–97
15. Groth P (1969) Crystal structure of 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxacyclononane
(trimeric acetone peroxide). Acta Chem Scand 23(4):1311–1329
16. Evans HK, Tulleners FAJ, Sanchez BL, Rasmussen CA (1986) An unusual explosive,
triacetonetriperoxide (TATP). J Forensic Sci 31(3):1119–1125
17. Ember L (2005) Biochemist arrested. Chem Eng News 83:20
18. Miller C (2007) Quality and contamination control in an explosives testing laboratory. In
American Chemical Society p NW-009 Abstracts 62nd Northwest Regional Meeting of the
American Chemical Society Boise ID United States
19. Dunayevskiy I, Tsekoun A, Prasanna M, Go R, Patel CKN (2007) High-sensitivity detection
of triacetone triperoxide (TATP) and its precursor acetone. Appl Opt 46(25):6397–6404
20. Mullen C, Huestis D, Coggiola M, Oser H (2006) Laser photoionization of triacetone
triperoxide (TATP) by femtosecond and nanosecond laser pulses. Int J Mass Spectrom 252
(1):69–72
21. Oxley JC, Smith JL, Moran J, Nelson K, Utley WE (2004) Training dogs to detect
Triacetone Triperoxide (TATP). In: Proc SPIE-Int Soc Opt Eng 5403(Pt 1, Sensors, and
Command, Control Communications, and Intelligence (C31) Technologies for Homeland
Security and Homeland Defense III), pp 349–353
22. Muller D, Levy A, Shelef R, Abramovich-Bar S, Sonenfeld D, Tamiri T (2004) Improved
method for the detection of TATP after explosion. J Forensic Sci 49(5):935–938
23. Scintrex Trace Systems. E3500 Trace Detector, Detects Explosives http://www.
scintrextrace.com/brochures/current/e3500.pdf
24. Synagen Guardian MS-ETD, Syagen Technology Inc, Guardian Explosives Trace Detection
(ETD), California, CA, USA. www.syagen.com/uploads/pdfs/news
25. ACRO Security Technologies. Detect & Protect with ACRO_PET. www.acrosec.com
26. Itzhaky H, Keinan E (2004) Method and kit for the detection of explosives. US Patent
6767717
27. Nomadics (2008) Detection of peroxides and explosives. (Inventors: Deans R, Rose A,
Bardon KM, Hancock LF, Swager TM) PCT/US2007/019248
28. Ladbeck RS, Kolla P, Karst U (2003) Trace analysis of peroxide-based explosives. Anal
Chem 75:731
29. Sigman ME, Clark CD, Caiano T, Mullen R (2008) Analysis of triacetone triperoxide
(TATP) and TATP synthetic intermediates by electrospray ionization mass spectrometry.
Rapid Commun Mass Spectrom 22(2):84–90
30. Roman FR, Pena-Quevedo AJ, Rivera LA (2005) Analytical method development for trace
detection of energetic acetone peroxides by GC-MS. American Chemical Society p
ANYL-097 230th ACS National Meeting Washington DC United States 28 Aug–1 Sept
31. Buttigieg GA, Knight AK, Denson S, Pommier C, Bonner DM (2003) Characterization of
the explosive triacetone triperoxide and detection by ion mobility spectrometry. Forensic Sci
Int 135(1):53–59
32. Sella DS (2008) Self-immolative dendritic probe for direct detection of triacetone
triperoxide. Chem Commu 44:5701–5703
33. Gaft M, Nagli M (2008) UV gated Raman spectroscopy for standoff detection of explosives.
Opt Mater 30:1739–1746
286 10 Triacetone Triperroxide (TATP)

34. Munoz RAA, Lu D, Cagan A, Wang J (2007) “One-step” simplified electrochemical sensing
of TATP based on its acid treatment. Analyst 132(6):560–565
35. Banerjee S, Mohapatra SK, Misra M, Mishra IB (2009) The detection of improvised
nonmilitary peroxide based explosives using a titania nanotube array sensor.
Nanotechnology 20(7):075502/1–075502/6
36. Apblett AW, Kiran BP, Malka S, Materer NF, Piquette A (2006) Nanotechnology for
neutralization of terrorist explosives. Ceram Trans 172(Ceramic Nanomaterials and
Nanotechnologies IV), pp 29–35
37. Cotte-Rodriguez I, Hernandez-Soto H, Chen H, Cooks RG (2008) In situ trace detection of
peroxide explosives by desorption electrospray ionization and desorption atmospheric
pressure. Chem Ionization Anal Chem (Washington, DC, US) 80(5):1512–1519
38. Calculated using Advanced Chemistry Development (ACD/Labs) Software V904 for Solaris
(1994–2008 ACD/Labs)
39. Canizo GN, Eyler GP (2007) Barreto, determination of the enthalpies of vaporization of
cyclic organic peroxides by correlation of changes in gas chromatographic retention times.
Chromato graphia 65:31–34
40. Oxley JC, Smith JL, Shinde K, Moran J (2005) Determination of the vapor density of
triacetone triperoxide (TATP) using a gas chromatography headspace technique. Propellants
Explos Pyrotech 30(2):127–130
41. Matyas R, Pachman J, Ang H-G (2008) Study of TATP: spontaneous transformation of
TATP to DADP. Propellants Explos Pyrotech 33:89–91
42. Oxley JC, Smith JL, Brady J, Dubnikova F, Kosloff R, Zeiri L, Zeiri Y (2008) Raman and
infrared fingerprint spectroscopy of peroxide-based explosives. Appl Spectrosc 62(8):906–
915
43. Pacheco-Londono L, Primera OM, Ramirez M, Ruiz O, Hernandez-Rivera S (2005) Review
of the various analytical techniques and algorithms for detection and quantification of
TATP. In: Proc SPIE-Int Soc Opt Eng 5778(Pt 1, Sensors, and Command, Control,
Communications, and Intelligence (C3I) Technologies for Homeland Defense IV), pp 317–
326
44. Brauer B, Dubnikova F, Zeiri Y, Kosloff R, Gerber RB (2008) Vibrational spectroscopy of
triacetone triperoxide (TATP): anharmonic fundamentals, overtones and combination bands.
Spectrochim Acta A Mol Biomol Spectrosc 71(4):1438–1445
45. Hiyoshi RI, Nakamura J, Brill TB (2007) Thermal decomposition of organic peroxides TATP
and HMTD by T-jump/FTIR spectroscopy. Propellants Explos Pyrotech 32(2):127–134
46. Mullen C, Huestis D, Coggiola M, Oser H (2006) Laser photoionization of triacetone
triperoxide (TATP) by femtosecond and nanosecond laser pulses Int J Mass Spectrom 252
(1):69–72. doi: 101016/jijms200601018
47. Matyas R, Pachman J (2007) Thermal stability of triacetone triperoxide. Sci Technol Energ
Mater 68(4):111–116
48. Armitt D, Zimmermann P, Ellis-Steinborner S (2008) Gas chromatography/mass spectrom-
etry analysis of triacetone triperoxide (TATP) degradation products rapid. Commun Mass
Spectrom 22(7):950–958
49. Bilusich D, Fitzgerald M, Armitt D, Ellis-Steinborner S (2008) 19th Intl Symp On the
Forensic Sci 6–9 October. Melbourne, Australia
50. Hanson D (2006) Officercom. 4 June 2006 updated 8 July 2008
51. Matyas R, Selesovsky J (2009) Power of TATP based explosives. J Hazard Mater 165(1–
3):95–99
52. Matyas R, Zeman S, Trzcinski W, Cudzilo S (2008) Detonation performance of TATP/
AN-based explosives. Propellants Explos Pyrotech 33(4):296–300
53. Zeman S, Trzcinski WA, Matyas R (2008) Some properties of explosive mixtures containing
peroxides Part I Relative performance and detonation of mixtures with triacetone triperoxide.
J Hazard Mater 154(1–3):192–198
54. Menning D, Ostmark H (2008) In: Schubert H, Kuznstov A (eds) Detection of Liquid
Explosives and Flammable Agents in Connection with Terrorism. Springer, pp 55–70
References 287

55. Fidler R, Legron T, Carvalho-Knighton K, Geiger CL, Sigman ME, Clausen CA (2009)
Degradation of TNT, RDX, and TATP using microscale mechanically alloyed bimetals. In:
ACS Symp Ser 1027(Environmental Applications of Nanoscale and Microscale Reactive
Metal Particles), pp 117–134
56. Bellamy AJ (1999) Triacetone triperoxide: its chemical destruction. J Forensic Sci 44
(3):603–608

Additional Scholarly Articles for Further Reading

57. Baconin J, Aveille J, Zoe J (1984) Experimental study of the spherical diverging detonation.
In: Proc Symp Explos Pyrotech 12th, pp 1/71–1/76
58. Bailey A, Bellerby JM, Kinloch SA (1992) The identification of bonding agents for TATB/
HTPB polymer bonded explosives. Philos Trans R Soc London, Ser A 339(1654):321–333
59. Belcher I, Drake RC, Fleming KA, Roberts RH (1991) Thermal modeling of confined
explosive systems. Int Annu Conf ICT 22nd (Combust React Kinet), pp 9/1–9/11
60. Belmas R, Plotard JP (1995) Physical origin of hot spots in pressed explosive compositions.
J Phys IV 5(C4, Approaches Microscopique et Macroscopique des Detonations), pp 61–87
doi: 10.1051/jp4:1995406
61. Benziger TM (1981) Manufacture of triaminotrinitrobenzene. Int Jahrestag—Fraunhofer-Inst
Treib- Explosivst(Chem Mech Technol Treib-Explosivst), pp 491–503
62. Billon HH (1994) The rheology of a high-concentration triaminotrinitrobenzene/
trinitrotoluene (TATB/TNT) suspension. Propellants Explos Pyrotech 19(5):245–248.
doi:10.1002/prep.19940190506
63. Blais NC, Greiner NR, Fernandez WJ (1990) Detonation chemistry studies of energetic
materials using laboratory scale samples. NATO ASI Ser, Ser C 309(Chem Phys Energ
Mater), pp 477–509
64. Brasher CL (1981) TATB synthesis: processes, problems and progress. Tech Bull—Tex Eng
Exp Stn 81–1:34–46
65. Breithaupt D, Kury J, McGuire R, Hallam J (1991) The extent of reaction of aluminum and
ammonium perchlorate in TATB-containing explosives. Int Annu Conf ICT 22nd (Combust
React Kinet), pp 6/1–6/7
66. Britt AD, Moniz WB, Chingas GC, Moore DW, Heller CA, Ko CL (1981) Free radicals of
TATB (1,3,5-triamino-2,4,6-trinitrobenzene). Propellants Explos 6(4):94–95
67. Cady HH (1986) Microstructural differences in TATB that result from manufacturing
techniques. Int Jahrestag—Fraunhofer-Inst Treib—Explosivst 17th (Anal Propellants
Explos: Chem Phys Methods), pp 53/1–53/14
68. Catalano E, Rolon CE (1983) A study of the thermal decomposition of confined
triaminotrinitrobenzene. The gaseous products and kinetics of evolution. Thermochim
Acta 61(1–2):37–51. doi:10.1016/0040-6031(83)80302-5
69. Chaykovsky M, Adolph HG (1990) Synthesis and properties of some trisubstituted
trinitrobenzenes. TATB analogs J Energ Mater 8(5):392–414. doi:10.1080/
07370659008225431
70. Cherin H, Lemoine D, Gautier L (1996) Sensitivity to projectile impact of pre-heated
explosive compositions. Int Annu Conf ICT 27th(Energetic Materials), pp 36.1–36.9
71. Cherin H, Lemoine D, Pauton M (1994) Sensitization by damage of explosive compositions.
Int Annu Conf ICT 25th (Energetic Materials-Analysis, Characterization and Test
Techniques), pp 101/1–101/9
72. Chisum ME (1991) Applications of negative ion analyses on the ELAN 250 ICP-MS. At
Spectrosc 12(5):155–159
73. Cochran SG, Tarver CM (1984) Modeling particle size and initial temperature effects on
shock initiation of TATB-based explosives. North-Holland, pp 593–596
288 10 Triacetone Triperroxide (TATP)

74. Cortili G, Zerbi G (1967) Chain conformations of poly(vinylidene fluoride) as derived from
its vibrational spectrum. Spectrochim Acta 23A(2):285–299
75. Delistraty J, Brandt H (1982) Detonation properties of 1,3,5-triamino-2,4,6-trinitrobenzene
when impacted by hypervelocity projectiles. Propellants Explos Pyrotech 7(5):113–122.
doi:10.1002/prep.19820070502
76. Dick JJ (1987) Short pulse initiation of plastic-bonded TATB explosive. J Energ Mater 5(3–
4):267–285. doi:10.1080/07370658708012355
77. Dick JJ, Forest CA, Ramsay JB, Seitz WL (1988) The Hugoniot and shock sensitivity of a
plastic-bonded TATB explosive PBX 9502. J Appl Phys 63(10):4881–4888. doi:10.1063/1.
340428
78. Doherty RM, Short JM, Kamlet MJ (1989) Improved prediction of cylinder test energies.
Combust Flame 76(3–4):297–306. doi:10.1016/0010-2180(89)90112-0
79. Doherty RM, Simpson RL (1997) A comparative evaluation of several insensitive high
explosives. Int Annu Conf ICT 28th (Combustion and Detonation), pp 32.1–32.23
80. Duraes L, Campos J, Gois JC (1995) Deflagration and detonation predictions using a new
equation of state. Int Annu Conf ICT 26th (Pyrotechnics), pp 67/1–67/13
81. Estes Z (1977) Summary of chlorine free synthesis of TATB. Process Development
Endeavor No. 106. Mason and Hanger-Silas Mason Co., Inc., p 5
82. Firsich DW, Guse MP (1984) On the photochemical phenomenon in TATB. J Energ Mater 2
(3):205–214. doi:10.1080/07370658408012334
83. Foltz MF (1993) Pressure dependence of the reaction propagation rate of TATB at high
pressure. Propellants Explos Pyrotech 18(4):210–216
84. Foltz MF, Ornellas DL, Pagoria PF, Mitchell AR (1996) Recrystallization and solubility of
1,3,5-triamino-2,4,6-trinitrobenzene in dimethyl sulfoxide. J Mater Sci 31(7):1893–1901.
doi:10.1007/BF00372205
85. Fried LE, Ruggiero AJ (1994) Energy Transfer Rates in Primary, Secondary, and Insensitive
Explosives. J Phys Chem 98(39):9786–9791. doi:10.1021/j100090a012
86. Fried LE, Souers PC (1996) BKWC: an empirical BKW parametrization based on cylinder
test data. Propellants, Explos, Pyrotech 21(4):215–223. doi:10.1002/prep.19960210411
87. Fried LE, Tarver C (1996) Molecular dynamics simulation of shocks in porous TATB
crystals. AIP Conf Proc 370 (Pt. 1, Shock Compression of Condensed Matter–1995),
pp 179–182
88. Glazkova AP, Kazarova JA (1992) About self-inhibition in deflagration of
1,3,5-triamino-2,4,6-trinitrobenzene (TATB). Int Annu Conf ICT 23rd (Waste Manage.
Energ. Mater. Polym.), pp 67/1–67/9
89. Greiner NR, Phillips DS, Johnson JD, Volk F (1988) Diamonds in detonation soot. Nature
(London) 333(6172):440–442. doi:10.1038/333440a0
90. Gubin SA, Odintsov VV, Pepekin VI (1991) Thermodynamic calculations of detonation
parameters. In: Proc Int Pyrotech Semin 16th, pp 325–335
91. Hadhoud MK, Shokry SA, El Morsi AK, Ragab S (1986) Study of kinetics and analysis of
the amination of pentanitroaniline to produce TATB. Int Jahrestag—Fraunhofer-Inst Treib—
Explosivst 17th (Anal Propellants Explos: Chem Phys Methods), pp 54/1–54/19
92. Harris BW (1985) TATB—strong basic reactions provide soluble derivatives for a simple,
qualitative high explosive spot test. J Energ Mater 3(2):81–93. doi:10.1080/
07370658508012336
93. Hertzberg M, Cashdollar KL, Zlochower IA, Green GM (1992) Explosives dust cloud
combustion. Symp (Int) Combust, [Proc] 24th, pp 1837–43 doi: 10.1016/S0082-0784(06)
80215-8
94. Hoffman DM, Matthews FM, Pruneda CO (1989) Dynamic mechanical and thermal analysis
of crystallinity development in Kel-F 800 and TATB/Kel-F 800 plastic bonded explosives.
Part I. Kel-F 800. Thermochim Acta 156(2):365–372. doi:10.1016/0040-6031(89)87203-X
95. Hua P (1995) Energy depression coefficients of TATB and other components. China
Ordnance Society, pp 377–381
Additional Scholarly Articles for Further Reading 289

96. Hutchinson CD (1988) The initiation of TATB-based insensitive high explosives in

diverging geometry. Int Annu Conf ICT 19th (Combust Detonation Phenom), pp 38/1–38/10
97. Kennedy DL (1995) The challenge of non-ideal detonation. J Phys IV 5 (C4, Approches
Microscopique et Macroscopique des Detonations), pp 191–207 doi: 10.1051/jp4:1995417
98. Kolb JR, Rizzo HF (1979) Growth of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB).
I. Anisotropic thermal expansion Propellants Explos 4(1):10–16
99. Kunz AB (1996) Ab initio investigation of the structure and electronic properties of the
energetic solids TATB and RDX. Phys Rev B: Condens Matter 53(15):9733–9738
100. Larson TE, Dimas P, Hannaford CE (1991) Electrostatic sensitivity testing of explosives at
Los Alamos. Inst Phys Conf Ser 118 (Electrostatics 1991), pp 107–17
101. Loughran ED, Wewerka EM, Rogers RN, Berlin JK (1975) The influence of metals on the
thermal decomposition of s-triaminotrinitrobenzene (TATB). Am. Def. Prep. Assoc., p I-E, 4 p
102. Loughran ED, Wewerka EM, Rogers RN, Berlin JK (1977) The influence of metals on the
thermal decomposition of s-triaminotrinitrobenzene (TATB). Inst Chem Treib—Explos,
pp 233–247
103. Mader C, Kershner JD (1992) Numerical modeling of the effect of temperature and particle
size on shock initiation properties of HMX and TATB. J Energ Mater 10(2–3):69–95.
doi:10.1080/07370659208018230
104. Mader CL (1996) Detonation performance. Nova Science Publishers, pp 165–249
105. Maienschein JL, Nichols AL III, Wardell JF (1995) Reactions of TATB-based explosive
with molten metal. Propellants Explos Pyrotech 20(6):287–293. doi:10.1002/prep.
19950200602
106. Makashir PS, Kurian EM (1996) Spectroscopic and thermal studies on the decomposition of
1,3,5-triamino-2,4,6-trinitrobenzene (TATB). J Therm Anal 46(1):225–236. doi:10.1007/
BF01979963
107. Mal’kov IY, Titov VM (1995) The regimes of diamond formation under detonation.
Elsevier, pp 666–669
108. Marcus Y (1987) The thermodynamics of solvation of ions. Part 2. The enthalpy of
hydration at 298.15 K. J Chem Soc, Faraday Trans 1 83(2):339–349 doi: 10.1039/
f19878300339
109. Marcus Y (1987) The thermodynamics of solvation of ions. Part 4. Application of the
tetraphenylarsonium tetraphenylborate (TATB) extrathermodynamic assumption to the
hydration of ions and to properties of hydrated ions. J Chem Soc, Faraday Trans 1 83
(9):2985–2992 doi: 10.1039/f19878302985
110. Martz HE, Schneberk DJ, Roberson GP, Azevedo SG, Lynch SK (1991) Computerized
tomography of high explosives. Plenum, pp 187–195
111. Miles MH, Gustaveson D, Devries KL (1983) Stress-induced radical generation in TATB.
J Mater Sci 18(11):3243–3248. doi:10.1007/BF00544148
112. Mitchell AR, Pagoria PF, Schmidt RD (1996) A new synthesis of TATB using inexpensive
starting materials and mild reaction conditions. Int Annu Conf ICT 27th (Energetic
Materials), pp 29.1–29.11
113. Morozov VG, et al. (1994) Experimentally proved numerical modeling of detonation
ignition and development in TATB-based HE in terms of desensitization by shock and
detonation waves interaction. Proc Int Pyrotech Semin 20th, pp 701–717
114. Oestmark H (1996) Shock induced sub-detonation chemical reactions in
1,3,5-triamino-2,4,6-trinitrobenzene. AIP Conf Proc 370 (Pt. 2, Shock Compression of
Condensed Matter–1995), pp 871–874
115. Oestmark H, Bergman H, Aaqvist G, Langlet A, Persson B (1991) Decomposition of NTO:
some initial observations. Proc Int Pyrotech Semin 16th, pp 874–886
116. Oxley JC, Smith JL, Wang W (1994) Compatibility of Ammonium Nitrate with
Monomolecular Explosives 1. J Phys Chem 98(14):3893–3900. doi:10.1021/j100065a053
117. Oxley JC, Smith JL, Wang W (1994) Compatibility of Ammonium Nitrate with
Monomolecular Explosives. 2. Nitroarenes. J Phys Chem 98(14):3901–3907. doi:10.1021/
j100065a054
290 10 Triacetone Triperroxide (TATP)

118. Pertuis C, Marteau D, Gautier L, Cherin H, Paillard C, Dupre G (1997) Reactivity of a

TATB-based explosive composition after mechanical damage. Int Annu Conf ICT 28th
(Combustion and Detonation), pp 15.1–15.13
119. Piunti RL, Brower KR (1995) Thermolysis of various energetic substances by exposure to
adiabatically compressed gas. J Energ Mater 13(1–2):107–139. doi:10.1080/
07370659508019346
120. Plaksin IY, Gerasimenko VF, Shutov VI, Gerasimov VM (1996) On sensitivity of
TATB-based shock wave damaged explosive. Int Annu Conf ICT 27th (Energetic
Materials), pp 141.1–141.13
121. Plaksin IY, et al. (1996) Evolution of explosion in TATB HE in the process of its expansion
into a free space followed by impact against hard barrier. AIP Conf Proc 370 (Pt. 2, Shock
Compression of Condensed Matter–1995), pp 875–878
122. Pritchard RH (1976) Compatibility of TATB PBX with weapons materials. Am Def Prep
Assoc, p III-A, 10 p
123. Pruneda CO, McGuire RR, Clements RE (1990) Development of a high-tensile-strain
plastic-bonded TATB explosive. Int Annu Conf ICT 21st (Technol Polym Compd Energ
Mater), pp 99/1–99/9
124. Ray SK, Sarkar S, Sinha S, Kundu KK (1994) Single-ion transfer energetics of some ions
based on TATB assumption in aqueous mixtures of N, N-dimethylformamide. Indian J
Chem Sect A: Inorg Bio-inorg Phys Theor Anal Chem 33A(9):805–815
125. Rigdon LP, Stephens FB, Harrar JE (1983) Precise assay of TATB by the determination of
total amino and nitro functional groups. Propellants Explos Pyrotech 8(6):206–211. doi:10.
1002/prep.830080607
126. Rivera T, Matuszak ML (1983) Surface properties of potential plastic-bonded explosives
(PBX). J Colloid Interface Sci 93(1):105–108. doi:10.1016/0021-9797(83)90389-2
127. Rizzo HF, Humphrey JR, Kolb JR (1981) Growth of 1,3,5-triamino-2,4,6-trinitrobenzene
(TATB). II. Control of growth by use of high Tg polymeric binders. Propellants Explos 6
(2):27–36
128. Rizzo HF, Humphrey JR, Kolb JR (1981) Growth of 1,3,5-triamino-2,4,6-trinitrobenzene
(TATB). II. Control of growth by use of high-Tg polymeric binders. Propellants Explos 6
(3):57–62
129. Rosen JM, Dickinson C (1969) Vapor pressures and heats of sublimation of some
high-melting organic explosives. J Chem Eng Data 14(1):120–124. doi:10.1021/
je60040a044
130. Seitz WL (1984) Short-duration shock initiation of triaminotrinitrobenzene (TATB).
North-Holland, pp 531–534
131. Sewell TD (1996) Monte Carlo simulations of crystalline TATB. Mater Res Soc Symp Proc
418 (Decomposition, Combustion, and Detonation Chemistry of Energetic Materials),
pp 67–72
132. Sharma J, et al. (1984) Comparative study of molecular fragmentation in sub-initiated TATB
caused by impact, UV, heat and electron beams. North-Holland, pp 543–546
133. Shlensky OF (1994) Vainshtein EF Prespinodal thermal decomposition of highly energetic
materials, vol 2. Russian Section of the Combustion Institute, pp 466–468
134. Shokry SA, Shawki SM, Elmorsi AK (1990) TATB plastic-bonded compositions. Int Annu
Conf ICT 21st (Technol Polym Compd Energ Mater), pp 100/1–100/16
135. Shorohov EV, Litvinov BV (1992) Shock compressibility of the TATB-based explosive
composition in the pressure range from 0.1 to 40 GPa. Oxford & IBH, pp 866–868
136. Shorohov EV, Litvinov BV (1995) Hugoniot adiabate of plasticized TATB-based explosive
compositions, vol 3, pp 295–298. Springer
137. Simpson RL, Pagoria PF, Mitchell AR, Coon CL (1994) Synthesis, properties and
performance of the high explosive ANTA. Propellants Explos Pyrotech 19(4):174–179.
doi:10.1002/prep.19940190405
Additional Scholarly Articles for Further Reading 291

138. Sinha S, Rudra S, Kundu KK (1993) Transfer energetics of some ions based on TATB
assumption in some quasi-isodielectric ethylene carbonate + water mixtures. Indian J Chem
Sect A: Inorg Bio-inorg Phys Theor Anal Chem 32A(1):1–11
139. Stolovy A, Jones EC Jr, Aviles JB Jr, Namenson AI, Fraser WA (1983) Exothermic
reactions in TATB initiated by an electron beam. J Chem Phys 78(1):229–235. doi:10.1063/
1.444545
140. Talukdar H, Kundu KK (1992) Transfer energetics of tetraalkylammonium ions in
aquo-organic systems and the solvent effect on hydrophobic hydration. J Phys Chem 96
(2):970–975. doi:10.1021/j100181a078
141. Tarver CM (1990) Modeling shock initiation and detonation divergence tests on
TATB-based explosives. Propellants Explos Pyrotech 15(4):132–142. doi:10.1002/prep.
19900150404
142. Tarver CM (1992) The structure of detonation waves in solid explosives. North-Holland,
pp 311–315
143. Tarver CM, Hoffman DM, Urtiew PA, Tao WC (1996) Shock initiation of TATB/FEFO
formulations. J Energ Mater 14(3–4):217–256. doi:10.1080/07370659608216066
144. Tarver CM, Kury JW, Breithaupt RD (1997) Detonation waves in triaminotrinitrobenzene.
J Appl Phys 82(8):3771–3782. doi:10.1063/1.365739
145. Trott WM, Renlund AM (1988) Single-pulse Raman scattering study of triaminotrini-
trobenzene under shock compression. J Phys Chem 92(21):5921–5925. doi:10.1021/
j100332a015
146. Trott WM, Renlund AM, Jungst RG (1985) Single-pulse Raman and photoacoustic
spectroscopy studies of triaminotrinitrobenzene (TATB) and related compounds. Proc
SPIE-Int Soc Opt Eng 540(Proc Southwest Conf Opt), pp 368–375 doi: 10.1117/12.976139
147. Upadhye RS, Watkins BE, Pruneda CO (1996) Recent advances in the molten salt
technology for the destruction of energetic materials. Int Annu Conf ICT 27th (Energetic
Materials), pp 110.1–110.13
148. Urbanski T, Vasudeva SK (1978) Heat resistant explosives. J Sci Ind Res 37(5):250–255
149. Urtiew PA, Tarver CM, Simpson RL (1996) Shock initiation of 2,4-dinitroimidazole
(2,4-DNI). AIP Conf Proc 370 (Pt. 2, Shock Compression of Condensed Matter–1995),
pp 887–890
150. Varghese AV, Kalidas C, Singh P, Hefter G (1995) Gibbs transfer energies and solvent
transport numbers of some copper(II) salts in methanol-dimethylformamide mixtures. Aust J
Chem 48(5):987–996. doi:10.1071/CH9950987
151. Volk F (1988) Detonation products of cast high explosives. Proc Int Pyrotech Semin 13th,
pp 835–851
152. Von Holtz E, Scribner K, Moody G, McGuire R (1990) The search for high-energy
low-vulnerability explosives. Int Annu Conf ICT 21st (Technol Polym Compd Energ
Mater), pp 12/1–12/9
153. Walker FE (1994) A new kinetics and the simplicity of detonation. Propellants Explos
Pyrotech 19(6):315–326. doi:10.1002/prep.19940190610
154. Wang Z, Chen Z (1991) Deflagration to detonation transition (DDT) study in mixed HMX
bed. Int Annu Conf ICT 22nd (Combust React Kinet), pp 91/1–91/10
155. Ward RL, Felver T, Pyper JW (1984) Bound and free moisture in explosives and plastics.
J Hazard Mater 9(1):69–76. doi:10.1016/0304-3894(84)80008-4
156. Zhang SQ, Wei YZ, Fang Q, Zhao F (1997) Detonation behavior of a TATB-based IHE. Int
Annu Conf ICT 28th (Combustion and Detonation), pp 76.1–76.11
Chapter 11
1,3,3-Trinitroazetidine (TNAZ)

Abstract 1,3,3-Trinitroazetidine (Molecular Formula: C3H4N4O6, TNAZ) has been

assessed as a potential high energy replacement for TNT. Australian industrial plant
is a melt-castable explosive that has been proposed as a potential replacement for
TNT. The structure of the compound has been confirmed by IR, NMR, mass, ele-
mental analysis and by X-ray crystallography. HPLC technique has been employed
to confirm the purity of TNAZ (>99%). The compound is further characterized by
thermal techniques and is found to undergo limited decomposition at its melting
point. Small scale sensitivity tests have also been carried out and the results show
that TNAZ is significantly more sensitive to mechanical stimuli than TNT.

11.1 Introduction

The thermophysical properties of 1,3,3-trinitroazetidine, commonly known as TNAZ

are included in this chapter. TNAZ is a four-membered ring high density explosive
with several desirable properties compared to the conventional explosives RDX and
HMX. It is a white crystalline melt-castable energetic material with performance
similar to HMX. It was first synthesized by Archibald et al. [1]. It is 30% more
energetic than TNT and 10% more than nitramines such as RDX and HMX [2]. The
spectra of TNAZ and ideal gas thermodynamic properties have been evaluated [3].

11.2 Synthesis

As mentioned earlier, the first synthesis of TNAZ was accomplished by Archibald

and Baum [1]. In spite of the fact that TNAZ is a simple molecule, its synthesis has
not proved easy by any means. The first process is the Fluorochem Process which is
described fully by Watt and Cliff [4]. A second process was developed at the
University of Florida by Katritzky et al. [5]. The major disadvantage of these two
processes in the use of epichlorohydrin was eliminated in the process developed by
Marchand et al. [6]. At the same time, Los Alamos National Laboratory developed

© US Government (outside the USA) 2018 293

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7_11
294 11 1,3,3-Trinitroazetidine (TNAZ)

another process [7, 8]. Two of these processes have been scaled up to make close to
1000 lb batches of TNAZ. A pilot plant has been successfully demonstrated.
Agrawal and Hogdson [9] summarize the Archibald et al., Marchand et al., and
Axenrod et al. [10] processes for the synthesis of TNAZ. Jadhav et al. [11] describe
a process involving cyclization of 1,3-dichloro-2,2-dinitropropane, and obtained
yields of 30%. A recent review of the synthesis and properties is provided by
Stepanova and Stepanova [12].
Table 11.1 lists the chemical names of TNAZ, and Table 11.2 lists physical
properties.
Solubility in different solvents is provided by Watt and Cliff [4] and shown in
Table 11.3. However the authors have not specified the temperature for these
values.

11.3 Phase Diagrams

McKenney et al. [20] report TNAZ/TNT binary phase diagram calculated using
enthalpy of fusion and melting points data. They used the simple relation

RlnX ¼ DHfus ½ð1=TÞð1=T0 Þ

where T is the melting point [K] of the eutectic, ΔHfus, T0, and X are enthalpy of
fusion, melting point, and mole fraction of either TNAZ or TNT, and R is the gas
constant. Table 11.4 lists the composition and the corresponding temperatures of
the eutectics of TNAZ/TNT.
Figure 11.1 shows data for two eutectics whose composition-temperature data
and other details are provided in their report. Eutectics with other energetic mate-
rials, HMX, Tetryl, and TNT [14] are listed in Table 11.5.

Table 11.1 Chemical names Properties Literature values References

of TNAZ
Formula C3H4N4O6
CA index Azetidine, 1,3,3-trinitro-,
name TNAZ
CAS number 97645-24-4
Structural NO2
formula N

O2N

NO2

Molecular 192
mass
11.4 Thermodynamic Properties 295

Table 11.2 Physical properties of TNAZ

Melting point (K) Amber-SRT: 390 [2]
Amber calculated: 462
Melting point (K) 373.74 ± 0.21 (100.59 ± 0.21 °C) [13]
Experimental. 374.74 (101 °C) [14]
Boiling point (K) 525.15 (252 °C) [14]
Stable up to (K) 513.15 (240 °C) [2]
Density (kg/m3) 1860 (1.86 g/cm3) [2]
1840 (1.84 g/cm3) [14]
Melting point (K) 374 [2]
Ionization potential (eV) 10.36 ± 0.1 [15]
Enthalpy of sublimation (kJ/mol) 95 [16]
63.22 [14]
Enthalpy of vaporization (kJ/mol) 66 [14]
Enthalpy of formation (kcal/mol) 30.7 [15]
8.7 and 2.81 [17]
8.7 [16]
30.7 [18]
Enthalpy of fusion (kcal/mol) 6.714 ± 0.115 [19]
6.7–7.2 [15]
C-J pressure (GPa) 35.68 [18]
C-J energy (kJ/cc) 4.38 [18]
C-J temperature (K) 4659 [18]
C-J shock velocity (m/ls) 8.95 [18]
E total of detonation (kJ/cc) 11.06 [18]
Enthalpy of explosion (cal/g) 1731 [17]
Detonation velocity (m/s) 9597 [17]

Table 11.3 Solubility in Solvent Solubility (g/mL)

different solvents
Ethyl acetate 0.436
Ethanol 0.055
Isopropanol 0.026
Acetone 0.442
Toluene 0.038
Iso-octane 0.014

11.4 Thermodynamic Properties

Ideal Gas Thermodynamic Properties at 1 bar [3] Made IR assignments and cal-
culated equilibrium composition and compared some experimental data.
The quantities of Cpo, So and ΔHTo were fitted in the following (NASA type)
polynomials:
296 11 1,3,3-Trinitroazetidine (TNAZ)

Table 11.4 Mol percent and calculated temperatures for the TNAZ/TNT system [20]
Mole % TNAZ Temperature (K) (°C)
0.0 354.15 (81.0)
4.7 351.85 (78.7)
11.6 348.25 (75.1)
23.5 341.45 (68.3)
34.2 334.75 (61.6)
34.5 334.55 (61.4) (Eutectic point)
38.9 338.55 (65.4)
44.1 342.85 (69.7)
54.2 350.25 (77.1)
68.7 359.05 (85.9)
81.6 365.75 (92.6)
96.6 372.55 (99.4)
100.0 373.95 (100.8)

Fig. 11.1 Experimental and calculated phase diagram for TNAZ/TNT system [20] (hsm indicates
Hot Stage Microscopy. Eu is eutectic.)

Table 11.5 Eutectic mixture composition and temperature

Additive M.P of additive (K) (°C) M.P. of eutectic (K) (°C) TNAZ (mole %)
TNT 353.75 (80.6) 333.15 (60.0) 63.3–65.0
Tetryl 402.65 (129.5) 354.65–354.66 (81.5–81.6) 63.3–65.0
HMX 557.25 (284.1) 369.05 (95.9) 97.9
11.4 Thermodynamic Properties 297

Cpo
¼ a1 þ a2 T þ a3 T 2 þ a4 T 3 þ a5 T 4
R

So T2 T3 T4
¼ a1 ‘nT þ a2 T þ a3 þ a4 þ a5 þ a7
R 2 3 4

DH To T T2 T3 T 4 a6
¼ a1 þ a2 þ a3 þ a4 þ a5 þ
RT 2 3 4 5 T

where a1, a2, a3, a4, a5, a6, a7 are the polynomial coefficients, R is universal gas
constant and temperature in K.
Table 11.6 lists the ideal gas thermodynamic properties calculated by Yu et al. [3].
Table 11.7 summarizes the coefficients for the thermochemical relations shown
above. Table 11.8 list ideal gas heat capacity and entropy calculated by Osmont
et al. [21] using Ab initio quantum technique.

Table 11.6 Ideal gas thermodynamic properties for TNAZ at 1 bar [3]
T(K) C°p J K−1 S° −(G°−H°298)/ (H–H°298) ΔlH0 ΔlG0 log10kf
mol−1 T (kJmol−1)
0 0.000 0.000 0.000 −20.954 170.971 170.911 00
100 47.963 273.233 442.763 −16.953 154.278 231.340 −120.83
200 83.151 315.355 368.737 −10.676 139.633 314.261 −82.075
298.15 134.990 358.096 358.096 0.000 128.449 402.491 −70.514
300 135.973 358.934 358.099 0.251 128.275 −404.193 −70.375
400 185.668 405.043 364.049 16.398 120.795 497.396 −64.952
500 226.313 451.018 376.865 37.076 116.592 592.092 −61.854
600 258.057 495.208 392.938 61.362 114.840 687.390 −59.842
700 282.708 536.918 410.558 88.452 114.883 782.833 −58.415
800 302.046 575.981 428.822 117.727 116.264 878.176 −57.338
900 317.431 612.479 447.224 148.730 118.641 973.275 −56.486
1000 329.844 646.588 465.474 181.115 121.784 1068.072 −55.789
1100 339.982 678.517 483.406 214.623 125.510 1162.527 55.203
1200 348.353 708.469 500.926 249.052 129.686 1256.619 54.698
1300 355.332 736.637 517.985 284.247 134.205 1350.351 54.257
1400 361.200 763.191 534.561 320.082 138.987 1443.727 53.865
1500 366.172 788.285 550.647 356.457 143.960 1536.747 53.513

Table 11.7 Coefficients of polynomials for ideal gas properties, specific heat, entropy and
enthalpy
Temp. (K) a1 a2 a3 a4 a5 a6 a7
1000–5000 2.228e1 2.662e-2 −1.0795e-5 1.990e-9 −1.375e-13 4.792e3 −9.799e1
298–1000 −4.374 7.087e-2 1.773e-5 −8.906e-8 4.458e-11 1.360e4 4.6786e1
298 11 1,3,3-Trinitroazetidine (TNAZ)

Table 11.8 Ideal gas heat capacity and entropy [22]

T (K) 300 400 500 600 800 1000 1500
Cpo (cal mol−1 K−1) 42.4 52.1 60.0 66.3 75.1 80.8 88.4
T (K) 2000 2500 3000 3500 4000 4500 5000
Cpo (cal mol−1 K−1) 91.9 93.7 94.8 95.4 95.9 96.2 96.4
T (K) 300 400 500 600 800 1000 1500
So,(cal mol−1 K−1) 109.8 123.4 135.9 147.5 167.8 185.3 219.7
T (K) 2000 2500 3000 3500 4000 4500 5000
So (cal mol−1 K−1) 245.6 266.4 283.6 298.2 311.0 322.3 332.4

11.5 Thermal Decomposition/Dissociation

Alavi et al. [18] made theoretical calculations on the thermal decomposition of TNAZ
and, present pathways and rate of decomposition equations. A detailed description of
the initial dissociation processes in TNAZ carried out by Photofrag-mentation
Translational Spectroscopy can be found elsewhere [23]. Yu et al. [3] studied the
thermal decomposition in a shock-tube at around 405 K and 500 torr pressure and
determined the composition of the products of decomposition by spectroscopy. They
provide spectra and equilibrium composition of the products of degradation.
To understand the environmental impact due to manufacture, storage, and use at
different sites, it is essential to know the stability of TNAZ in soil. Jenkins et al.
[22] carried out such stability studies of several energetic materials including
TNAZ. Their work showed that the half-life in soil is less than 24 h for different
soils. Table 11.9 some more properties evaluated by Advanced Chemistry
Development (ACD/Labs) Software V8.14 for Solaris.

Table 11.9 Other properties calculated and not listed above [24]
Bioconcentration factor 1.0 pH 1 to pH 10 Temp, K: 298.15 (25 °C)
Flash point 543.65 ± 30.1 (270.5 ± 30.1 ° Freely rotatable bonds, 3
C)
H acceptors 10
H donors 0
H donor/acceptor sum 10
Koc 33.7 pH 1 and Temp, K: 298.15 (25 °C)
logP 0.277 ± 0.663 Temp, K: 298.15 (25 °C)
Mass intrinsic solubility 1.1 g/L Slightly soluble Temp, 25 K: 298.15 (25 °C)
Molar intrinsic solubility 5.8−3 (mol/L), Sparingly soluble Temp, K: 298.15 (25 °C)
Molar volume 104.3 ± 5.0 (cm3/mol) Temp, 293.15 (20 °C),
Press: 760 Torr
Molecular weight 192.09
pKa −15.72 ± 0.20 Most Basic, K: 298.15 (25 °C)
Polar surface area 141 A2
Vapor pressure 4.64  10−11 Torr Temp, K: 298.15 (25 °C)
References 299

References

1. Archibald TG, Gilardi R, Baum K, George C (1990) Synthesis and x-ray crystal structure of
1,3,3-trinitroazetidine. J Org Chem 55(9):2920–2924
2. Agrawal PM, Rice BM, Zheng L, Velardez GF, Thompson DL (2006) Molecular dynamics
simulations of the melting of 1,3,3-Trinitroazetidine. J Phys Chem B 110(11):5721–5726
3. Yu C-L, Zhang Y-X, Bauer SH (1998) Estimation of the equilibrium distribution of products
generated during high temperature pyrolyses of 1,3,3-trinitroazetidine; thermochemical
parameters. J Mol Structure (Theochem) 432:63–68
4. Watt DS, Cliff MD (1998) TNAZ based melt-cast explosives: technology review and AMRL
Research Directions, DSTO Aeronautical and Maritime Research Laboratory, AR-010-600,
July 1998
5. Katritzky AR, Cundy DJ, Chen J (1994) Novel syntheses of 1,3,3-trinitroazetidine.
J Heterocycl Chem 31(2):271–275
6. Marchand AP, Rajagopal D, Bott SG, Archibald TG (1995) A novel approach to the
synthesis of 1,3,3-trinitroazetidine. J Org Chem 60(15):4943–4946
7. Coburn MD, Hiskey MA, Archibald TG (1998) Scale-up and waste-minimization of the Los
Alamos process for 1,3,3-trinitroazetidine (TNAZ). Waste Manage (Oxford) 17(2/3):143–
146
8. Nissan R, Ruppert W (2005) More than a decade of green energetics R&D research. Joint
Services Environmental Management Conference Columbus, OH, US. Army RDECOM/
Hughes Assoc. INC
9. Axenrod T, Watnick C, Yazdekhasti H, Dave PR (1993) Synthesis of 1,3,3-trinitroazetidine.
Tetrahedron Lett 34(42):6677–6680
10. Agrawal JP, Hogdson RD (2007) Organic chemistry of explosives. Wiley, New York, NY,
pp 265–269
11. Jadhav HS, Talawar MB, Dhavale DD, Asthana SN, Krishnamurthy VN (2006) Alternate
method for synthesis of 1,3,3-trinitroazetidine (TNAZ): next generation melt-castable
high-energy material. Indian J Chem Technol 13(1):41–46
12. Stepanova EV, Stepanova AI (2015) Synthesis and properties of 1,3,3-trinitroazetidine, 58
(11):3–15
13. Sućeska M, Rajić M, Mateĉić-Muśyanić S, Zeman S, Jalovŷ Z (2003) Kinetics and heats of
sublimation and evaporation of 1,3,3-trinitroazetidine (TNAZ). J Therm Anal Calorim 74
(3):853–866
14. Akhavan J (2004) Chemistry of explosives. 2nd edn. RSC Paperbacks, Cambridge, UK, p 47
15. Politzer P, Lane ME, Concha MC, Redfern PC (1995) Comparative computational analysis
of some nitramine and difluoramine structures, dissociation energies and heats of formation.
J Mol Struct (Theochem) 338(1–3):249–255
16. Garland NL, McElvany SW (1998) Ionization potentials of TNAZ and its decomposition
products. Chem Phys Lett 297:147–153
17. Simpson RL, Garza RG, Foltz MF, Ornellas DL, Urtiew PA (1994) Characterisation of
TNAZ. UCRL-ID-119672, Lawerence Livermore National Laboratory
18. Dewey MA, Blau RJ, Doll DW, Lee KE, Braithwaite PC (2003) ARDEC explosives
development: melt/pour explosives containing TNAZ. Thiokol Corporation. In: Insensitive
munitions & energetic materials technology symposium, March 10–13, 2003. Orlando, FL
19. Liu M-H, Chen C, Hong Y-S (2005) Theoretical study of the unimolecular decomposition
mechanisms of energetic TNAD and TNAZ explosives. Int J Quantum Chem 102(4):398–
408
20. McKenney RL, Floyd TG, Stevens WE (1997) Binary phase diagram series:
1,3,3-trinitroazetidine (TNAZ)/2,4,6-trinitrotoluene (TNT). Wright Laboratory, Armament
Directorate Report, WL-TR-1997–7001, January 1997
300 11 1,3,3-Trinitroazetidine (TNAZ)

21. Osmont L, Catoire I, Gökalp V, Yang V (2007) Ab initio quantum chemical predictions of
enthalpies of formation, heat capacities, and entropies of gas-phase energetic compounds.
Combust Flame 151(1–2):262–273
22. Jenkins TF, Bartolini C, Ranney TA (2003) Stability of CL-20, TNAZ, HMX, RDX, NG,
and PETN in moist, unsaturated soil. ERDC/CRREL TR-03-7, April 2003
23. Liu Y, Liu Z-N, C-m Yin (2004) Phase diagram and eutectic of binary systems for
1,3,3-trinitroazetidine (TNAZ) with some energetic materials. Hanneng Cailiao 12(Suppl.
1):227–230
24. Annex DS, Allman JC, Lee YT (1991) Chemistry of energetic materials. In Olah GA,
Squire DR (eds) Academic Press, New York, NY, pp 27–54

Additional Scholarly Articles for Further Reading

25. Agrawal PM, Rice BM, Zheng L, Velardez GF, Thompson DL (2006) Molecular dynamics
simulations of the melting of 1,3,3-trinitroazetidine. J Phys Chem B 110(11):5721–5726.
https://doi.org/10.1021/jp056690
26. Alavi S, Reilly LM, Thompson DL (2003) Theoretical predictions of the decomposition
mechanism of 1,3,3-trinitroazetidine (TNAZ). J Chem Phys 119(16):8297–8304. https://doi.
org/10.1063/1.1611471
27. Anderson K, Homsy J, Behrens R, Bulusu S (1997) Mechanistic and kinetic studies of the
thermal decomposition of TNAZ and NDNAZ. CPIA Publ 657 (JANNAF Propulsion
Systems Hazards Subcommittee Meeting, vol 1), pp 37–51
28. Anex DS, Allman JC, Lee YT (1991) Studies of initial dissociation processes in
1,3,3-trinitroazetidine by photofragmentation translational spectroscopy. Academic,
pp 27–54
29. Archibald TG, Gilardi R, Baum K, George C (1990) Synthesis and x-ray crystal structure of
1,3,3-trinitroazetidine. J Org Chem 55(9):2920–2924. https://doi.org/10.1021/jo00296a066
30. Astrat’ev AA, Stepanov AI, Dashko DV (2013) Synthesis, energetic and some chemical
properties of new explosive—3,4-bis(4’-nitrofurazan-3’-yl)furazan (BNTF). University of
Pardubice, Institute of Energetic Materials, pp 482–496
31. Aubuchon CM, Rector KD, Holmes W, Fayer MD (1999) Nitro group asymmetric stretching
mode lifetimes of molecules used in energetic materials. Chem Phys Lett 299(1):84–90.
https://doi.org/10.1016/S0009-2614(98)01241-X
32. Axenrod T, Watnick C, Yazdekhasti H, Dave PR (1995) Synthesis of 1,3,3-trinitroazetidine
via the Oxidative Nitrolysis of N-p-Tosyl-3-azetidinone Oxime. J Org Chem 60(7):1959–
1964. https://doi.org/10.1021/jo00112a014
33. Bakhtiar R, Bulusu S (1995) Molecular complexes of cyclodextrins: application of ion-spray
mass spectrometry to the study of complexes with selected nitramines. Rapid Commun Mass
Spectrom 9(14):1391–1394. https://doi.org/10.1002/rcm.1290091413
34. Bartnik R, Cal D, Marchand AP, Alihodzic S, Devasagayaraj A (1998) New method for the
generation and trapping of 1-azabicyclo [1.1.0] butane. Application to the synthesis of
1,3-dinitroazetidine. Synth Commun 28(21):3949–3954. https://doi.org/10.1080/
00397919808004953
35. Bartnik R, Marchand AP (1997) Synthesis and chemistry of substituted 1-azabicyclo [1.1.0]
butanes. Synlett (9):1029–1039. http://doi.org/10.1055/s-1997-1520
36. Bauer SH, Zhang Y-X (1999) Stability tests of TNAZ—thermal and shock impact. J Energ
Mater 17(2 & 3):161–176. https://doi.org/10.1080/07370659908216101
37. Bottaro JC (1996) Recent advances in explosives and solid propellants. Chem Ind (London)
(7):249–252
Additional Scholarly Articles for Further Reading 301

38. Braithwaite PC, Hatch RL, Lee K, Wardle RB (1998) Development of high performance
CL-20 explosive formulations. In: International annual conference on ICT 29th (Energetic
Materials), pp 4.1–4.7
39. Cahill S, Bulusu S (1993) Molecular complexes of explosives with cyclodextrins.
I. Characterization of complexes with the nitramines RDX, HMX and TNAZ in solution
by proton NMR spin-lattice relaxation time measurements. Magn Reson Chem 31(8):731–
735. https://doi.org/10.1002/mrc.1260310808
40. Cahill S, Rinzler AG, Owens FJ, Bulusu S (1994) Molecular complexes of explosives with
cyclodextrins. II. Preparation and characterization of a solid complex ofb-cyclodextrin with
the nitramine 1,3,3-trinitroazetidine (TNAZ). J Phys Chem 98(28):7095–7100. https://doi.
org/10.1021/j100079a033
41. Calculated using Advanced Chemistry Development (ACD/Labs) Software V8.14 for
Solaris (© 1994–2008 ACD/Labs)
42. Chakka S, Boddu VM, Maloney SW, Toghiani RK, Damavarapu R (2009) Vapor pressures
and melting points of select munitions compounds. American Institute of Chemical
Engineers, pp chakk1/1-chakk1/9
43. Chapman RD et al (1995) Phase behavior in TNAZ-based and other explosive formulations.
American Defense Preparedness Association, pp 192–197
44. Coburn MD, Hiskey MA, Archibald TG (1998) Scale-up and waste-minimization of the Los
Alamos process for 1,3,3-trinitroazetidine (TNAZ). Waste Manage (Oxford) 17(2/3):143–
146. https://doi.org/10.1016/S0956-053X(97)10013-7
45. Coburn MD, Hiskey MA, Oxley JC, Smith JL, Zheng W, Rogers E (1998) Synthesis and
spectra of some 2H-, 13C-, and 15 N-labeled isomers of 1,3,3-trinitroazetidine and
3,3-dinitroazetidinium nitrate. J Energ Mater 16(2 & 3):73–99. https://doi.org/10.1080/
07370659808217506
46. Crowder GA, McKenney RL Jr (1999) Vibrational analysis of high-energy compounds:
1,3,3-trinitroazetidine and 1-acetyl-3,3-dinitroazetidine. J Energ Mater 17(1):49–68. https://
doi.org/10.1080/07370659908216095
47. Dubovik AV, Kozak GD, Aleshkina EA (2007) Theoretical estimation of explosion hazard
of NTO, FOX-7, TNAZ, and CL-20. University of Pardubice, pp 484–495
48. Dudek K, Marecek P, Jalovy Z (2002) Some properties of cast TNAZ mixtures. In:
International annual conference on ICT 33rd (Energetic Materials), pp 53/1–53/7
49. Dudek K, Marecek P, Jalovy Z (2001) Synthesis and some properties of
1,3,3-trinitroazetidine (TNAZ). University of Pardubice, pp 75–80
50. Dudek K, Marecek P, Vavra P (2000) Laboratory testing of HNIW mixtures. In:
International annual conference on ICT 31st (Energetic Materials), pp 110/1–110/6
51. Fan X, Li J, Zhang Y, Zhang W, Kang X (2005) Characteristics of the smokeless CMDB
propellants with 1,3,3-trinitroazetidine. Huozhayao Xuebao 28(4):35–40
52. Florczak B, Lipinska K (2001) Thermochemical properties of composite propellants
combustion products. University of Pardubice, pp 86–98
53. Fuchs B, Stec D, III (2007) Computational survey of representative energetic materials as
propellants for microthruster applications. In: Proceedings of SPIE-international society
optics engineering 6556 (Micro (MEMS) and Nanotechnologies for Defense and Security),
pp 65561B/1–65561B/12. http://doi.org/10.1117/12.721756
54. Garland NL, McElvany SW (1998) Ionization potentials of TNAZ and its decomposition
products. Chem Phys Lett 297(1,2):147–153. http://doi.org/10.1016/S0009-2614(98)01113-
0
55. Garland NL, Nelson HH (1998) Laser-induced decomposition of TNAZ. J Phys Chem B 102
(15):2663–2667. https://doi.org/10.1021/JP980201D
56. Hayashi K, Kumagai T, Nagao Y (2000) Improved synthesis of an energetic material,
1,3,3-trinitroazetidine exploiting 1-azabicyclo [1.1.0] butane. Heterocycles 53(2):447–452
302 11 1,3,3-Trinitroazetidine (TNAZ)

57. Hill LG, Seitz WL, Kramer JF, Murk DM, Medina RS (1996) Wedge test data for three new
explosives: LAX112, 2,4-DNI, and TNAZ. In: AIP conference on proceedings 370 (Pt. 2,
Shock Compression of Condensed Matter–1995), pp 803–806
58. Jadhav HS, Dhavale DD, Talawar MB, Asthana SN, Krishnamurthy VN (2003) 1-(3’,5’-
dinitrophenyl)-3,3-dinitroazetidine: a new energetic materials. University of Pardubice,
pp 153–159
59. Jadhav HS, Talawar MB, Dhavale DD, Asthana SN, Krishnamurthy VN (2006) Alternate
method for synthesis of 1,3,3-trinitroazetidine (TNAZ): next generation melt-castable
high-energy material. Indian J Chem Technol 13(1):41–46
60. Jalovy Z, Zeman S, Suceska M, Vavra P, Dudek K, Rajic M (2001) 1,3,3-trinitroazetidine
(TNAZ), Part I syntheses and properties. J Energ Mater 19(2 & 3):219–239. https://doi.org/
10.1080/07370650108216127
61. Jizhen L, Xuezhong F, Xiping F, Fengqi Z, Rongzu H (2006) Compatibility study of
1,3,3-trinitroazetidine with some energetic components and inert materials. J Therm Anal
Calorim 85(3):779–784. https://doi.org/10.1007/s10973-005-7370-8
62. Katorov DV, Rudakov GF, Ladonin AV, Zhilin VF, Veselova EV, Vyalova NA (2007)
Preparation of low-melting explosive compositions based on 1,3,3-trinitroazetidine. Cent
Eur J Energ Mater 4(1–2):125–133
63. Katritzky AR, Cundy DJ, Chen J (1994) Novel syntheses of 1,3,3-trinitroazetidine.
J Heterocycl Chem 31(2):271–275. https://doi.org/10.1002/jhet.5570310202
64. Keshavarz MH (2007) Determining heats of detonation of non-aromatic energetic
compounds without considering their heats of formation. J Hazard Mater 142(1–2):54–57.
https://doi.org/10.1016/j.jhazmat.2006.07.057
65. Keshavarz MH, Moghadas MH, Tehrani MK (2009) Relationship between the electrostatic
sensitivity of nitramines and their molecular structure. Propellants Explos Pyrotech 34
(2):136–141. https://doi.org/10.1002/prep.200700264
66. Keshavarz MH, Yousefi MH (2008) Heats of sublimation of nitramines based on simple
parameters. J Hazard Mater 152(3):929–933. https://doi.org/10.1016/j.jhazmat.2007.07.067
67. Kim JS, Kim H, Kwon Y (2009) Synthesis of glycidyldinitroazetidine (GDNAZ) as an
energetic monomers containing explosophoric group. In: International annual conference on
ICT 40th (Energetic Materials), pp 53/1–53/11
68. Konrad S, Doris K (2000) Synthesis and properties of TNAZ. In: International annual
conference on ICT 31st (Energetic Materials), pp 10/1–10/12
69. Lanzerotti MYD, Autera J, Sharma J (1996) Crystal growth of TNAZ during high
acceleration. In: AIP conference proceedings 370 (Pt. 1, Shock Compression of Condensed
Matter–1995), pp 243–246
70. Lanzerotti Y, Sharma J (2002) Mechanical behavior of energetic materials during high
acceleration. In: AIP conference proceedings on 620 (Shock Compression of Condensed
Matter, Pt. 2), pp 853–855
71. Lanzerotti Y, Sharma J (2003) Mechanical behavior of energetic materials during high
acceleration. In: Materials research society symposium proceedings 759(Granular
Material-Based Technologies), pp 155–159
72. Lanzerotti Y, Sharma J (2001) Mechanical behavior of energetic materials at high
acceleration. Kluwer Academic/Plenum Publishers, pp 367–369
73. Li J, Zhang W, Wang B, Fan X, Liu Z (2005) Studies on the combustion characteristics and
the thermal behavior of CMDB and NEPE propellants with 1,3,3-trinitroazetidine.
Huozhayao Xuebao 28(2):16–20, 38
74. J-z Li, G-f Zhang, Fan X-z Hu, R-z Pan Q (2006) Thermal behavior of
1,3,3-trinitroazetidine. J Anal Appl Pyrolysis 76(1–2):1–5. https://doi.org/10.1016/j.jaap.
2005.04.008
Additional Scholarly Articles for Further Reading 303

75. Liao L-Q et al (2012) Compatibility of PNIMMO with some energetic materials. J Therm
Anal Calorim 109(3):1571–1576. https://doi.org/10.1007/s10973-011-1905-y
76. Liu M-H, Chen C, Hong Y-S (2004) Empirical methods for estimating the detonation
properties of energetic TNAZ molecular derivatives. J Theor Comput Chem 3(3):379–389.
https://doi.org/10.1142/S0219633604001100
77. Liu M-H, Chen C, Hong Y-S (2005) Theoretical study of the unimolecular decomposition
mechanisms of energetic TNAD and TNAZ explosives. Int J Quantum Chem 102(4):398–
408. https://doi.org/10.1002/qua.20284
78. Long GT, Wight CA (2002) Thermal decomposition of a melt-castable high explosive:
isoconversional analysis of TNAZ. J Phys Chem B 106(10):2791–2795. https://doi.org/10.
1021/jp012859o
79. Ma H-X et al (2010) Molecular structure, thermal behavior and adiabatic time-to-explosion
of 3,3-dinitroazetidinium picrate. J Mol Struct 981(1–3):103–110. https://doi.org/10.1016/j.
molstruc.2010.07.036
80. Makhova NN, Ovchinnikov IV (2008) New variant of 1,3,3-trinitroazetidine synthesis. vol
Pt. 2. University of Pardubice, pp 639–641
81. Marchand AP, Rajagopal D, Bott SG, Archibald TG (1995) A novel approach to the
synthesis of 1,3,3-trinitroazetidine. J Org Chem 60(15):4943–4946. https://doi.org/10.1021/
jo00120a049
82. Marecek P, Dudek K (2002) Cast TNAZ mixtures. University of Pardubice, pp 164–168
83. Marecek P, Dudek K, Vavra P (2001) Laboratory testing of TNAZ mixtures. In:
International annual conference on ICT 32nd (Energetic Materials), pp 90/1–90/8
84. McKenney RL Jr. et al (1998) Synthesis and thermal properties of 1,3-dinitro-3- (1’,3’-
dinitroazetidin-3’-yl)azetidine (TNDAZ) and its admixtures with 1,3,3-trinitroazetidine
(TNAZ). [Erratum to document cited in CA129:161458]. J Energ Mater 16(2 & 3):198–235
85. McKenney RL Jr et al (1998) Synthesis and thermal properties of 1,3-dinitro-3-
(1,3-dinitro-3-azetidinyl) azetidine (TNDAZ) and its admixtures with
1,3,3-trinitroazetidine (TNAZ). J Energ Mater 16(1):1–22. https://doi.org/10.1080/
07370659808216090
86. McKenney RL Jr, Stevens WE (2000) Binary phase diagram series: 1,3,3-trinitroazetidine
(TNAZ)/1,3,5-trinitrobenzene (TNB). J Energ Mater 18(4):241–273. https://doi.org/10.
1080/07370650008219112
87. McKenney RL Jr, Stevens WE, Floyd TG (1998) Binary phase diagram series:
1,3,3-trinitroazetidine (TNAZ)/2,4,6-trinitrotoluene (TNT). J Energ Mater 16(4):245–278.
https://doi.org/10.1080/07370659808230234
88. McKenney RL Jr, Stevens WE, Floyd TG (1999) Binary phase diagram series:
1,3,3-trinitroazetidine (TNAZ)/N-Acetyl-3,3-dinitroazetidine (ADNAZ). J Energ Mater 17
(2 & 3):113–140. https://doi.org/10.1080/07370659908216099
89. Mondal T, Saritha B, Ghanta S, Roy TK, Mahapatra S, Durga Prasad M (2009) On some
strategies to design new high energy density molecules. J Mol Struct Theochem 897(1–
3):42–47. https://doi.org/10.1016/j.theochem.2008.11.013
90. Mostak P, Stancl M (2006) New trends in detection of explosives. University of Pardubice,
pp 61–74
91. Nedel’ko VV et al (2009) Thermal decomposition of 1,3,3-trinitroazetidine in the gas phase,
solution, and melt. Russ Chem Bull 58(10):2028–2034. https://doi.org/10.1007/s11172-009-
0277-y
92. Nedelko VV, Korsounskii BL, Chukanov NV, Larikova TS, Makhova NN, Ovchinnikov IV
(2006) Thermal decomposition of 1,3,3-trinitroazetidine in gas, solution and melt. In:
International annual conference on ICT 37th (Energetic Materials), pp 154/1–154/12
304 11 1,3,3-Trinitroazetidine (TNAZ)

93. Oehrle SA (1994) Analysis of CL-20 and TNAZ in the presence of other nitroaromatic and
nitramine explosives using HPLC with photodiode array (PDA) detection. J Energ Mater 12
(4):211–222. https://doi.org/10.1080/07370659408018651
94. Oehrle SA (1996) Analysis of nitramine and nitroaromatic explosives by micellar
electrokinetic capillary chromatography (MECC). J Energ Mater 14(1):47–56. https://doi.
org/10.1080/07370659608216057
95. Oftadeh M, Khozani MH, Radhoosh M, Keshavarz MH (2011) DFT molecular orbital
calculations of initial step in decomposition pathways of TNAZ and some of its derivatives
with -F, -CN and -OCH3 groups. Comput Theor Chem 964(1–3):262–268. https://doi.org/
10.1016/j.comptc.2011.01.007
96. Oftadeh M, Selahvarzi S, Keshavarz MH (2013) Intermolecular interactions between TNAZ
and H2O: a DFT study. Cent Eur J Energ Mater 10(2):289–300
97. Oxley J, Smith J, Zheng W, Rogers E, Coburn M (1997) Thermal Decomposition Pathways
of 1,3,3-Trinitroazetidine (TNAZ), Related 3,3-Dinitroazetidium Salts, and 15 N, 13C, and
2H Isotopomers. J Phys Chem A 101(24):4375–4383. https://doi.org/10.1021/JP9700950
98. Oxley JC, Kooh AB, Szekeres R, Zheng W (1994) Mechanisms of nitramine thermolysis.
J Phys Chem 98(28):7004–7008. https://doi.org/10.1021/j100079a019
99. Oyumi Y, Brill TB (1985) Thermal decomposition of energetic materials. 4. High-rate,
in situ, thermolysis of the four, six, and eight membered, oxygen-rich, gem-dinitroalkyl
cyclic nitramines, TNAZ, DNNC, and HNDZ. Combust Flame 62(3):225–231.https://doi.
org/10.1016/0010-2180(85)90148-8
100. Parr TP, Hanson-Parr DM (1996) Solid propellant diffusion flame structure. In: Symposium
(International) combust, [Proceedings] 26th (vol 2):1981–1987
101. Persson B, Ostmark H, Bergman H (1997) An HPLC method for analysis of HNIW and
TNAZ in an explosive mixture. Propellants Explos Pyrotech 22(4):238–239. https://doi.org/
10.1002/prep.19970220411
102. Pietrzyk S, Nowaczewski J, Bladek J (2007) Analysis of novel high energetic explosives:
HNIW, TEX, TNAZ, DADNE. University of Pardubice, pp 853–858
103. Politzer P, Seminario JM (1993) Energy changes associated with some decomposition steps
of 1,3,3-trinitroazetidine. A non-local density functional study. Chem Phys Lett 207(1):27–
30. https://doi.org/10.1016/0009-2614(93)85006-A
104. Porollo AA, Pivina TS, Ivshin VP (1998) Theoretical technique for modeling of
1,3,3-trinitroazetidine (TNAZ) thermal decomposition. In: Proceedings on international
pyrotech seminar 24th, pp 445–455
105. Rice VM et al (2001) Theoretical chemistry: applications in energetic materials research.
Khim Fiz 20(10):9–13
106. Sarlauskas J et al (2014) Modern nitramines TNAZ and CL-20 (HNIW): their
electron-accepting potency, enzymatic reactivity and cytotoxicity. vol 2. University of
Pardubice, Institute of Energetic Materials, pp 987–1004
107. Shao Y-H, Ren X-N, Liu Z-R (2010) An investigation on eutectic binary phase diagram of
volatilizable energetic materials by high pressure DSC. J Therm Anal Calorim 101(3):1135–
1141. https://doi.org/10.1007/s10973-009-0620-4
108. Shao YH, Ren XN, Liu ZR, Zhang X (2011) Ternary phase diagrams of DNTF and TNAZ
and their eutectics. J Therm Anal Calorim 103(2):617–623. https://doi.org/10.1007/s10973-
010-0993-4
109. Sheffield SA, Gustavsen RL, Alcon RR (1996) Hugoniot and initiation measurements on
TNAZ explosive. In: AIP conference on proceedings 370 (Pt. 2, Shock Compression of
Condensed Matter–1995), pp 879–882
110. Shu Y, Li H, Huang Y, Liu S (2003) Synthesis of N-acetyl-3,3-dinitroazetidine. University
of Pardubice, pp 543–546
Additional Scholarly Articles for Further Reading 305

111. Sikder N, Sikder AK, Bulakh NR, Gandhe BR (2004) 1,3,3-Trinitroazetidine (TNAZ), a
melt-cast explosive: synthesis, characterization and thermal behaviour. J Hazard Mater 113
(1–3):35–43. https://doi.org/10.1016/j.jhazmat.2004.06.002
112. Sikder N, Sikder AK, Bulakh NR, Gandhe BR (2004) 1,3,3-Trinitroazetidine (TNAZ), a
melt-cast explosive: synthesis, characterization and thermal behaviour. J Hazard Mater 113
(1–3):35–43
113. Sikder N, Sikder AK, Bulakh NR, Gandhe BR (2004) 1,3,3-Trinitroazetidine (TNAZ), a
melt-cast explosive: synthesis, characterization and thermal behaviour. J Hazard Mater 113
(1–3):35–43. https://doi.org/10.1016/j.jhazmat.2004.06.002
114. Simpson RL, Urtiew PA, Tarver CM (1996) Shock initiation of 1,3,3-trinitroazetidine
(TNAZ). In: AIP conference on proceedings 370 (Pt. 2, Shock Compression of Condensed
Matter–1995), pp 883–886
115. Sinditskii VP, Egorshev VY, Berezin MV, Rudakov GF, Ladonin AV, Katorov DV (2005)
Combustion behavior and flame structure of a melt-castable high explosive
1,3,3-trinitroazetidine (TNAZ). In: International annual conference on ICT 36th (Energetic
Materials), pp 78/1–78/7
116. Singh A, Sikder N, Sikder AK (2005) Improved synthesis of an energetic material,
1,3,3-trinitroazetidine (TNAZ) exploiting 2-iodoxy benzoic acid (IBX) as an oxidising
agent. Indian J Chem, Sect B: Org Chem Incl Med Chem 44B(12):2560–2563
117. Suceska M, Rajic M, Zeman S, Jalovy Z (2001) 1,3,3-trinitroazetidine (TNAZ). Study of
thermal behaviour. Part II. J Energ Mater 19(2 & 3):241–254 http://doi.org/10.1080/
07370650108216128
118. Suceska M, Zeman S, Rajic M, Jalovy Z (2001) Theoretical prediction of TNAZ detonation
properties. University of Pardubice, pp 308–318
119. Suseska M, Rajis M, Matecis-Musanis S, Zeman S, Jalovy Z (2003) Kinetics and heats of
sublimation and evaporation of 1,3,3-trinitroazetidine (TNAZ). J Therm Anal Calorim 74
(3):853–866. https://doi.org/10.1023/B:JTAN.0000011017.65451.96
120. Talawar MB et al (2006) Effect of organic additives on the mitigation of volatility of
1-nitro-3,3’-dinitroazetidine (TNAZ): next generation powerful melt castable high energy
material. J Hazard Mater 134(1–3):8–18. https://doi.org/10.1016/j.jhazmat.2003.10.008
121. Thompson CA, Rice JK, Russell TP, Seminario JM, Politzer P (1997) Vibrational analysis of
1,3,3-trinitroazetidine using matrix isolation infrared spectroscopy and quantum chemical
calculations. J Phys Chem A 101(42):7742–7748. https://doi.org/10.1021/JP971173M
122. Thompson CA, Russell TP, Concha MC, Politzer P (1997) Comparing quantum chemical
calculations for azetidine strained ring compounds. American Chemical Society, pp
COMP-125
123. Turker L (2013) Detonation velocity—a molecular aspect. Adv Chem Model 4:223–236
124. Turker L, Atalar T (2011) 1,3,3-Trinitroazetidine (TNAZ) and some of its constitutional
isomers: a DFT study. vol 2. University of Pardubice, Institute of Energetic Materials,
pp 982–993
125. Turker L, Varis S (2012) Desensitization of TNAZ via molecular structure modification and
explosive properties—a DFT study. Acta Chim Slov 59(4):749–759
126. Veals JD, Thompson DL (2014) Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ):
A density functional theory and ab initio study. J Chem Phys 140(15):154306/1–154306/10
http://doi.org/10.1063/1.4870652
127. Wakeham GP, Chung DD, Nelson KA (2002) Femtosecond time-resolved spectroscopy of
energetic materials. Thermochim Acta 384(1–2):7–21. https://doi.org/10.1016/S0040-6031
(01)00774-2
128. Wilcox CF, Zhang YX, Bauer SH (2000) The thermochemistry of TNAZ
(1,3,3-trinitroazetidine) and related species: models for calculating heats of formation.
J Mol Struct: THEOCHEM 528:95–109. https://doi.org/10.1016/S0166-1280(99)00475-3
306 11 1,3,3-Trinitroazetidine (TNAZ)

129. Wilcox CF, Zhang YX, Bauer SH (2001) The thermochemistry of TNAZ
(1,3,3-trinitroazetidine) and related species: G3(MP2)//B3LYP heats of formation. J Mol
Struct: THEOCHEM 538:67–72. https://doi.org/10.1016/S0166-1280(00)00646-1
130. Xue L, Zhao F-Q, Xing X-L, Gao H-X, Yi J-H, Hu R-Z (2009) Dissolution properties of
1,3,3-trinitroazetidine in ethyl acetate and N. N-dimethylformamide. Wuli Huaxue Xuebao
25(12):2413–2416
131. Yan B et al (2014) Thermodynamic properties, detonation characterization and free radical
of N-2’,4’-dinitrophenyl-3,3-dinitroazetidine. J Chem Thermodyn 69:152–156. https://doi.
org/10.1016/j.jct.2013.10.014
132. Yan Q-L, Zeman S, Elbeih A (2012) Recent advances in thermal analysis and stability
evaluation of insensitive plastic bonded explosives (PBXs). Thermochim Acta 537:1–12.
https://doi.org/10.1016/j.tca.2012.03.009
133. Yu CL, Zhang YX, Bauer SH (1998) Estimation of the equilibrium distribution of products
generated during high temperature pyrolyses of 1,3,3-trinitroazetidine; thermochemical
parameters. J Mol Struct: THEOCHEM 432(1):63–68. https://doi.org/10.1016/S0166-1280
(97)87495-7
134. Zeman S, Atalar T (2009) A new view of relationships of the N–N bond dissociation
energies of cyclic nitramines. Part III. Relationship with detonation velocity. J Energ Mater
27(3):217–229. http://doi.org/10.1080/07370650802640374
135. Zhang J, Hu J-W, Wang J-L, Chen L-Z (2011) Solubility of 1,3,3-trinitroazetidine in
ethanol + water systems from (293.15 K to 323.15 K). J Solution Chem 40(4):703–708.
http://doi.org/10.1007/s10953-011-9673-7
136. Zhang J, Hu R, Zhu C, Feng G, Long Q (1997) Thermal behavior of 1,3,3-trinitroazetidine.
Thermochim Acta 298(1–2):31–35. https://doi.org/10.1016/S0040-6031(97)00056-7
137. Zhang J, Hu R, Zhu C, Feng G, Long Q (1996) Thermal behavior of 1,3,3-trinitroazetidine.
Beijing Institute of Technology Press, pp 133–138
138. Zhang M, Shi Z, Bai Y, Gao Y, Hu R, Zhao F (2006) Using molecular recognition of
b-Cyclodextrin to determine molecular weights of low-molecular-weight explosives by
MALDI-TOF mass spectrometry. J Am Soc Mass Spectrom 17(2):189–193. https://doi.org/
10.1016/j.jasms.2005.10.005
139. Zhang X, Yang J, Wang T, Gong X, Wang G (2014) A theoretical study on the stability and
detonation performance of 2,2,3,3-tetranitroaziridine (TNAD). J Phys Org Chem 27(6):532–
539. https://doi.org/10.1002/poc.3297
140. Zhang Y-X, Bauer SH (1998) Gas-Phase Pyrolysis of 1,3,3-trinitroazetidine: shock tube
kinetics. J Phys Chem A 102(29):5846–5856. https://doi.org/10.1021/JP980931L
141. Zhang Y-X, Bauer SH (1999) Gas-phase decomposition mechanisms of C-NO2, N-NO2
energetic materials: reevaluations. Int J Chem Kinet 31(9):655–673 http://doi.org/10.1002/
(SICI)1097-4601(1999)31:9<655::AID-KIN7>3.0.CO;2-M
142. Zhang Y-X, Bauer SH (1999) Gas-phase decomposition mechanisms of C-NO2, N-NO2
energetic materials: reevaluations. Int J Chem Kinet 31(9):655–673. http://doi.org/10.1002/
(SICI)1097-4601(1999)31:9<655::AID-KIN7>3.0.CO;2-M
143. Zhao Q, Zhang S, Li QS (2005) A direct ab initio dynamics study of the initial
decomposition steps of gas phase 1,3,3-trinitroazetidine. Chem Phys Lett 412(4–6):317–321.
https://doi.org/10.1016/j.cplett.2005.07.014
144. Zhao Q, Zhang S, Li QS (2005) The influence of ring strain and conjugation on the reaction
energies of the NO2 fission of nitramines: a DFT study. Chem Phys Lett 407(1–3):105–109.
https://doi.org/10.1016/j.cplett.2005.03.059
145. Zheng W, Dong X, Rogers E, Oxley JC, Smith JL (1997) Improvements in the determination
of decomposition gases from 1,3,3-trinitroazetidine and
5-nitro-2,4-dihydro-3H-1,2,4-traizol-3-one using capillary gas chromatography-mass spec-
trometry. J Chromatogr Sci 35(10):478–482. https://doi.org/10.1093/chromsci/35.10.478
Additional Scholarly Articles for Further Reading 307

146. Zheng W, Dong X, Rogers E, Oxley JC, Smith JL (1997) Improvements in the determination
of decomposition gases from 1,3,3-trinitroazetidine and 5-nitro-2,4-dihydro-3H-1,2,4-
traizol-3-one using capillary gas chromatography-mass spectrometry. J Chromatogr Sci 35
(10):478–482. https://doi.org/10.1093/chromsci/35.10.478
147. Zheng W, Rogers E, Coburn M, Oxley J, Smith J (1997) Mass spectral fragmentation
pathways in 1,3,3-trinitroazetidine. J Mass Spectrom 32(5):525–532. https://doi.org/10.
1002/(SICI)1096-9888(199705)32:5<525:AID-JMS505>3.0.CO;2-7
Appendix 1
Unit

Table A.1. Conversion Factors

Overview

The International System of Units (SI) is a modernized version of the metric system
established by international agreement. The metric system of measurement was
developed during the French Revolution and was first promoted in the U.S. by
Thomas Jefferson. Its use was legalized in the U.S. in 1866. In 1902, proposed
congressional legislation requiring the U.S. Government to use the metric system
exclusively was defeated by a single vote.
SI provides a logical and interconnected framework for all measurements in
science, industry, and commerce. The metric system is much simpler to use than the
existing English system since all its units of measurement are divisible by 10.

Conversion Factors

The following list provides the conversion relationship between U.S. customary
units and SI (International System) units. The proper conversion procedure is to
multiply the specified value on the left (primarily U.S. customary values) by the
conversion factor exactly as given below and then round to the appropriate number
of significant digits desired. For example, to convert 11.4 ft to m:
11.4  0.3048 = 3.47472, which rounds to 3.47 m. Do not round either value
before performing the multiplication, as accuracy would be reduced. A complete
guide to the SI system and its use can be found in ASTM E 380, Metric Practice.
Select this link for an explanation of WSDOT's foot to meter conversion method
(http://www.wsdot.wa.gov/Reference/metrics/foottometer.htm).
Note that Convert.exe (http://www.wsdot.wa.gov/NR/rdonlyres/4A1238B7-
69FC-434E-8BF0-317AA149F5C0/0/convert.exe) uses the 1959 conversion fac-
tors for distance (http://www.wsdot.wa.gov/Reference/metrics/foottometer.htm) i.e.
the 1959 definitions of inch and foot and their derived measurements, the ton to
kilogram conversion factor differs from the conversion factor published on this page
© US Government (outside the USA) 2018 309
D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7
310 Appendix 1: Unit

by 1 in the 7th digit, the Fahrenheit to Kelvin conversion factor differs by 0.017° K,
the BTU/h to watt conversion differs by 3 in the 4th digit, and the ft/sec2 to m/sec2
conversion differs by 1 in the 6th digit.

Conversion Symbols

The prefixes and symbols listed below are commonly used to form names and
symbols of the decimal multiples and sub multiples of the SI units.

SI Prefixes for decimal multiples

Number Factor Name Symbol
1,000,000,000,000,000,000,000,000 1024 yotta Y
1,000,000,000,000,000,000,000 1021 zetta Z
1,000,000,000,000,000,000 1018 exa E
1,000,000,000,000,000 1015 peta P
1,000,000,000,000 1012 tera T
1,000,000,000 109 giga G
1,000,000 106 mega M
1000 103 kilo k
100 102 hecto h
10 101 deca da
0.1 10−1 deci d
0.01 10−2 centi c
0.001 10−3 milli m
0.000001 10−6 micro µ
0.000000001 10−9 nano n
0.000000000001 10−12 pico p
0.000000000000001 10−15 femto f
0.000000000000000001 10−18 atto a
0.000000000000000000001 10−21 zepto z
0.000000000000000000000001 10−24 yocto y

Table A.2. Commercial standards

As used in the standard item table Metric equivalent

Acre Hectare (ha)
Cubic foot Cubic meter (m3)
Cubic yard Cubic meter (m3)
Gallon/Mgallon Liter (l), Cubic meter (m3)
(continued)
Appendix 1: Unit 311

(continued)
As used in the standard item table Metric equivalent
Hundred Hundred for traffic buttons
Hundred weight Kilogram (kg)
Linear foot Meter (m)
Mboard feet Cubic meter (m3)
Mile Kilometer (km)
Nautical mile Nautical Mile
Pound Kilogram (kg) for Mass newton (N) for Force
Square foot Square meter (m2)
Square yard Square meter (m2)
Ton Tonne (t)
Units of measurement used in special Metric equivalent
provisions and general special
provisions
Gage; Gauge Metal thickness gage (mm)
Fahrenheit Temperature kelvin (K) or degree Celsius (C)
Fathom Water depth Meter (m)
Foot/Lbs Torque Newton-meter (N-m)
Lbs/Sq. In Pressures Kilopascal (kPa) megapascal (MPa)
(if very large number)
Lbs/Sq. Ft Kilopascal (kPa)
Lbs/Sq Yd Kilopascal (kPa)
Inch Linear Millimeter (mm)
Kips; Ksi Tension Kilopascal (kPa) or megapascal (MPa)
Lbs/Acre Erosion control Kilograms/hectare
Lbs/Cu. Ft. Density Kilogram per cubic meter (kg/m3)
Mil Thickness Micrometer (um)
Ft. Lbs./Sec. Horse power Watt (W)
Units of measurements used Metric equivalent
on contract plans
Degrees/Bearings No change for surveying
Stationing 1000 m = 1 Station
Mileposts This one is still under review as mile posts are part of the
signing issue. Use mileposts for now, but also state
kilometerposts
Elevations Meter (m)
Units of measurements used in commercial Metric equivalent
standards
Gals/Hr Or Min (Pumps) Liters Per Second (l/s)
500 Gallon Tanks Cubic Meter (m3) But It Could Also
Possi
Bly Be In Liter (l)
(continued)
312 Appendix 1: Unit

(continued)
Units of measurements used in commercial Metric equivalent
standards
55 Gallon Drums Cubic meter (m3) or Liter (l) For Liquid
94 Lbs/Sack (Cement) Kilogram (kg)
Diameter of reinforcing steel Millimeter (mm)
Lbs/Ft of reinforcing steel Kilogram per meter kg/m)
Bushel Cubic Meter (m3)

Table A.3. Length Factors

Length Conversion Factors

Length
To convert from To Multiply by
mile (US Statute) kilometer (km) 1.609347
inch (in) millimeter (mm) 25.4a
inch (in) centimeter (cm) 2.54a
inch (in) meter (m) 0.0254a
foot (ft) meter (m) 0.3048a
yard (yd) meter (m) 0.9144a
a
Indicates that the factor given is exact

Area Conversion Factors

Area
square foot (sq ft) square meter (sq m) 0.09290304 E
square inch (sq in) square meter (sq m) 0.00064516 E
square yard (sq yd) square meter (sq m) 0.83612736 E
acre (ac) hectare (ha) 0.4047

Volume Conversion Factors

Volume
cubic inch (cu in) cubic meter (cu m) 0.00001639
cubic foot (cu ft) cubic meter (cu m) 0.02831685
cubic yard (cu yd) cubic meter (cu m) 0.7645549
U.S. liquida
gallon (gal) cubic meter (cu m) 0.00378541
(continued)
Appendix 1: Unit 313

(continued)
Volume
gallon (gal) liter 3.785
fluid ounce (fl oz) milliliters (ml) 29.57353
fluid ounce (fl oz) cubic meter (cu m) 0.00002957
a
One U.S. gallon equals 0.8327 Canadian gallon

Force Conversion Factors

Force
kip (1000 lb) kilogram (kg) 453.6
kip (1000 lb) newton (N) 4448.222
pound (lb) avoirdupois kilogram (kg) 0.4535924
pound (lb) newton (N) 4.448222

Pressure or Stress Conversion Factors

Pressure or stress
kip per square inch (ksi) megapascal (MPa) 6.894757
pound per square foot (psf) kilogram per square meter (kg/sq m) 4.8824
pound per square foot (psf) pascal (Pa) 47.88
pound per square inch (psi) pascal (Pa) 6894.757
pound per square inch (psi) megapascal (MPa) 0.00689476

Mass conversion factors

Mass (weight)
pound (lb) avoirdupois kilogram (kg) 0.4535924
ton, 2000 lb kilogram (kg) 907.1848
grain kilogram (kg) 0.0000648
Mass (weight) per length
kip per linear foot (klf) kilogram per meter (kg/m) 0.001488
pound per linear foot (plf) kilogram per meter (kg/m) 1.488
Mass per volume (density)
pound per cubic foot (pcf) kilogram per cubic meter (kg/cu m) 16.01846
pound per cubic yard (lb/cu yd) kilogram per cubic meter (kg/cu m) 0.5933

Temperature conversion factors

Temperature
degree Fahrenheit (°F) degree Celsius (°C) tc = (tF-32)/1.8
(continued)
314 Appendix 1: Unit

(continued)
degree Fahrenheit (°F) Kelvin (K) tk = (tF + 459.7)/1.8
Kelvin (K) degree Celsius (°C) tc = tk-273.15
Energy and heat
British thermal unit (Btu) Joule (J) 1055.056
calorie (cal) Joule (J) 4.1868E
Btu/degree F  hr  ft2 W/m2—°K 5.678263
kilowatt-hour (kwh) Joule (J) 3,600,000E
British thermal unit per pound (Btu/lb) Calories per gram (cal/g) 0.55556
British thermal unit per hour (Btu/hr) Watt (W) 0.2930711

Power conversion factors

Power
horsepower (hp) (550 ft-lb/sec) watt (W) 745.6999 E
Velocity
mile per hour (mph) kilometer per hour (km/hr) 1.60934
mile per hour (mph) meter per second (m/s) 0.44704
Permeability
darcy centimeter per second (cm/sec) 0.000968
feet per day (ft/day) centimeter per second (cm/sec) 0.000352
Note
t–A pascal equals 1000 N/m2
One U.S. gallon of water weighs 8.34 pounds (U.S.) at 60° F
One cubic foot of water weighs 62.4 pounds (U.S.)
One milliliter of water has a mass of 1 g and has a volume of 1 M3
One U.S. bag of cement weighs 94 lbs

More useful conversion factors

Quantity From English units To metric units Multiply bya
Length
mile km 1.609347
yard m 0.9144b
foot m 0.3048b
inch mm 25.40b
Area
square mile km2 2.590
acre m2 4047
acre hectare 0.4047
square yard m2 0.8361
square foot m2 0.09290
square inch mm2 645.2
(continued)
Appendix 1: Unit 315

(continued)
Quantity From English units To metric units Multiply bya
Volume
acre foot m3 1 233
cubic yard m3 0.7646
cubic foot m3 0.02832
cubic foot L (1000 cm3) 28.32
100 board feet m3 0.2360
gallon L (1000 cm3) 3.785
Mass
lb kg 0.4536
kip (1000 lb) Metric ton (1000 kg) 0.4536
Mass/unit length
plf kg/m 1.488
Mass/unit area
psf kg/m2 4.882
Mass density
pcf kg/m3 16.02
Force
lb N 4.448
kip kN 4.448
Force/unit length
plf N/m 14.59
klf kN/m 14.59
Pressure, stress, modules of elasticity
psf Pa 47.88
ksf kPa 47.88
psi kPa 6.895
ksi MPa 6.895
Bending moment, torque, moment of force
ft-lb N
m 1.356
ft-kip kN
m 1.356
a
4 significant digits
b
Denotes exact conversion

Quantity From English units To metric units Multiply bya

Moment of mass
lb . ft kg
m 0.1383
Moment of inertia
lb . ft2 kg
m2 0.04214
(continued)
316 Appendix 1: Unit

(continued)
Quantity From English units To metric units Multiply bya
Second moment of area
in4 mm4 416,200
Section modulus
in3 mm3 16,390
Power
ton (refrig) kW 3.517
Btu/s kW 1.054
hp (electric) W 745.7
Btu/h W 0.2931
Volume rate of flow
ft3/s m3/s 0.02832
cfm m3/s 0.0004719
cfm L/s 0.4719
mgd m3/s 0.0438
Velocity, speed
ft/s m/s 0.3048b
Acceleration
f/s2 m/s2 0.3048
Momentum
lb . ft/sec kg
m/s 0.1383
Angular momentum
lb . ft2/s kg
m 2/s 0.04214
Plane Angle
degree rad 0.01745
mrad 17.45
a
4 significant digits
b
Denotes exact conversion

Pavement Conversion Factors

Metric conversion—Pavements
Roadway Dimensions Bridge Ht. PCCP Thickness’
Resilient Modulus
ft m ft m (inches) (mm) psi MPa
Lane
12 3.6 14.5 4.4 9 225 3000 21
Shoulder
4 1.2 16.0 4.9 10 250 4000 28
10 3.0 11 275 5000 34
12 300 10,000 69
(continued)
Appendix 1: Unit 317

(continued)
Metric conversion—Pavements
Roadway Dimensions Bridge Ht. PCCP Thickness’
Resilient Modulus
ft m ft m (inches) (mm) psi MPa
12,000 83
15,000 103
20,000 138

Typical density values Axle loads Tire loads (per tire

width)
pcf kg/m2 lbs KN lbs/inch kg/mm
PCCP 150 2403 18,000 80 500 9
ACP 137/0.10’ depth 2439

Pavement Marking Conversion Chart

Wet material thickness Edge line coverage Area coverage
English Metric English Met./ Metric English Met./ Metric
mils mm Ft/gal Eng. M/Liter SF/gal Eng. SM/Lit
(0.001′′) (0.001 M) M/gal SM/gal
1.0 0.025 4832 1473 393.7 1611 150 39.37
10.0 0.254 483 147 39.4 161 15 3.94
15.0 0.381 322 98.2 26.2 107 10 2.62
19.7 0.500 245 74.8 20.0 82 7.6 2.00
20.0 0.508 242 73.6 19.7 81 7.5 1.97
25.0 0.635 193 58.9 15.7 64 6.0 1.57
30.0 0.762 161 49.1 13.1 54 5.0 1.31
35.0 0.889 138 42.1 11.2 46 4.3 1.12
39.4 1.000 123 37.4 10.0 41 3.8 1.00
40.0 1.016 121 36.8 9.8 40 3.7 0.98
45.0 1.143 107 32.7 8.7 36 3.3 0.87
49.2 1.250 98 29.9 8.0 33 3.0 0.80
50.0 1.270 97 29.5 7.9 32 3.0 0.79
59.1 1.500 82 24.9 6.7 27 2.5 0.67
60.0 1.524 81 24.5 6.6 27 2.5 0.66
78.7 2.000 61 18.7 5.0 20 1.9 0.50
88.6 2.250 55 16.6 4.4 18 1.7 0.44
90.0 2.286 54 16.4 4.4 18 1.7 0.44
98.4 2.500 49 15.0 4.0 16 1.5 0.40
100.0 2.540 48 14.7 3.9 16 1.5 0.39
(continued)
318 Appendix 1: Unit

(continued)
Wet material thickness Edge line coverage Area coverage
English Metric English Met./ Metric English Met./ Metric
mils mm Ft/gal Eng. M/Liter SF/gal Eng. SM/Lit
(0.001′′) (0.001 M) M/gal SM/gal
118.1 3.000 41 12.5 3.3 14 1.3 0.33
120.0 3.048 40 12.3 3.3 13 1.2 0.33
236.2 6.000 20 6.2 1.7 7 0.6 0.17
250.0 6.350 19 5.9 1.6 6 0.6 0.16
255.9 6.500 19 5.8 1.5 6 0.6 0.15
260.0 6.604 19 5.7 1.5 6 0.6 0.15
WDB 4.22.97

Table A.3. Length Factors

Sheet Metal Conversion Factors

Sheet Metal Most specification references use gage number followed by the dec-
imal inch thickness. Example: 22 gage (0.034 inch) Metric specifications use the
absolute mm thickness. It is not the intent of this guidance to change the thickness
of currently used sheeting. The following chart may be used to specify sheet metal.
The thickness under “Specify” is thinner than the actual gage thickness, since
specifications give minimum thickness.

Gage Inch Exact (mm) Specify (mm) Percent thinner than “Exact” value
32 0.0134 0.3404 0.34 0.1
30 0.0157 0.3988 0.39 2.2
28 0.0187 0.4750 0.47 1.1
26 0.0217 0.5512 0.55 0.2
24 0.0276 0.7010 0.70 0.1
22 0.0336 0.8534 0.85 0.4
20 0.0396 1.0058 1.0 0.6
18 0.0516 1.3106 1.3 0.8
16 0.0635 1.6129 1.6 0.8
14 0.0785 1.9939 1.9 4.7
12 0.1084 2.7534 2.7 1.9
10 0.1382 3.5103 3.5 0.3
8 0.1681 4.2697 4.2 1.6
Appendix 1: Unit 319

This schedule was developed since no existing material was found to clearly
identify existing sheeting in metric units. Until a more efficient method is developed
to address this issue, specifiers may wish to retain the gage number in specifica-
tions, and couple this with a rounded mm size in parenthesis.

Reinforcing Steel Conversion Factors

Reinforcing Steel
WSDOT Metric projects will continue to use U.S. Customary units on PS&E’s.
The following table shows the current U.S. customary rebar sizes in relationship
to the respective diameters and cross-sectional areas.

U.S. customary Customary English system Metric equivalent

designation Diameter Area (in2) Diameter Area
(in.) (mm) (mm2)
#3 0.375 0.11 9.5 71
#4 0.500 0.20 12.7 127
#5 0.625 0.31 15.9 198
#6 0.750 0.44 19.1 285
#7 0.875 0.60 22.2 388
#8 1.000 0.79 25.4 507
#9 1.125 1.00 28.6 641
#10 1.270 1.27 32.3 817
#11 1.410 1.56 35.8 1007
#14 1.693 2.25 43.0 1452
#18 2.257 4.00 57.3 2581

Table A.5. Wire

Wire Conversion Factors

Seven-Wire, Uncoated Strand for Prestressed Concrete Structures The pre-

stressing industry again uses the soft conversion for all dimensional units of pre-
stressing wire. This soft conversion is utilized worldwide and a copy of the
equivalent physical properties for Grade 270 low-relaxation strand, as provided by
Florida Wire and Cable Company, is provided:
320 Appendix 1: Unit

270 Grade low-relaxation ASTM A-416

Nominal strand Minimum strength Area
diameter
(mm) (in.) (kN) (lb.) (mm2) (in2)
10 (3/8) 102.3 (23,000) 54.8 (0.085)
11 (7/16) 137.9 (31,000) 74.2 (0.115)
12 (15/32) 160.1 (36,000) 85.8 (0.133)
13 (1/2) 183.7 (41,300) 98.7 (0.153)
14 (9/16) 230.0 (51,700) 123.9 (0.192)
15 (0.600) 260.6 (58,600) 140.0 (0.217)

Table A.6. Sieves

Sieve Conversion Factors

Sieves
Sieve designation (W)
Standard Alternative Nominal Permissible Intermediate Maximum Nominal
(mm) (in.) sieve variation of tollerance individual wire
opening average (mm) opening diameter
(in.) opening from (mm) (mm)
the standard
sieve
designation
(mm)
(y) + or (x) (x)
125 5 5 3.70 130.0 130.9 8.00
106 4.24 4.24 3.20 110.2 111.1 6.40
100 4 4 3.00 104.0 104.8 6.30
90 3 1/2 3.5 2.70 93.6 94.4 6.08
75 3 3 2.20 78.1 78.7 5.80
63 2 1/2 2.5 1.90 65.6 66.2 5.50
53 2.12 2.12 1.60 55.2 55.7 5.15
50 2 2 1.50 52.1 52.6 5.05
45 1 3/4 1.75 1.40 46.9 47.4 4.85
37.5 1 1/2 1.5 1.10 39.1 39.5 4.59
31.5 1 1/4 1.25 1.00 32.9 33.2 4.23
26.5 1.06 1.06 0.80 27.7 28.0 3.90
25.0 1 1 0.80 26.1 26.4 3.80
(continued)
Appendix 1: Unit 321

(continued)
Sieve designation (W)
Standard Alternative Nominal Permissible Intermediate Maximum Nominal
(mm) (in.) sieve variation of tollerance individual wire
opening average (mm) opening diameter
(in.) opening from (mm) (mm)
the standard
sieve
designation
(mm)
(y) + or (x) (x)
22.4 0.875 0.70 23.4 23.7 3.50
19.0 3/4 0.750 0.60 19.9 20.1 3.30
16.0 0.625 0.50 16.7 17.0 3.00
13.2 0.530 0.530 0.41 13.83 14.05 2.75
12.5 1/2 0.500 0.39 13.10 13.31 2.67
11.2 7/16 0.438 0.35 11.75 11.94 2.45
9.50 0.375 0.30 9.97 10.16 2.27
8.00 5/16 0.312 0.25 8.41 8.58 2.07
6.70 0.265 0.265 0.21 7.05 7.20 1.87
6.30 1/4 0.250 0.20 6.64 6.78 1.82
5.60 No. 3 1/2 0.223 0.18 5.90 6.04 1.68
4.75 No. 4 0.187 0.15 5.02 5.14 1.54
4.00 No. 5 0.157 0.13 4.23 4 35 1.37
3.35 No. 6 0.132 0.11 3.55 3.66 1.23
2.80 No. 7 0.11 0.095 2.975 3.070 1.10
2.36 No. 8 0.0937 0.080 2.515 2.600 1.00
2.00 No. 10 0.0787 0.070 2.135 2.215 0.900
1.70 No. 12 0.0661 0.060 1.820 1.890 0.810
1.40 No. 14 0.0555 0.050 1.505 1.565 0.725
1.18 No. 16 0.0469 0.045 1.270 1.330 0.650
1.00 No. 18 0.0394 0.040 1.080 1.135 0.580
0.850 No. 20 0.0331 0.035 0.925 0.970 0.510
0.710 No. 25 0.0278 0.030 0.775 0.815 0.450
0.600 No. 30 0.0234 0.025 0.660 0.695 0.390
0.500 No. 35 0.0197 0.020 0.550 0.585 0.340
0.425 No. 40 0.0165 0.019 0.471 0.502 0.290
0.355 No. 45 0.0139 0.016 0.396 0.425 0.247
0.300 No. 50 0.0117 0.014 0.337 0.363 0.215
0.250 No. 60 0.0098 0.012 0.283 0.306 0.180
0.212 No. 70 0.0083 0.010 0.242 0.263 0.152
0.180 No. 80 0.0070 0.009 0.207 0.227 0.131
0.150 No. 100 0.0059 0.008 0.174 0.192 0.110
(continued)
322 Appendix 1: Unit

(continued)
Sieve designation (W)
Standard Alternative Nominal Permissible Intermediate Maximum Nominal
(mm) (in.) sieve variation of tollerance individual wire
opening average (mm) opening diameter
(in.) opening from (mm) (mm)
the standard
sieve
designation
(mm)
(y) + or (x) (x)
0.125 No. 120 0.0049 0.007 0.147 0.163 0.091
0.106 No. 140 0.0041 0.006 0.126 0.141 0.076
0.090 No. 170 0.0035 0.005 0.108 0.122 0.064
0.075 No. 200 0.0029 0.005 0.091 0.103 0.053
0.063 No. 230 0.0025 0.004 0.077 0.089 0.044
0.053 No. 270 0.0021 0.004 0.066 0.076 0.037
0.045 No. 325 0.0017 0.003 0.057 0.066 0.030
0.038 No. 400 0.0015 0.003 0.048 0.057 0.025
0.032 No. 450 0.0012 0.003 0.042 0.050 0.028
0.025 No. 500 0.0010 0.003 0.034 0.041 0.025
0.020 No. 635 0.0008 0.003 0.029 0.035 0.020

Table A.7. Hard Conversions

Hard conversions for construction materials

Hard conversion for construction materials
Structural Steel (M270)
Grade Min. tensile strength Min. yield strength Min. yield strength
(MPa) (MPa) (ksi)
36 400 250 36
50 450 345 50
50W 485 345 50
70W 620 480 70
Appendix 1: Unit 323

Reinforcing Bars (M31M)

Grade Tensile and yield strengths
Metric English Tensile strength Min. yield strength Min. yield strength
Value Value (MPa) (MPa) (ksi)
300 40 500 300 40
400 60 600 400 60

Common concrete strengths (f’c)

Metric (MPa) 20 28 35 43 48 55
English (psi) 3000 4000 5000 6000 7000 8000

Coefficient of thermal expansion

Metric value English value
Steel 0.0000117/°C 0.0000065/°F
Concrete 0.0000108/°C 0.000006/°F

Unit Weights
Metric value English value
Steel 7848.3 kg/m3 490 pcf
Concrete 2402.5 kg/m3 150 pcf

Table A.8. The Construction Trades

The Construction Trades

Here are the metric units that will be used by the construction trades. The term
“length” includes all linear measurements–length, width, height, thickness, diam-
eter, and circumference.

Quantity Unit Symbol

Surveying
length kilometer, meter km, m
area square kilometer km2
hectare (10,000 m2) ha
square meter m2
(continued)
324 Appendix 1: Unit

(continued)
Quantity Unit Symbol
°
plane angle degree (non metric)
minute (non metric) ′
second (non metric) ′′
Excavating
length meter, millimeter m
volume cubic meter m3
Trucking
distance kilometer km
volume cubic meter m3
mass metric ton (1000 kg) t
Paving
length meter, millimeter m, mm
area square meter m2
Concrete
length meter, millimeter m, mm
area square meter m2
volume cubic meter m3
temperature degree Celsius °C
water capacity liter (1000 cm) L
mass (weight) kilogram, gram kg, g
cross-sectional area square millimeter mm2

Table A.9. Pipe

Pipe Conversion Factors

Pipe is one of the most ubiquitous products in construction. It is made of a wide

variety of materials, including galvanized steel, black steel, copper, cast iron,
concrete, and various plastics such as ABS, PVC, CPVC, polyethylene, and
polybutylene, among others.
But like wood 2-by-4’s which are not really 2 inches by 4 inches, pipe is
identified by “nominal” or “trade” names that are related only loosely to actual
dimensions. For instance, a 2-inch galvanized steel pipe has n inside diameter of
about 2-1/8 inches and an outside diameter of about 2-5/8 inches. It is called
“2-inch pipe” only for the sake of convenience.
Since few, if any, pipe products have actual dimensions that are in even, round
inch-pound numbers, there is no need to convert them to even, round metric
numbers. Instead, only their names will change–from inch-pound to metric. Pipe
Appendix 1: Unit 325

cross sections will not change. Fittings, flanges, couplings, valves, and other piping
components will be renamed in like manner as will pipe threads. Here are the
inch-pound names for pipe products (called NPS or “nominal pipe size”) and their
metric equivalents (called DN or “diameter nominal”). The metric names conform
to International Standards Organization (ISO) usage and apply to all plumbing,
natural gas, heating oil, drainage, and miscellaneous piping used in buildings and
civil works projects.

NPS (′′) DN (mm) NPS (′′) DN (mm)

1/8 6 8 200
3/16 7 10 250
1/4 8 12 300
3/8 10 14 350
1/2 15 16 400
5/8 18 18 450
3/4 20 20 500
1 25 24 600
1–1/4 32 28 700
1–1/2 40 30 750
2 50 32 800
2–1/2 65 36 900
3 80 40 1000
3–1/2 90 44 1100
4 100 48 1200
4–1/2 115 52 1300
5 125 56 1400
6 150 60 1500
For pipe over 60 inches, use 1 inch equals 25 mm

Proposed metric CSP diameter sizes

Proposed metric (mm) Current standard (inches)
150 6
200 8
250 10
300 12
375 15
450 18
525 21
600 24
675 27
750 30
825 33
(continued)
326 Appendix 1: Unit

(continued)
Proposed metric CSP diameter sizes
Proposed metric (mm) Current standard (inches)
900 36
1050 42
1200 48
1350 54
1500 60
1650 66
1800 72
1950 78
2100 84
2250 90
2400 96
2550 102
2700 108
2850 114
3000 120
3150 126
3300 132
3450 138
3600 144

Current (inches) Corrugation sizes proposed (mm)

2 2/3  1/2 68  13
31 76  25
51 125  25
3/4  3/4  7 1/2 19  19  191
3/4  1  11 1/2 19  25  292

Pipe wall thickness

Current gage Nominal thickness (inches) Proposed nominal thickness (mm)
16 0.064 1.6
14 0.079 2.0
12 0.109 2.8
10 0.138 3.5
8 0.168 4.3
Appendix 1: Unit 327

Pipe arch sizes

Corrugations Corrugations
inches (mm) inches (mm)
2 2/3  1/2 68  13 31&51 76  25 & 125  25
Span  Rise Span  Rise Span  Rise Span  Rise
17  13 425  325 53  41 1325  1025
21  15 525  375 60  46 1500  1150
24  18 600  450 66  51 1650  1275
28  20 700  500 73  55 1825  1375
35  24 875  600 81  59 2025  1475
42  29 1050  725 87  63 2175  1575
49  33 1225  825 95  67 2375  1675
57  38 1425  950 103  71 2575  1775
64  43 1600 x 1075 112  75 2800  1875
71  47 1775  1175 117  79 2925  1975
77  52 1925  1300 128  83 3200  2075
83  57 2075  1425 137  87 3425  2175
142  91 3550  2275
Note millimeters equal to inches 25. Assumed pipe diameters will be 25

Pipe arch sizes

Corrugations (inches) Corrugations (mm)
3/4  3/4  7 1/2 19  19  191
Span  Rise Span  Rise
20  16 500  400
23  19 575  475
27  21 675  525
33  26 825  650
40  31 1000  775
46  36 1150  900
53  41 1325  1025
60  46 1500  1150
66  51 1650  1275
73  55 1825  1375
81  59 2025  1475
87  63 2175  1575
95  67 2375  1675
Note millimeters equal to inches 25. Assumed pipe diameters will be 25
328 Appendix 1: Unit

Structural plate conversion factors

Structural plate dimensions
6  2 Corrugation
31 inch corner radius
Span (ft-in.) Rise (ft-in.) R (ft.) R (ft.)
13–3 9–4 6.68 16.05
14–11 10–2 7.48 18.98
16–6 11–0 8.29 21.93
18–1 11–10 9.09 24.98
19–8 12–8 9.90 28.04

Structural plate dimensions

152  51 Corrugation
787 mm corner radius (mm)
Span Rise R R
4039 2845 2036 4892
4547 3099 2280 5785
5029 3353 2527 6684
5512 3607 2771 7614
5994 3861 3018 8547

Structural plate thickness

Current specification Proposed
Gage Inches Millimeters
12 0.111 2.5
10 0.140 3.5
8 0.170 4.5
7 0.188 –
5 0.218 5.5
3 0.249 6.5
1 0.280 7.0
5/16 0.318 8.0
3/8 0.377 9.5
Appendix 2
Munitions and Dual-Use Items

Items, information, and software subject to US Export Control Laws and used in a
university environment are generally categorized on the following two lists:

US Munitions List (USML)—(ITAR)

Published by the US State Department in its International Traffic in Arms

Regulations (ITAR):
• Category I
Firearms, Close Assault Weapons, and Combat Shotguns
• Category II
Materials, Chemicals, Microorganisms, and Toxins
• Category III
Ammunition/Ordnance
• Category IV
Launch Vehicles, Guided Missiles, Ballistic Missiles, Rockets, Torpedoes,
Bombs, and Mines
• Category V
Explosives and Energetic Materials, Propellants, Incendiary Agents, and Their
Constituents
• Category VI
Vessels of War and Special Naval Equipment
• Category VII
Tanks and Military Vehicles
• Category VIII
Aircraft and Associated Equipment
• Category IX
Military Training Equipment
• Category X
Protective Personnel Equipment

© US Government (outside the USA) 2018 329

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7
330 Appendix 2: Munitions and Dual-Use Items

• Category XI
Military Electronics
• Category XII
Fire Control, Range Finder, Optical, Guidance, and Control Equipment
• Category XIII
Auxiliary Military Equipment
• Category XIV
Toxicological Agents, Including Chemical Agents, Biological Agents, and
Associated Equipment
• Category XV
Spacecraft Systems and Associated Equipment
• Category XVI
Nuclear Weapons, Design, and Testing Related Items
• Category XVII
Classified Articles, Technical Data, and Defense Services Not Otherwise
Enumerated
• Category XVIII
Directed Energy Weapons
• Category XX
Submersible Vessels, Oceanographic, and Associated Equipment

Commerce Control List (CCL)—(EAR)

Published by the US Commerce Department in its Export Administration

Regulations (EAR)
• Category 0
Nuclear Materials, Facilities and Equipment (and Miscellaneous Items)
• Category 1
Materials, Chemicals, Microorganisms, and Toxins
• Category 2
Materials Processing
• Category 3
Electronics Design, Development, and Production
• Category 4
Computers
• Category 5
Part 1: Telecommunications
Part 2: Information Security
• Category 6
Sensors and Lasers
• Category 7
Navigation and Avionics
Appendix 2: Munitions and Dual-Use Items 331

• Category 8
Marine
• Category 9
Propulsion Systems, Space Vehicles, and Related Equipment

Pathogens and Toxins

Department of Commerce dual-use export control-listed pathogens and toxins are
listed below. These pathogens and toxins are found on the Commerce Control List
(CCL) in Category 1 at ECCNs 1C351 through 1C360. Please note that export
controls also apply to genetic elements and genetically modified organisms that
contain DNA associated with the pathogenicity of these biological materials. Severe
civil and/or criminal penalties apply to international shipments without an export
license of ANY export controlled pathogen or genetic material containing the
controlled DNA.
You will need to contact Stanford’s Export Control Officer if your research
requires an export controlled pathogen or genetic material containing the controlled
DNA to be sent outside of the US so that an export license application can be
prepared. Export licenses take 4–6 weeks for approval, so please plan in advance.
Also note that the International Traffic in Arms Regulations (ITAR) controls
certain military-related toxins and pathogens at Category XIV of the US Munitions
List (USML). The ITAR treats as a defense article any “biological agent or bio-
logically derived substance specifically developed or modified to increase its
capability to produce casualties in humans or livestock or to degrade equipment or
damage crops.” These ITAR export control-listed biological materials will also
require an export license. Furthermore, foreign nationals may not access
ITAR-controlled biological materials or their disclosure-restricted technologies in
the US without government approval.
In the unlikely event that you need access to a disclosure-restricted ITAR
controlled biological material or its technology at Stanford, you must first contact
Steve Eisner as required by the RPH Chapter: Export Control before receipt.
A
African horse sickness virus
African swine fever virus
Andean potato latent virus (Potato Andean latent tymovirus)
Andes virus
Avian Influenza identified as having high pathogenicity

Toxins
Abrin
Aflatoxins
332 Appendix 2: Munitions and Dual-Use Items

B
Bacillus anthracis
Blue Tongue virus
Brucella abortus
Brucella melitensis
Brucella suis
Burkholderia mallei (Pseudomonas mallei)
Burkholderia pseudomallei

Toxins
Botulinum toxins

C
Chapare virus
Chikungunya virus
Chlamydophilia psittaci (Chlamydia psittaci)
Choclo virus
Clavibacter michiganensis subspecies sepedonicus (Corynebacterium
sepedonicum)
Clostridium Argentinense, botulinum neurotoxin producing strains (Clostricium
botulinum Type G)
Clostridium baratii, botulinum neurotoxin producing strains
Clostridium botulinum
Clostridium butyricum
Clostridium perfringens (epsilon toxin producing type)
Coccidioides immitis
Coccidioides posadasii
Cochliobolus miyabeanus (Helminthosporium oryzae)
Colletotrichum kahawae (Colleototrichum coffeanum var. virulans)
Congo-Crimean haemorrhagic fever virus
Coxiella burnetii

Toxins
Cholera toxin
Clostridium perfringens toxin
Conotoxins

D
Dengue fever virus
Dobrava-Belgrade virus

Toxins
Diacetoxyscirpenol toxin
Appendix 2: Munitions and Dual-Use Items 333

E
Eastern equine encephalitis virus
Ebola virus

F
Foot and Mouth Disease virus
Francisella tularensis

G
Goat Pox virus
Guanarito virus

H
Hantaan virus
Hendra virus

Toxins
HT-2 toxin

I
none listed

J
Japanese Encephalitis virus
Junin virus

K
Kyasanur Forest virus

L
Laguna Negra virus
Lassa fever virus
Louping Ill virus
Lujo virus
Lumpy Skin Disease virus
Lymphocytic choriomeningitis virus
Lyssa virus
334 Appendix 2: Munitions and Dual-Use Items

M
Machupo virus
Magnaporthea grisea (Pyricularia oryzae)
Marburg virus
Microcyclus ulei (Dothidella ulei)
Monkeypox virus
Murray Valley encephalitis virus
Mycoplasma capricolum subspecies capripneumonaie (strain F38)
Mycoplasma mycoides subspecies mycoides small colony (contagious bovine
pleuroneumo nia)

Toxins
Microcystin (Cyanginosin)
Modeccin toxin

N
Newcastle disease virus
Nipah virus

O
Omsk haemorrhagic fefer virus
Oropouche Virus

P
Peronosclerospora philippinensis (Peronosclerospora sacchari)
Peste des Petitis Ruminants virus
Phoma glycinicola (Pyrenochaeta glycines)
Porcine enterovirus type 9 (swine vesicular disease virus)
Porcine herpes virus (Aujeszky’s disease)
Potato spindle tuber viroid
Powassan virus
Puccinia Graminis (Puccinia graminis f. sp. Tritici)
Puccinia striiformis (Puccinia glumarum)

Q
none listed
Appendix 2: Munitions and Dual-Use Items 335

R
Ralstonia solanacearum Race 3, biovar 2
Rathayibacter toxicus
Reconstructed replication competent forms of the 1918 pandemic influenza
virus containing any portion of the coding regions of all eight gene sement
Rickettsia prowazekii
Rift Valley fever virus
Rinderpest virus
Rocio virus

Toxins
Ricin

S
Sabia virus
Salmonella typhi
SARS-associated coronavirus (SARS-CoV)
Sclerophthora rayssiae var.zeae
Seoul virus
Sheep Pox virus
Shigella dysenteriae
Sin Nombre virus
St. Louis encephalitis
Swine Fever virus (Hog cholera virus)
Synchytrium endobioticum

Toxins
Saxitoxin
Shiga toxin
Shiga toxin producing Escherichia coli (STEC) of serogroups 026, 045, 0103,
0104, 0111, 0121, 0145, 0157, and other shiga toxin producing serogoups
(EGEC or VTEC)
Staphylococcus aureus enterotoxins, hemolysin alpha toxin, and toxic shock
syndrome toxin (Staphylococcus enterotoxin F)

T
Teschen Disease virus
Thecaphora solani
Tick-borne encephalitis virus (Far Eastern Subtype)
Tick-borne encephalitis virus (Siberian Subtype)
Tilletia indica
336 Appendix 2: Munitions and Dual-Use Items

Toxins
T-2 toxin
Tetrodotoxin

U
None listed

V
Variola virus
Venezuelan Equine Encephalitis virus
Vesicular stomatitis virus
Vibrio cholerae

Toxins
Verotoxin and other Shiga-like ribosome inactivating proteins
Viscum Album Lectin 1 (Viscumin)
Volkensin toxin

W, X, Y, Z
Western Equine Encephalitis virus
Xanthmonas alibilineans
Xanthmonas axonopodis pv. Citri (Xanthomonas campestris pv. citri)
Xanthomonas oryzae pv. Oryzae (Pseudomonas campestris pv. Oryzae)
Yellow fever virus
Yersinia pestis
*AI viruses that have an intravenous pathogenicity index in 6-week-old chickens
greater than 1.2; AI viruses that cause at least 75% mortality in 4–8 week old
chickens infected intravenously; AI viruses of the H5 or H7 should be submitted to
further testing.
Chemicals, Chemical Agent Precursors, Propellants, Explosives, and Energetic
Materials
The ITAR controls certain military-related chemicals, chemical agent precursors,
propellants, explosives and energetic materials at Category V and Category XIV of
the US Munitions List (USML). In addition, under the provisions of the
International Chemical Weapons Convention, the United States may require special
declarations related to chemical shipments under either the ITAR or the EAR. For
your convenience, we've created this reference list.
Appendix 3
Chemical Weapons Convention (CWC)

Chemical Weapons Convention (CWC) Schedule 2 and 3 chemicals and families of

chemicals not controlled by ECCN 1C350 or by the Department of State under the
ITAR.
a. CWC Schedule 2 chemicals and mixtures containing Schedule 2 chemicals:
a:1. Toxic chemicals, as follows, and mixtures containing toxic chemicals:
a:1:a. PFIB: 1,1,3,3,3-Pentafluoro-2-(trifluoromethyl)-1-propene (C.A.S.
382-21-8) and mixtures in which PFIB constitutes more than 1% of
the weight of the mixture;
a:1:b. [RESERVED].
a:2. Precursor chemicals, as follows, and mixtures in which at least one of the
following precursor chemicals constitutes more than 10% of the weight of
the mixture:
a:2:a. Chemicals, except for those listed in Schedule 1, containing a phos-
phorus atom to which is bonded one methyl, ethyl, or propyl (normal
or iso) group but not further carbon atoms.
Note: 1C355.a.2.a does not control Fonofos: O-Ethyl S-phenyl ethylphospho-
nothiolothionate (C.A.S. 944-22-9).
a:2:b. FAMILY: N,N-Dialkyl (Me, Et, n-Pr or i-Pr) phosphoramidic dihalides;
a:2:c. FAMILY: Dialkyl (Me, Et, n-Pr or i-Pr) N,N-dialkyl (Me, Et, n-Pr, or
i-Pr)-phosphoramidates;
a:2:d. FAMILY: N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethyl-2-chlorides and
corresponding protonated salts;
a:2:e. FAMILY: N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethane-2-ols and
corresponding protonated salts;
Note: 1C355.a.2.e. does not control N,N-Dimethylaminoethanol and corre-
sponding protonated salts (C.A.S. 108-01-0) or N,N-Diethylaminoethanol and
corresponding protonated salts (C.A.S. 100-37-8).

© US Government (outside the USA) 2018 337

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7
338 Appendix 3: Chemical Weapons Convention (CWC)

a:2:f. FAMILY: N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethane-2-thiols and

corresponding protonated salts.

b. CWC Schedule 3 chemicals and mixtures containing Schedule 3 chemicals:

b:1. Toxic chemicals, as follows, and mixtures in which at least one of th fol-
lowing toxic chemicals constitutes 30% or more of the weight of the
mixture:
b:1:a. Phosgene: Carbonyl dichloride (C.A.S. 75-44-5);
b:1:b. Cyanogen chloride (C.A.S. 506-77-4);
b:1:c. Hydrogen cyanide (C.A.S. 74-90-8);
b:1:d. Chloropicrin: Trichloronitromethane (CAS 76-06-2).
b:2. Precursor chemicals, as follows, and mixtures in which at least one of the
following precursor chemicals constitutes 30% or more of the weight of the
mixture:
b:2:a. [RESERVED];
b:2:b. Methyldiethanolamine (C.A.S. 105-59-9).
Category V—Explosives and Energetic Materials, Propellants, Incendiary
Agents and Their Constituents
*(a) Explosives, and mixtures thereof:

(1) ADNBF (aminodinitrobenzofuroxan or 7-Amino

4,6-dinitrobenzofurazane-1-oxide) (CAS 97096.–78.–1);
(2) BNCP (cis-bis (5-nitrotetrazolato) tetra amine-cobalt (III) perchlorate) (CAS
117412.–28.–9);
(3) CL.–14 (diamino dinitrobenzofuroxan or
5,7-diamino-4,6-dinitrobenzofurazane-1-oxide) (CAS 117907.–74.–1);
(4) CL.–20 (HNIW or Hexanitrohexaazaisowurtzitane); (CAS 135285.–90-4);
chlathrates of CL.–20 (see paragraphs (g)(3) and (4) of this category);
(5) CP (2-(5-cyanotetrazolato) penta aminecobalt (III) perchlorate); (CAS
70247.–32.–4);
(6) DADE (1,1-diamino-2,2-dinitroethylene, FOX7);
(7) DDFP (1,4-dinitrodifurazanopiperazine);
(8) DDPO (2,6-diamino-3,5-dinitropyrazine-1-oxide, PZO); (CAS 194486.–77.–6);
(9) DIPAM (3,3′-Diamino-2,2′,4,4′,6,6′-hexanitrobiphenyl or dipicramide)
(CAS 17215.–44.–0);
(10) DNGU (DINGU or dinitroglycoluril) (CAS 55510.–04.–8);
Appendix 3: Chemical Weapons Convention (CWC) 339

(11) Furazans, as follows:

(i) DAAOF (diaminoazoxyfurazan);
(ii) DAAzF (diaminoazofurazan) (CAS 78644.–90.–3);
(12) HMX and derivatives (see paragraph (g)(5) of this category):
(i) HMX (Cyclotetramethylenetetranitramine; octahydro-1,3,5,7
tetranitro-1,3,5,7-tetrazine;
1,3,5,7-tetranitro-1,3,5,7-tetraza-cyclooctane; octogen, octogene)
(CAS 2691.41.–0);
(ii) Diflouroaminated analogs of HMX;
(iii) K.–55 (2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo [3,3,0]-octanone-3,
tetranitrosemiglycouril,or keto-bicyclic HMX) (CAS 130256-72.–3);
(13) HNAD (hexanitroadamantane) (CAS 143850.–71.–9);
(14) HNS (hexanitrostilbene) (CAS 20062.–22.–0);
(15) Imidazoles, as follows:
(i) BNNII (Octohydro-2,5-bis(nitroimino) imidazo [4,5-d]Imidazole);
(ii) DNI (2,4-dinitroimidazole) (CAS 5213.–49.–0);
(iii) FDIA (1-fluoro-2,4-dinitroimidazole);
(iv) NTDNIA (N-(2-nitrotriazolo)-2,4-dinitro-imidazole);
(v) PTIA (1-picryl-2,4,5-trinitroimidazole);
(16) NTNMH (1-(2-nitrotriazolo)-2-dinitromethylene hydrazine);
(17) NTO (ONTA or 3-nitro-1,2,4-triazol-5-one) (CAS 932.–64.–9);
(18) Polynitrocubanes with more than four nitro groups;
(19) PYX (2,6-Bis(picrylamino)-3,5-dinitropyridine) (CAS 38082.–89.–2);
(20) RDX and derivatives:
(i) RDX (cyclotrimethylenetrinitramine), cyclonite, T4, hexahydro-
1,3,5-trinitro-1,3,5-triazine,1,3,5-trinitro-1,3,5-triaza-cyclohexane, hex-
ogen, or hexogene) (CAS 121.–82.–4);
(ii) Keto-RDX (K.–6 or 2,4,6-trinitro-2,4,6-triazacyclohexanone (CAS
115029.–35.–1);
(21) TAGN (Triaminoguanidinenitrate) (CAS 4000.–16.–2);
(22) TATB (Triaminotrinitrobenzene) (CAS 3058.–38.–6) (see paragraph (g)(7)
of this category);
(23) TEDDZ (3,3,7,7-tetrabis(difluoroamine) octahydro-1,5-dinitro-1,5-diazocine;
(24) Tetrazoles, as follows:
(i) NTAT (nitrotriazol aminotetrazole);
(ii) NTNT (1-N-(2-nitrotriazolo)-4-nitrotetrazole);
(25) Tetryl (trinitrophenylmethylnitramine) (CAS 479.–45.–8);
(26) TNAD (1,4,5,8-tetranitro-1,4,5,8-tetraazadecalin) (CAS 135877-16.–6)(see
paragraph (g)(6) of this category);
340 Appendix 3: Chemical Weapons Convention (CWC)

(27) TNAZ (1,1,3-trinitroazetidine) (CAS 97645.–24.–4) (see paragraph (g)(2) of

this category);
(28) TNGU (SORGUYL or tetranitroglycoluril) (CAS 55510.–03.–7);
(29) TNP (1,4,5,8-tetranitro-pyridazino [4,5-d] pyridazine) (CAS 229176.–04.–9);
(30) Triazines, as follows:
(i) DNAM (2-oxy-4,6-dinitroamino-s-triazine) (CAS 19899.–80.–0);
(ii) NNHT (2-nitroimino-5-nitro-hexahydro-1,3,5 triazine) (CAS 130400.–
13.–4);
(31) Triazoles, as follows:
(i) 5-azido-2-nitrotriazole;
(ii) ADHTDN (4-amino-3,5-dihydrazino-1,2,4-triazole dinitramide)
(CAS 1614.–08.–0);
(iii) ADNT (1-amino-3,5-dinitro-1,2,4-triazole);
(iv) BDNTA ([Bis-dinitrotriazole]amine);
(v) DBT (3,3□-dinitro-5,5-bi-1,2,4-triazole) (CAS 30003.–46.–4);
(vi) DNBT (dinitrobistriazole) (CAS 70890.–46.–9);
(vii) NTDNA (2-nitrotriazole 5-dinitramide) (CAS 75393.–84.–9);
(viii) NTDNT (1-N-(2-nitrotriazolo) 3,5-dinitro-triazole);
(ix) PDNT (1-picryl-3,5-dinitrotriazole);
(x) TACOT (tetranitrobenzotriazolobenzotriazole) (CAS 25243.–36.–1);
(32) Any explosive not listed elsewhere in paragraph (a) of this category with a
detonation velocity exceeding 8700 m/s at maximum density or a detonation
pressure exceeding 34 Gpa (340 kbar).
(33) Other organic explosives not listed elsewhere in paragraph (a) of this cate-
gory yielding detonation pressures of 25 Gpa (250 kbar) or more that will
remain stable at temperatures of 523 K (250 °C) or higher for periods of
5 min or longer;
(34) Diaminotrinitrobenzene (DATB) (CAS 1630.–08.–6);
(35) Any other explosive not elsewhere identified in this category specifically
designed, modified, adapted, or configured (e.g., formulated) for military
application.

*(b) Propellants:

(1) Any United Nations (UN) Class 1.1 solid propellant with a theoretical specific
impulse (under standard conditions) of more than 250 s for non-metallized, or
270 s for metalized compositions;
(2) Any UN Class 1.3 solid propellant with a theoretical specific impulse (under
standard conditions) of more than 230 s for non-halogenized, or 250 s for
non-metallized compositions;
(3) Propellants having a force constant of more than 1200 kJ/Kg;
Appendix 3: Chemical Weapons Convention (CWC) 341

(4) Propellants that can sustain a steady-state burning rate more than 38 mm/s
under standard conditions (as measured in the form of an inhibited single
strand) of 6.89 Mpa (68.9 bar) pressure and 294 K (21 °C);
(5) Elastomer modified cast double based propellants with extensibility at maxi-
mum stress greater than 5% at 233 K (40 C);
(6) Any propellant containing substances listed in Category V;
(7) Any other propellant not elsewhere identified in this category specifically
designed, modified, adapted, or configured (e.g., formulated) for military
application.

(c) Pyrotechnics, fuels and related substances, and mixtures thereof:

(1) Alane (aluminum hydride)(CAS 7784.–21.–6);

(2) Carboranes; decaborane (CAS 17702.–41.–9); pentaborane and derivatives
thereof;
(3) Hydrazine and derivatives:
(i) Hydrazine (CAS 302.–01.–2) in concentrations of 70% or more (not
hydrazine mixtures specially formulated for corrosion control);
(ii) Monomethyl hydrazine (CAS 60.–34.–4);
(iii) Symmetrical dimethyl hydrazine (CAS 540.–73.–8);
(iv) Unsymmetrical dimethyl hydrazine (CAS 57.–14.–7);
(4) Liquid fuels specifically formulated for use by articles covered by
Categories IV, VI, and VIII;
(5) Spherical aluminum powder (CAS 7429.–90.–5) in particle sizes of 60
micrometers or less manufactured from material with an aluminum content of
99% or more;
(6) Metal fuels in particle form whether spherical, atomized, spheroidal, flaked
or ground, manufactured from material consisting of 99% or more of any of
the following:
(i) Metals and mixtures thereof:
(a) Beryllium (CAS 7440.–41.–7) in particle sizes of less than 60
micrometers;
(b) Iron powder (CAS 7439.–89.–6) with particle size of 3 m crome
ters or less produced by reduction of iron oxide with hydrogen;
(ii) Mixtures, which contain any of the following:
(a) Boron (CAS 7440.–42.–8) or boron carbide (CAS 12069.–32.–8)
fuels of 85% purity or higher and particle sizes of less than 60
micrometers;
(b) Zirconium (CAS 7440.–67.–7), magnesium (CAS 7439.–95.–4 or
alloys of these in particle sizes of less than 60 micrometers;
342 Appendix 3: Chemical Weapons Convention (CWC)

(iii) Explosives and fuels containing the metals or alloys listed in para-
graphs (c)(6)(i) and(c)(6)(ii) of this category whether or not the metals
or alloys are encapsulated in aluminum, magnesium, zirconium, or
beryllium;
(7) Pyrotechnics and pyrophoric materials specifically formulated for military
purposes to enhance or control the production of radiated energy in any part
of the IR spectrum.
(8) Titanium subhydride (TiHn) of stoichiometry equivalent to n = 0.65.–1.68;
(9) Military materials containing thickeners for hydrocarbon fuels specially
formulated for use in flame throwers or incendiary munitions; metal stearates
or palmates (also known as octol); and M1, M2 and M3 thickeners;
(10) Any other pyrotechnic, fuel and related substance and mixture thereof not
elsewhere identified in this category specifically designed, modified, adapted,
or configured (e.g., formulated) for military application.

(d) Oxidizers, to include:

(1) ADN (ammonium dinitramide or SR.–12) (CAS 140456.–78.–6);
(2) AP (ammonium perchlorate) (CAS 7790.–98.–9);
(3) BDNPN (bis,2,2-dinitropropylnitrate) (CAS 28464.–24.–6);
(4) DNAD (1,3-dinitro-1,3-diazetidine) (CAS 78246.–06.–7);
(5) HAN (Hydroxylammonium nitrate) (CAS 13465.–08.–2);
(6) HAP (hydroxylammonium perchlorate) (CAS 15588.–62.–2);
(7) HNF (Hydrazinium nitroformate) (CAS 20773.–28.–8);
(8) Hydrazine nitrate (CAS 37836.–27.–4);
(9) Hydrazine perchlorate (CAS 27978.–54.–7);
(10) Liquid oxidizers comprised of or containing inhibited red fuming nitric acid
(IRFNA) (CAS 8007.–58.–7) or oxygen diflouride;
(11) Perchlorates, chlorates, and chromates composited with powdered metal or
other high energy fuel components controlled by this category;
(12) Any other oxidizer not elsewhere identified in this category specifically
designed, modified, adapted, or configured (e.g., formulated) for military
application.

*(e) Binders, and mixtures thereof:

(1) AMMO (azidomethylmethyloxetane and its polymers) (CAS 90683.–29.–7)

(see paragraph (g)(1) of this category);
(2) BAMO (bisazidomethyloxetane and its polymers) (CAS 17607.–20.–4) (see
paragraph (g)(1)of this category);
(3) BTTN (butanetrioltrinitrate) (CAS 6659.–60.–5) (see paragraph (g)(8) of this
category);
Appendix 3: Chemical Weapons Convention (CWC) 343

(4) FAMAO (3-difluoroaminomethyl-3-azidomethyl oxetane) and its polymers;

(5) FEFO (bis-(2-fluoro-2,2-dinitroethyl)formal) (CAS 17003.–79.–1);
(6) GAP (glycidylazide polymer) (CAS 143178.–24.–9) and its derivatives;
(7) HTPB (hydroxyl terminated polybutadiene) with a hydroxyl functionality
equal to or greater than 2.2 and less than or equal to 2.4, a hydroxyl value of
less than 0.77 meq/g, and a viscosity at 30 °C of less than 47 poise (CAS
69102.–90.–5);
(8) NENAS (nitratoethylnitramine compounds) (CAS 17096.–47.–8, 85068-
73.–1 and 82486.–82.–6);
(9) Poly-NIMMO (poly nitratomethylmethyoxetane, poly-NMMO, (poly
[3-nitratomethyl-3-methyl oxetane]) (CAS 84051.–81.–0);
(10) Energetic monomers, plasticizers and polymers containing nitro, azido
nitrate, nitraza or difluoromaino groups specially formulated for military use;
(11) TVOPA 1,2,3-Tris [1,2-bis(difluoroamino) ethoxy]propane; tris vinoxy
propane adduct; (CAS 53159.–39.–0);
(12) Polynitrorthocarbonates;
(13) FPF.–1 (poly-2,2,3,3,4,4-hexafluoro pentane-1,5-diolformal) (CAS 376.–
90.–9);
(14) FPF.–3 (poly-2,4,4,5,5,6,6-heptafluoro-2-trifluoromethyl-3-oxaheptane-1,7-
diolformal);
(15) PGN (Polyglycidylnitrate or poly(nitratomethyl oxirane); poly-GLYN);
(CAS 27814.–48.–8);
(16) N-methyl-p-nitroaniline;
(17) Low (less than 10,000) molecular weight, alcohol-functionalized, poly
(epichlorohydrin); poly(epichlorohydrindiol); and triol;
(18) Bis(2,2-dinitropropyl) formal and acetal;
(19) Any other binder and mixture thereof not elsewhere identified in this cate-
gory specifically designed, modified, adapted, or configured (e.g., formu-
lated) for military application.

(f) Additives:
(1) Basic copper salicylate (CAS 62320.–94.–9);
(2) BHEGA (Bis-(2-hydroxyethyl)glycolamide) (CAS 17409.–41.–5);
(3) Ferrocene Derivatives:
(i) Butacene (CAS 125856.–62.–4);
(ii) Catocene (2,2-Bis-ethylferrocenyl propane) (CAS 37206.–42.–1);
(iii) Ferrocene carboxylic acids;
(iv) n-butyl-ferrocene (CAS 31904.–29.–7);
(4) Lead beta-resorcylate (CAS 20936.–32.–7);
(5) Lead citrate (CAS 14450.–60.–3);
(6) Lead-copper chelates of beta-resorcylate or salicylates (CAS 68411.–07.–4);
(7) Lead maleate (CAS 19136.–34.–6);
(8) Lead salicylate (CAS 15748.–73.–9);
344 Appendix 3: Chemical Weapons Convention (CWC)

(9) Lead stannate (CAS 12036.–31.–6);

(10) MAPO (tris-1-(2-methyl)aziridinyl phosphine oxide) (CAS 57.–39.–6);
BOBBA.–8 (bis(2-methyl aziridinyl) 2-(2-hydroxypropanoxy) propylamino
phosphine oxide); and other MAPO derivatives;
(11) Methyl BAPO (Bis(2-methyl aziridinyl) methylamino phosphine oxide)
(CAS 85068.–72.–0);
(12) (12) 3-Nitraza-1,5 pentane diisocyanate (CAS 7406.–61.–9);
(13) Organo-metallic coupling agents, specifically:
(i) Neopentyl[diallyl]oxy, tri [dioctyl] phosphatotitanate (CAS 103850.–
22.–2); also known as titanium IV, 2,2[bis 2-propenolato-methyl,
butanolato, tris (dioctyl) phosphato] (CAS 110438.– 25.–0), or LICA
12 (CAS 103850.–22.–2);
(ii) Titanium IV, [(2-propenolato-1) methyl, n-propanolatomethyl]
butanolato-1, tris(dioctyl)pyrophosphate, or KR3538;
(iii) Titanium IV, [2-propenolato-1)methyl, propanolatomethyl]
butanolato-1, tris(dioctyl) phosphate;
(14) Polyfunctional aziridine amides with isophthalic, trimesic (BITA or butylene
imine trimesamide), isocyanuric, or trimethyladipic backbone structures and
2-methyl or 2-ethyl substitutions on the aziridine ring and its polymers;
(15) Superfine iron oxide (Fe2O3 hematite) with a specific surface area more than
250 m2/g and an average particle size of 0.003 [micro]m or less (CAS 1309.–
37.–1);
(16) TEPAN (tetraethylenepentaamineacrylonitrile) (CAS 68412.–45.–3); cya-
noethylated polyamines and their salts;
(17) TEPANOL (Tetraethylenepentaamineacrylo-nitrileglycidol) (CAS 110445.–
33.–5); cyanoethylated polyamines adducted with glycidol and their salts;
(18) TPB (triphenyl bismuth) (CAS 603.–33.–8);
(19) PCDE (Polycyanodifluoroaminoethyleneoxide);
(20) BNO (Butadienenitrileoxide);
(21) Any other additive not elsewhere identified in this category specifically
designed, modified, adapted, or configured (e.g., formulated) for military
application.

(g) Precursors, as follows:

(1) BCMO (bischloromethyloxetane) (CAS 142173.–26.–0) (see paragraphs (e)
(1) and (2) of this category);
(2) Dinitroazetidine-t-butyl salt (CAS 125735.–38.–8) (see paragraph (a)(27) of
this category);
(3) HBIW (hexabenzylhexaazaisowurtzitane) (CAS 124782.–15.–6) (see para-
graph (a)(4) of this category);
(4) TAIW (tetraacetyldibenzylhexa-azaisowurtzitane) (see paragraph (a)(4) of this
category);
Appendix 3: Chemical Weapons Convention (CWC) 345

(5) TAT (1, 3, 5, 7-tetraacetyl-1, 3, 5, 7-tetraaza-cyclooctane) (CAS 41378.–98.–

7) (see paragraph (a)(12) of this category);
(6) Tetraazadecalin (CAS 5409.–42.–7) (see paragraph (a)(26) of this category);
(7) 1,3,5-trichorobenzene (CAS 108.–70.–3) (see paragraph (a)(22) of this
category);
(8) 1,2,4-trihydroxybutane (1,2,4-butanetriol) (CAS 3068.–00.–6) (see paragraph
(e)(3) of this category);
(i) The following interpretations explain and amplify the terms used in this
category and elsewhere in this subchapter.

(1) Category V contains explosives, energetic materials, propellants and

pyrotechnics and specially formulated fuels for aircraft, missile and naval
applications. Explosives are solid, liquid or gaseous substances or mixtures of
substances, which, in their primary, booster or main charges in warheads,
demolition or other military applications, are required to detonate.
(2) Paragraph (c)(6)(ii)(A) of this category does not control boron and boron
carbide enriched with boron-10 (20% or more of total boron-10 content.
(3) The resulting product of the combination of any controlled or non-controlled
substance compounded or mixed with any item controlled by this subchapter
is also subject to the controls of this category.

Note 1: To assist the exporter, an item has been categorized by the most
common use. Also, a reference has been provided to the related controlled
precursors (e.g., see paragraph (a)(12) of this category). Regardless of where the
item has been placed in the category, all exports are subject to the controls of
this subchapter.
Note 2: Chemical Abstract Service (CAS) registry numbers do not cover all the
substances and mixtures controlled by this category. The numbers are provided
as examples to assist the government agencies in the license review process and
the exporter when completing their
ECCN 1C350 Chemicals that may be used as precursors for toxic chemical
agents.
b. Australia Group-controlled precursor chemicals also identified as Schedule 2
chemicals under the CWC, as follows, and mixtures in which at least one of the
following chemicals constitutes 30% or more of the weight of the mixture:
b:1. (C.A.S. #7784-34-1) Arsenic trichloride;
b:2. (C.A.S. #76-93-7) Benzilic acid;
b:3. (C.A.S. #78-38-6) Diethyl ethylphosphonate;
b:4. (C.A.S. #15715-41-0) Diethyl methylphosphonite;
b:5. (C.A.S.#2404-03-7) Diethyl-N,N-dimethylphosphoroamidate;
b:6. (C.A.S. #5842-07-9) N,N-Diisopropyl-beta-aminoethane thiol;
346 Appendix 3: Chemical Weapons Convention (CWC)

b:7. (C.A.S. #4261-68-1) N,N-Diisopropyl-beta-aminoethyl chloride

hydrochloride;
b:8. (C.A.S. #96-80-0) N,N-Diisopropyl-beta-aminoethanol;
b:9. (C.A.S. #96-79-7), N,N-Diisopropyl-beta-aminoethyl chloride;
b:10. (C.A.S. #6163-75-3) Dimethyl ethylphosphonate;
b:11. (C.A.S. #756-79-6) Dimethyl methylphosphonate;
b:12. (C.A.S. #1498-40-4) Ethyl phosphonous dichloride [Ethyl phosphinyl di
chloride;
b:13. (C.A.S. #430-78-4) Ethyl phosphonus difluoride [Ethyl phosphinyl
difluoride];
b:14. (C.A.S. #1066-50-8) Ethyl phosphonyl dichloride;
b:15. [RESERVED]
b:16. [RESERVED]
b:17. [RESERVED]
b:18. (C.A.S. #464-07-3) Pinacolyl alcohol;
b:19. (C.A.S. #1619-34-7) 3-Quinuclidinol;
b:20. (C.A.S. #111-48-8) Thiodiglycol;
b:21. (C.A.S. #993-13-5) Methylphosphonic acid;
b:22. (C.A.S. #683-08-9) Diethyl methylphosphonate;
24. b.23. (C.A.S. #677-43-0) N,N-dimethylamino-phosphoryl dichloride;
b:24. (C.A.S. #676-98-2) Methylphosphonothioic dichloride.

c. Australia Group-controlled precursor chemicals also identified as Schedule 3

chemicals under the CWC, as follows, and mixtures in which at least one of
the following chemicals constitutes 30% or more of the weight of the
mixture:
c:1. (C.A.S. #762-04-9) Diethyl phosphite;
c:2. (C.A.S. #868-85-9) Dimethyl phosphate (dimethyl hydrogen phosphite);
c:3. (C.A.S. #10025-87-3) Phosphorus oxychloride;
c:4. (C.A.S. #10026-13-8) Phosphorus pentachloride;
c:5. (C.A.S. #7719-12-2) Phosphorus trichloride;
c:6. (C.A.S. #10025-67-9) Sulfur monochloride;
c:7. (C.A.S. #10545-99-0) Sulfur dichloride;
c:8. (C.A.S. #7719-09-7) Thionyl chloride;
c:9. (C.A.S. #102-71-6) Triethanolamine;
c:10. (C.A.S. #122-52-1) Triethyl phosphite;
c:11. (C.A.S. #121-45-9) Trimethyl phosphite
c:12. (C.A.S. #139-87-7) Ethyldiethanolamine.

d. Other Australia Group-controlled precursor chemicals not also identified as

Schedule 1, 2, or 3 chemicals under the CWC, as follows, and mixtures in
which at least one of the following chemicals constitutes 30% or more of the
weight of the mixture:
Appendix 3: Chemical Weapons Convention (CWC) 347

d:1. (C.A.S. #1341-49-7) Ammonium hydrogen fluoride;

d:2. (C.A.S. #107-07-3) 2-Chloroethanol;
d:3. (C.A.S. #100-37-8) N,N-Diethylaminoethanol;
d:4. (C.A.S. #108-18-9) Di-isopropylamine;
d:5. (C.A.S. #124-40-3) Dimethylamine;
d:6. (C.A.S. #506-59-2) Dimethylamine hydrochloride;
d:7. (C.A.S. #7664-39-3) Hydrogen fluoride;
d:8. (C.A.S. #3554-74-3) 3-Hydroxyl-1-methylpiperidine;
d:9. (C.A.S. #76-89-1) Methyl benzilate;
d:10. (C.A.S. #1314-80-3) Phosphorus pentasulfide;
d:11. (C.A.S. #75-97-8) Pinacolone;
d:12. (C.A.S. #151-50-8) Potassium cyanide;
d:13. (C.A.S. #7789-23-3) Potassium fluoride;
d:14. (C.A.S. #7789-29-9) Potassium bifluoride;
d:15. (C.A.S. #3731-38-2) 3-Quinuclidone;
d:16. (C.A.S. #1333-83-1) Sodium bifluoride;
d:17. (C.A.S. #143-33-9) Sodium cyanide;
d:18. (C.A.S. #7681-49-4) Sodium fluoride;
d:19. (C.A.S. #1313-82-2) Sodium sulfide;
d:20. (C.A.S. #637-39-8) Triethanolamine hydrochloride;
d:21. (C.A.S. #116-17-6) Tri-isopropyl phosphite;
d:22. (C.A.S. #2465-65-8) O,O-diethyl phosphorothioate;
d:23. (C.A.S. #298-06-6) O,O-diethyl phosphorodithioate;
d:24. (C.A.S. #16893-85-9) Sodium hexafluorosilicate.
Appendix 4
Chemical Weapons Convention Bulletin

News, Background and Comment on Chemical and Biological Warfare

Issues ISSUE NO. 21 SEPTEMBER 1993 Quarterly Journal of the Harvard Sussex
Program on CBW Armament and Arms Limitation
Guest Article by Dr. RJ Mathews 1–3

CWC Non-Signatory States 3

Progress in The Hague: Quarterly Review 4–9 Editorial comment: The AG and the
CWC 5 Forthcoming events 9.
News Chronology: May–August 1993 10–27 New Board Member 17 Obituary:
Charles Flowerree 22 Recent Publications 27–28 Particular chemicals or families of
chemicals have been placed on one of the three CWC schedules based on a number
of factors, including the risk that the particular chemical poses to the objectives of
the CWC, and, in the case of commercially produced chemicals, on the practicality
of subjecting the chemical to a particular monitoring regime. A major factor in the
development of these schedules has been the recognition that it would be
impractical, and in many cases unnecessary, to have a monitoring system that will
guarantee the non-diversion of every relevant chemical from industrial applications
to CW use. Instead, the system will focus on monitoring an appropriate range of
key chemicals, which will sustain confidence in the overall CWC regime.
Each Schedule is subdivided into Part A—Toxic Chemicals, and Part B—
Precursor Chemicals.
Schedule 1 contains chemicals that are deemed to pose a high risk to the pur-
poses of the CWC, but which have very limited, if any, commercial applications.
Part A includes nerve agents (including tabun, sarin and VX, and their homologues
or “family” members), blister agents (including sulphur mustard) and certain toxins.
Part B includes nerve agent precursors for binary chemical weapons. Each stat party
to the CWC will be permitted to produce and use Schedule 1 chemicals for
research, medical, pharmaceutical or protective purposes (for example, testing gas
masks) provided the types and quantities of the Schedule

© US Government (outside the USA) 2018 349

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7
350 Appendix 4: Chemical Weapons Convention Bulletin

1 chemicals are strictly limited to those which can be justified for such purposes.
In addition, the aggregate amount of such chemicals that a State Party may acquire
annually, or possess at any given time, must not exceed one tonne. The types of
facilities that are permitted to produce these chemicals are clearly defined in the
CWC text. These facilities will be required to make annual declarations of relevant
activities, and will be subject to international monitoring. Schedule 2 contains
chemicals that are deemed to pose a significant risk to the purposes of the CWC.
Part A contains toxic chemicals that could be used as chemical warfare agents (for
example, amiton, which was developed as a pesticide in the 1950s but found to be
too toxic for that purpose). Part B contains key precursors to chemicals in Schedule
1 or Schedule 2 Part A. Some of these chemicals have limited commercial appli-
cations. For example, thiodiglycol is used in the printing industry but is also a key
precursor which is readily converted into sulphur mustard. It has been agreed that
there will be no restrictions on the quantities of chemicals in Schedule 2 that a State
Party can produce, process or consume. However, facilities that produce, process or
consume chemicals in Schedule 2 in quantities above agreed thresholds will be
required to make annual declarations, and will be subject to international onsite
annual declarations, and will be subject to international onsite inspections.
Schedule 3 contains other chemicals that are considered to pose a risk to the
purposes of the CWC. Part A includes “dual purpose” toxic chemicals such as
phosgene (which was used as chemical weapon in World War 1, but which cur-
rently has large commercial applications in the production of a range of products
including plastics and pesticides). Part B includes other precursors for chemical
warfare agents, for example, trimethyl phosphite, which is a precursor for insecti-
cides and flame retardants, and also a precursor for nerve agents. It has been agreed
that there will be no restrictions on the quantities of chemicals in Schedule 3 that a
State Party can produce, process or consume. However, facilities that produce
chemicals in Schedule 3 in quantities above agreed thresholds will be required to
make annual declarations, and will be subject to international on-site inspections.
Comparison of the Lists
From the above discussion it can be appreciated that while the major focus of
concern of both the Australia Group and the CWC are the same CW agents, the
objectives are rather different. In particular, the objective of the AGL is to stop the
inadvertent supply of CW precursors to a small number of nations that have chosen
to produce chemical weapons. Thus, the AGL contains CW precursors but not CW
agents. On the other hand, the objective of the verification measures under the
CWC is to provide assurance to each State Party to the CWC that the other States
Parties to the CWC are complying with their obligations under the CWC, including
not to produce chemical weapons. Therefore, the CWC
Schedules include CW agents and their precursors. It is not surprising that many
of the individual precursor chemicals on the AGL are also covered under the CWC
schedules, either as an individually listed chemical or as a member of a family of
chemicals. However, because of the more limited and highly focussed nature of the
objectives of the AGL, some of the precursor chemicals which are early in the
Appendix 4: Chemical Weapons Convention Bulletin 351

production process and/or are widely produced in industry (and hence not con-
sidered suitable for effective monitoring under the CWC) have been included on the
AGL, because they are either known or suspected to have been sought for CW
purposes. Such precursors include:
• The fluoride chemicals (chemicals 14, 24, 41, 42, 43 and 44) for the pr duction
of sarin-family nerve agents;
• Early precursors for a number of CW agents, including sulphur mustard
(chemicals 15 and 50), tabun (chemicals 16, 20, 40 and 45), soman (chemical
39), VX (chemical 48), amiton (chemical 47) and certain psychochemical agents
(chemical 37).
The cyanide salts (chemicals 40 and 45) may also be used for the production of
hydrogen cyanide and cyanogen chloride, which were used as CW agents in WW1
and are covered by Schedule 3 of the CWC. It is interesting to note that two sulphur
mustard precursors (sulphur monochloride and sulphur dichloride) which were
listed in Schedule 3 of the CWC in 1986 were not CWCB 21 Page 2 September
1993 added to the AGL until June 1992. These chemicals were initially considered
for inclusion to the AGL in 1986. However, the information available to the AG at
that time was that CW proliferators were choosing to produce sulphur mustard by
the thiodiglycol process rather than the sulphur chloride/ethylene process. This
issue has been regularly reviewed by the AG, and the decision to add the two
chemicals to the AGL (chemicals 51 and 52) was made after information became
available indicating that the chemicals have recently been sought for CW purposes
(and openly advertised for that purpose by one company within a non-participating
country). It is also interesting to note that thionyl chloride (chemical 9), which was
on the original AGL of 40 chemicals 1986, was included Schedule 3 of the CWC
for the firs time in 1989. Thus the addition of chemicals to both the AGL and the
schedules of the CWC should be seen as
A dynamic process.
Australia Group Export Control List: Chemical Weapons Precursors Chemical
name and CAS number CWC schedule

1. thiodiglycol [111-48-8] 2B
2. phosphoryl chloride [10025-87-3] 3B
3. dimethyl methylphosphonate [756-79-6] 2B
4. methylphosphonyl difluoride (DF) [676-99-3] 1B
5. methylphosphonyl dichloride (DC) [676-97-1] 2B
6. dimethyl phosphite (DMP) [868-85-9] 3B
7. phosphorus trichloride [7719-12-2] 3B
8. trimethyl phosphite (TMP) [121-45-9] 3B
9. thionyl chloride [7719-09-7] 3B
10. 3-hydroxy-1-methylpiperidine [3554-74-3] –
352 Appendix 4: Chemical Weapons Convention Bulletin

11. 2-N,N-diisopropylaminoethyl chloride [96-79-7] 2B

12. 2-N,N-diisopropylaminoethyl mercaptan [5842-07-9] 2B
13. 3-quinuclidinol [1619-34-7] 2B
14. potassium fluoride [7789-23-3] –
15. 2-chloroethanol [107-07-3] –
16. dimethylamine [124-40-3] –
17. diethyl ethylphosphonate [78-38-6] 2B
18. diethyl N,N-dimethylphosphoramidate [2404-03-7] 2B
19. diethyl phosphite [762-04-9] 3B
20. dimethylamine hydrochloride [506-59-2] –
21. ethylphosphonous dichloride [1498-40-4] 2B
22. ethylphosphonyl dichloride [1066-50-8] 2B
23. ethylphosphonyl difluoride [753-98-0] 1B
24. hydrogen fluoride [7664-39-3] –
25. methyl benzilate [76-89-1] –
26. methylphosphonous dichloride [676-83-5] 2B
27. 2-N,N-diisopropylaminoethyl alcohol [96-80-0] 2B
28. 28 pinacolyl alcohol [464-07-3] 2B
29. ethyl 2-diisopropylaminoethyl methylphosphonite (QL) [57856-11-8] 1B
30. triethyl phosphite [122-52-1] 3B
31. arsenic trichloride [7784-34-1] 2B
32. benzilic acid [76-93-7] 2B
33. diethyl methylphosphonite [15715-41-0] 2B
34. dimethyl ethylphosphonate [6163-75-3] 2B
35. ethylphosphonous difluoride [430-78-4] 2B
36. methylphosphonous difluoride [753-59-3] 2B
37. 3-quinuclidone [3731-38-2] –
38. phosphorus pentachloride [10026-13-8] 3B
39. pinacolone [75-97-8] –
40. potassium cyanide [151-50-8] –
41. potassium bifluoride [7789-29-9] –
42. ammonium bifluoride [1341-49-7] –
43. sodium bifluoride [1333-83-1] –
44. sodium fluoride [7681-49-4] –
45. sodium cyanide [143-33-9] –
46. tris-ethanolamine [102-71-6] 3B
47. phosphorus pentasulphide [1314-80-3] –
48. diisopropylamine [108-18-9] –
49. 2-diethylaminoethanol [100-37-8] –
50. sodium sulphide [1313-82-2] –
51. sulphur monochloride [10025-67-9] 3B
52. sulphur dichloride [100545-99-0] 3B
53. tris-ethanolamine hydrochloride [637-39-8] –
54. 2-N,N-diisopropylaminoethyl chloride hydrochloride [4261-68-1] 2B
Appendix 4: Chemical Weapons Convention Bulletin 353

CWC Non-Signatory State (as of 1 September 1993)

• Angola
• Botswana
• Chad
• Djibouti
• Egypt
• Lesotho
• Libya
• Mozambique
• Sao Tome & Principe
• Somalia
• Sudan
• Swaziland
• Tanzania
• Bhutan
• Iraq
• Jordan
• Korea, North
• Lebanon
• Maldives
• Solomon Islands
• Syria
• Taiwan
• Vanuatu
• Bosnia-Hercegovina
• Macedonia, FYR of
• Turkmenistan
• Uzbekistan
• Yugoslavia
• Antigua & Barbuda
• Bahamas
• Barbados
• Belize
• Grenada
• Guyana
• Jamaica
• St Christopher & Nevis
• St Vincent & Grenadines
• Suriname
• Trinidad & Tobago
• Andorra
• Monaco
354 Appendix 4: Chemical Weapons Convention Bulletin

September 1993 Page 3 CWCB 21

• UN Storage Compatibility Groupings
Under the UNO system, there are 13 storage compatibility groupings, which
further categorize Class 1 explosives by their form or composition, ease of
ignition, and sensitivity to detonation.
• SCG A–Bulk-initiating explosives that have the necessary sensitivity to friction,
heat, or percussion (shock) to make them suitable for use as initiating elements
in an explosive train. A distinction is made between primary initiating explo-
sives and nonprimary initiating explosives. Examples of primary initiating
explosives are lead azide, lead styphnate, mercury fulminate, and tetracene.
Examples of nonprimary initiating explosives are dry forms of cyclotetram-
ethylene tetranitramine (HMX), cyclotrimethylene trinitramine (RDX), and
pentaerythritol tetranitrate (PETN).
• SCG B–Detonators and similar initiating devices that do not contain two or
more independent safety features. This group also consists of items that contain
initiating explosives designed to initiate or continue the functioning of an
explosives train. Examples are blasting caps, small arms primers, fuzes, and
detonators of all types.
• SCG C–Bulk propellants, propelling charges, and devices containing propellant
with or without their own means of initiation. Upon initiation, these items will
deflagrate, explode, or detonate. Examples are single-, double-, and triple-base
propellants; composite propellants; rocket motors (solid propellant); and
ammunition with inert projectiles.
• SCG D–High explosives (HE) and devices containing HE without their own
means of initiation and without a propelling charge. This group includes
explosives and ammunition that can be expected to explode or detonate when
any given item or component thereof is initiated. This group does not include
devices containing initiating explosives with independent safety features.
Examples are wet HMX, plastic-bonded explosives (explosives formulated with
a desensitizing plastic binder), trinitrotoluene (TNT), and black powder.
• SCG E–Explosives devices that lack their own means of initiation but contain
or have a propelling charge (other than one containing a flammable or hyper-
golic liquid). Examples are artillery ammunition, rockets, and guided missiles.
• SCG F–Explosives devices that have their own means of initiation and with or
without propelling charge. Examples are grenades, sounding devices, and
similar items with an in-line explosive train in the initiator.
• SCG G–Pyrotechnic materials and devices containing pyrotechnic materials.
Examples are devices that, when functioning, result in illumination, smoke, or
an incendiary, lachrymatory, or sound effect.
• SCG H–Ammunition containing both explosives and white phosphorus (WP) or
other pyrophoric material. Ammunition in this group contains fillers that are
spontaneously flammable when exposed to the atmosphere. Examples are WP,
plasticized white phosphorus (PWP), or other ammunition containing pyr-
ophoric material.
Appendix 4: Chemical Weapons Convention Bulletin 355

• SCG J–Ammunition containing both explosives and flammable liquids or gels.

Ammunition in this group contains flammable liquids or gels other than those
that are spontaneously flammable when exposed to water or the atmosphere.
Examples are liquid- or gel-filled incendiary ammunition, fuel-air explosive
(FAE) devices, flammable liquid-fueled missiles, and torpedoes.
• SCG K–Ammunition containing both explosives and toxic chemical agents.
Ammunition in this group contains chemicals specifically designed for inca-
pacitating effects more severe than lachrymation. Examples are artillery or
mortar ammunition (fuzed or unfuzed), grenades, and rockets or bombs filled
with a lethal or incapacitating chemical agent.
• SCG L–Explosives or ammunition not included in other SC/HC groups. This
group includes explosives or ammunition with characteristics that do not permit
storage with other similar or dissimilar materials. Examples are damaged or
suspect explosives devices or containers, explosives that have undergone severe
testing, fuel-air explosive devices, and water-activated devices. Also included
are experimental explosives, explosives of temporary interest, newly synthe-
sized compounds, new mixtures, and salvaged explosives, unless established as
being compatible with the original materials. Types of explosives in this group
presenting similar hazards may be stored together.
• SCG N–Hazard Division 1.6 ammunition containing only extremely insensitive
detonating substances (IEDS). Examples are bombs and warheads. If dissimilar
Group N munitions, such as MK 82 and MK 84 bombs, are mixed together and
have not been tested to assure nonpropagation, the mixed munitions are con-
sidered to be Hazard Division 1.2, Storage and Compatibility Group D, for
purposes of transportation and storage.
• SCG S–Explosives, explosives devices, or ammunition presenting no significant
hazard. Explosives ammunition, so designated or packed that, when in storage,
all hazardous explosives effects are confined and self-contained within the item
or package. Materials in this group are such that an incident that destroys all
items in a single pack will not be communicated to other packs. Examples are
thermal batteries, cable cutters, explosive actuators, and other ammunition items
packaged to meet the criteria of this group.

Group A–Initiating explosives (* indicates primary initiating explosives)

CL-20 (Hexanitrohexaazaisowurtzitane; dry)
CP (5-Cyanotetrazolpentaamine Cobalt III perchlorate)
HMX (Cyclotetramethylene tetranitramine; dry)
*Lead azide
*Lead styphnate
*Mercury fulminate
*Nitrocellulose (dry)
PETN (Pentaerythritol tetranitrate; dry)
RDX (Cyclotrimethylene trinitramine; dry)
356 Appendix 4: Chemical Weapons Convention Bulletin

*TATNB (Triazidotrinitrobenzene)
*Tetracene
Group B–Detonators and similar initiating devices
Blasting caps
Detonators (excluding EBW and slapper)
Explosive bolts
Fragmenting actuators
Ignitors
Low-energy initiators (LEIs)
MDF (mild detonating fuze) detonator assemblies
Pressure cartridges
Primers
Squibs
Group C–Bulk propellant, propellant charges, and devices containing
propellants with or without their own means of initiation
Smokeless powder
Pistol and rifle powder
Rocket-motor solid propellants
Group D–High explosives and devices containing explosives without their
own means of initiation (* indicates that classification may change
depending on nitrogen and moisture content. Contact Hazards Control
Department explosives safety personnel for additional guidance.)
Ammonium picrate
Baratol
Black Powder
Boracitol
Chemical lenses
CL-20 (Hexanitrohexaazaisowurtzitane; wet)
Compositions A, B, and C (all types)
Cyclotols (<85% RDX)
DATB (Diaminotrinitrobenzene)
Detasheet
Detonating cord (primacord or mild detonating fuze)
bis-Dinitropropyl adipate
bis-Dinitropropyl glutarate
bis-Dinitropropyl maleate
Dinitropropane
Dinitropropanol
Dinitropropyl acrylate monomer (DNPA)
Dinitroproply acrylate polymer (PDNPA)
EBW and slapper detonators
Elastomeric plastic bonded explosives
Appendix 4: Chemical Weapons Convention Bulletin 357

Explosive D
GAP (Glyceryl azide polymer)
HMX (Cyclotetramethylene tetranitramine; wet)
HMX/wax (formulated with at least 1% wax)
HNS (Hexanitrostilbene; wet or dry)
Linear-shaped charge
Methyl dinitropentanoate
Mild detonating fuze (MDF)
NG/TA (Nitroglycerine-triacetine)
*Nitrocellulose (wet)
Nitroguanidine (NQ)
Octol (<75% HMX)
Pentolite
PETN (Pentaerythritol tetranitrate; wet)
PETN/extrudable binder
PGN (Polyglycidyl nitrate)
Plane wave lenses (composed of SC/HC Group D explosives)
Plastic-bonded explosive, PBX (a SC/HC Group D formulated with a
desensitizing binder)
Potassium picrate
Primacord
RDX (Cyclotrimethylene trinitramine; wet)
Shaped charges (composed of SC/HC Group D explosives)
TATB (Triamino trinitrobenzene)
TATB/DATB mixtures
TEGDN (Triethylene glycol dinitrate)
Tetryl
TMETN (Trimethylolethane trinitrate)
TNAZ (Trinitoazetidine)
TNT (Trinitrotoluene)
Group E–Explosives devices without their own means of initiation and with
propelling charge
Artillery ammunition
Rockets (e.g., M66 LAW)
Group F–Explosives devices with detonators and detonating trains
assembled to the devices and with propelling charge
Grenades
Sounding devices
358 Appendix 4: Chemical Weapons Convention Bulletin

Group G–Pyrotechnic material and devices that produce an incendiary,

illumination, lachrymatory, smoke, or sound effect
Smoke pots/grenades
Flares
Incendiary ammunition
Group H–Ammunition containing both explosives and white phosphorus
(WP) or other pyrophoric material
White phosphorus
Plasticized white phosphorus
Group J–Ammunition containing both explosives and flammable liquids or
gels.
Liquid- or gel-filled incendiary ammunition
Fuel-air explosive (FAE) devices
Flammable liquid-fueled missiles
Torpedoes
Group K–Ammunition containing both explosives and toxic chemicals
Artillery or mortar ammunition (fuzed or unfuzed), grenades, rockets, or
bombs filled with a lethal or incapacitating agent
Group L–Explosives or other ammunition not included in other storage
compatibility groups
Damaged or suspect explosives devices or containers
Explosives that have undergone severe testing
Experimental explosives, explosives of temporary interest, newly synthe-
sized compounds, new mixtures, and some salvaged explosives
Group N–Hazard Class/Division 1.6 ammunition containing only extremely
insensitive detonating substances (EIDS)
Bombs
Warheads
Group S–Explosives, explosives devices, or ammunition presenting no sig-
nificant hazard
Propellant cartridge-actuated devices (which yield a nonfragmenting,
nonflame-producing controlled reaction). Examples include cable cutters,
cartridge-actuated valves, and linear actuators (e.g., dimple, piston, or bel-
lows motors)
Safety fuse
Most small arms ammunition below 50 caliber
Thermal batteries
Appendix 5
CAS RN Reportable Chemicals

ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA

1 (1,2‐Phenylenebis 23564‐06‐9 ☐ ☐ ☑ ☐ ☐ ☑
(iminocarbonothioyl)) biscarbamic acid
diethyl ester
2 (4‐Chloro‐2‐methylphenoxy) acetate 3653‐48‐3 ☐ ☑ ☑ ☐ ☐ ☑
sodium salt
3 (4‐Chloro‐2‐methylphenoxy) acetic 94‐74‐6 ☐ ☑ ☑ ☐ ☐ ☑
acid
4 apha.‐(2‐Chlorophenyl)‐.alpha.‐4‐ 60168‐88‐9 ☐ ☑ ☑ ☐ ☐ ☑
chlorophenyl)‐5‐pyrimidinemethanol
5 alpha.‐Butyl‐.alpha.‐(4‐chlorophenyl)‐ 88671‐89‐0 ☐ ☑ ☑ ☐ ☐ ☑
1H‐1,2,4‐triazole‐1‐propanenitrile
6 1-METHYL 1H‐TETRAZOLE 16681‐77‐9 ☑ ☐ ☐ ☐ ☐ ☑
7 1‐(2‐(2,4‐Dichlorophenyl)‐2‐(2‐ 35554‐44‐0 ☐ ☑ ☑ ☐ ☐ ☑
propenyloxy)ethyl)‐1H‐imidazole
8 1‐(2‐(2,4‐Dichlorophenyl)‐4‐propyl‐ 60207‐90‐1 ☐ ☑ ☑ ☐ ☐ ☑
1,3‐dioxolan‐2‐yl)‐methyl‐1H‐1,2,4,‐
triazol
9 1‐(3‐Chloroallyl)‐3,5,7‐triaza‐1‐ 4080‐31‐3 ☐ ☑ ☑ ☐ ☐ ☑
azoniaadamantane chloride
10 1‐(4‐Chlorophenoxy)‐3,3‐dimethyl‐1‐ 43121‐43‐3 ☐ ☑ ☑ ☐ ☐ ☑
(1H‐1,2,4‐triazol‐1‐yl)‐2‐butanone
11 1,1,2,2‐Tetrachloroethane 79‐34‐5 ☐ ☑ ☑ ☑ ☑ ☑
12 1,1,2‐Trichloroethane 79‐00‐5 ☐ ☑ ☑ ☑ ☑ ☑
13 1,1‐Dichloro‐1,2,2,3,3‐ 13474‐88‐9 ☐ ☑ ☑ ☐ ☑ ☑
pentafluoropropane
14 1,1‐Dichloro‐1,2,2‐trifluoroethane 812‐04‐4 ☐ ☑ ☑ ☐ ☑ ☑
15 1,1‐Dichloro‐1,2,3,3,3‐ 111512‐56‐2 ☐ ☑ ☑ ☐ ☑ ☑
pentafluoropropane
16 1,1‐Dichloro‐1‐fluoroethane 1717‐00‐6 ☐ ☑ ☑ ☐ ☑ ☑
17 1,1‐Dichloroethylene 75‐35‐4 ☑ ☑ ☑ ☑ ☐ ☑
18 1,1‐Dichloropropane 78‐99‐9 ☐ ☑ ☑ ☐ ☐ ☑
19 1,1‐Difluoroethane 75‐37‐6 ☑ ☑ ☑ ☐ ☐ ☑
20 1,1‐Difluoroethylene 75‐38‐7 ☑ ☑ ☑ ☐ ☐ ☑
21 1,2,3,4,6,7,8,9‐octachlorodibenzofuran 39001‐02‐0 ☐ ☑ ☑ ☐ ☐ ☑
22 1,2,3,4,6,7,8,9‐octachlorodibenzo‐p‐ 3268‐87‐9 ☐ ☑ ☑ ☐ ☐ ☑
dioxin
(continued)

© US Government (outside the USA) 2018 359

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7
360 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
23 1,2,3,4,6,7,8‐heptachlorodibenzofuran 67562‐39‐4 ☐ ☑ ☑ ☐ ☐ ☑
24 1,2,3,4,6,7,8‐heptachlorodibenzo‐p‐ 35822‐46‐9 ☐ ☑ ☑ ☐ ☐ ☑
dioxin
25 1,2,3,4,7,8,9‐heptachlorodibenzofuran 55673‐89‐7 ☐ ☑ ☑ ☐ ☐ ☑
26 1,2,3,4,7,8‐hexachlorodibenzofuran 70648‐26‐9 ☐ ☑ ☑ ☐ ☐ ☑
27 1,2,3,4,7,8‐hexachlorodibenzo‐p‐dioxin 39227‐28‐6 ☐ ☑ ☑ ☐ ☐ ☑
28 1,2,3,6,7,8‐hexachlorodibenzofuran 57117‐44‐9 ☐ ☑ ☑ ☐ ☐ ☑
29 1,2,3,6,7,8‐hexachlorodibenzo‐p‐dioxin 57653‐85‐7 ☐ ☑ ☑ ☐ ☐ ☑
30 1,2,3,7,8,9‐hexachlorodibenzofuran 72918‐21‐9 ☐ ☑ ☑ ☐ ☐ ☑
31 1,2,3,7,8,9‐hexachlorodibenzo‐p‐dioxin 19408‐74‐3 ☐ ☑ ☑ ☐ ☐ ☑
32 1,2,3,7,8‐pentachlorodibenzofuran 57117‐41‐6 ☐ ☑ ☑ ☐ ☐ ☑
33 1,2,3,7,8‐pentachlorodibenzo‐p‐dioxin 40321‐76‐4 ☐ ☑ ☑ ☐ ☐ ☑
34 1,2,3‐Trichloropropane 96‐18‐4 ☐ ☑ ☑ ☐ ☐ ☑
35 1,2,4,5‐Tetrachlorobenzene 95‐94‐3 ☐ ☑ ☑ ☐ ☐ ☑
36 1,2,4‐Trichlorobenzene 120‐82‐1 ☐ ☑ ☑ ☑ ☐ ☑
37 1,2,4‐Trimethylbenzene 95‐63‐6 ☐ ☑ ☑ ☐ ☐ ☑
38 1,2‐Bis(2‐chloroethylthio)ethane 3563‐36‐8 ☑ ☐ ☐ ☐ ☐ ☑
39 1,2‐Dibromo‐3‐chloropropane 96‐12‐8 ☐ ☑ ☑ ☑ ☑ ☑
40 1,2‐Dichloro‐1,1,2,3,3‐ 422‐44‐6 ☐ ☑ ☑ ☐ ☐ ☑
pentafluoropropane
41 1,2‐Dichloro‐1,1,2‐trifluoroethane 354‐23‐4 ☐ ☑ ☑ ☐ ☐ ☑
42 1,2‐Dichloro‐1,1,3,3,3‐ 431‐86‐7 ☐ ☑ ☑ ☐ ☐ ☑
pentafluoropropane
43 1,2‐Dichloro‐1,1‐difluoroethane 1649‐08‐7 ☐ ☑ ☑ ☐ ☐ ☑
44 1,2‐Dichloroethylene 156‐60‐5 ☐ ☑ ☑ ☐ ☐ ☑
45 1,2‐Dichloroethylene 540‐59‐0 ☐ ☑ ☑ ☐ ☐ ☑
46 1,2‐Diphenylhydrazine 122‐66‐7 ☐ ☑ ☑ ☑ ☐ ☑
47 1,2‐Epoxybutane 106‐88‐7 ☐ ☑ ☑ ☑ ☐ ☑
48 1,2‐Ethylenediamine 107‐15‐3 ☑ ☑ ☑ ☐ ☑ ☑
49 1,2‐Phenylenediamine 95‐54‐5 ☐ ☑ ☑ ☐ ☐ ☑
50 1,2‐Phenylenediamine dihydrochloride 615‐28‐1 ☐ ☑ ☑ ☐ ☐ ☑
51 1,3,5‐Trinitrobenzene 99‐35‐4 ☑ ☑ ☑ ☐ ☐ ☑
52 1,3,5‐Trinitrohexahydro‐s‐triazine 121‐82‐4 ☑ ☐ ☐ ☐ ☐ ☑
53 1,3‐Benzenedicarbonitrile, 2,4,5,6‐ 1897‐45‐6 ☐ ☑ ☑ ☐ ☐ ☑
tetrachloro‐
54 1,3‐Bis(2‐chloroethylthio)propane 63905‐10‐2 ☑ ☑ ☑ ☐ ☐ ☑
55 1,3‐Bis(methylisocyanate)cyclohexane 38661‐72‐2 ☐ ☑ ☑ ☐ ☐ ☑
56 1,3‐Butadiene 106‐99‐0 ☑ ☑ ☑ ☑ ☑ ☑
57 1,3‐Dichloro‐1,1,2,2,3‐ 507‐55‐1 ☐ ☑ ☑ ☐ ☐ ☑
pentafluoropropane
58 1,3‐Dichloro‐1,1,2,3,3‐ 136013‐79‐1 ☐ ☑ ☑ ☐ ☐ ☑
pentafluoropropane
59 1,3‐Dichlorobenzene 541‐73‐1 ☐ ☑ ☑ ☐ ☐ ☑
60 1,3‐Dichloropropane 142‐28‐9 ☐ ☑ ☑ ☐ ☐ ☑
61 1,3‐Dichloropropene 542‐75‐6 ☐ ☑ ☑ ☑ ☑ ☑
62 1,3‐Pentadiene, mixture of cis and trans 504‐60‐9 ☑ ☑ ☑ ☐ ☐ ☑
63 1,3‐Phenylene diisocyanate 123‐61‐5 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 361

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
64 1,3‐Phenylenediamine 108‐45‐2 ☐ ☑ ☑ ☐ ☐ ☑
65 1,3‐Propane sultone 1120‐71‐4 ☐ ☑ ☑ ☑ ☐ ☑
66 1,4‐Bis(2‐chloroethylthio)butane 142868‐93‐7 ☑ ☐ ☐ ☐ ☐ ☑
67 1,4‐Bis(methylisocyanate)cyclohexane 10347‐54‐3 ☐ ☑ ☑ ☐ ☐ ☑
68 1,4‐Cyclohexane diisocyanate 2556‐36‐7 ☐ ☑ ☑ ☐ ☐ ☑
69 1,4‐Dichlorobenzene(p) 106‐46‐7 ☐ ☑ ☑ ☑ ☐ ☑
70 1,4‐Dioxane (1,4‐Diethyleneoxide) 123‐91‐1 ☐ ☑ ☑ ☑ ☑ ☑
71 1,4‐Naphthoquinone 130‐15‐4 ☐ ☑ ☑ ☐ ☐ ☑
72 1,4‐Phenylene diisocyanate 104‐49‐4 ☐ ☑ ☑ ☐ ☐ ☑
73 1,4‐Phenylenediamine dihydrochloride 624‐18‐0 ☐ ☑ ☑ ☐ ☐ ☑
74 1,5‐bis[(2‐chloroethyl)thio]‐n‐pentane 142868‐94‐8 ☑ ☐ ☐ ☐ ☐ ☑
75 1,5‐Naphthalene diisocyanate 3173‐72‐6 ☐ ☑ ☑ ☐ ☐ ☑
76 1‐Acetyl‐2‐thiourea 591‐08‐2 ☐ ☑ ☑ ☐ ☐ ☑
77 1‐Amino‐2‐methylanthraquinone 82‐28‐0 ☐ ☑ ☑ ☐ ☐ ☑
78 1‐Bromo‐1‐(bromomethyl)‐1,3‐ 35691‐65‐7 ☐ ☑ ☑ ☐ ☐ ☑
propanedicarbonitrile
79 1‐Butene 106‐98‐9 ☑ ☑ ☑ ☐ ☐ ☑
80 1‐Butene 25167‐67‐3 ☑ ☑ ☑ ☐ ☐ ☑
81 1‐Butyne 107‐00‐6 ☑ ☑ ☑ ☐ ☐ ☑
82 1‐Chloro‐1,1,2,2‐tetrafluoroethane 354‐25‐6 ☐ ☑ ☑ ☐ ☐ ☑
83 1‐Chloro‐1,1‐difluoroethane 75‐68‐3 ☐ ☑ ☑ ☐ ☐ ☑
84 1H‐Azepine‐1 carbothioic acid, 2212‐67‐1 ☐ ☑ ☑ ☐ ☐ ☑
hexahydro‐S‐ethyl ester
85 1H‐TETRAZOLE 288‐94‐8 ☑ ☐ ☐ ☐ ☐ ☑
86 1H‐Tetrazole‐1‐acetic acid 21732‐17‐2 ☑ ☐ ☐ ☐ ☐ ☑
87 1‐Pentene 109‐67‐1 ☑ ☑ ☑ ☐ ☐ ☑
88 2‐((Ethoxyl((1‐methylethyl)amino] 25311‐71‐1 ☐ ☑ ☑ ☐ ☐ ☑
phosphinothioyl]oxy) benzoic acid 1‐
methy
89 2‐(1‐(Ethoxyimino) butyl)‐5‐(2‐ 74051‐80‐2 ☐ ☑ ☑ ☐ ☐ ☑
(ethylthio)propyl)‐3‐hydroxyl‐2‐
cyclohexen‐1‐
90 2‐(3,4‐Dichlorophenyl)‐4‐methyl‐1,2,4‐ 20354‐26‐1 ☐ ☑ ☑ ☐ ☐ ☑
oxadiazolidine‐3,5‐dione
91 2‐(4‐((6‐Chloro‐2‐benzoxazolylen)oxy) 66441‐23‐4 ☐ ☑ ☑ ☐ ☐ ☑
phenoxy)propanoic acid, ethyl ester
92 2‐(4‐((6‐Chloro‐2‐quinoxalinyl)oxy] 76578‐14‐8 ☐ ☑ ☑ ☐ ☐ ☑
phenoxy) propanoic acid ethyl ester
93 2‐(4‐(2,4‐Dichlorophenoxy)phenoxy) 51338‐27‐3 ☐ ☑ ☑ ☐ ☐ ☑
propanoic acid, methyl ester
94 2‐(4‐Methoxy‐6‐methyl‐1,3,5‐triazin‐2‐ 101200‐48‐0 ☐ ☑ ☑ ☐ ☐ ☑
yl)‐methylamino)carbonyl)amino)sulfo
95 2‐(Diisopropylamino)ethanol 96‐80‐0 ☑ ☐ ☐ ☐ ☐ ☑
96 2‐(Diisopropylamino)ethyl chloride 4261‐68‐1 ☑ ☐ ☐ ☐ ☐ ☑
hydrochloride
97 2,2,4‐Trimethylhexamethylene 16938‐22‐0 ☐ ☑ ☑ ☐ ☐ ☑
diisocyanate
98 2,2,4‐Trimethylpentane 540‐84‐1 ☐ ☑ ☑ ☑ ☐ ☑
99 2,2'‐Bioxirane 1464‐53‐5 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
362 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
100 2,2‐Dibromo‐3‐nitrilopropionamide 10222‐01‐2 ☐ ☑ ☑ ☐ ☐ ☑
101 2,2‐Dichloro‐1,1,1,3,3‐ 128903‐21‐9 ☐ ☑ ☑ ☐ ☐ ☑
pentafluoropropane
102 2,2‐Dichloro‐1,1,1‐trifluoroethane 306‐83‐2 ☐ ☑ ☑ ☐ ☐ ☑
103 2,2'‐Dichloro‐N‐methyldiethylamine 51‐75‐2 ☑ ☑ ☑ ☐ ☐ ☑
104 2,2‐Dichloropropionic acid 75‐99‐0 ☐ ☑ ☑ ☐ ☐ ☑
105 2,2‐Dimethyl‐3‐(2‐methyl‐1‐ 7696‐12‐0 ☐ ☑ ☑ ☐ ☐ ☑
propenyl)cyclopropanecarboxylic acid
(1,3,4,5,6,
106 2,2‐Dimethyl‐3‐(2‐methyl‐1‐ 26002‐80‐2 ☐ ☑ ☑ ☐ ☐ ☑
propenyl)cyclopropanecarboxylic acid
(3‐phenox
107 2,2‐Dimethylpropane 463‐82‐1 ☑ ☑ ☑ ☐ ☐ ☑
108 2,2'‐Thiodiethanol 111‐48‐8 ☑ ☐ ☐ ☐ ☐ ☑
109 2,3,4,6,7,8‐hexachlorodibenzofuran 60851‐34‐5 ☐ ☑ ☑ ☐ ☐ ☑
110 2,3,4,6‐Tetrachlorophenol 58‐90‐2 ☐ ☑ ☑ ☐ ☐ ☑
111 2,3,4,7,8‐pentachlorodibenzofuran 57117‐31‐4 ☐ ☑ ☑ ☐ ☐ ☑
112 2,3,4‐Trichlorophenol 15950‐66‐0 ☐ ☑ ☑ ☐ ☐ ☑
113 2,3,5‐Trichlorophenol 933‐78‐8 ☐ ☑ ☑ ☐ ☐ ☑
114 2,3,5‐Trimethylphenyl 2655‐15‐4 ☐ ☑ ☑ ☐ ☐ ☑
methylcarbamate
115 2,3,6‐Trichlorophenol 933‐75‐5 ☐ ☑ ☑ ☐ ☐ ☑
116 2,3,7,8‐tetrachlorodibenzofuran 51207‐31‐9 ☐ ☑ ☑ ☐ ☐ ☑
117 2,3,7,8‐Tetrachlorodibenzo‐p‐dioxin 1746‐01‐6 ☐ ☑ ☑ ☑ ☑ ☑
118 2,3,‐Dihydro‐5,6‐dimethyl‐1,4‐dithiin 55290‐64‐7 ☐ ☑ ☑ ☐ ☐ ☑
1,1,4,4‐tetraoxide
119 2,3‐Dichloro‐1,1,1,2,3‐ 422‐48‐0 ☐ ☑ ☑ ☐ ☐ ☑
pentafluoropropane
120 2,3‐Dichloropropene 78‐88‐6 ☐ ☑ ☑ ☐ ☐ ☑
121 2,4,4‐Trimethylhexamethylene 15646‐96‐5 ☐ ☑ ☑ ☐ ☐ ☑
diisocyanate
122 2,4,5‐T acid 93‐76‐5 ☐ ☑ ☑ ☐ ☐ ☑
123 2,4,5‐T amines 6369‐97‐7 ☐ ☑ ☑ ☐ ☐ ☑
124 2,4,5‐T amines 3813‐14‐7 ☐ ☑ ☑ ☐ ☐ ☑
125 2,4,5‐T amines 2008‐46‐0 ☐ ☑ ☑ ☐ ☐ ☑
126 2,4,5‐T amines 1319‐72‐8 ☐ ☑ ☑ ☐ ☐ ☑
127 2,4,5‐T amines 6369‐96‐6 ☐ ☑ ☑ ☐ ☐ ☑
128 2,4,5‐T esters 2545‐59‐7 ☐ ☑ ☑ ☐ ☐ ☑
129 2,4,5‐T esters 25168‐15‐4 ☐ ☑ ☑ ☐ ☐ ☑
130 2,4,5‐T esters 1928‐47‐8 ☐ ☑ ☑ ☐ ☐ ☑
131 2,4,5‐T esters 61792‐07‐2 ☐ ☑ ☑ ☐ ☐ ☑
132 2,4,5‐T esters 93‐79‐8 ☐ ☑ ☑ ☐ ☐ ☑
133 2,4,5‐T salts 13560‐99‐1 ☐ ☑ ☑ ☐ ☐ ☑
134 2,4,5‐TP esters 32534‐95‐5 ☐ ☑ ☑ ☐ ☐ ☑
135 2,4,5‐Trichlorophenol 95‐95‐4 ☐ ☑ ☑ ☑ ☐ ☑
136 2,4,6‐Trichlorophenol 88‐06‐2 ☐ ☑ ☑ ☑ ☐ ☑
137 2,4,6‐Trinitroaniline 26952‐42‐1 ☑ ☑ ☑ ☐ ☐ ☑
138 2,4,6‐Trinitroaniline 489‐98‐5 ☑ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 363

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
139 2,4,6‐Trinitroanisole 606‐35‐9 ☑ ☑ ☑ ☐ ☐ ☑
140 2,4,6‐Trinitrobenzenesulfonic acid 7432‐77‐1 ☑ ☑ ☑ ☐ ☐ ☑
dihydrate
141 2,4,6‐Trinitrobenzenesulfonic acid 37006‐19‐2 ☑ ☑ ☑ ☐ ☐ ☑
dihydrate
142 2,4,6‐Trinitrobenzenesulfonic acid dry 2508‐19‐2 ☑ ☑ ☑ ☐ ☐ ☑
143 2,4,6‐Trinitrobenzoic acid 129‐66‐8 ☑ ☑ ☑ ☐ ☐ ☑
144 2,4,6‐Trinitro‐m‐cresol 602‐99‐3 ☑ ☑ ☑ ☐ ☐ ☑
145 2,4,6‐Trinitrophenetole 4732‐14‐3 ☑ ☑ ☑ ☐ ☐ ☑
146 2,4,6‐Trinitrotoluene 118‐96‐7 ☑ ☑ ☑ ☐ ☐ ☑
147 2,4,7‐Trinitro‐9‐fluorenone 129‐79‐3 ☑ ☑ ☑ ☐ ☐ ☑
148 2,4‐D 2‐ethyl‐4‐methylpentyl ester 53404‐37‐8 ☐ ☑ ☑ ☐ ☐ ☑
149 2,4‐D 2‐ethylhexyl ester 1928‐43‐4 ☐ ☑ ☑ ☐ ☐ ☑
150 2,4‐D butoxyethyl ester 1929‐73‐3 ☐ ☑ ☑ ☐ ☐ ☑
151 2,4‐D butyl ester 94‐80‐4 ☐ ☑ ☑ ☐ ☐ ☑
152 2,4‐D chlorocrotyl ester 2971‐38‐2 ☐ ☑ ☑ ☐ ☐ ☑
153 2,4‐D Esters 94‐79‐1 ☐ ☑ ☑ ☐ ☐ ☑
154 2,4‐D Esters 53467‐11‐1 ☐ ☑ ☑ ☐ ☐ ☑
155 2,4‐D Esters 25168‐26‐7 ☐ ☑ ☑ ☐ ☐ ☑
156 2,4‐D Esters 94‐11‐1 ☐ ☑ ☑ ☐ ☐ ☑
157 2,4‐D Esters 1928‐38‐7 ☐ ☑ ☑ ☐ ☐ ☑
158 2,4‐D Esters 1928‐61‐6 ☐ ☑ ☑ ☐ ☐ ☑
159 2,4‐D Esters 1320‐18‐9 ☐ ☑ ☑ ☐ ☐ ☑
160 2,4‐D sodium salt 2702‐72‐9 ☐ ☑ ☑ ☐ ☐ ☑
161 2,4‐D, salts and esters 94‐75‐7 ☐ ☑ ☑ ☑ ☐ ☑
162 2,4‐DB 94‐82‐6 ☐ ☑ ☑ ☐ ☐ ☑
163 2,4‐Diaminoanisole 615‐05‐4 ☐ ☑ ☑ ☐ ☐ ☑
164 2,4‐Diaminoanisole sulfate 39156‐41‐7 ☐ ☑ ☑ ☐ ☐ ☑
165 2,4‐Dichlorophenol 120‐83‐2 ☐ ☑ ☑ ☐ ☐ ☑
166 2,4'‐Diisocyanatodiphenyl sulfide 75790‐87‐3 ☐ ☑ ☑ ☐ ☐ ☑
167 2,4‐Dimethylphenol 105‐67‐9 ☐ ☑ ☑ ☐ ☐ ☑
168 2,4‐Dinitrophenol 51‐28‐5 ☐ ☑ ☑ ☑ ☐ ☑
169 2,4‐Dinitrotoluene 121‐14‐2 ☐ ☑ ☑ ☑ ☐ ☑
170 2,4‐DP 120‐36‐5 ☐ ☑ ☑ ☐ ☐ ☑
171 2,4‐Toluene diamine 95‐80‐7 ☐ ☑ ☑ ☑ ☑ ☑
172 2,5‐Cyclohexadiene‐1,4‐dione, 2,3,5‐ 68‐76‐8 ☐ ☑ ☑ ☐ ☐ ☑
tris(1‐aziridinyl)‐
173 2,5‐Dinitrophenol 329‐71‐5 ☐ ☑ ☑ ☐ ☐ ☑
174 2,6‐Dichlorophenol 87‐65‐0 ☐ ☑ ☑ ☐ ☐ ☑
175 2,6‐Dinitrophenol 573‐56‐8 ☐ ☑ ☑ ☐ ☐ ☑
176 2,6‐Dinitrotoluene 606‐20‐2 ☐ ☑ ☑ ☐ ☐ ☑
177 2‐Acetylaminofluorene 53‐96‐3 ☐ ☑ ☑ ☑ ☑ ☑
178 2‐Aminoanthraquinone 117‐79‐3 ☐ ☑ ☑ ☐ ☐ ☑
179 2‐Butene 107‐01‐7 ☑ ☑ ☑ ☐ ☐ ☑
180 2‐Butene, 1,4‐dichloro‐ 764‐41‐0 ☐ ☑ ☑ ☐ ☐ ☑
181 2‐Chloro‐1,1,1,2‐tetrafluoroethane 2837‐89‐0 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
364 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
182 2‐Chloro‐1,1,1‐trifluoroethane 75‐88‐7 ☐ ☑ ☑ ☐ ☐ ☑
183 2‐Chloro‐1,3,5‐trinitrobenzene 88‐88‐0 ☑ ☐ ☐ ☐ ☐ ☑
184 2‐Chloro‐1‐propene 557‐98‐2 ☑ ☑ ☑ ☐ ☐ ☑
185 2‐Chloro‐6‐(trichloromethyl)pyridine 1929‐82‐4 ☐ ☑ ☑ ☐ ☐ ☑
186 2‐Chloroacetophenone 532‐27‐4 ☐ ☑ ☑ ☑ ☐ ☑
187 2‐Chloroethyl vinyl ether 110‐75‐8 ☐ ☑ ☑ ☐ ☐ ☑
188 2‐Chloroethylchloromethylsulfide 2625‐76‐5 ☑ ☐ ☐ ☐ ☐ ☑
189 2‐Chloro‐N‐(((4‐methoxy‐6‐methyl‐ 64902‐72‐3 ☐ ☑ ☑ ☐ ☐ ☑
1,3,5‐triazin‐2‐yl)amino]carbonyl)
benzene
190 2‐Chloro‐N‐(1‐methylethyl)‐N‐ 1918‐16‐7 ☐ ☑ ☑ ☐ ☐ ☑
phenylacetamide
191 2‐Chloronaphthalene 91‐58‐7 ☐ ☑ ☑ ☐ ☐ ☑
192 2‐Chlorophenol 95‐57‐8 ☐ ☑ ☑ ☐ ☐ ☑
193 2‐Cyclohexyl‐4,6‐dinitrophenol 131‐89‐5 ☐ ☑ ☑ ☐ ☐ ☑
194 2‐Methoxyethanol 109‐86‐4 ☐ ☑ ☑ ☐ ☐ ☑
195 2‐Methyl‐1‐butene 563‐46‐2 ☑ ☑ ☑ ☐ ☐ ☑
196 2‐Methylaziridine 75‐55‐8 ☑ ☑ ☑ ☑ ☐ ☑
197 2‐Methylpropane 75‐28‐5 ☑ ☑ ☑ ☐ ☐ ☑
198 2‐Methylpropene 115‐11‐7 ☑ ☑ ☑ ☐ ☐ ☑
199 2‐Methylpyridine 109‐06‐8 ☐ ☑ ☑ ☐ ☐ ☑
200 2‐Nitrophenol 88‐75‐5 ☐ ☑ ☑ ☐ ☐ ☑
201 2‐Nitropropane 79‐46‐9 ☐ ☑ ☑ ☑ ☑ ☑
202 2‐PENTENE,(E)‐ 646‐04‐8 ☑ ☑ ☑ ☐ ☐ ☑
203 2‐PENTENE,(Z)‐ 627‐20‐3 ☑ ☑ ☑ ☐ ☐ ☑
204 2‐Propyl methylphosphonochloridate 1445‐76‐7 ☑ ☐ ☐ ☐ ☐ ☑
205 3‐((Ethylamino) 31218‐83‐4 ☐ ☑ ☑ ☐ ☐ ☑
methoxyphosphinothioyl)oxy)‐2‐
butenoic acid, 1‐methylethyl
206 3‐(2,2‐Dichloroethenyl)‐2,2‐ 52645‐53‐1 ☐ ☑ ☑ ☐ ☐ ☑
dimethylcyclopropane carboxylic acid
(3‐phenox
207 3‐(2,4‐Dichloro‐5‐(1‐methylethoxy) 19666‐30‐9 ☐ ☑ ☑ ☐ ☐ ☑
phenyl)‐5‐(1,1‐dimethylethyl)‐1,3,4‐
oxadi
208 3‐(2‐Chloro‐3,3,3‐trifluoro‐1‐ 68085‐85‐8 ☐ ☑ ☑ ☐ ☐ ☑
propenyl)‐2,2‐
dimethylcyclopropanecarboxylic a
209 3‐(3,5‐Dichlorophenyl)‐5‐ethenyl‐5‐ 50471‐44‐8 ☐ ☑ ☑ ☐ ☐ ☑
methyl‐2,4‐oxazolidinedione
210 3,3‐Dichloro‐1,1,1,2,2‐ 422‐56‐0 ☐ ☑ ☑ ☐ ☐ ☑
pentafluoropropane
211 3,3‐Dichlorobenzidene 91‐94‐1 ☐ ☑ ☑ ☑ ☑ ☑
212 3,3'‐Dichlorobenzidine dihydrochloride 612‐83‐9 ☐ ☑ ☑ ☐ ☐ ☑
213 3,3'‐Dichlorobenzidine sulfate 64969‐34‐2 ☐ ☑ ☑ ☐ ☐ ☑
214 3,3‐Dimethoxybenzidine 119‐90‐4 ☐ ☑ ☑ ☑ ☐ ☑
215 3,3'‐Dimethoxybenzidine‐4,4'‐ 91‐93‐0 ☐ ☑ ☑ ☐ ☐ ☑
diisocyanate
216 3,3'‐Dimethyl benzidine 119‐93‐7 ☐ ☑ ☑ ☑ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 365

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
217 3,3‐Dimethyl‐2‐butanol 464‐07‐3 ☑ ☐ ☐ ☐ ☐ ☑
218 3,3'‐Dimethyl‐4,4'‐diphenylene 91‐97‐4 ☐ ☑ ☑ ☐ ☐ ☑
diisocyanate
219 3,3'‐Dimethylbenzidine dihydrochloride 612‐82‐8 ☐ ☑ ☑ ☐ ☐ ☑
220 3,3'‐Dimethylbenzidine dihydrofluoride 41766‐75‐0 ☐ ☑ ☑ ☐ ☐ ☑
221 3,3'‐Dimethyldiphenylmethane‐4,4'‐ 139‐25‐3 ☐ ☑ ☑ ☐ ☐ ☑
diisocyanate
222 3,4,5‐Trichlorophenol 609‐19‐8 ☐ ☑ ☑ ☐ ☐ ☑
223 3,4‐Dinitrotoluene 610‐39‐9 ☐ ☑ ☑ ☐ ☐ ☑
224 3,6‐Dichloro‐2‐methoxybenzoic acid, 1982‐69‐0 ☐ ☑ ☑ ☐ ☐ ☑
sodium salt
225 3‐Chloro‐1,1,1‐trifluoropropane 460‐35‐5 ☐ ☑ ☑ ☐ ☐ ☑
226 3‐Chloropropionitrile 542‐76‐7 ☐ ☑ ☑ ☐ ☐ ☑
227 3‐Iodo‐2‐propynyl butylcarbamate 55406‐53‐6 ☐ ☑ ☑ ☐ ☐ ☑
228 3‐Methyl‐1‐butene 563‐45‐1 ☑ ☑ ☑ ☐ ☐ ☑
229 3‐Methylcholanthrene 56‐49‐5 ☐ ☑ ☑ ☐ ☐ ☑
230 3‐Quinuclidinol 1619‐34‐7 ☑ ☐ ☐ ☐ ☐ ☑
231 4‐(Dipropylamino)‐3,5‐ 19044‐88‐3 ☐ ☑ ☑ ☐ ☐ ☑
dinitrobenzenesulfonamide
232 4,4¬‐Methylenedianiline 101‐77‐9 ☐ ☑ ☑ ☑ ☐ ☑
233 4,4'‐Diisocyanatodiphenyl ether 4128‐73‐8 ☐ ☑ ☑ ☐ ☐ ☑
234 4,4‐Methylene bis(2‐chloroaniline) 101‐14‐4 ☐ ☑ ☑ ☑ ☐ ☑
235 4,4'‐Methylenebis(N,N‐dimethyl) 101‐61‐1 ☐ ☑ ☑ ☐ ☐ ☑
benzenamine
236 4,6‐Dinitro‐o‐cresol, and salts 534‐52‐1 ☐ ☑ ☑ ☑ ☐ ☑
237 4‐Aminoazobenzene 60‐09‐3 ☐ ☑ ☑ ☐ ☐ ☑
238 4‐Aminobiphenyl 92‐67‐1 ☐ ☑ ☑ ☑ ☑ ☑
239 4‐Aminopyridine 504‐24‐5 ☐ ☑ ☑ ☐ ☐ ☑
240 4‐Bromophenyl phenyl ether 101‐55‐3 ☐ ☑ ☑ ☐ ☐ ☑
241 4‐Chloro‐5‐(methylamino)‐2‐[3‐ 27314‐13‐2 ☐ ☑ ☑ ☐ ☐ ☑
(trifluoromethyl)phenyl]‐3(2H)‐
pyridazinone
242 4‐Chloro‐alpha‐(1‐methylethyl) 51630‐58‐1 ☐ ☑ ☑ ☐ ☐ ☑
benzeneacetic acid cyano(3‐
phenoxyphenyl)m
243 4‐Chloro‐o‐toluidine, hydrochloride 3165‐93‐3 ☐ ☑ ☑ ☐ ☐ ☑
244 4‐Chlorophenyl phenyl ether 7005‐72‐3 ☐ ☑ ☑ ☐ ☐ ☑
245 4‐Methyldiphenylmethane‐3,4‐ 75790‐84‐0 ☐ ☑ ☑ ☐ ☐ ☑
diisocyanate
246 4‐Nitrobiphenyl 92‐93‐3 ☐ ☑ ☑ ☐ ☐ ☑
247 4‐Nitrophenol 100‐02‐7 ☐ ☑ ☑ ☑ ☑ ☑
248 5‐(2‐Chloro‐4‐(trifluoromethyl) 72178‐02‐0 ☐ ☑ ☑ ☑ ☐ ☑
phenoxy)‐N‐methylsulfonyl)‐2‐
nitrobenzamide
249 5‐(Aminomethyl)‐3‐isoxazolol 2763‐96‐4 ☐ ☑ ☑ ☐ ☐ ☑
250 5‐(Phenylmethyl)‐3‐furanyl)methyl— 10453‐86‐8 ☐ ☑ ☑ ☐ ☐ ☑
2,2‐dimethyl‐3‐(2‐methyl‐1‐
propenyl)cycl
251 5,7‐Dinitro‐1,2,3‐benzoxadiazole 87‐31‐0 ☑ ☐ ☐ ☐ ☐ ☑
(continued)
366 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
252 5‐Chloro‐3‐(1,1‐dimethylethyl)‐6‐ 5902‐51‐2 ☐ ☑ ☑ ☐ ☐ ☑
methyl‐2,4(1H,3H)‐pyrimidinedione
253 5‐Nitrobenzotriazole 2338‐12‐7 ☑ ☐ ☐ ☐ ☐ ☑
254 5‐Nitro‐o‐anisidine 99‐59‐2 ☐ ☑ ☑ ☐ ☐ ☑
255 7,12‐Dimethylbenz[a]anthracene 57‐97‐6 ☐ ☑ ☑ ☐ ☐ ☑
256 7H‐Dibenzo(c,g)carbazole 194‐59‐2 ☐ ☑ ☑ ☐ ☐ ☑
257 Abamectin 71751‐41‐2 ☐ ☑ ☑ ☐ ☐ ☑
258 Acenaphthene 83‐32‐9 ☐ ☑ ☑ ☐ ☐ ☑
259 ACENAPHTHENE, 5‐NITRO‐ 602‐87‐9 ☐ ☐ ☐ ☐ ☑ ☑
260 Acenaphthylene 208‐96‐8 ☐ ☑ ☑ ☐ ☐ ☑
261 Acephate 30560‐19‐1 ☐ ☑ ☑ ☐ ☐ ☑
262 Acetaldehyde 75‐07‐0 ☑ ☑ ☑ ☑ ☐ ☑
263 Acetaldehyde, trichloro‐ 75‐87‐6 ☐ ☑ ☑ ☐ ☐ ☑
264 Acetamide 60‐35‐5 ☐ ☑ ☑ ☑ ☐ ☑
265 ACETAMIDE, N‐(4‐(5‐NITRO‐2‐ 531‐82‐8 ☐ ☐ ☐ ☐ ☑ ☑
FURYL)‐2‐THIAZOLYL)‐
266 ACETAMIDE, THIO‐ 62‐55‐5 ☐ ☑ ☑ ☐ ☑ ☑
267 Acetic acid 64‐19‐7 ☐ ☑ ☑ ☐ ☐ ☑
268 ACETIC ACID, METHOXY((l‐OXO‐ 77402‐03‐0 ☐ ☐ ☐ ☐ ☑ ☑
2‐PROPENYL)AMINO)‐, METHYL
ESTER
269 ACETIC ACID, NITRILOTRI‐ 139‐13‐9 ☐ ☑ ☑ ☐ ☑ ☑
270 Acetic anhydride 108‐24‐7 ☐ ☑ ☑ ☐ ☐ ☑
271 Acetone 67‐64‐1 ☑ ☑ ☑ ☐ ☐ ☑
272 Acetone thiosemicarbazide 1752‐30‐3 ☐ ☑ ☑ ☐ ☐ ☑
273 Acetonitrile 75‐05‐8 ☐ ☑ ☑ ☑ ☐ ☑
274 ACETONITRILE, HYDROXY‐ 107‐16‐4 ☐ ☑ ☑ ☐ ☑ ☑
275 ACETONITRILE, PHENYL‐ 140‐29‐4 ☐ ☑ ☑ ☐ ☑ ☑
276 ACETOPHENETIDIDE, p‐ 62‐44‐2 ☐ ☑ ☑ ☐ ☑ ☑
277 Acetophenone 98‐86‐2 ☐ ☑ ☑ ☑ ☐ ☑
278 Acetyl bromide 506‐96‐7 ☑ ☑ ☑ ☐ ☐ ☑
279 Acetyl chloride 75‐36‐5 ☑ ☑ ☑ ☐ ☐ ☑
280 Acetyl iodide 507‐02‐8 ☑ ☐ ☐ ☐ ☐ ☑
281 Acetylene 74‐86‐2 ☑ ☑ ☑ ☐ ☐ ☑
282 Ac ifluorfen,sodium salt 62476‐59‐9 ☐ ☑ ☑ ☐ ☐ ☑
283 Acrolein 107‐02‐8 ☑ ☑ ☑ ☑ ☑ ☑
284 Acrylamide 79‐06‐1 ☐ ☑ ☑ ☑ ☑ ☑
285 Acrylic acid 79‐10‐7 ☐ ☑ ☑ ☑ ☐ ☑
286 ACRYLIC ACID, 2‐ 2439‐35‐2 ☐ ☐ ☐ ☐ ☑ ☑
(DIMETHYLAMINO)ETHYL ESTER
287 Acrylonitrile 107‐13‐1 ☑ ☑ ☑ ☑ ☑ ☑
288 Acryloyl chloride 814‐68‐6 ☑ ☑ ☑ ☐ ☐ ☑
289 Adipic acid 124‐04‐9 ☐ ☑ ☑ ☐ ☐ ☑
290 Adiponitrile 111‐69‐3 ☐ ☑ ☑ ☐ ☐ ☑
291 a‐Hydroxyisobutyronitrile 75‐86‐5 ☑ ☑ ☑ ☐ ☑ ☑
292 Alachlor 814‐68‐6 ☐ ☑ ☑ ☐ ☐ ☑
293 Aldicarb 116‐06‐3 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 367

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
294 Aldicarb sulfone 1646‐88‐4 ☐ ☑ ☑ ☐ ☐ ☑
295 Aldrin 309‐00‐2 ☐ ☑ ☑ ☐ ☐ ☑
296 Allene 463‐49‐0 ☑ ☑ ☑ ☐ ☐ ☑
297 Allyl alcohol 107‐18‐6 ☑ ☑ ☑ ☐ ☐ ☑
298 Allyl chloride 107‐05‐1 ☐ ☑ ☑ ☑ ☐ ☑
299 Allylamine 107‐11‐9 ☑ ☑ ☑ ☐ ☑ ☑
300 ALLYLTRICHLOROSILANE 107‐37‐9 ☑ ☐ ☐ ☐ ☐ ☑
301 alpha‐Endosulfan 959‐98‐8 ☐ ☑ ☑ ☐ ☐ ☑
302 alpha‐BHC 319‐84‐6 ☐ ☑ ☑ ☐ ☐ ☑
303 Aluminum (fume or dust) 3012‐65‐5 ☐ ☑ ☑ ☐ ☐ ☑
304 Aluminum bromide 7727‐15‐3 ☑ ☐ ☐ ☐ ☐ ☑
305 Aluminumchloride 7446‐70‐0 ☑ ☐ ☐ ☐ ☐ ☑
306 Aluminum oxide(fibrous forms) 3012‐65‐5 ☐ ☑ ☑ ☐ ☐ ☑
307 Aluminum phosphide 20859‐73‐8 ☑ ☑ ☑ ☐ ☐ ☑
308 Aluminum sulfate 10043‐01‐3 ☐ ☑ ☑ ☐ ☐ ☑
309 ALUMINUM, 1779‐25‐5 ☐ ☐ ☐ ☐ ☑ ☑
CHLORODIISOBUTYL‐
310 Ametryn 834‐12‐8 ☐ ☑ ☑ ☐ ☐ ☑
311 Aminopterin 54‐62‐6 ☐ ☑ ☑ ☐ ☐ ☑
312 Amiton 78‐53‐5 ☑ ☑ ☑ ☐ ☐ ☑
313 Amiton oxalate 3734‐97‐2 ☐ ☑ ☑ ☐ ☐ ☑
314 Amitraz 33089‐61‐1 ☐ ☑ ☑ ☐ ☐ ☑
315 Ammonia gas 7664‐41‐7 ☑ ☑ ☑ ☐ ☐ ☑
316 Ammonium acetate 631‐61‐8 ☐ ☑ ☑ ☐ ☐ ☑
317 Ammonium benzoate 1863‐63‐4 ☐ ☑ ☑ ☐ ☐ ☑
318 Ammonium bicarbonate 1066‐33‐7 ☐ ☑ ☑ ☐ ☐ ☑
319 Ammonium bichromate 7789‐09‐5 ☐ ☑ ☑ ☐ ☐ ☑
320 Ammonium bifluoride 1341‐49‐7 ☐ ☑ ☑ ☐ ☐ ☑
321 Ammonium bisulfite 10192‐30‐0 ☐ ☑ ☑ ☐ ☐ ☑
322 Ammonium carbamate 1111‐78‐0 ☐ ☑ ☑ ☐ ☐ ☑
323 Ammonium carbonate 506‐87‐6 ☐ ☑ ☑ ☐ ☐ ☑
324 Ammonium chloride 12125‐02‐9 ☐ ☑ ☑ ☐ ☐ ☑
325 Ammonium chromate 7788‐98‐9 ☐ ☑ ☑ ☐ ☐ ☑
326 Ammonium citrate, dibasic 3012‐65‐5 ☐ ☑ ☑ ☐ ☐ ☑
327 Ammonium fluoborate 13826‐83‐0 ☐ ☑ ☑ ☐ ☐ ☑
328 Ammonium fluoride 12125‐01‐8 ☐ ☑ ☑ ☐ ☐ ☑
329 Ammonium hydroxide 1336‐21‐6 ☐ ☑ ☑ ☐ ☐ ☑
330 Ammonium nitrate 6484‐52‐2 ☑ ☐ ☐ ☐ ☐ ☑
331 Ammonium oxalate 6009‐70‐7 ☐ ☑ ☑ ☐ ☐ ☑
332 Ammonium oxalate 14258‐49‐2 ☐ ☑ ☑ ☐ ☐ ☑
333 Ammonium oxalate 5972‐73‐6 ☐ ☑ ☑ ☐ ☐ ☑
334 Ammonium perchlorate 7790‐98‐9 ☑ ☐ ☐ ☐ ☐ ☑
335 Ammonium picrate, <10% water 131‐74‐8 ☑ ☑ ☑ ☐ ☐ ☑
336 Ammonium silicofluoride 16919‐19‐0 ☐ ☑ ☑ ☐ ☐ ☑
337 Ammonium sulfamate 7773‐06‐0 ☐ ☑ ☑ ☐ ☐ ☑
338 AMMONIUM SULFATE 7783‐20‐2 ☐ ☐ ☐ ☐ ☑ ☑
(continued)
368 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
339 Ammonium sulfide 12135‐76‐1 ☐ ☑ ☑ ☐ ☐ ☑
340 Ammonium sulfite 10196‐04‐0 ☐ ☑ ☑ ☐ ☐ ☑
341 Ammonium tartrate 14307‐43‐8 ☐ ☑ ☑ ☐ ☐ ☑
342 Ammonium tartrate 3164‐29‐2 ☐ ☑ ☑ ☐ ☐ ☑
343 Ammonium thiocyanate 1762‐95‐4 ☐ ☑ ☑ ☐ ☐ ☑
344 Ammonium vanadate 7803‐55‐6 ☐ ☑ ☑ ☐ ☐ ☑
345 Amphetamine 300‐62‐9 ☐ ☑ ☑ ☐ ☐ ☑
346 Amyl acetate 628‐63‐7 ☐ ☑ ☑ ☐ ☐ ☑
347 Amyltrichlorosilane 107‐72‐2 ☑ ☐ ☐ ☐ ☐ ☑
348 ANALINE,((5‐CHLORO‐8‐ 303‐47‐9 ☐ ☐ ☐ ☐ ☑ ☑
HYDROXY‐3‐METHYL‐ l‐OXO‐7‐
ISOCHROMANYL) CAR
349 Anilazine 101‐05‐3 ☐ ☑ ☑ ☐ ☐ ☑
350 Aniline 62‐53‐3 ☐ ☑ ☑ ☑ ☐ ☑
351 Aniline, 2,4,6‐trimethyl‐ 88‐05‐1 ☐ ☑ ☑ ☐ ☐ ☑
352 ANILINE, 4,4'‐OXYDI‐ 101‐80‐4 ☐ ☑ ☑ ☐ ☑ ☑
353 ANILINE, 4,4'‐THIODI‐ 139‐65‐1 ☐ ☑ ☑ ☐ ☑ ☑
354 ANILINE, P‐CHLORO 106‐47‐8 ☐ ☑ ☑ ☐ ☑ ☑
355 ANISIDINE, 5‐METHYL‐,o‐ 120‐71‐8 ☐ ☑ ☑ ☐ ☑ ☑
356 Anthracene 120‐12‐7 ☐ ☑ ☑ ☐ ☐ ☑
357 ANTHRACENEDIONE, 1,4,5,8‐ 2475‐45‐8 ☐ ☐ ☑ ☐ ☑ ☑
TETRAAMINO‐,
358 ANTHRAQUINONE, 1,8‐ 117‐10‐2 ☐ ☐ ☑ ☐ ☑ ☑
DIHYDROXY‐
359 ANTHRAQUINONE, 2‐METHYL‐1‐ 129‐15‐7 ☐ ☐ ☑ ☐ ☑ ☑
NITRO‐
360 Antimony 7440‐36‐0 ☐ ☑ ☑ ☐ ☐ ☑
361 Antimony hydride 7803‐52‐3 ☑ ☐ ☐ ☐ ☐ ☑
362 ANTIMONY OXIDE 1309‐64‐4 ☐ ☑ ☑ ☐ ☑ ☑
363 Antimony pentachloride 7647‐18‐9 ☐ ☑ ☑ ☐ ☐ ☑
364 Antimony potassium 28300‐74‐5 ☐ ☑ ☑ ☐ ☐ ☑
365 Antimony tribromide 7789‐61‐9 ☐ ☑ ☑ ☐ ☐ ☑
366 Antimony trichloride 10025‐91‐9 ☐ ☑ ☑ ☐ ☐ ☑
367 Antimony trifluoride 7783‐56‐4 ☐ ☑ ☑ ☐ ☐ ☑
368 Antimony(V) fluoride 7783‐70‐2 ☑ ☑ ☑ ☐ ☐ ☑
369 Antimycin A 1397‐94‐0 ☐ ☑ ☑ ☐ ☐ ☑
370 ANTU 86‐88‐4 ☐ ☑ ☑ ☐ ☐ ☑
371 Aroclor 1016 12674‐11‐2 ☐ ☑ ☑ ☐ ☐ ☑
372 Aroclor 1221 11104‐28‐2 ☐ ☑ ☑ ☐ ☐ ☑
373 Aroclor 1232 11141‐16‐5 ☐ ☑ ☑ ☐ ☐ ☑
374 Aroclor 1242 53469‐21‐9 ☐ ☑ ☑ ☐ ☐ ☑
375 Aroclor 1248 12672‐29‐6 ☐ ☑ ☑ ☐ ☐ ☑
376 Aroclor 1254 11097‐69‐1 ☐ ☑ ☑ ☐ ☐ ☑
377 Aroclor 1260 11096‐82‐5 ☐ ☑ ☑ ☐ ☐ ☑
378 ARSENIC 7440‐38‐2 ☐ ☑ ☑ ☐ ☑ ☑
379 Arsenic acid 1327‐52‐2 ☐ ☑ ☑ ☐ ☐ ☑
380 Arsenic acid 7778‐39‐4 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 369

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
381 Arsenic disulfide 1303‐32‐8 ☐ ☑ ☑ ☐ ☐ ☑
382 Arsenic pentoxide 1303‐28‐2 ☐ ☑ ☑ ☐ ☐ ☑
383 Arsenic trioxide 1327‐53‐3 ☐ ☑ ☑ ☐ ☐ ☑
384 Arsenic trisulfide 1303‐33‐9 ☐ ☑ ☑ ☐ ☐ ☑
385 Arsenic (III) chloride 7784‐34‐1 ☑ ☑ ☑ ☐ ☐ ☑
386 Arsine 7784‐42‐1 ☑ ☑ ☑ ☐ ☐ ☑
387 Asbestos 1332‐21‐4 ☐ ☑ ☑ ☑ ☐ ☑
388 Auramine 492‐80‐8 ☐ ☑ ☑ ☐ ☐ ☑
389 AZEPIN‐2‐ONE, HEXAHYDRO‐, 2H- 105‐60‐2 ☐ ☐ ☐ ☐ ☑ ☑
390 Azinphos‐ethyl 2642‐71‐9 ☐ ☑ ☑ ☐ ☐ ☑
391 Azinphos‐methyl 86‐50‐0 ☐ ☑ ☑ ☐ ☐ ☑
392 AZIRINO(2',3'3,4)PYRROLO(1,2‐a) 50‐07‐7 ☐ ☑ ☑ ☐ ☑ ☑
INDOLE‐4,7‐DIONE,CARBAMATE
(ESTER)
393 AZOBENZENE 1103‐33‐3 ☐ ☐ ☐ ☐ ☑ ☑
394 Barban 101‐27‐9 ☐ ☑ ☑ ☐ ☐ ☑
395 Barium 7440‐39‐3 ☐ ☑ ☑ ☐ ☐ ☑
396 BARIUM AZIDE (wet) 18810‐58‐7 ☑ ☐ ☐ ☐ ☐ ☑
397 Barium cyanide 542‐62‐1 ☐ ☑ ☑ ☐ ☐ ☑
398 Bendiocarb 22781‐23‐3 ☐ ☑ ☑ ☐ ☐ ☑
399 Bendiocarb phenol 22961‐82‐6 ☐ ☑ ☑ ☐ ☐ ☑
400 Benfluralin 1861‐40‐1 ☐ ☑ ☑ ☐ ☐ ☑
401 Benomyl 17804‐35‐2 ☐ ☑ ☑ ☐ ☐ ☑
402 BENZ(A)ANTHRACENE 56‐55‐3 ☐ ☑ ☑ ☐ ☑ ☑
403 Benz[c]acridine 225‐51‐4 ☐ ☑ ☑ ☐ ☐ ☑
404 Benzamide 55‐21‐0 ☐ ☑ ☑ ☐ ☐ ☑
405 Benzamide, 3,5‐dichloro‐N‐(1,1‐ 23950‐58‐5 ☐ ☑ ☑ ☐ ☐ ☑
dimethyl‐2‐propynyl
406 Benzenamine, 3‐(trifluoromethyl)‐ 98‐16‐8 ☐ ☑ ☑ ☐ ☐ ☑
407 BENZENAMINE, 4‐((4‐ 569‐61‐9 ☐ ☐ ☐ ☐ ☑ ☑
AMINOPHENYL) (4‐IMINO‐2,5‐
CYCLOHEXADIEN‐ 1‐ YLIDE
408 Benzenamine, N‐phenyl‐, hexanitro 35860‐31‐2 ☑ ☐ ☐ ☐ ☐ ☑
derivative
409 Benzene (including benzene from 71‐43‐2 ☐ ☑ ☑ ☑ ☑ ☑
gasoline)
410 BENZENE, (DICHLOROMETHYL)‐ 98‐87‐3 ☐ ☑ ☑ ☐ ☑ ☑
411 Benzene, 1‐(chloromethyl)‐4‐nitro‐ 100‐14‐1 ☐ ☑ ☑ ☐ ☐ ☑
412 Benzene, 1,1'‐(1,2‐Ethenediyl)‐Bis 20062‐22‐0 ☑ ☐ ☐ ☐ ☐ ☑
2,4,6‐Trinitro‐
413 BENZENE, 1,3‐BIS(l‐ 28178‐42‐9 ☐ ☐ ☐ ☐ ☑ ☑
METHYLETHYL)‐2‐ISOCYANATO
414 Benzene, 2,4‐dichloro‐1‐(4‐ 1836‐75‐5 ☐ ☑ ☑ ☐ ☐ ☑
nitrophenoxy)‐
415 BENZENE, 4‐ALLYL‐1,2‐ 94‐59‐7 ☐ ☑ ☑ ☐ ☑ ☑
(METHYLENEDIOXY)‐
416 Benzeneamine, N‐hydroxy‐N‐nitroso, 135‐20‐6 ☐ ☑ ☑ ☐ ☐ ☑
ammonium salt
(continued)
370 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
417 Benzenearsonic acid 98‐05‐5 ☐ ☑ ☑ ☐ ☐ ☑
418 Benzeneethanamine, alpha,alpha‐ 122‐09‐8 ☐ ☑ ☑ ☐ ☐ ☑
dimethyl‐
419 Benzenemethanol, 4‐chloro‐.alpha.‐4‐ 115‐32‐2 ☐ ☑ ☑ ☐ ☐ ☑
chlorophenyl)‐.alpha.‐(trichloromethyl)
420 Benzenesulfonyl chloride 98‐09‐9 ☐ ☑ ☑ ☐ ☐ ☑
421 BENZENETHIOL 108‐98‐5 ☐ ☑ ☑ ☐ ☑ ☑
422 Benzidine 92‐87‐5 ☐ ☑ ☑ ☑ ☑ ☑
423 BENZIDINE, 3,3'‐DIMETHOXY‐, 20325‐40‐0 ☐ ☑ ☑ ☐ ☑ ☑
DIHYDROCHLORIDE
424 Benzilic acid 76‐93‐7 ☑ ☐ ☐ ☐ ☐ ☑
425 Benzimidazole, 4,5‐dichloro‐2‐ 3615‐21‐2 ☐ ☑ ☑ ☐ ☐ ☑
(trifluoromethyl)‐
426 Benzo(a)phenanthrene 218‐01‐9 ☐ ☑ ☑ ☐ ☐ ☑
427 Benzo(j)fluoranthene 205‐82‐3 ☐ ☑ ☑ ☐ ☐ ☑
428 Benzo(k)fluoranthene 207‐08‐9 ☐ ☑ ☑ ☐ ☐ ☑
429 Benzo(rst)pentaphene 189‐55‐9 ☐ ☑ ☑ ☐ ☐ ☑
430 Benzo[a]pyrene 50‐32‐8 ☐ ☑ ☑ ☐ ☐ ☑
431 Benzo[b]fluoranthene 205‐99‐2 ☐ ☑ ☑ ☐ ☐ ☑
432 Benzo[g,h,i]perylene 191‐24‐2 ☐ ☑ ☑ ☐ ☐ ☑
433 Benzoic acid 65‐85‐0 ☐ ☑ ☑ ☐ ☐ ☑
434 Benzoic acid , 5‐(2‐chloro‐4‐ 77501‐63‐4 ☐ ☑ ☑ ☐ ☐ ☑
(trifluoromethyl)phenoxy)‐2‐nitro‐, 2‐
ethoxy‐1‐m
435 Benzonitrile 100‐47‐0 ☐ ☑ ☑ ☐ ☐ ☑
436 Benzotrichloride 98‐07‐7 ☐ ☑ ☑ ☑ ☑ ☑
437 Benzoyl chloride 98‐88‐4 ☐ ☑ ☑ ☐ ☐ ☑
438 Benzoyl peroxide 94‐36‐0 ☐ ☑ ☑ ☐ ☐ ☑
439 Benzyl chloride 100‐44‐7 ☐ ☑ ☑ ☑ ☑ ☑
440 Beryllium 7440‐41‐7 ☐ ☑ ☑ ☐ ☐ ☑
441 Beryllium chloride 7787‐47‐5 ☐ ☑ ☑ ☐ ☐ ☑
442 Beryllium fluoride 7787‐49‐7 ☐ ☑ ☑ ☐ ☐ ☑
443 Beryllium nitrate 13597‐99‐4 ☐ ☑ ☑ ☐ ☐ ☑
444 Beryllium nitrate 7787‐55‐5 ☐ ☑ ☑ ☐ ☐ ☑
445 BERYLLIUM SULFATE, 7787‐56‐6 ☐ ☐ ☐ ☐ ☑ ☑
TETRAHYDRATE (114)
446 beta‐Endosulfan 33213‐65‐9 ☐ ☑ ☑ ☐ ☐ ☑
447 beta‐BHC 319‐85‐7 ☐ ☑ ☑ ☐ ☐ ☑
448 beta‐Propiolactone 57‐57‐8 ☐ ☑ ☑ ☑ ☑ ☑
449 Bicyclo[2.2.1]heptane‐2‐carbonitrile, 5‐ 15271‐41‐7 ☐ ☑ ☑ ☐ ☐ ☑
chloro‐6‐((((methylamino)carbonyl)ox
450 Bifenthrin 82657‐04‐3 ☐ ☑ ☑ ☐ ☐ ☑
451 Biphenyl 92‐52‐4 ☐ ☑ ☑ ☑ ☐ ☑
452 BIPHENYLOL, 2‐ 90‐43‐7 ☐ ☑ ☑ ☐ ☑ ☑
453 Bis(2‐chloro‐1‐methylethyl)ether 108‐60‐1 ☐ ☑ ☑ ☐ ☐ ☑
454 Bis(2‐chloroethoxy) methane 111‐91‐1 ☐ ☑ ☑ ☐ ☐ ☑
455 Bis(2‐Chloroethyl)sulfide 505‐60‐2 ☑ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 371

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
456 Bis(2‐chloroethylthio)methane 63869‐13‐6 ☑ ☐ ☐ ☐ ☐ ☑
457 Bis(2‐chloroethylthioethyl) ether 63918‐89‐8 ☑ ☐ ☐ ☐ ☐ ☑
458 Bis(2‐chloroethylthiomethyl)ether 63918‐90‐1 ☑ ☐ ☐ ☐ ☐ ☑
459 Bis(2‐chlorovinyl)chloroarsine 40334‐69‐8 ☑ ☐ ☐ ☐ ☐ ☑
460 Bis(2‐ethylhexyl)phthalate (DEHP) 117‐81‐7 ☐ ☑ ☑ ☑ ☐ ☑
461 Bis(chloromethyl)ether 542‐88‐1 ☑ ☑ ☑ ☑ ☐ ☑
462 Bis(tributyltin) oxide 56‐35‐9 ☐ ☑ ☑ ☐ ☐ ☑
463 Bitoscanate 4044‐65‐9 ☐ ☑ ☑ ☐ ☐ ☑
464 BLEOMYCIN 11116‐32‐8 ☐ ☐ ☐ ☐ ☑ ☑
465 BLEOMYCIN, SULFATE 9041‐93‐4 ☐ ☐ ☐ ☐ ☑ ☑
466 BORON 7440‐42‐8 ☐ ☐ ☐ ☐ ☑ ☑
467 Boron tribromide 10294‐33‐4 ☑ ☐ ☐ ☐ ☐ ☑
468 Boron trichloride 10294‐34‐5 ☑ ☑ ☑ ☐ ☑ ☑
469 Boron trifluoride methyl etherate 353‐42‐4 ☑ ☑ ☑ ☐ ☐ ☑
470 Boron trifluoride, gas 7637‐07‐2 ☑ ☑ ☑ ☐ ☐ ☑
471 Bromacil 314‐40‐9 ☐ ☑ ☑ ☐ ☐ ☑
472 Bromacil, lithium salt 53404‐19‐6 ☐ ☑ ☑ ☐ ☐ ☑
473 Bromadiolone 28772‐56‐7 ☐ ☑ ☑ ☐ ☐ ☑
474 BROMIC acid , POTASSIUM SALT 7758‐01‐2 ☐ ☑ ☑ ☐ ☑ ☑
475 Bromine 7726‐95‐6 ☑ ☑ ☑ ☐ ☑ ☑
476 Bromine chloride 13863‐41‐7 ☑ ☐ ☐ ☐ ☐ ☑
477 Bromine pentafluoride 7789‐30‐2 ☑ ☐ ☐ ☐ ☐ ☑
478 Bromine trifluoride 7787‐71‐5 ☑ ☐ ☐ ☐ ☐ ☑
479 Bromoacetone 598‐31‐2 ☐ ☑ ☑ ☐ ☐ ☑
480 Bromochlorodifluoromethane 353‐59‐3 ☐ ☑ ☑ ☐ ☐ ☑
481 Bromoform 75‐25‐2 ☐ ☑ ☑ ☑ ☑ ☑
482 Bromomethane 74‐83‐9 ☑ ☑ ☑ ☑ ☑ ☑
483 Bromotrifluoroethylene 598‐73‐2 ☑ ☑ ☑ ☐ ☐ ☑
484 Bromotrifluoromethane 75‐63‐8 ☐ ☑ ☑ ☐ ☐ ☑
485 Bromoxynil 1689‐84‐5 ☐ ☑ ☑ ☐ ☐ ☑
486 Bromoxynil octanoate 1689‐99‐2 ☐ ☑ ☑ ☐ ☐ ☑
487 Brucine 357‐57‐3 ☐ ☑ ☑ ☐ ☐ ☑
488 Butane 106‐97‐8 ☑ ☑ ☑ ☐ ☐ ☑
489 BUTANE, (+‐)‐1,2,3,4‐DIEPOXY‐ 298‐18‐0 ☐ ☐ ☐ ☐ ☑ ☑
490 BUTANE, 1,2‐EPOXY‐ ☐ ☑ ☑ ☐ ☑ ☑
491 BUTANEDIOL, 55‐98‐1 ☐ ☐ ☐ ☐ ☑ ☑
DIMETHANESULFONATE, 1,4‐
492 BUTEN‐2‐ONE 3‐ 78‐94‐4 ☐ ☑ ☑ ☐ ☑ ☑
493 BUTENE, 1,4‐DICHLORO‐,(E)‐,2‐ 110‐57‐6 ☐ ☑ ☑ ☐ ☑ ☑
494 BUTENE, 2,3‐ 303‐04‐8 ☐ ☐ ☐ ☐ ☑ ☑
DICHLOROHEXAFLUORO‐,2‐
495 Butyl acetate 123‐86‐4 ☐ ☑ ☑ ☐ ☐ ☑
496 Butyl acrylate 141‐32‐2 ☐ ☑ ☑ ☐ ☐ ☑
497 Butylamine 109‐73‐9 ☐ ☑ ☑ ☐ ☐ ☑
498 Butylethylcarbamothioic acid S‐propyl 1114‐71‐2 ☐ ☑ ☑ ☐ ☐ ☑
ester
(continued)
372 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
499 BUTYL‐N‐NITROSO‐1‐BUTAMINE, 924‐16‐3 ☐ ☑ ☑ ☐ ☑ ☑
N‐
500 Butyltrichlorosilane 7521‐80‐4 ☑ ☐ ☐ ☐ ☐ ☑
501 Butyraldehyde 123‐72‐8 ☐ ☑ ☑ ☐ ☐ ☑
502 Butyric acid 107‐92‐6 ☐ ☑ ☑ ☐ ☐ ☑
503 BUTYRIC acid 305‐03‐3 ☐ ☑ ☑ ☐ ☑ ☑
504 C.I. acid Green 338 4680‐78‐8 ☐ ☑ ☑ ☐ ☐ ☑
505 C.I. Basic Green 4218 569‐64‐2 ☐ ☑ ☑ ☐ ☐ ☑
506 C.I. Basic Red 1 989‐38‐8 ☐ ☑ ☑ ☐ ☐ ☑
507 C.I. Direct Black 1937‐37‐7 ☐ ☑ ☑ ☐ ☐ ☑
508 C.I. Direct Blue 28407‐37‐6 ☐ ☑ ☑ ☐ ☐ ☑
509 C.I. Direct Blue 6 2602‐46‐2 ☐ ☑ ☑ ☐ ☐ ☑
510 C.I. Direct Brown 95 16071‐86‐6 ☐ ☑ ☑ ☐ ☐ ☑
511 C.I. Disperse Yellow 3 2832‐40‐8 ☐ ☑ ☑ ☐ ☐ ☑
512 C.I. Food Red 15 81‐88‐9 ☐ ☑ ☑ ☐ ☐ ☑
513 C.I. Vat Yellow 4 128‐66‐5 ☐ ☑ ☑ ☐ ☐ ☑
514 Cacodylic acid 75‐60‐5 ☐ ☑ ☑ ☐ ☐ ☑
515 CADMIUM 7440‐43‐9 ☐ ☑ ☑ ☐ ☑ ☑
516 Cadmium acetate 543‐90‐8 ☐ ☑ ☑ ☐ ☐ ☑
517 Cadmium bromide 7789‐42‐6 ☐ ☑ ☑ ☐ ☐ ☑
518 CADMIUM CHLORIDE 10108‐64‐2 ☐ ☑ ☑ ☐ ☑ ☑
519 CADMIUM OXIDE 1306‐19‐0 ☐ ☑ ☑ ☐ ☑ ☑
520 Cadmium stearate 2223‐93‐0 ☐ ☑ ☑ ☐ ☐ ☑
521 Calcium arsenate 7778‐44‐1 ☐ ☑ ☑ ☐ ☐ ☑
522 Calcium arsenite 52740‐16‐6 ☐ ☑ ☑ ☐ ☐ ☑
523 Calcium carbide 75‐20‐7 ☐ ☑ ☑ ☐ ☐ ☑
524 Calcium chromate 13765‐19‐0 ☐ ☑ ☑ ☐ ☐ ☑
525 Calcium cyanamide 156‐62‐7 ☐ ☑ ☑ ☑ ☐ ☑
526 Calcium cyanide 592‐01‐8 ☐ ☑ ☑ ☐ ☐ ☑
527 Calcium dithionite 15512‐36‐4 ☑ ☐ ☐ ☐ ☐ ☑
528 Calcium dodecylbenz enesulfonate 26264‐06‐2 ☐ ☑ ☑ ☐ ☐ ☑
529 Calcium hypochlorite 7778‐54‐3 ☐ ☑ ☑ ☐ ☐ ☑
530 Calcium phosphide 1305‐99‐3 ☑ ☑ ☑ ☐ ☐ ☑
531 Cantharidin 56‐25‐7 ☐ ☑ ☑ ☐ ☐ ☑
532 Captan 133‐06‐2 ☐ ☑ ☑ ☑ ☐ ☑
533 Carbachol chloride 51‐83‐2 ☐ ☑ ☑ ☐ ☐ ☑
534 Carbamic acid , diethylthio‐, S‐(p‐ 28249‐77‐6 ☐ ☑ ☑ ☐ ☐ ☑
chlorobenzyl)
535 Carbamic acid , methyl‐, O‐(((2,4‐ 26419‐73‐8 ☐ ☑ ☑ ☐ ☐ ☑
dimethyl‐1,3‐dithiolan‐2‐yl)methylene)
amin
536 CARBAMIC acid , METHYL‐,2,3‐ 1563‐66‐2 ☐ ☑ ☑ ☐ ☑ ☑
DIHYDRO‐2,2‐DIMETHYL‐7‐
BENZOFURANYLES
537 Carbamodithioic acid , 1,2‐ 12122‐67‐7 ☐ ☑ ☑ ☐ ☐ ☑
ethanediylbis‐, zinc complex
(continued)
Appendix 5: CAS RN Reportable Chemicals 373

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
538 Carbamothioic acid , bis(1‐ 2303‐16‐4 ☐ ☑ ☑ ☐ ☐ ☑
methylethyl)‐S‐(2,3‐dichloro‐2‐
propenyl)ester
539 Carbamothioic acid , dipropyl‐, S‐ 52888‐80‐9 ☐ ☑ ☑ ☐ ☐ ☑
(phenylmethyl) ester
540 Carbaryl 63‐25‐2 ☐ ☑ ☑ ☑ ☐ ☑
541 Carbendazim 10605‐21‐7 ☐ ☑ ☑ ☐ ☐ ☑
542 Carbofuran phenol 1563‐38‐8 ☐ ☑ ☑ ☐ ☐ ☑
543 Carbon disulfide 75‐15‐0 ☑ ☑ ☑ ☑ ☐ ☑
544 Carbon monoxide gas 630‐08‐0 ☑ ☐ ☐ ☐ ☐ ☑
545 Carbon tetrachloride 56‐23‐5 ☐ ☑ ☑ ☑ ☑ ☑
546 Carbonyl fluoride 353‐50‐4 ☑ ☑ ☑ ☐ ☐ ☑
547 Carbonyl sulfide 463‐58‐1 ☑ ☑ ☑ ☑ ☐ ☑
548 Carbophenothion 786‐19‐6 ☐ ☑ ☑ ☐ ☐ ☑
549 Carbosulfan 55285‐14‐8 ☐ ☑ ☑ ☐ ☐ ☑
550 Carboxin 5234‐68‐4 ☐ ☑ ☑ ☐ ☐ ☑
551 CARBOXYLIC acid ,3‐beta,20‐alpha‐ 50‐55‐5 ☐ ☑ ☑ ☐ ☑ ☑
YOHIMBAN‐16‐beta‐
552 CARRAGEENAN,DEGRADED 9000‐07‐1 ☐ ☑ ☑ ☐ ☑ ☑
553 Catechol 120‐80‐9 ☐ ☑ ☑ ☑ ☑ ☑
554 CFC‐11 75‐69‐4 ☐ ☐ ☐ ☐ ☐ ☑
555 CFC‐114 76‐14‐2 ☐ ☑ ☑ ☐ ☐ ☑
556 CFC‐115 76‐15‐3 ☐ ☑ ☑ ☐ ☐ ☑
557 CFC‐12 75‐71‐8 ☐ ☑ ☑ ☐ ☐ ☑
558 CFC‐13 75‐72‐9 ☐ ☑ ☑ ☐ ☐ ☑
559 Chinomethionat 2439‐01‐2 ☐ ☑ ☑ ☐ ☐ ☑
560 Chloramben 133‐90‐4 ☐ ☑ ☑ ☑ ☐ ☑
561 Chlordane 57‐74‐9 ☐ ☑ ☑ ☑ ☑ ☑
562 Chlorfenvinfos 470‐90‐6 ☐ ☑ ☑ ☐ ☐ ☑
563 Chlorimuron ethyl 90982‐32‐4 ☐ ☑ ☑ ☐ ☐ ☑
564 Chlorine dioxide, gas 10049‐04‐4 ☑ ☑ ☑ ☐ ☐ ☑
565 Chlorine monoxide 7791‐21‐1 ☑ ☑ ☑ ☐ ☐ ☑
566 Chlorine pentafluoride 13637‐63‐3 ☑ ☐ ☐ ☐ ☐ ☑
567 Chlorine trifluoride 7790‐91‐2 ☑ ☐ ☐ ☐ ☐ ☑
568 Chlorine, gas 7782‐50‐5 ☑ ☑ ☑ ☑ ☐ ☑
569 Chlormephos 24934‐91‐6 ☐ ☑ ☑ ☐ ☐ ☑
570 Chlormequat chloride 999‐81‐5 ☐ ☑ ☑ ☐ ☐ ☑
571 Chlornaphazine 494‐03‐1 ☐ ☑ ☑ ☐ ☐ ☑
572 Chloroacetaldehyde 107‐20‐0 ☐ ☑ ☑ ☐ ☐ ☑
573 Chloroacetic acid 79‐11‐8 ☐ ☑ ☑ ☑ ☑ ☑
574 Chloroacetyl chloride 79‐04‐9 ☑ ☐ ☐ ☐ ☐ ☑
575 Chlorobenzene 108‐90‐7 ☐ ☑ ☑ ☑ ☐ ☑
576 Chlorobenzilate 510‐15‐6 ☐ ☑ ☑ ☑ ☐ ☑
577 Chlorodifluoromethane 75‐45‐6 ☐ ☑ ☑ ☐ ☐ ☑
578 Chloroethyl chloroformate 627‐11‐2 ☐ ☑ ☑ ☐ ☐ ☑
579 Chloroform 67‐66‐3 ☑ ☑ ☑ ☑ ☑ ☑
580 Chloromethane 74‐87‐3 ☑ ☑ ☑ ☑ ☐ ☑
(continued)
374 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
581 Chloromethyl methyl ether 107‐30‐2 ☑ ☑ ☑ ☑ ☑ ☑
582 Chlorophacinone 3691‐35‐8 ☐ ☑ ☑ ☐ ☐ ☑
583 Chloropicrin 76‐06‐2 ☑ ☑ ☑ ☐ ☑ ☑
584 Chloroprene 126‐99‐8 ☐ ☑ ☑ ☑ ☑ ☑
585 Chlorosulfonic acid 7790‐94‐5 ☑ ☑ ☑ ☐ ☐ ☑
586 Chlorotetrafluoroethane 63938‐10‐3 ☐ ☑ ☑ ☐ ☐ ☑
587 Chlorotrifluoroethylene 79‐38‐9 ☑ ☑ ☑ ☐ ☐ ☑
588 Chlorotrimethylsilane 75‐77‐4 ☑ ☑ ☑ ☐ ☐ ☑
589 Chloroxuron 1982‐47‐4 ☐ ☑ ☑ ☐ ☐ ☑
590 Chlorpyrifos 2921‐88‐2 ☐ ☑ ☑ ☐ ☐ ☑
591 Chlorpyrifos methyl 5598‐13‐0 ☐ ☑ ☑ ☐ ☐ ☑
592 Chlorthiophos 21923‐23‐9 ☐ ☑ ☑ ☐ ☐ ☑
593 Chromic acetate 1066‐30‐4 ☐ ☑ ☑ ☐ ☐ ☑
594 Chromic acid 7738‐94‐5 ☐ ☑ ☑ ☐ ☐ ☑
595 Chromic acid 11115‐74‐5 ☐ ☑ ☑ ☐ ☐ ☑
596 CHROMIC acid , DIPOTASSIUM 7789‐00‐6 ☐ ☑ ☑ ☐ ☑ ☑
SALT
597 Chromic chloride 10025‐73‐7 ☐ ☑ ☑ ☐ ☐ ☑
598 CHROMIC SULFATE 10101‐53‐8 ☐ ☑ ☑ ☐ ☑ ☑
599 Chromium 7440‐47‐3 ☐ ☑ ☑ ☐ ☐ ☑
600 Chromium oxychloride (CrCl2O2) 14977‐61‐8 ☑ ☐ ☐ ☐ ☐ ☑
601 CHROMIUM(VI) OXIDE (13) 1333‐82‐0 ☐ ☐ ☐ ☐ ☑ ☑
602 Chromous chloride 10049‐05‐5 ☐ ☑ ☑ ☐ ☐ ☑
603 CHRYSENE, 5‐METHYL‐ 3697‐24‐3 ☐ ☑ ☑ ☐ ☑ ☑
604 CHRYSENE, 6‐NITRO‐ 7496‐02‐8 ☐ ☐ ☐ ☐ ☑ ☑
605 CINNAMIC acid , 3,4‐DIHYDROXY‐ 331‐39‐5 ☐ ☐ ☐ ☐ ☑ ☑
606 cis‐2‐Butene 590‐18‐1 ☑ ☑ ☑ ☐ ☐ ☑
607 Cobalt 7440‐48‐4 ☐ ☑ ☑ ☐ ☐ ☑
608 COBALT(2+) OXIDE 1307‐96‐6 ☐ ☐ ☐ ☐ ☑ ☑
609 COBALT(II) CHLORIDE 7646‐79‐9 ☐ ☐ ☑ ☐ ☑ ☑
610 Cobalt, ((2,2'‐(1,2‐ethanediylbis 62207‐76‐5 ☐ ☑ ☑ ☐ ☐ ☑
(nitrilomethylidyne))bis(6‐
fluorophenylato))(2
611 COBALT, Dl‐mu‐ 10210‐68‐1 ☐ ☑ ☑ ☐ ☑ ☑
CARBONYLHEXACARBONYLDI‐,
(Co‐Co)
612 Cobaltous bromide 7789‐43‐7 ☐ ☑ ☑ ☐ ☐ ☑
613 Cobaltous formate 544‐18‐3 ☐ ☑ ☑ ☐ ☐ ☑
614 Cobaltous sulfamate 14017‐41‐5 ☐ ☑ ☑ ☐ ☐ ☑
615 Colchicine 64‐86‐8 ☐ ☑ ☑ ☐ ☐ ☑
616 Copper 7440‐50‐8 ☐ ☑ ☑ ☐ ☐ ☑
617 Copper cyanide 544‐92‐3 ☐ ☑ ☑ ☐ ☐ ☑
618 Coumaphos 56‐72‐4 ☐ ☑ ☑ ☐ ☐ ☑
619 COUMARIN, 3‐(alpha‐ 81‐81‐2 ☐ ☑ ☑ ☐ ☑ ☑
ACETONYLBENZYL)‐4‐
HYDROXY‐
620 Coumatetralyl 5836‐29‐3 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 375

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
621 Creosote 8001‐58‐9 ☐ ☑ ☑ ☐ ☐ ☑
622 Cresols/Cresylic acid (isomers and 1319‐77‐3 ☐ ☑ ☑ ☑ ☐ ☑
mixture)
623 Crimidine 535‐89‐7 ☐ ☑ ☑ ☐ ☐ ☑
624 Crotonaldehyde (cis and trans) 4170‐30‐3 ☑ ☑ ☑ ☐ ☐ ☑
625 Crotonaldehyde, trans‐ 123‐73‐9 ☑ ☑ ☑ ☐ ☐ ☑
626 Cumene 98‐82‐8 ☐ ☑ ☑ ☑ ☐ ☑
627 Cumene hydroperoxide 80‐15‐9 ☐ ☑ ☑ ☐ ☐ ☑
628 Cupric acetate 142‐71‐2 ☐ ☑ ☑ ☐ ☐ ☑
629 Cupric acetoarsenite 12002‐03‐8 ☐ ☑ ☑ ☐ ☐ ☑
630 Cupric chloride 7447‐39‐4 ☐ ☑ ☑ ☐ ☐ ☑
631 Cupric nitrate 3251‐23‐8 ☐ ☑ ☑ ☐ ☐ ☑
632 Cupric oxalate 5893‐66‐3 ☐ ☑ ☑ ☐ ☐ ☑
633 Cupric sulfate 7758‐98‐7 ☐ ☑ ☑ ☐ ☐ ☑
634 Cupric sulfate, ammoniated 10380‐29‐7 ☐ ☑ ☑ ☐ ☐ ☑
635 Cupric tartrate 815‐82‐7 ☐ ☑ ☑ ☐ ☐ ☑
636 Cyanazine 21725‐46‐2 ☐ ☑ ☑ ☐ ☐ ☑
637 Cyanides (soluble salts and complexes) 57‐12‐5 ☐ ☑ ☑ ☐ ☐ ☑
638 Cyanogen 460‐19‐5 ☑ ☑ ☑ ☐ ☐ ☑
639 CYANOGEN BROMIDE 506‐68‐3 ☐ ☑ ☑ ☐ ☑ ☑
640 Cyanogen chloride 506‐77‐4 ☑ ☑ ☑ ☐ ☐ ☑
641 Cyanogen iodide 506‐78‐5 ☐ ☑ ☑ ☐ ☐ ☑
642 Cyanophos 2636‐26‐2 ☐ ☑ ☑ ☐ ☐ ☑
643 Cycloate 1134‐23‐2 ☐ ☑ ☑ ☐ ☐ ☑
644 Cyclohexane 110‐82‐7 ☐ ☑ ☑ ☐ ☐ ☑
645 CYCLOHEXANE, NITRO‐ 1122‐60‐7 ☐ ☑ ☑ ☐ ☑ ☑
646 Cyclohexanol 108‐93‐0 ☐ ☑ ☑ ☐ ☐ ☑
647 Cyclohexanone 108‐94‐1 ☐ ☑ ☑ ☐ ☐ ☑
648 CYCLOHEXENE, 4‐VINYL‐1‐ 100‐40‐3 ☐ ☑ ☑ ☐ ☑ ☑
649 Cycloheximide 66‐81‐9 ☐ ☑ ☑ ☐ ☐ ☑
650 Cyclohexylamine 108‐91‐8 ☑ ☑ ☑ ☐ ☐ ☑
651 CYCLOPENTA(c)FURO(3',2'4,5) 1162‐65‐8 ☐ ☐ ☐ ☐ ☑ ☑
FURO(2,3‐h) (l)BENZOPYRAN‐1,11‐
DIONE
652 Cyclophosphamide 50‐18‐0 ☐ ☑ ☑ ☐ ☐ ☑
653 Cyclopropane 75‐19‐4 ☑ ☑ ☑ ☐ ☐ ☑
654 CYCLOSPORIN A 59865‐13‐3 ☐ ☐ ☐ ☐ ☑ ☑
655 Cyclotetramethylene tetranitramine (dry 2691‐41‐0 ☑ ☐ ☐ ☐ ☐ ☑
or not stabilized)
656 Cyfluthrin 68359‐37‐5 ☐ ☑ ☑ ☐ ☐ ☑
657 Daunomycin 20830‐81‐3 ☐ ☑ ☑ ☐ ☐ ☑
658 Dazomet 533‐74‐4 ☐ ☑ ☑ ☐ ☐ ☑
659 Dazomet, sodium salt 53404‐60‐7 ☐ ☑ ☑ ☐ ☐ ☑
660 DDD 72‐54‐8 ☐ ☑ ☑ ☐ ☐ ☑
661 DDE 3547‐04‐4 ☐ ☑ ☑ ☑ ☐ ☑
662 DECABORANE(14) 17702‐41‐9 ☐ ☑ ☑ ☐ ☑ ☑
663 Decabromodiphenyl oxide 1163‐19‐5 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
376 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
664 DECYL ALCOHOL 112‐30‐1 ☐ ☐ ☐ ☐ ☑ ☑
665 DEF 78‐48‐8 ☐ ☑ ☑ ☐ ☐ ☑
666 delta‐BHC 319‐86‐8 ☐ ☑ ☑ ☐ ☐ ☑
667 Demeton 8065‐48‐3 ☐ ☑ ☑ ☐ ☐ ☑
668 Demeton‐S‐methyl 919‐86‐8 ☐ ☑ ☑ ☐ ☐ ☑
669 Desmedipham 13684‐56‐5 ☐ ☑ ☑ ☐ ☐ ☑
670 Deuterium bromide, gas 13536‐59‐9 ☑ ☐ ☐ ☐ ☐ ☑
671 Deuterium chloride, gas 7698‐05‐7 ☑ ☐ ☐ ☐ ☐ ☑
672 Dialifor 10311‐84‐9 ☐ ☑ ☑ ☐ ☐ ☑
673 Diaminotoluene 496‐72‐0 ☐ ☑ ☑ ☐ ☐ ☑
674 Diaminotoluene 823‐40‐5 ☐ ☑ ☑ ☐ ☐ ☑
675 Diaminotoluene (mixed isomers) 25376‐45‐8 ☐ ☑ ☑ ☐ ☐ ☑
676 Diazinon 333‐41‐5 ☐ ☑ ☑ ☐ ☐ ☑
677 Diazodinitrophenol, wetted with not 4682‐03‐5 ☑ ☐ ☐ ☐ ☐ ☑
less than 40% water
678 Diazomethane 334‐88‐3 ☐ ☑ ☑ ☑ ☐ ☑
679 Dibenz(a,h)acridine 226‐36‐8 ☐ ☑ ☑ ☐ ☐ ☑
680 DIBENZ(a,h)ANTHRACENE 53‐70‐3 ☐ ☑ ☑ ☐ ☑ ☑
681 Dibenz(a,j)acridine 224‐42‐0 ☐ ☑ ☑ ☐ ☐ ☑
682 Dibenzo(a,e)fluoranthene 5385‐75‐1 ☐ ☑ ☑ ☐ ☐ ☑
683 Dibenzo(a,e)pyrene 192‐65‐4 ☐ ☑ ☑ ☐ ☐ ☑
684 Dibenzo(a,h)pyrene 189‐64‐0 ☐ ☑ ☑ ☐ ☐ ☑
685 Dibenzo(a,l)pyrene 191‐30‐0 ☐ ☑ ☑ ☐ ☐ ☑
686 Dibenzofurans 132‐64‐9 ☐ ☑ ☑ ☑ ☐ ☑
687 Diborane 19287‐45‐7 ☑ ☑ ☑ ☐ ☐ ☑
688 Dibromotetrafluoroethane 124‐73‐2 ☐ ☑ ☑ ☐ ☐ ☑
689 Dibutylphthalate 84‐74‐2 ☐ ☑ ☑ ☑ ☐ ☑
690 Dicamba 1918‐00‐9 ☐ ☑ ☑ ☐ ☐ ☑
691 Dichlobenil 1194‐65‐6 ☐ ☑ ☑ ☐ ☐ ☑
692 Dichlone 117‐80‐6 ☐ ☑ ☑ ☐ ☐ ☑
693 Dichloran 99‐30‐9 ☐ ☑ ☑ ☐ ☐ ☑
694 Dichloro(methyl)phenylsilane 149‐74‐6 ☑ ☑ ☑ ☐ ☐ ☑
695 Dichloro‐1,1,2‐trifluoroethane 90454‐18‐5 ☐ ☑ ☑ ☐ ☐ ☑
696 Dichlorobenzene 25321‐22‐6 ☐ ☑ ☑ ☐ ☐ ☑
697 Dichlorodiethylsilane 1719‐53‐5 ☑ ☐ ☐ ☐ ☐ ☑
698 Dichlorodiphenylsilane 80‐10‐4 ☑ ☐ ☐ ☐ ☐ ☑
699 Dichloroethyl ether (Bis(2‐chloroethyl) 111‐44‐4 ☐ ☑ ☑ ☑ ☑ ☑
ether)
700 Dichlorofluoromethane 75‐43‐4 ☐ ☑ ☑ ☐ ☐ ☑
701 Dichloromethylsilane 75‐54‐7 ☑ ☐ ☐ ☐ ☐ ☑
702 Dichloropentafluoropropane 127564‐92‐5 ☐ ☑ ☑ ☐ ☐ ☑
703 Dichlorophene 97‐23‐4 ☐ ☑ ☑ ☐ ☐ ☑
704 Dichlorophenylarsine 696‐28‐6 ☐ ☑ ☑ ☐ ☐ ☑
705 Dichloropropane 26638‐19‐7 ☐ ☑ ☑ ☐ ☐ ☑
706 Dichloropropane Dichloropropene 8003‐19‐8 ☐ ☑ ☑ ☐ ☐ ☑
(mixture)
(continued)
Appendix 5: CAS RN Reportable Chemicals 377

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
707 Dichloropropene 26952‐23‐8 ☐ ☑ ☑ ☐ ☐ ☑
708 Dichlorosilane 4109‐96‐0 ☑ ☑ ☑ ☐ ☐ ☑
709 Dichlorotrifluoroethane 34077‐87‐7 ☐ ☑ ☑ ☐ ☐ ☑
710 Dichlorvos 62‐73‐7 ☐ ☑ ☑ ☑ ☐ ☑
711 Dicrotophos 141‐66‐2 ☐ ☑ ☑ ☐ ☐ ☑
712 Dicyclopentadiene 77‐73‐6 ☐ ☑ ☑ ☐ ☐ ☑
713 Dieldrin 60‐57‐1 ☐ ☑ ☑ ☐ ☐ ☑
714 Diethanolamine 111‐42‐2 ☐ ☑ ☑ ☑ ☐ ☑
715 Diethatyl ethyl 38727‐55‐8 ☐ ☑ ☑ ☐ ☐ ☑
716 Diethyl ethylphosphonate 78‐38‐6 ☑ ☐ ☐ ☐ ☐ ☑
717 Diethyl phosphite 762‐04‐9 ☑ ☐ ☐ ☐ ☐ ☑
718 Diethyl phthalate 84‐66‐2 ☐ ☑ ☑ ☐ ☐ ☑
719 Diethyl sulfate 64‐67‐5 ☐ ☑ ☑ ☑ ☑ ☑
720 Diethylamine 109‐89‐7 ☐ ☑ ☑ ☐ ☐ ☑
721 DIETHYLAMINE, 55‐86‐7 ☐ ☐ ☐ ☐ ☑ ☑
HYDROCHLORIDE
722 Diethylarsine 692‐42‐2 ☐ ☑ ☑ ☐ ☐ ☑
723 Diethyldiisocyanatobenzene 134190‐37‐7 ☐ ☑ ☑ ☐ ☐ ☑
724 Diethyleneglycol dinitrate 693‐21‐0 ☑ ☐ ☐ ☐ ☐ ☑
725 Diethyl‐N,N‐ 2404‐03‐7 ☑ ☐ ☐ ☐ ☐ ☑
dimethylphosphoroamidate
726 Diethyl‐p‐nitrophenyl phosphate 311‐45‐5 ☐ ☑ ☑ ☐ ☐ ☑
727 Diflubenzuron 35367‐38‐5 ☐ ☑ ☑ ☐ ☐ ☑
728 Digitoxin 71‐63‐6 ☐ ☑ ☑ ☐ ☐ ☑
729 Diglycidyl ether 2238‐07‐5 ☐ ☑ ☑ ☐ ☐ ☑
730 Digoxin 20830‐75‐5 ☐ ☑ ☑ ☐ ☐ ☑
731 Dihydrosafrole 94‐58‐6 ☐ ☑ ☑ ☐ ☐ ☑
732 Dimefox 115‐26‐4 ☐ ☑ ☑ ☐ ☐ ☑
733 Dimethoate 60‐51‐5 ☐ ☑ ☑ ☐ ☐ ☑
734 Dimethyl aminoazobenzene 60‐11‐7 ☐ ☑ ☑ ☑ ☑ ☑
735 Dimethyl carbamoyl chloride 79‐44‐7 ☐ ☑ ☑ ☑ ☑ ☑
736 Dimethyl chlorothiophosphate 2524‐03‐0 ☐ ☑ ☑ ☐ ☐ ☑
737 Dimethyl ether 115‐10‐6 ☑ ☑ ☑ ☐ ☐ ☑
738 Dimethyl ethylphosphonate 6163‐75‐3 ☑ ☐ ☐ ☐ ☐ ☑
739 Dimethyl formamide 68‐12‐2 ☐ ☑ ☑ ☑ ☐ ☑
740 Dimethyl phosphite 868‐85‐9 ☑ ☐ ☐ ☐ ☑ ☑
741 Dimethyl phthalate 131‐11‐3 ☐ ☑ ☑ ☑ ☐ ☑
742 Dimethyl sulfate 77‐78‐1 ☐ ☑ ☑ ☑ ☑ ☑
743 Dimethylamine 124‐40‐3 ☑ ☑ ☑ ☐ ☐ ☑
744 Dimethylamine dicamba 2300‐66‐5 ☐ ☑ ☑ ☐ ☐ ☑
745 Dimethyldichlorosilane 75‐78‐5 ☑ ☑ ☑ ☐ ☐ ☑
746 Dimethylmethylphosphonate 756‐79‐6 ☑ ☐ ☐ ☐ ☐ ☑
747 Dimethyl‐p‐phenylenediamine 99‐98‐9 ☐ ☑ ☑ ☐ ☐ ☑
748 Dimetilan 644‐64‐4 ☐ ☑ ☑ ☐ ☐ ☑
749 Dinitrobenzene(mixed isomers) 25154‐54‐5 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
378 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
750 Dinitrobutyl phenol 88‐85‐7 ☐ ☑ ☑ ☐ ☐ ☑
751 Dinitroglycoluril 55510‐04‐8 ☑ ☐ ☐ ☐ ☐ ☑
752 Dinitrophenol 25550‐58‐7 ☑ ☑ ☑ ☐ ☐ ☑
753 Dinitr oresorcinol, wetted with not less 35860‐51‐6 ☑ ☐ ☐ ☐ ☐ ☑
than15% water by mass
754 Din itrosobenzene 25550‐55‐4 ☑ ☐ ☐ ☐ ☐ ☑
755 Dinitrotoluene (mixed isomers) 25321‐14‐6 ☐ ☑ ☑ ☐ ☐ ☑
756 Dinocap 39300‐45‐3 ☐ ☑ ☑ ☐ ☐ ☑
757 Di‐n‐octyl phthalate 117‐84‐0 ☐ ☑ ☑ ☐ ☐ ☑
758 Dinoterb 1420‐07‐1 ☐ ☑ ☑ ☐ ☐ ☑
759 Dioxathion 78‐34‐2 ☐ ☑ ☑ ☐ ☐ ☑
760 Diphacinone 82‐66‐6 ☐ ☑ ☑ ☐ ☐ ☑
761 Diphenamid 957‐51‐7 ☐ ☑ ☑ ☐ ☐ ☑
762 Diphenylamine 122‐39‐4 ☐ ☑ ☑ ☐ ☐ ☑
763 Diphosphoramide, octamethyl‐ 152‐16‐9 ☐ ☑ ☑ ☐ ☐ ☑
764 Dipicryl sulfide, dry 2217‐06‐3 ☑ ☐ ☐ ☐ ☐ ☑
765 Dipotassium endothall 2164‐07‐0 ☐ ☑ ☑ ☐ ☐ ☑
766 DIPROPIONATE, 9‐'CHLORO‐1 6‐ 5534‐09‐8 ☐ ☐ ☐ ☐ ☑ ☑
beta‐METHYL‐11 ‐beta, 17,21‐
TRIHYDROXY‐,
767 Dipropyl isocinchomeronate 136‐45‐8 ☐ ☑ ☑ ☐ ☐ ☑
768 Dipropylamine 142‐84‐7 ☐ ☑ ☑ ☐ ☐ ☑
769 DIPROPYLAMINE, N‐NITROSO‐ 621‐64‐7 ☐ ☑ ☑ ☐ ☑ ☑
770 Diquat 2764‐72‐9 ☐ ☑ ☑ ☐ ☐ ☑
771 Diquat 85‐00‐7 ☐ ☑ ☑ ☐ ☐ ☑
772 Disodium cyanodithioimidocarbonate 138‐93‐2 ☐ ☑ ☑ ☐ ☐ ☑
773 DISULFIDE, DIMETHYL 624‐92‐0 ☐ ☑ ☑ ☐ ☑ ☑
774 Disulfoton 298‐04‐4 ☐ ☑ ☑ ☐ ☐ ☑
775 Dithiazanine iodide 514‐73‐8 ☐ ☑ ☑ ☐ ☐ ☑
776 Dithiobiuret 541‐53‐7 ☐ ☑ ☑ ☐ ☐ ☑
777 Diuron 330‐54‐1 ☐ ☑ ☑ ☐ ☐ ☑
778 Dodecylbenzenesulfonic acid 27176‐87‐0 ☐ ☑ ☑ ☐ ☐ ☑
779 Dodecylguanidine monoacetate 2439‐10‐3 ☐ ☑ ☑ ☐ ☐ ☑
780 Dodecyltrichlorosilane 4484‐72‐4 ☑ ☐ ☐ ☐ ☐ ☑
781 d‐trans‐Allethrin 28057‐48‐9 ☐ ☑ ☑ ☐ ☐ ☑
782 Emetine, dihydrochloride 316‐42‐7 ☐ ☑ ☑ ☐ ☐ ☑
783 Endosulfan 115‐29‐7 ☐ ☑ ☑ ☐ ☐ ☑
784 Endosulfan sulfate 1031‐07‐8 ☐ ☑ ☑ ☐ ☐ ☑
785 Endothall 145‐73‐3 ☐ ☑ ☑ ☐ ☐ ☑
786 Endothion 2778‐04‐3 ☐ ☑ ☑ ☐ ☐ ☑
787 Endrin 72‐20‐8 ☐ ☑ ☑ ☐ ☐ ☑
788 Endrin aldehyde 7421‐93‐4 ☐ ☑ ☑ ☐ ☐ ☑
789 Epichlorohydrin 106‐89‐8 ☑ ☑ ☑ ☑ ☑ ☑
790 Epinephrine 51‐43‐4 ☐ ☑ ☑ ☐ ☐ ☑
791 EPN 2104‐64‐5 ☐ ☑ ☑ ☐ ☐ ☑
792 EPTC 759‐94‐4 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 379

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
793 Ergocalciferol 50‐14‐6 ☐ ☑ ☑ ☐ ☐ ☑
794 Ergotamine tartrate 379‐79‐3 ☐ ☑ ☑ ☐ ☐ ☑
795 Ethanamine 75‐04‐7 ☐ ☑ ☑ ☐ ☐ ☑
796 Ethane 74‐84‐0 ☑ ☑ ☑ ☐ ☑ ☑
797 Ethane, 1,1,1,2‐tetrachloro‐ 630‐20‐6 ☐ ☑ ☑ ☐ ☐ ☑
798 ETHANE, 1,1,1‐TRICHLORO‐2,2‐BIS 50‐29‐3 ☐ ☑ ☑ ☐ ☑ ☑
(p‐CHLOROPHENYL)‐
799 Ethane, 1,1,2‐trichloro‐1,2,2,‐trifluoro‐ 76‐13‐1 ☐ ☑ ☑ ☐ ☐ ☑
800 ETHANE, IODO‐ 75‐03‐6 ☐ ☐ ☐ ☐ ☐ ☑
801 Ethanesulfonyl chloride, 2‐chloro‐ 1622‐32‐8 ☐ ☑ ☑ ☐ ☐ ☑
802 Ethanethiol 75‐08‐1 ☑ ☑ ☑ ☐ ☐ ☑
803 Ethanimidothioic acid , 2‐ 30558‐43‐1 ☐ ☑ ☑ ☐ ☐ ☑
(dimethylamino)‐N‐hydroxy‐2‐oxo‐,
methyl ester
804 Ethanimidothioic acid , N‐ 16752‐77‐5 ☐ ☑ ☑ ☐ ☐ ☑
[[methylamino)carbonyl]
805 Ethanol, 1,2‐dichloro‐, acetate 10140‐87‐1 ☐ ☑ ☑ ☐ ☐ ☑
806 Ethanol 2,2'‐oxybis‐, dicarbamate 5952‐26‐1 ☐ ☑ ☑ ☐ ☐ ☑
807 ETHANOL, ‐CHLORO‐ 107‐07‐3 ☐ ☑ ☑ ☐ ☑ ☑
808 Ethanol, 2‐ethoxy‐ 110‐80‐5 ☐ ☑ ☑ ☐ ☐ ☑
809 ETHANOL, 2‐FLUORO‐ 371‐62‐0 ☐ ☑ ☑ ☐ ☑ ☑
810 ETHANOL, N‐NITROSOIMINODI‐ 1116‐54‐7 ☐ ☑ ☑ ☐ ☑ ☑
811 Ethion 563‐12‐2 ☐ ☑ ☑ ☐ ☐ ☑
812 Ethoprop 13194‐48‐4 ☐ ☑ ☑ ☐ ☐ ☑
813 Ethyl acetate 141‐78‐6 ☐ ☑ ☑ ☐ ☐ ☑
814 Ethyl acrylate 140‐88‐5 ☐ ☑ ☑ ☑ ☑ ☑
815 Ethyl benzene 100‐41‐4 ☐ ☑ ☑ ☑ ☐ ☑
816 Ethyl bis(2‐chloroethyl)amine 538‐07‐8 ☑ ☑ ☑ ☐ ☐ ☑
817 Ethyl carbamate (Urethane) 51‐79‐6 ☐ ☑ ☑ ☐ ☐ ☑
818 Ethyl chloride 75‐00‐3 ☑ ☑ ☑ ☑ ☐ ☑
819 Ethyl ether 60‐29‐7 ☑ ☑ ☑ ☑ ☐ ☑
820 ETHYL ISOCYANATE 109‐90‐0 ☐ ☐ ☐ ☐ ☑ ☑
821 Ethyl methacrylate 97‐63‐2 ☐ ☑ ☑ ☐ ☐ ☑
822 Ethyl nitrite 109‐95‐5 ☑ ☑ ☑ ☐ ☐ ☑
823 Ethyl vinyl ether 109‐92‐2 ☑ ☑ ☑ ☐ ☐ ☑
824 ETHYLAMINE,N‐METHYL‐N‐ 10595‐95‐6 ☐ ☐ ☐ ☐ ☑ ☑
NITROSO‐
825 Ethylene 74‐85‐1 ☑ ☑ ☑ ☐ ☐ ☑
826 Ethylene dibromide (Dibromoethane) 106‐93‐4 ☐ ☑ ☑ ☑ ☑ ☑
827 Ethylene dichloride (1,2‐ 107‐06‐2 ☐ ☑ ☑ ☑ ☑ ☑
Dichloroethane)
828 Ethylene glycol 107‐21‐1 ☐ ☑ ☑ ☑ ☐ ☑
829 Ethylene oxide 75‐21‐8 ☑ ☑ ☑ ☑ ☑ ☑
830 Ethylene thiourea 96‐45‐7 ☐ ☑ ☑ ☑ ☑ ☑
831 ETHYLENE, 1,1‐DICHLORO‐2,2‐BIS 72‐55‐9 ☐ ☑ ☑ ☐ ☑ ☑
(p‐CHLOROPHENYL)‐
(continued)
380 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
832 Ethylenebisdithiocarbamic acid , salts 111‐54‐6 ☐ ☑ ☑ ☐ ☐ ☑
& esters
833 Ethylenediamine‐tetraacetic acid 60‐00‐4 ☐ ☑ ☑ ☐ ☐ ☑
(EDTA)
834 Ethyleneimine 151‐56‐4 ☑ ☑ ☑ ☑ ☑ ☑
835 Ethylidene dichloride (1,1‐ 75‐34‐3 ☐ ☑ ☑ ☑ ☐ ☑
Dichloroethane)
836 Ethylphosphonic dichloride 1066‐50‐8 ☑ ☐ ☐ ☐ ☐ ☑
837 Ethylphosphonyl difluoride 753‐98‐0 ☑ ☐ ☐ ☐ ☐ ☑
838 Ethylthiocyanate 542‐90‐5 ☐ ☑ ☑ ☐ ☐ ☑
839 Famphur 52‐85‐7 ☐ ☑ ☑ ☐ ☐ ☑
840 Fenamiphos 22224‐92‐6 ☐ ☑ ☑ ☐ ☐ ☑
841 Fenbutatin oxide 13356‐08‐6 ☐ ☑ ☑ ☐ ☐ ☑
842 Fenoxycarb 72490‐01‐8 ☐ ☑ ☑ ☐ ☐ ☑
843 Fenpropathrin 39515‐41‐8 ☐ ☑ ☑ ☐ ☐ ☑
844 Fensulfothion 115‐90‐2 ☐ ☑ ☑ ☐ ☐ ☑
845 Ferbam 14484‐64‐1 ☐ ☑ ☑ ☐ ☐ ☑
846 Ferric ammonium citrate 1185‐57‐5 ☐ ☑ ☑ ☐ ☐ ☑
847 Ferric ammonium oxalate 2944‐67‐4 ☐ ☑ ☑ ☐ ☐ ☑
848 Ferric ammonium oxalate 55488‐87‐4 ☐ ☑ ☑ ☐ ☐ ☑
849 Ferric chloride 7705‐08‐0 ☐ ☑ ☑ ☐ ☐ ☑
850 Ferric fluoride 7783‐50‐8 ☐ ☑ ☑ ☐ ☐ ☑
851 Ferric nitrate 10421‐48‐4 ☐ ☑ ☑ ☐ ☐ ☑
852 Ferric sulfate 10028‐22‐5 ☐ ☑ ☑ ☐ ☐ ☑
853 Ferrous ammonium sulfate 10045‐89‐3 ☐ ☑ ☑ ☐ ☐ ☑
854 Ferrous chloride 7758‐94‐3 ☐ ☑ ☑ ☐ ☐ ☑
855 Ferrous sulfate 7782‐63‐0 ☐ ☑ ☑ ☐ ☐ ☑
856 Ferrous sulfate 7720‐78‐7 ☐ ☑ ☑ ☐ ☐ ☑
857 Fluazifop butyl 69806‐50‐4 ☐ ☑ ☑ ☐ ☐ ☑
858 Fluenetil 4301‐50‐2 ☐ ☑ ☑ ☐ ☐ ☑
859 Fluoranthene 206‐44‐0 ☐ ☑ ☑ ☐ ☐ ☑
860 FLUORANTHENE, 3‐NITRO‐ 892‐21‐7 ☐ ☐ ☐ ☐ ☑ ☑
861 Fluorene 86‐73‐7 ☐ ☑ ☑ ☐ ☐ ☑
862 Fluorine 7782‐41‐4 ☑ ☑ ☑ ☐ ☐ ☑
863 Fluoroacetamide 640‐19‐7 ☐ ☑ ☑ ☐ ☐ ☑
864 Fluoroacetic acid 144‐49‐0 ☐ ☑ ☑ ☐ ☐ ☑
865 Fluoroacetic acid , sodium salt 62‐74‐8 ☐ ☑ ☑ ☐ ☐ ☑
866 Fluoroacetyl chloride 359‐06‐8 ☐ ☑ ☑ ☐ ☐ ☑
867 Fluorosulfonic acid 7789‐21‐1 ☑ ☐ ☐ ☐ ☐ ☑
868 Folpet 133‐07‐3 ☐ ☑ ☑ ☐ ☐ ☑
869 Fonofos 944‐22‐9 ☐ ☑ ☑ ☐ ☐ ☑
870 Formaldehyde, 37% solution with 10‐15% ☑ ☑ ☑ ☑ ☑ ☑
871 Formetanate hydrochloride 23422‐53‐9 ☐ ☑ ☑ ☐ ☐ ☑
872 Formic acid 64‐18‐6 ☐ ☑ ☑ ☐ ☐ ☑
873 FORMIC acid , CHLORO‐, ALLYL 2937‐50‐0 ☐ ☐ ☐ ☑ ☐ ☑
ESTER
(continued)
Appendix 5: CAS RN Reportable Chemicals 381

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
874 FORMIC acid , CHLORO‐, ETHYL 541‐41‐3 ☐ ☑ ☑ ☑ ☐ ☑
ESTER
875 Formothion 2540‐82‐1 ☐ ☑ ☑ ☐ ☐ ☑
876 Formparanate 17702‐57‐7 ☐ ☑ ☑ ☐ ☐ ☑
877 Fosthietan 21548‐32‐3 ☐ ☑ ☑ ☐ ☐ ☑
878 Fuberidazole 3878‐19‐1 ☐ ☑ ☑ ☐ ☐ ☑
879 Fumaric acid 110‐17‐8 ☐ ☑ ☑ ☐ ☐ ☑
880 FURALDEHYDE, 5‐NITRO‐, 59‐87‐0 ☐ ☐ ☐ ☐ ☑ ☑
SEMICARBAZONE, 2‐
881 Furan 110‐00‐9 ☑ ☑ ☑ ☐ ☐ ☑
882 Furan, tetrahydro‐ 109‐99‐9 ☐ ☑ ☑ ☐ ☐ ☑
883 Furfural 98‐01‐1 ☐ ☑ ☑ ☐ ☐ ☑
884 Gallium trichloride 13450‐90‐3 ☐ ☑ ☑ ☐ ☐ ☑
885 Germane 7782‐65‐2 ☑ ☐ ☐ ☐ ☐ ☑
886 Germanium(IV) fluoride 7783‐58‐6 ☑ ☐ ☐ ☐ ☐ ☑
887 GLUCOPYRANOSE, 2‐DEOXY‐2‐(3‐ 18883‐66‐4 ☐ ☑ ☑ ☐ ☑ ☑
METHYL‐3‐NITROSOUREIDO)‐, D‐
888 GLUCOPYRANOSIDE, (METHYL‐ 14901‐08‐7 ☐ ☐ ☐ ☐ ☑ ☑
ONN‐AZOXY)METHYL‐, beta‐D‐
889 GLUTAMIC acid 59‐05‐2 ☐ ☐ ☐ ☐ ☑ ☑
890 Glycidylaldehyde 765‐34‐4 ☐ ☑ ☑ ☐ ☐ ☑
891 GOLD (1‐THIO‐D‐ 12192‐57‐3 ☐ ☐ ☐ ☐ ☑ ☑
GLUCOPYRANOSATO)‐
892 GUANIDINE, 1‐METHYL‐3‐NITRO‐ 70‐25‐7 ☐ ☑ ☑ ☐ ☑ ☑
1‐NITROSO‐
893 Guanyl nitrosaminoguanyltetrazene 109‐27‐3 ☑ ☐ ☐ ☐ ☐ ☑
894 HCFC‐121 354‐14‐3 ☐ ☑ ☑ ☐ ☐ ☑
895 HCFC‐121a 354‐11‐0 ☐ ☑ ☑ ☐ ☐ ☑
896 Heptachlor 76‐44‐8 ☐ ☑ ☑ ☑ ☐ ☑
897 Heptachlor epoxide 1024‐57‐3 ☐ ☑ ☑ ☐ ☐ ☑
898 Hexachlorobenzene 118‐74‐1 ☐ ☑ ☑ ☑ ☑ ☑
899 Hexachlorobutadiene 87‐68‐3 ☐ ☑ ☑ ☑ ☐ ☑
900 Hexachlorocyclohexane (all isomers) 608‐73‐1 ☐ ☑ ☑ ☐ ☐ ☑
901 Hexachlorocyclopentadiene 77‐47‐4 ☐ ☑ ☑ ☑ ☑ ☑
902 Hexachloroethane 67‐72‐1 ☐ ☑ ☑ ☑ ☑ ☑
903 Hexachloronaphthalene 1335‐87‐1 ☐ ☑ ☑ ☐ ☐ ☑
904 Hexachloropropene 1888‐71‐7 ☐ ☑ ☑ ☐ ☐ ☑
905 Hexafluoroacetone 684‐16‐2 ☑ ☐ ☐ ☐ ☐ ☑
906 Hexamethylene‐1,6‐diisocyanate 822‐06‐0 ☐ ☑ ☑ ☑ ☐ ☑
907 Hexamethylenediamine, N,N'‐dibutyl‐ 4835‐11‐4 ☐ ☑ ☑ ☐ ☐ ☑
908 Hexamethylphosphoramide 680‐31‐9 ☐ ☑ ☑ ☑ ☑ ☑
909 Hexane 110‐54‐3 ☐ ☑ ☑ ☑ ☐ ☑
910 Hexazinone 51235‐04‐2 ☐ ☐ ☐ ☐ ☐ ☑
911 Hexotonal 67713‐16‐0 ☑ ☐ ☐ ☐ ☐ ☑
912 Hexyltrichlorosilane 928‐65‐4 ☑ ☐ ☐ ☐ ☐ ☑
913 HYDANTOIN, 1‐((5‐ 67‐20‐9 ☐ ☑ ☑ ☐ ☑ ☑
NITROFURFURYLIDENE)AMINO)‐
(continued)
382 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
914 HYDANTOIN, 5,5‐DIPHENYL‐ 57‐41‐0 ☐ ☑ ☑ ☐ ☑ ☑
915 Hydramethylnon 67485‐29‐4 ☐ ☑ ☑ ☐ ☐ ☑
916 Hydrazine sulfate 10034‐93‐2 ☐ ☑ ☑ ☐ ☐ ☑
917 Hydrazine, 1,2‐diethyl‐ 1615‐80‐1 ☐ ☑ ☑ ☐ ☐ ☑
918 Hydrazine 1,2‐dimethyl‐ 540‐73‐8 ☐ ☑ ☑ ☐ ☐ ☑
919 Hydrazine anhydrous 302‐01‐2 ☑ ☑ ☑ ☑ ☑ ☑
920 Hydrogen bromide, gas 10035‐10‐6 ☑ ☐ ☐ ☐ ☐ ☑
921 Hydrogen chloride, gas 7647‐01‐0 ☑ ☑ ☑ ☑ ☐ ☑
922 Hydrogen cyanide aqueous solution 74‐90‐8 ☑ ☑ ☑ ☐ ☐ ☑
923 Hydrogen fluoride gas 7664‐39‐3 ☑ ☑ ☑ ☑ ☐ ☑
924 Hydrogen gas 1333‐74‐0 ☑ ☑ ☑ ☐ ☐ ☑
925 Hydrogen iodide, anhydrous 10034‐85‐2 ☑ ☐ ☐ ☐ ☐ ☑
926 Hydrogen peroxide, 30‐60 % aqueous 7722‐84‐1 ☑ ☑ ☑ ☐ ☑ ☑
solution
927 Hydrogen selenide gas 7783‐07‐5 ☑ ☑ ☑ ☐ ☐ ☑
928 Hydrogen sulfide 7783‐06‐4 ☑ ☑ ☑ ☐ ☐ ☑
929 Hydroquinone 123‐31‐9 ☐ ☑ ☑ ☑ ☑ ☑
930 IMFERON 9004‐66‐4 ☐ ☐ ☐ ☐ ☑ ☑
931 IMIDAZOLE‐4‐CARBOXAMIDE, 5‐ 4342‐03‐4 ☐ ☐ ☐ ☐ ☑ ☑
(3,3‐DIMETHYL‐1‐TRIAZENO)‐
932 IMIDAZOLIDINONE, 1‐((5‐ 555‐84‐0 ☐ ☐ ☐ ☐ ☑ ☑
NITROFURFURYLIDENE)AMINO)‐,
2‐
933 Indeno(1,2,3‐cd)pyrene 193‐39‐5 ☐ ☑ ☑ ☐ ☐ ☑
934 Iodine pentafluoride 7783‐66‐6 ☑ ☑ ☑ ☐ ☐ ☑
935 IOSYANATE, T‐BUTYL 7188‐38‐7 ☐ ☐ ☐ ☐ ☑ ☑
936 Iron(0)pentacarbonyl 13463‐40‐6 ☑ ☑ ☑ ☐ ☑ ☑
937 iso‐Amyl acetate 123‐92‐2 ☐ ☑ ☑ ☐ ☐ ☑
938 Isobenzan 297‐78‐9 ☐ ☑ ☑ ☐ ☐ ☑
939 iso‐Butyl acetate 110‐19‐0 ☐ ☑ ☑ ☐ ☐ ☑
940 Isobutyl alcohol 78‐83‐1 ☐ ☑ ☑ ☐ ☐ ☑
941 iso‐Butylamine 78‐81‐9 ☐ ☑ ☑ ☐ ☐ ☑
942 Isobutyraldehyde 78‐84‐2 ☐ ☑ ☑ ☐ ☐ ☑
943 iso‐Butyric acid 79‐31‐2 ☐ ☑ ☑ ☐ ☐ ☑
944 Isobutyronitrile 78‐82‐0 ☑ ☑ ☑ ☐ ☐ ☑
945 ISOCYANATE, N‐BUTYL 111‐36‐4 ☐ ☐ ☐ ☐ ☑ ☑
946 ISOCYANIC acid , ,4‐ 102‐36‐3 ☐ ☑ ☑ ☐ ☑ ☑
DICHLOROPHENYL ESTER
947 ISOCYANIC acid , METHYLENE 4098‐71‐9 ☐ ☑ ☑ ☐ ☑ ☑
(3,5,5‐TRIMETHYL‐3,1‐
CYCLOHEXYLENE)ESTER
948 ISOCYANIC acid , METHYLENEDI‐ 5124‐30‐1 ☐ ☑ ☑ ☐ ☑ ☑
4,1‐CYCLOHEXYLENE ESTER
949 Isodrin 465‐73‐6 ☐ ☑ ☑ ☐ ☐ ☑
950 ISONICOTINIC acid HYDRAZIDE 54‐85‐3 ☐ ☐ ☐ ☐ ☑ ☑
951 Isopentane 78‐78‐4 ☑ ☑ ☑ ☐ ☐ ☑
952 Isophorone 78‐59‐1 ☐ ☑ ☑ ☑ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 383

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
953 Isoprene 78‐79‐5 ☑ ☑ ☑ ☐ ☐ ☑
954 Isopropanolamine dodecylbenzene 42504‐46‐1 ☐ ☑ ☑ ☐ ☐ ☑
sulfonate
955 Isopropyl alcohol (mfg‐strong acid 67‐63‐0 ☐ ☑ ☑ ☐ ☐ ☑
process)
956 Isopropyl chloride 75‐29‐6 ☑ ☑ ☑ ☐ ☐ ☑
957 Isopropyl chloroformate 108‐23‐6 ☑ ☑ ☑ ☐ ☐ ☑
958 ISOPROPYL ETHANE 1943‐83‐5 ☐ ☐ ☐ ☐ ☑ ☑
FLUOROPHOSPHONATE
959 Isopropylamine 75‐31‐0 ☑ ☑ ☑ ☐ ☐ ☑
960 Isopropylmethylpyrazolyl 119‐38‐0 ☐ ☑ ☑ ☐ ☐ ☑
dimethylcarbamate
961 Isosafrole 120‐58‐1 ☐ ☑ ☑ ☐ ☐ ☑
962 Kepone 143‐50‐0 ☐ ☑ ☑ ☐ ☐ ☑
963 LACTONITRILE 78‐97‐7 ☐ ☑ ☑ ☐ ☑ ☑
964 Lasiocarpine 303‐34‐4 ☐ ☑ ☑ ☐ ☐ ☑
965 LEAD 7439‐92‐1 ☐ ☑ ☑ ☐ ☑ ☑
966 Lead acetate 301‐04‐2 ☐ ☑ ☑ ☐ ☐ ☑
967 Lead arsenate 7784‐40‐9 ☐ ☑ ☑ ☐ ☐ ☑
968 Lead arsenate 10102‐48‐4 ☐ ☑ ☑ ☐ ☐ ☑
969 Lead arsenate 7645‐25‐2 ☐ ☑ ☑ ☐ ☐ ☑
970 Lead azide 13424‐46‐9 ☑ ☐ ☐ ☐ ☐ ☑
971 Lead chloride 7758‐95‐4 ☐ ☑ ☑ ☐ ☐ ☑
972 Lead fluoborate 13814‐96‐5 ☐ ☑ ☑ ☐ ☐ ☑
973 Lead fluoride 7783‐46‐2 ☐ ☑ ☑ ☐ ☐ ☑
974 Lead iodide 10101‐63‐0 ☐ ☑ ☑ ☐ ☐ ☑
975 Lead nitrate 10099‐74‐8 ☐ ☑ ☑ ☐ ☐ ☑
976 Lead phosphate 7446‐27‐7 ☐ ☑ ☑ ☐ ☐ ☑
977 Lead stearate 56189‐09‐4 ☐ ☑ ☑ ☐ ☐ ☑
978 Lead stearate 7428‐48‐0 ☐ ☑ ☑ ☐ ☐ ☑
979 Lead stearate 1072‐35‐1 ☐ ☑ ☑ ☐ ☐ ☑
980 Lead stearate 52652‐59‐2 ☐ ☑ ☑ ☐ ☐ ☑
981 Lead styphnate, wetted with not less 15245‐44‐0 ☑ ☐ ☐ ☐ ☐ ☑
than 20% water, or mixture of alcohol
982 Lead subacetate 1335‐32‐6 ☐ ☑ ☑ ☐ ☐ ☑
983 Lead sulfate 15739‐80‐7 ☐ ☑ ☑ ☐ ☐ ☑
984 Lead sulfate 7446‐14‐2 ☐ ☑ ☑ ☐ ☐ ☑
985 Lead sulfide 1314‐87‐0 ☐ ☑ ☑ ☐ ☐ ☑
986 Lead thiocyanate 592‐87‐0 ☐ ☑ ☑ ☐ ☐ ☑
987 Leptophos 21609‐90‐5 ☐ ☑ ☑ ☐ ☐ ☑
988 Lewisite 541‐25‐3 ☑ ☑ ☑ ☐ ☐ ☑
989 Lindane (all isomers) 58‐89‐9 ☐ ☑ ☑ ☑ ☑ ☑
990 Linuron 330‐55‐2 ☐ ☑ ☑ ☐ ☐ ☑
991 Lithium amide 7782‐89‐0 ☑ ☐ ☐ ☐ ☐ ☑
992 Lithium carbonate 554‐13‐2 ☐ ☑ ☑ ☐ ☐ ☑
993 Lithium chromate 14307‐35‐8 ☐ ☑ ☑ ☐ ☐ ☑
994 Lithium hydride 7580‐67‐8 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
384 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
995 Lithium nitride 26134‐62‐3 ☑ ☐ ☐ ☐ ☐ ☑
996 Magnesium aluminum phosphide 864738‐69‐2 ☑ ☐ ☐ ☐ ☐ ☑
997 Magnesium aluminum phosphide 134884‐20‐1 ☑ ☐ ☐ ☐ ☐ ☑
998 Magnesium aluminum phosphide 864738‐68‐1 ☑ ☐ ☐ ☐ ☐ ☑
999 Magnesium amide 7803‐54‐5 ☑ ☐ ☐ ☐ ☐ ☑
1000 Magnesium phosphide 12057‐74‐8 ☑ ☐ ☐ ☐ ☐ ☑
1001 Malathion 121‐75‐5 ☐ ☑ ☑ ☐ ☐ ☑
1002 Maleic acid 110‐16‐7 ☐ ☑ ☑ ☐ ☐ ☑
1003 Maleic anhydride 108‐31‐6 ☐ ☑ ☑ ☑ ☐ ☑
1004 Maleic hydrazide 123‐33‐1 ☐ ☑ ☑ ☐ ☐ ☑
1005 MALEIMIDE, N,N'‐(m‐ 3006‐93‐7 ☐ ☐ ☐ ☐ ☑ ☑
PHENYLENE)Dl‐
1006 Malononitrile 109‐77‐3 ☐ ☑ ☑ ☐ ☐ ☑
1007 MANGANESE 7439‐96‐5 ☐ ☑ ☑ ☐ ☐ ☑
1008 MANGANESE, (ETHYLENEBIS 12427‐38‐2 ☐ ☑ ☑ ☐ ☑ ☑
(DITHIOCARBAMATO))‐
1009 Manganese, bis 15339‐36‐3 ☐ ☑ ☑ ☐ ☑ ☑
(dimethylcarbamodithioato‐S,S')‐
1010 MANGANESE, TRICARBONYL 12108‐13‐3 ☐ ☑ ☑ ☐ ☐ ☑
METHYLCYCLOPENTADIENYL
1011 Mannitol hexanitrate 15825‐70‐4 ☑ ☐ ☐ ☐ ☑ ☑
1012 MBT 149‐30‐4 ☐ ☑ ☑ ☐ ☐ ☑
1013 m‐Cresol 108‐39‐4 ☐ ☑ ☑ ☑ ☐ ☑
1014 m‐Dinitrobenzene 99‐65‐0 ☐ ☑ ☑ ☐ ☐ ☑
1015 Mecoprop 93‐65‐2 ☐ ☑ ☑ ☐ ☐ ☑
1016 MELAMINE 108‐78‐1 ☐ ☐ ☐ ☐ ☑ ☑
1017 Melphalan 148‐82‐3 ☐ ☑ ☑ ☐ ☐ ☑
1018 MENTHA‐6,8‐DIEN‐2‐ONE, (S)‐(+)‐, 2244‐16‐8 ☐ ☐ ☐ ☐ ☑ ☑
p‐
1019 Mephosfolan 950‐10‐7 ☐ ☑ ☑ ☐ ☐ ☑
1020 Mercaptodimethur 2032‐65‐7 ☐ ☑ ☑ ☐ ☐ ☑
1021 Mercuric acetate 1600‐27‐7 ☐ ☑ ☑ ☐ ☐ ☑
1022 Mercuric chloride 7487‐94‐7 ☐ ☑ ☑ ☐ ☐ ☑
1023 Mercuric cyanide 592‐04‐1 ☐ ☑ ☑ ☐ ☐ ☑
1024 Mercuric nitrate 10045‐94‐0 ☐ ☑ ☑ ☐ ☐ ☑
1025 Mercuric oxide 21908‐53‐2 ☐ ☑ ☑ ☐ ☐ ☑
1026 Mercuric sulfate 7783‐35‐9 ☐ ☑ ☑ ☐ ☐ ☑
1027 Mercuric thiocyanate 592‐85‐8 ☐ ☑ ☑ ☐ ☐ ☑
1028 Mercurous nitrate 7782‐86‐7 ☐ ☑ ☑ ☐ ☐ ☑
1029 Mercurous nitrate 10415‐75‐5 ☐ ☑ ☑ ☐ ☐ ☑
1030 MERCURY 7439‐97‐6 ☐ ☑ ☑ ☐ ☑ ☑
1031 Mercury fulminate 628‐86‐4 ☑ ☑ ☑ ☐ ☐ ☑
1032 MERCURY, CHLOROMETHYL‐ 115‐09‐3 ☐ ☐ ☐ ☐ ☑ ☑
1033 Merphos 150‐50‐5 ☐ ☑ ☑ ☐ ☑ ☑
1034 Methacrylic anhydride 760‐93‐0 ☐ ☑ ☑ ☐ ☐ ☑
1035 Methacryloyl chloride 920‐46‐7 ☐ ☑ ☑ ☐ ☐ ☑
1036 MethacryloyloxyEthyl isocyanate 30674‐80‐7 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 385

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1037 Metham sodium 137‐42‐8 ☐ ☑ ☑ ☐ ☐ ☑
1038 Methamidophos 10265‐92‐6 ☐ ☑ ☑ ☐ ☐ ☑
1039 Methane 74‐82‐8 ☑ ☑ ☑ ☐ ☐ ☑
1040 METHANE, BROMODICHLORO‐ 75‐27‐4 ☐ ☑ ☑ ☐ ☑ ☑
1041 METHANE, CHLORODIBROMO‐ 124‐48‐1 ☐ ☑ ☑ ☐ ☑ ☑
1042 METHANE,CHLOROFLUORO‐ 593‐70‐4 ☐ ☐ ☐ ☐ ☑ ☑
1043 METHANESULFONIC acid , ETHYL 62‐50‐0 ☐ ☑ ☑ ☐ ☑ ☑
ESTER
1044 METHANESULFONIC acid , 66‐27‐3 ☐ ☐ ☐ ☐ ☑ ☑
METHYL ESTER
1045 Methanesulfonyl fluoride 558‐25‐8 ☐ ☑ ☑ ☐ ☐ ☑
1046 Methanethiol 74‐93‐1 ☑ ☑ ☑ ☐ ☐ ☑
1047 Methanol 67‐56‐1 ☐ ☑ ☑ ☑ ☐ ☑
1048 METHANOL, (METHYL‐ONN‐ 592‐62‐1 ☐ ☐ ☐ ☐ ☑ ☑
AZOXY)‐, ACETATE (ester)
1049 Methapyrilene 91‐80‐5 ☐ ☑ ☑ ☐ ☐ ☑
1050 Methidathion 950‐37‐8 ☐ ☑ ☑ ☑ ☐ ☑
1051 Methoxychlor 72‐43‐5 ☐ ☑ ☑ ☐ ☑ ☑
1052 Methoxyethylmercuric acetate 151‐38‐2 ☐ ☑ ☑ ☐ ☐ ☑
1053 Methyl 2‐chloroacrylate 80‐63‐7 ☐ ☑ ☑ ☐ ☐ ☑
1054 Methyl acrylate 96‐33‐3 ☐ ☑ ☑ ☑ ☐ ☑
1055 Methyl chloroform (1,1,1‐ 71‐55‐6 ☐ ☑ ☑ ☐ ☐ ☑
Trichloroethane)
1056 Methyl chloroformate 79‐22‐1 ☑ ☑ ☑ ☐ ☑ ☑
1057 Methyl ethyl ketone 78‐93‐3 ☐ ☑ ☑ ☐ ☐ ☑
1058 Methyl ethyl ketone peroxide 1338‐23‐4 ☐ ☑ ☑ ☐ ☐ ☑
1059 Methyl formate 107‐31‐3 ☑ ☑ ☑ ☑ ☐ ☑
1060 Methyl iodide (Iodomethane) 74‐88‐4 ☐ ☑ ☑ ☑ ☐ ☑
1061 Methyl isobutyl ketone (Hexone) 108‐10‐1 ☐ ☑ ☑ ☑ ☑ ☑
1062 Methyl isocyanate 624‐83‐9 ☑ ☑ ☑ ☐ ☑ ☑
1063 METHYL ISOTHIOCYANATE 556‐61‐6 ☐ ☑ ☑ ☑ ☐ ☑
1064 Methyl methacrylate 80‐62‐6 ☐ ☑ ☑ ☐ ☐ ☑
1065 Methyl parathion 298‐00‐0 ☐ ☑ ☑ ☐ ☐ ☑
1066 Methyl phenkapton 3735‐23‐7 ☐ ☑ ☑ ☐ ☐ ☑
1067 Methyl phosphonyl difluoride 676‐99‐3 ☑ ☐ ☐ ☐ ☑ ☑
1068 METHYL SULFIDE 75‐18‐3 ☐ ☐ ☐ ☑ ☐ ☑
1069 Methyl tert butyl ether 1634‐04‐4 ☐ ☑ ☑ ☐ ☐ ☑
1070 Methyl thiocyanate 556‐64‐9 ☑ ☑ ☑ ☐ ☐ ☑
1071 Methyl vinyl ether 107‐25‐5 ☑ ☑ ☑ ☐ ☐ ☑
1072 Methylacrylonitrile 126‐98‐7 ☑ ☑ ☑ ☐ ☐ ☑
1073 Methylamine, anhydrous 74‐89‐5 ☑ ☑ ☑ ☐ ☐ ☑
1074 Methylchlorosilane 993‐00‐0 ☑ ☐ ☐ ☐ ☐ ☑
1075 Methylene bromide 74‐95‐3 ☐ ☑ ☑ ☐ ☐ ☑
1076 Methylene chloride (Dichloromethane) 75‐09‐2 ☐ ☑ ☑ ☑ ☑ ☑
1077 Methylene diphenyl diisocyanate 101‐68‐8 ☐ ☑ ☑ ☑ ☑ ☑
(MDI)
(continued)
386 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1078 Methylhydrazine 60‐34‐4 ☑ ☑ ☑ ☑ ☑ ☑
1079 Methylmercuric dicyanamide 502‐39‐6 ☐ ☑ ☑ ☐ ☐ ☑
1080 Methylphosphonic dichloride 676‐97‐1 ☑ ☑ ☑ ☐ ☑ ☑
1081 Methylthiouracil 56‐04‐2 ☐ ☑ ☑ ☐ ☐ ☑
1082 Methyltrichlorosilane 75‐79‐6 ☑ ☑ ☑ ☐ ☐ ☑
1083 Metiram 9006‐42‐2 ☐ ☑ ☑ ☐ ☐ ☑
1084 Metolcarb 1129‐41‐5 ☐ ☑ ☑ ☐ ☐ ☑
1085 Metribuzin 21087‐64‐9 ☐ ☑ ☑ ☐ ☐ ☑
1086 Mevinphos 7786‐34‐7 ☐ ☑ ☑ ☐ ☐ ☑
1087 Mexacarbate 315‐18‐4 ☐ ☑ ☑ ☐ ☐ ☑
1088 Michler's ketone 90‐94‐8 ☐ ☑ ☑ ☐ ☐ ☑
1089 m‐Nitrophenol 554‐84‐7 ☐ ☑ ☑ ☐ ☐ ☑
1090 m‐Nitrotoluene 99‐08‐1 ☐ ☑ ☑ ☐ ☐ ☑
1091 Molybdenum trioxide 1313‐27‐5 ☐ ☑ ☑ ☐ ☐ ☑
1092 MONOCROTALINE 315‐22‐0 ☐ ☐ ☐ ☐ ☑ ☑
1093 Monocrotophos 6923‐22‐4 ☐ ☑ ☑ ☐ ☐ ☑
1094 MORPHOLINE 110‐91‐8 ☐ ☐ ☐ ☐ ☑ ☑
1095 m‐Xylenes 108‐38‐3 ☐ ☑ ☑ ☑ ☐ ☑
1096 N‐(1‐Ethylpropyl)‐3,4‐dimethyl‐2,6‐ 40487‐42‐1 ☐ ☑ ☑ ☐ ☐ ☑
dinitrobenzenamine
1097 N‐(2‐Chloro‐4‐(trifluoromethyl) 69409‐94‐5 ☐ ☑ ☑ ☐ ☐ ☑
phenyl)‐DL‐valine(+)‐cyano(3‐
phenoxyphenyl)
1098 N‐(2‐Chloroethyl)diisopropylamine 96‐79‐7 ☑ ☐ ☐ ☐ ☐ ☑
1099 N‐(3,4‐Dichlorophenyl)propanamide 709‐98‐8 ☐ ☑ ☑ ☐ ☐ ☑
1100 N‐(5‐(1,1‐Dimethylethyl)‐1,3,4‐ 34014‐18‐1 ☐ ☑ ☑ ☐ ☐ ☑
thiadiazol‐2‐yl)‐N,N'‐dimethylurea
1101 N,N'‐(1,4‐Piperazinediylbis(2,2,2‐ 26644‐46‐2 ☐ ☑ ☑ ☐ ☐ ☑
trichloroethylidene)) bisformamide
1102 N,N'‐Bis(1‐methylethyl)‐6‐methylthio‐ 7287‐19‐6 ☐ ☑ ☑ ☐ ☐ ☑
1,3,5‐triazine‐2,4‐diamine
1103 N,N‐Diethylaniline 91‐66‐7 ☐ ☑ ☑ ☐ ☐ ☑
1104 N,N‐Dimethylaniline 121‐69‐7 ☐ ☑ ☑ ☑ ☐ ☑
1105 N,N‐Dimethylhydrazine 57‐14‐7 ☑ ☑ ☑ ☑ ☑ ☑
1106 N,N‐ 677‐43‐0 ☑ ☐ ☐ ☐ ☐ ☑
Dimethylphosphoramidodichloridate
1107 Nabam 142‐59‐6 ☐ ☑ ☑ ☐ ☐ ☑
1108 Naled 300‐76‐5 ☐ ☑ ☑ ☐ ☐ ☑
1109 Naphthalene 91‐20‐3 ☐ ☑ ☑ ☑ ☐ ☑
1110 NAPHTHALENE DISULFONIC acid , 6459‐94‐5 ☐ ☑ ☑ ☐ ☑ ☑
1,3‐
1111 NAPHTHALENE DISULFONIC acid , 2429‐74‐5 ☐ ☐ ☐ ☐ ☑ ☑
2,7‐
1112 NAPHTHALENE DISULFONIC acid , 915‐67‐3 ☐ ☐ ☐ ☐ ☑ ☑
3‐HYDROXY‐4‐((4‐SULFO‐1‐
NAPHTHYL)AZO
1113 NAPHTHALENE DISULFONIC acid , 3761‐53‐3 ☐ ☑ ☑ ☐ ☑ ☑
3‐HYDROXY‐4‐(2,4‐XYLYLAZO)‐
DISODIUM S
(continued)
Appendix 5: CAS RN Reportable Chemicals 387

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1114 NAPHTHALENEDIAMINE, 1,5‐ 2243‐62‐1 ☐ ☐ ☐ ☐ ☑ ☑
1115 Naphthenic acid 1338‐24‐5 ☐ ☑ ☑ ☐ ☐ ☑
1116 NAPHTHOL, 1‐(2,4‐XYLYLAZO)‐, 2‐ 3118‐97‐6 ☐ ☑ ☑ ☐ ☑ ☑
1117 NAPHTHOL, 1‐(o‐TOLYLAZO)‐, 2‐ 2646‐17‐5 ☐ ☐ ☐ ☐ ☑ ☑
1118 NAPHTHOL, 1‐(PHENYLAZO)‐, 2‐ 842‐07‐9 ☐ ☑ ☑ ☐ ☑ ☑
1119 NAPHTHYLAMINE,2‐ 91‐59‐8 ☐ ☑ ☑ ☐ ☑ ☑
1120 NAPHTHYLAMINE, alpha‐ 134‐32‐7 ☐ ☐ ☐ ☐ ☑ ☑
1121 NAPHTHYLAMINE, N‐PHENYL‐, 2‐ 135‐88‐6 ☐ ☑ ☑ ☐ ☑ ☑
1122 n‐Butyl alcohol 71‐36‐3 ☐ ☐ ☐ ☐ ☐ ☑
1123 N‐Ethyldiethanolamine 139‐87‐7 ☑ ☑ ☑ ☐ ☐ ☑
1124 NICKEL 7440‐02‐0 ☐ ☑ ☑ ☐ ☑ ☑
1125 Nickel ammonium sulfate 15699‐18‐0 ☐ ☑ ☑ ☐ ☐ ☑
1126 Nickel carbonyl 13463‐39‐3 ☑ ☑ ☑ ☐ ☐ ☑
1127 Nickel chloride 37211‐05‐5 ☐ ☑ ☑ ☐ ☐ ☑
1128 Nickel chloride 7718‐54‐9 ☐ ☑ ☑ ☐ ☐ ☑
1129 Nickel cyanide 557‐19‐7 ☐ ☑ ☑ ☐ ☐ ☑
1130 Nickel hydroxide 12054‐48‐7 ☐ ☑ ☑ ☐ ☐ ☑
1131 Nickel nitrate 14216‐75‐2 ☐ ☑ ☑ ☐ ☐ ☑
1132 Nickel sulfate 7786‐81‐4 ☐ ☑ ☑ ☐ ☐ ☑
1133 NICOTINE 54‐11‐5 ☐ ☑ ☑ ☐ ☑ ☑
1134 NICOTINE, SULFATE (21) 65‐30‐5 ☐ ☑ ☑ ☐ ☑ ☑
1135 Nitric acid , with less than70% Nitric 7697‐37‐2 ☑ ☑ ☑ ☐ ☑ ☑
acid
1136 Nitrobenzene 98‐95‐3 ☐ ☑ ☑ ☑ ☐ ☑
1137 Nitrocellulose, dry or wet with less than 9004‐70‐0 ☑ ☐ ☐ ☐ ☐ ☑
25% water or alcohol
1138 NITROGEN DIOXIDE 10102‐44‐0 ☐ ☑ ☑ ☐ ☑ ☑
1139 Nitrogen monoxide 10102‐43‐9 ☑ ☑ ☑ ☐ ☑ ☑
1140 Nitrogen tetroxide, gas 10544‐72‐6 ☑ ☑ ☑ ☐ ☑ ☑
1141 Nitrogen trioxide 10544‐73‐7 ☑ ☐ ☐ ☐ ☐ ☑
1142 Nitroglycerin 55‐63‐0 ☑ ☑ ☑ ☐ ☐ ☑
1143 Nitroguanidine, dry or wetted with 556‐88‐7 ☑ ☐ ☐ ☐ ☐ ☑
<20% water by mass
1144 Nitromethane 75‐52‐5 ☑ ☐ ☐ ☐ ☐ ☑
1145 Nitrophenol (mixed isomers) 25154‐55‐6 ☐ ☑ ☑ ☐ ☐ ☑
1146 Nitrostarch 9056‐38‐6 ☑ ☐ ☐ ☐ ☐ ☑
1147 Nitrosyl chloride 2696‐92‐6 ☑ ☐ ☐ ☐ ☐ ☑
1148 Nitrotoluene 1321‐12‐6 ☐ ☑ ☑ ☐ ☐ ☑
1149 Nitrotriazolone 932‐64‐9 ☑ ☐ ☐ ☐ ☐ ☑
1150 Nitrourea 556‐89‐8 ☑ ☐ ☐ ☐ ☐ ☑
1151 NITROUS acid , SODIUM SALT 7632‐00‐0 ☐ ☑ ☑ ☐ ☑ ☑
1152 N‐Methyl‐2‐pyrrolidone 872‐50‐4 ☐ ☑ ☑ ☐ ☐ ☑
1153 N‐Methyldiethanolamine 105‐59‐9 ☑ ☐ ☐ ☐ ☐ ☑
1154 N‐Methylolacrylamide 924‐42‐5 ☐ ☑ ☑ ☐ ☐ ☑
1155 N‐Nitrosodiethylamine 55‐18‐5 ☐ ☑ ☑ ☐ ☐ ☑
1156 N‐Nitrosodimethylamine 62‐75‐9 ☐ ☑ ☑ ☑ ☑ ☑
(continued)
388 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1157 N‐Nitrosodiphenylamine 86‐30‐6 ☐ ☑ ☑ ☐ ☐ ☑
1158 N‐Nitrosomethylvinylamine 4549‐40‐0 ☐ ☑ ☑ ☐ ☐ ☑
1159 N‐Nitrosomorpholine 59‐89‐2 ☐ ☑ ☑ ☑ ☑ ☑
1160 N‐Nitroso‐N‐methylurea 684‐93‐5 ☐ ☑ ☑ ☑ ☑ ☑
1161 N‐Nitroso‐N‐methylurethane 615‐53‐2 ☐ ☑ ☑ ☐ ☐ ☑
1162 N‐Nitrosonornicotine 16543‐55‐8 ☐ ☑ ☑ ☐ ☐ ☑
1163 Nonyltrichlorosilane 5283‐67‐0 ☑ ☐ ☐ ☐ ☐ ☑
1164 Norbormide 991‐42‐4 ☐ ☑ ☑ ☐ ☑ ☑
1165 NORBORNENE‐2,3‐ 115‐28‐6 ☐ ☑ ☑ ☐ ☐ ☑
DICARBOXYLIC acid , 1,4,5,6,7,7‐
HEXACHLORO‐,5‐
1166 N‐Pentane 109‐66‐0 ☑ ☑ ☑ ☐ ☐ ☑
1167 N‐PROPYL ISOCYANATE 110‐78‐1 ☐ ☐ ☐ ☐ ☑ ☑
1168 n‐Propylamine 107‐10‐8 ☐ ☑ ☑ ☐ ☐ ☑
1169 O‐(2‐(Diethylamino)‐6‐methyl‐4‐ 29232‐93‐7 ☐ ☑ ☑ ☐ ☐ ☑
pyrimidinyl)‐O,O‐Dimethyl
phosphorothioate
1170 O‐(4‐Bromo‐2‐chlorophenyl)‐O‐ethyl‐ 41198‐08‐7 ☐ ☑ ☑ ☐ ☐ ☑
S‐propylphosphorothioate
1171 O,O‐Diethyl O‐pyrazinyl 297‐97‐2 ☐ ☑ ☑ ☐ ☐ ☑
phosphorothioate
1172 O,O‐Diethyl S‐Methyl dithiophosphate 3288‐58‐2 ☐ ☑ ☑ ☐ ☐ ☑
1173 O,O‐Dimethyl O‐(3‐methyl‐4‐ 55‐38‐9 ☐ ☑ ☑ ☐ ☐ ☑
(methylthio) phenyl) ester,
phosphorothioic aci
1174 o‐Anisidine 90‐04‐0 ☐ ☑ ☑ ☑ ☐ ☑
1175 o‐Anisidine hydrochloride 134‐29‐2 ☐ ☑ ☑ ☐ ☐ ☑
1176 o‐Cresol 95‐48‐7 ☐ ☑ ☑ ☑ ☐ ☑
1177 Octachloronaphthalene 2234‐13‐1 ☐ ☑ ☑ ☐ ☐ ☑
1178 Octachlorostyrene 29082‐74‐4 ☐ ☑ ☑ ☐ ☐ ☑
1179 Octolite 57607‐37‐1 ☑ ☐ ☐ ☐ ☐ ☑
1180 Octonal 78413‐87‐3 ☑ ☐ ☐ ☐ ☐ ☑
1181 Octyltrichlorosilane 5283‐66‐9 ☑ ☐ ☐ ☐ ☐ ☑
1182 o‐Dianisidine hydrochloride 111984‐09‐9 ☐ ☑ ☑ ☐ ☐ ☑
1183 o‐Dichlorobenzene 95‐50‐1 ☐ ☑ ☑ ☐ ☐ ☑
1184 o‐Dinitrobenzene 528‐29‐0 ☐ ☑ ☑ ☐ ☐ ☑
1185 O‐Ethyl O‐(4‐(methylthio)phenyl) 35400‐43‐2 ☐ ☑ ☑ ☐ ☐ ☑
phosphorodithioic acid S‐propyl ester
1186 6O‐Ethyl S‐2‐diisopropylaminoethyl 50782‐69‐9 ☑ ☑ ☑ ☐ ☐ ☑
methylphosphonothiote
1187 o‐Ethyl‐2‐diisopropylaminoethyl 57856‐11‐8 ☑ ☐ ☐ ☐ ☐ ☑
Methyl phosphonite
1188 o‐Nitrotoluene 88‐72‐2 ☐ ☑ ☑ ☐ ☐ ☑
1189 O‐Pinacolyl 7040‐57‐5 ☑ ☐ ☐ ☐ ☐ ☑
methylphosphonochloridate
1190 o‐Pinacolyl methylphosphonofluoridate 96‐64‐0 ☑ ☐ ☐ ☐ ☐ ☑
1191 Osmium oxide OsO4 (T‐4)‐ 20816‐12‐0 ☐ ☑ ☑ ☐ ☐ ☑
1192 o‐Toluidine 95‐53‐4 ☐ ☑ ☑ ☑ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 389

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1193 o‐Toluidine hydrochloride 636‐21‐5 ☐ ☑ ☑ ☐ ☐ ☑
1194 Ouabain 630‐60‐4 ☐ ☑ ☑ ☐ ☐ ☑
1195 OXABICYCLO(4.1.0)HEPTANE 3‐ 106‐87‐6 ☐ ☐ ☐ ☐ ☑ ☑
(EPOXYETHYL)‐, 7‐
1196 Oxamyl 23135‐22‐0 ☐ ☑ ☑ ☐ ☐ ☑
1197 Oxetane, 3,3‐bis(chloromethyl)‐ 78‐71‐7 ☐ ☑ ☑ ☐ ☐ ☑
1198 Oxydisulfoton 2497‐07‐6 ☐ ☑ ☑ ☐ ☐ ☑
1199 Oxyfluorfen 42874‐03‐3 ☐ ☑ ☑ ☐ ☐ ☑
1200 Oxygen difluoride 7783‐41‐7 ☑ ☐ ☐ ☐ ☐ ☑
1201 o‐Xylenes 95‐47‐6 ☐ ☑ ☑ ☑ ☐ ☑
1202 Ozone 10028‐15‐6 ☐ ☑ ☑ ☐ ☐ ☑
1203 p‐Anisidine 104‐94‐9 ☐ ☑ ☑ ☐ ☐ ☑
1204 Paraformaldehyde 30525‐89‐4 ☐ ☑ ☑ ☐ ☐ ☑
1205 Paraldehyde 123‐63‐7 ☐ ☑ ☑ ☐ ☐ ☑
1206 Paraquat dichloride 1910‐42‐5 ☐ ☑ ☑ ☐ ☐ ☑
1207 Paraquat methosulfate 2074‐50‐2 ☐ ☑ ☑ ☐ ☐ ☑
1208 Parathion 56‐38‐2 ☐ ☑ ☑ ☑ ☐ ☑
1209 p‐Chloro‐m‐cresol 59‐50‐7 ☐ ☑ ☑ ☐ ☐ ☑
1210 p‐Chloro‐o‐toluidine 95‐69‐2 ☐ ☑ ☑ ☐ ☐ ☑
1211 p‐Chlorophenyl isocyanate 104‐12‐1 ☐ ☑ ☑ ☐ ☐ ☑
1212 p‐Cresol 106‐44‐5 ☐ ☑ ☑ ☑ ☐ ☑
1213 p‐Dinitrobenzene 100‐25‐4 ☐ ☑ ☑ ☐ ☐ ☑
1214 Pentaborane 19624‐22‐7 ☐ ☑ ☑ ☐ ☐ ☑
1215 Pentachlorobenzene 608‐93‐5 ☐ ☑ ☑ ☐ ☐ ☑
1216 Pentachloroethane 76‐01‐7 ☐ ☑ ☑ ☐ ☐ ☑
1217 Pentachloronitrobenzene 82‐68‐8 ☐ ☑ ☑ ☑ ☐ ☑
(Quintobenzene)
1218 Pentachlorophenol 87‐86‐5 ☐ ☑ ☑ ☑ ☑ ☑
1219 Pentadecylamine 2570‐26‐5 ☐ ☑ ☑ ☐ ☐ ☑
1220 Pentaerythritol, tetranitrate 78‐11‐5 ☑ ☐ ☐ ☐ ☐ ☑
1221 Pentobarbital sodium 57‐33‐0 ☐ ☑ ☑ ☐ ☐ ☑
1222 Pentolite, dry or wetted with <15% 8066‐33‐9 ☑ ☐ ☐ ☐ ☐ ☑
water, by mass
1223 Peracetic acid 79‐21‐0 ☑ ☑ ☑ ☐ ☑ ☑
1224 Perchloryl fluoride 7616‐94‐6 ☑ ☐ ☐ ☐ ☐ ☑
1225 Perfluoroisobutylene 382‐21‐8 ☑ ☐ ☐ ☐ ☐ ☑
1226 Phenanthrene 85‐01‐8 ☐ ☑ ☑ ☐ ☐ ☑
1227 Phenol 108‐95‐2 ☐ ☑ ☑ ☑ ☑ ☑
1228 PHENOL, (1,1‐DIMETHYLETHYL)‐ 25013‐16‐5 ☐ ☐ ☐ ☐ ☑ ☑
4‐METHOXY‐
1229 PHENOL, 2,2'‐METHYLENEBIS 70‐30‐4 ☐ ☑ ☑ ☐ ☑ ☑
(3,4,6‐TRICHLORO‐
1230 Phenol 2,2'‐thiobis[4‐chloro‐6‐methyl‐ 4418‐66‐0 ☐ ☑ ☑ ☐ ☐ ☑
1231 Phenol, 3‐(1‐methylethyl)‐, 64‐00‐6 ☐ ☑ ☑ ☐ ☐ ☑
methylcarbamate
1232 PHENOL, 4,4'‐ISOPROPYLIDENEDI‐ 80‐05‐7 ☐ ☑ ☑ ☐ ☑ ☑
1233 PHENOL, 4‐AMINO‐2‐NITRO‐ 119‐34‐6 ☐ ☐ ☐ ☐ ☑ ☑
(continued)
390 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1234 PHENOL, P‐CHLORO‐ 106‐48‐9 ☐ ☐ ☐ ☐ ☑ ☑
1235 PHENOTHIAZINE, 2‐CHLORO‐10‐ 69‐09‐0 ☐ ☐ ☐ ☐ ☑ ☑
(3‐(DIMETHYLAMINO)PROPYL)‐,
MONOHYDR
1236 Phenoxarsine, 10,10'‐oxydi‐ 58‐36‐6 ☐ ☑ ☑ ☐ ☐ ☑
1237 PHENYLENEDIAMINE, 4‐ 5131‐60‐2 ☐ ☐ ☐ ☐ ☐ ☑
CHLORO‐, m
1238 PHENYLENEDIAMINE, 4‐ 95‐83‐0 ☐ ☐ ☐ ☐ ☑ ☑
CHLORO‐,o‐
1239 Phenylhydrazine hydrochloride 59‐88‐1 ☐ ☑ ☑ ☐ ☑ ☑
1240 Phenylmercuric acetate 62‐38‐4 ☐ ☑ ☑ ☐ ☐ ☑
1241 Phenylsilatrane 2097‐19‐0 ☐ ☑ ☑ ☐ ☐ ☑
1242 Phenylthiourea 103‐85‐5 ☐ ☑ ☑ ☐ ☐ ☑
1243 Phenyltrichlorosilane 98‐13‐5 ☑ ☑ ☑ ☐ ☐ ☑
1244 Phorate 298‐02‐2 ☐ ☑ ☑ ☐ ☐ ☑
1245 Phosacetim 4104‐14‐7 ☐ ☑ ☑ ☐ ☐ ☑
1246 Phosfolan 947‐02‐4 ☐ ☑ ☑ ☐ ☐ ☑
1247 Phosgene, gas 75‐44‐5 ☑ ☑ ☑ ☑ ☐ ☑
1248 Phosphamidon 13171‐21‐6 ☐ ☑ ☑ ☐ ☐ ☑
1249 Phosphine 7803‐51‐2 ☑ ☑ ☑ ☑ ☐ ☑
1250 PHOSPHINE, PHENYL‐ 638‐21‐1 ☐ ☐ ☐ ☐ ☑ ☑
1251 PHOSPHONIC acid , (2,2,2‐ 52‐68‐6 ☐ ☑ ☑ ☐ ☑ ☑
TRICHLORO‐1‐HYDROXYETHYL)‐
DIMETHYL ESTER
1252 PHOSPHONIC acid , (2‐ 16672‐87‐0 ☐ ☐ ☐ ☐ ☑ ☑
CHLOROETHYL)‐
1253 PHOSPHONIUM, TETRABUTYL‐, 3115‐68‐2 ☐ ☐ ☐ ☐ ☑ ☑
BROMIDE
1254 PHOSPHONIUM, TETRABUTYL‐, 2304‐30‐5 ☐ ☐ ☐ ☐ ☑ ☑
CHLORIDE
1255 Phosphonothioic acid , methyl‐, O‐(4‐ 2665‐30‐7 ☐ ☑ ☑ ☐ ☐ ☑
nitrophenyl) O‐phenyl ester
1256 Phosphonothioic acid , methyl‐, O‐ethyl 2703‐13‐1 ☐ ☑ ☑ ☐ ☐ ☑
O‐(4‐(methylthio)phenyl) ester
1257 PHOSPHORIC acid 7664‐38‐2 ☐ ☑ ☑ ☐ ☑ ☑
1258 Phosphoric acid , 2‐chloro‐1‐(2,3,5‐ 961‐11‐5 ☐ ☑ ☑ ☐ ☐ ☑
trichlorophenyl) ethenyl Dimethyl ester
1259 Phosphoric acid , Dimethyl 4‐ 3254‐63‐5 ☐ ☑ ☑ ☐ ☐ ☑
(methylthio) phenyl ester
1260 PHOSPHOROCHLORIDIC acid , 814‐49‐3 ☐ ☑ ☑ ☐ ☑ ☑
DIETHYL ESTER
1261 PHOSPHOROCHLORIDOTHIOIC 2524‐04‐1 ☐ ☐ ☐ ☐ ☑ ☑
acid , O,O‐DIETHYL ESTER
1262 PHOSPHORODICHLORIDOTHIOIC 1498‐64‐2 ☐ ☐ ☐ ☐ ☑ ☑
acid , O‐ETHYL ESTER
1263 PHOSPHOROFLUORIDIC acid , BIS 55‐91‐4 ☐ ☑ ☑ ☐ ☑ ☑
(l‐METHYLETHYL) ESTER
1264 Phosphorothioic acid , O,O‐dimethyl‐5‐ 2587‐90‐8 ☐ ☑ ☑ ☐ ☐ ☑
(2‐(methylthio)ethyl)ester
1265 Phosphorous trichloride 7719‐12‐2 ☑ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 391

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1266 PHOSPHORUS OXIDE 1314‐56‐3 ☐ ☐ ☐ ☐ ☑ ☑
1267 Phosphorus oxychloride 10025‐87‐3 ☑ ☑ ☑ ☐ ☑ ☑
1268 Phosphorus pentachloride 10026‐13‐8 ☑ ☑ ☑ ☐ ☑ ☑
1269 Phosphorus pentasulfide 1314‐80‐3 ☑ ☑ ☑ ☐ ☐ ☑
1270 Phosphorus, red 7723‐14‐0 ☑ ☑ ☑ ☑ ☐ ☑
1271 PHTHALIC acid , BENZYL BUTYL 85‐68‐7 ☐ ☑ ☑ ☐ ☑ ☑
ESTER
1272 Phthalic anhydride 85‐44‐9 ☐ ☑ ☑ ☑ ☐ ☑
1273 Physostigmine 57‐47‐6 ☐ ☑ ☑ ☐ ☐ ☑
1274 Physostigmine, salicylate(1:1) 57‐64‐7 ☐ ☑ ☑ ☐ ☐ ☑
1275 PICOLINIC acid , 4‐AMINO‐3,5,6‐ 1918‐02‐1 ☐ ☑ ☑ ☐ ☑ ☑
TRICHLORO‐
1276 Picric acid , moist (10 to 40% water) 88‐89‐1 ☑ ☑ ☑ ☐ ☐ ☑
1277 Picrotoxin 124‐87‐8 ☐ ☑ ☑ ☐ ☐ ☑
1278 Piperidine 110‐89‐4 ☑ ☑ ☑ ☐ ☐ ☑
1279 PIPERIDINE, 1‐NITROSO‐ 100‐75‐4 ☐ ☑ ☑ ☐ ☑ ☑
1280 Piperonyl butoxide 51‐03‐6 ☐ ☑ ☑ ☐ ☐ ☑
1281 Pirimifos‐ethyl 23505‐41‐1 ☐ ☑ ☑ ☐ ☐ ☑
1282 PLATINUM(II), 15663‐27‐1 ☐ ☐ ☐ ☑ ☐ ☑
DIAMMINEDICHLORO‐, cis‐
1283 PLUMBANE, TETRAETHYL‐ 78‐00‐2 ☐ ☑ ☑ ☑ ☐ ☑
1284 p‐Nitroaniline 100‐01‐6 ☐ ☑ ☑ ☐ ☐ ☑
1285 p‐Nitrosodiphenylamine 156‐10‐5 ☐ ☑ ☑ ☐ ☐ ☑
1286 p‐Nitrotoluene 99‐99‐0 ☐ ☑ ☑ ☐ ☐ ☑
1287 Polychlorinated biphenyls(Aroclors) 1336‐36‐3 ☐ ☑ ☑ ☑ ☑ ☑
1288 Polymeric diphenylmethane 9016‐87‐9 ☐ ☑ ☑ ☐ ☐ ☑
diisocyanate
1289 POLYVINYL ALCOHOL 9002‐89‐5 ☐ ☐ ☐ ☐ ☑ ☑
1290 Potassium arsenate 7784‐41‐0 ☐ ☑ ☑ ☐ ☐ ☑
1291 Potassium arsenite 10124‐50‐2 ☐ ☑ ☑ ☐ ☐ ☑
1292 Potassium bichromate 7778‐50‐9 ☐ ☑ ☑ ☐ ☐ ☑
1293 Potassium chlorate 3811‐04‐9 ☑ ☐ ☐ ☐ ☐ ☑
1294 Potassium cyanide 151‐50‐8 ☑ ☑ ☑ ☐ ☐ ☑
1295 Potassium dimethyldithiocarbamate 128‐03‐0 ☐ ☑ ☑ ☐ ☐ ☑
1296 Potassium hydroxide 1310‐58‐3 ☐ ☑ ☑ ☐ ☐ ☑
1297 Potassium nitrate 7757‐79‐1 ☑ ☐ ☐ ☐ ☐ ☑
1298 Potassium N‐methyldithiocarbamate 137‐41‐7 ☐ ☑ ☑ ☐ ☐ ☑
1299 Potassium perchlorate 7778‐74‐7 ☑ ☐ ☐ ☐ ☐ ☑
1300 Potassium permanganate 7722‐64‐7 ☐ ☑ ☑ ☐ ☐ ☑
1301 Potassium phosphide 20770‐41‐6 ☑ ☐ ☐ ☐ ☐ ☑
1302 Potassium silver cyanide 506‐61‐6 ☐ ☑ ☑ ☐ ☐ ☑
1303 p‐Phenylenediamine 106‐50‐3 ☐ ☑ ☑ ☐ ☐ ☑
1304 Promecarb 2631‐37‐0 ☐ ☑ ☑ ☐ ☑ ☑
1305 Propane 74‐98‐6 ☑ ☑ ☑ ☐ ☐ ☑
1306 PROPANE, 1,2‐EPOXY‐3‐ 122‐60‐1 ☐ ☐ ☐ ☐ ☑ ☑
PHENOXY‐
1307 Propanenitrile 107‐12‐0 ☑ ☑ ☑ ☐ ☑ ☑
(continued)
392 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1308 PROPANOL, 2,3‐EPOXY‐1‐ 556‐52‐5 ☐ ☐ ☐ ☐ ☑ ☑
1309 PROPANONE, 1,1,3‐TRICHLORO‐, 921‐03‐9 ☐ ☐ ☐ ☐ ☑ ☑
2‐
1310 PROPANONE, 1,3‐DICHLORO‐, 2‐ 534‐07‐6 ☐ ☑ ☑ ☐ ☐ ☑
1311 PROPANONE, 1‐CHLORO‐, 2‐ 78‐95‐5 ☐ ☐ ☐ ☐ ☐ ☑
1312 Propargite 2312‐35‐8 ☐ ☑ ☑ ☐ ☐ ☑
1313 Propargyl bromide 106‐96‐7 ☐ ☑ ☑ ☐ ☑ ☑
1314 Propene 115‐07‐1 ☑ ☑ ☑ ☐ ☑ ☑
1315 PROPENE, 1‐CHLORO‐2‐METHYL‐ 513‐37‐1 ☐ ☐ ☐ ☐ ☑ ☑
1316 PROPENE, 3‐CHLORO‐2‐METHYL‐ 563‐47‐3 ☐ ☑ ☑ ☐ ☐ ☑
1317 PROPENE‐1,1‐DIOL, 2‐METHYL‐, 10476‐95‐6 ☐ ☑ ☑ ☐ ☐ ☑
DIACETATE, 2‐
1318 PROPENYL CHLORIDE 590‐21‐6 ☑ ☑ ☑ ☐ ☐ ☑
1319 Propham 122‐42‐9 ☐ ☑ ☑ ☐ ☐ ☑
1320 Propionaldehyde 123‐38‐6 ☐ ☑ ☑ ☑ ☐ ☑
1321 Propionic acid 79‐09‐4 ☐ ☑ ☑ ☐ ☐ ☑
1322 Propionic anhydride 123‐62‐6 ☐ ☑ ☑ ☐ ☐ ☑
1323 Propiophenone, 4'‐amino 70‐69‐9 ☐ ☑ ☑ ☐ ☐ ☑
1324 Propoxur (Baygon) 114‐26‐1 ☐ ☑ ☑ ☑ ☐ ☑
1325 Propyl chloroformate 109‐61‐5 ☑ ☑ ☑ ☐ ☐ ☑
1326 Propylene dichloride (1,2‐ 78‐87‐5 ☐ ☑ ☑ ☑ ☑ ☑
Dichloropropane)
1327 Propylene oxide 75‐56‐9 ☑ ☑ ☑ ☑ ☑ ☑
1328 PROPYN‐1‐OL, 2 107‐19‐7 ☐ ☑ ☑ ☐ ☑ ☑
1329 Propyne 74‐99‐7 ☑ ☑ ☑ ☐ ☐ ☑
1330 Prothoate 2275‐18‐5 ☐ ☑ ☑ ☐ ☐ ☑
1331 p‐Toluidine 106‐49‐0 ☐ ☑ ☑ ☐ ☐ ☑
1332 PURINE, 6‐((l‐METHYL‐4‐ 446‐86‐6 ☐ ☐ ☐ ☐ ☑ ☑
NITROIMIDAZOL‐5‐YL)THIO)‐
1333 p‐Xylenes 106‐42‐3 ☐ ☑ ☑ ☑ ☑ ☑
1334 PYRAZ0LIDINEDIONE, 4‐BUTYL‐ 50‐33‐9 ☐ ☐ ☐ ☐ ☑ ☑
1,2‐DIPHENYL‐, 3,5‐
1335 PYRENE 129‐00‐0 ☐ ☑ ☑ ☐ ☑ ☑
1336 PYRENE, 1,3‐DINITRO‐ 75321‐20‐9 ☐ ☐ ☐ ☐ ☑ ☑
1337 PYRENE, 1,6‐DINITRO‐ 42397‐64‐8 ☐ ☐ ☐ ☐ ☐ ☑
1338 PYRENE, 1‐NITRO‐ 5522‐43‐0 ☐ ☑ ☑ ☐ ☐ ☑
1339 Pyrethrins 121‐29‐9 ☐ ☑ ☑ ☐ ☐ ☑
1340 Pyrethrins 121‐21‐1 ☐ ☑ ☑ ☐ ☐ ☑
1341 Pyrethrins 8003‐34‐7 ☐ ☑ ☑ ☐ ☐ ☑
1342 Pyridine 110‐86‐1 ☐ ☑ ☑ ☐ ☐ ☑
1343 PYRIDINE, 2,6‐DIAMINO‐3‐ 136‐40‐3 ☐ ☐ ☐ ☐ ☑ ☑
(PHENYLAZO)‐,
MONOHYDROCHLORIDE
1344 Pyridine, 2‐methyl‐5‐vinyl‐ 140‐76‐1 ☐ ☑ ☑ ☐ ☐ ☑
1345 Pyridine, 4‐nitro‐, 1‐oxide 1124‐33‐0 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 393

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1346 Pyriminil 53558‐25‐1 ☐ ☑ ☑ ☐ ☐ ☑
1347 PYRROLE‐2,5‐DIONE, 1,1'‐(4‐ 6422‐83‐9 ☐ ☐ ☐ ☐ ☑ ☑
METHYL‐1,3‐PHENYLENE)BIS‐,
1H‐
1348 PYRROLIDINE, 1‐NITROSO‐ 930‐55‐2 ☐ ☑ ☑ ☐ ☑ ☑
1349 PYRROLIDINONE, 1‐ 6837‐24‐7 ☐ ☑ ☑ ☐ ☑ ☑
CYCLOHEXYL‐, 2‐
1350 Quinoline 91‐22‐5 ☐ ☑ ☑ ☑ ☐ ☑
1351 QUINOLINE, 2‐AMINO‐3‐METHYL‐ 76180‐96‐6 ☐ ☐ ☐ ☐ ☑ ☑
3H‐IMIDAZO(4,5‐f)
1352 QUINOLINOL, 8‐ 148‐24‐3 ☐ ☐ ☐ ☐ ☑ ☑
1353 Quinone 106‐51‐4 ☐ ☑ ☑ ☑ ☐ ☑
1354 R‐(‐)‐3‐Quinuclidinyl benzilate 62869‐69‐6 ☑ ☐ ☐ ☐ ☐ ☑
1355 Resorcinol 108‐46‐3 ☐ ☑ ☑ ☐ ☐ ☑
1356 Resorcinol, 2,4,6‐trinitro‐ 82‐71‐3 ☑ ☐ ☐ ☐ ☐ ☑
1357 RESORCINOL, DIGLYCIDYL‐ 101‐90‐6 ☐ ☑ ☑ ☐ ☑ ☑
1358 S‐(2‐(Ethylsulfinyl)ethyl) O,O‐ 301‐12‐2 ☐ ☑ ☑ ☐ ☐ ☑
Dimethyl ester phosphorothioic acid
1359 Saccharin (manufacturing) 81‐07‐2 ☐ ☑ ☑ ☐ ☐ ☑
1360 Salcomine 14167‐18‐1 ☐ ☑ ☑ ☐ ☐ ☑
1361 Sarin 107‐44‐8 ☑ ☑ ☑ ☐ ☐ ☑
1362 sec‐Amyl acetate 626‐38‐0 ☐ ☑ ☑ ☐ ☐ ☑
1363 sec‐Butyl acetate 105‐46‐4 ☐ ☑ ☑ ☐ ☐ ☑
1364 sec‐Butyl alcohol 78‐92‐2 ☐ ☑ ☑ ☐ ☐ ☑
1365 sec‐Butylamine 513‐49‐5 ☐ ☑ ☑ ☐ ☐ ☑
1366 sec‐Butylamine 13952‐84‐6 ☐ ☑ ☑ ☐ ☐ ☑
1367 SELENIC acid , DISODIUM SALT 13410‐01‐0 ☐ ☑ ☑ ☐ ☑ ☑
1368 Selenious acid 7783‐00‐8 ☐ ☑ ☑ ☐ ☐ ☑
1369 Selenious acid , dithallium(1+) salt 12039‐52‐0 ☐ ☑ ☑ ☐ ☐ ☑
1370 Selenium 7782‐49‐2 ☐ ☑ ☑ ☐ ☐ ☑
1371 Selenium dioxide 7446‐08‐4 ☐ ☑ ☑ ☐ ☐ ☑
1372 Selenium hexafluoride 7783‐79‐1 ☑ ☐ ☐ ☐ ☐ ☑
1373 Selenium oxychloride 7791‐23‐3 ☐ ☑ ☑ ☐ ☐ ☑
1374 Selenium sulfide 7488‐56‐4 ☐ ☑ ☑ ☐ ☐ ☑
1375 Selenourea 630‐10‐4 ☐ ☑ ☑ ☐ ☐ ☑
1376 Semicarbazide hydrochloride 563‐41‐7 ☐ ☑ ☑ ☐ ☐ ☑
1377 SERINE, DIAZOACETATE (ESTER) 115‐02‐6 ☐ ☑ ☑ ☐ ☑ ☑
1378 Silane, (4‐aminobutyl)diethoxymethyl‐ 3037‐72‐7 ☐ ☑ ☑ ☐ ☐ ☑
1379 Silane, gas 7803‐62‐5 ☑ ☑ ☑ ☐ ☐ ☑
1380 SILANETRIAMINE, N,N,N',N',N``,N''‐ 15112‐89‐7 ☐ ☐ ☐ ☐ ☑ ☑
HEXAMETHYL‐
1381 SILICA, AMORPHOUS FUMED 112945‐52‐5 ☐ ☐ ☐ ☐ ☑ ☑
1382 SILICA, CRYSTALLINE QUARTZ 14808‐60‐7 ☐ ☐ ☐ ☐ ☑ ☑
1383 Silicon tetrafluoride 7783‐61‐1 ☑ ☐ ☐ ☐ ☐ ☑
1384 Silver 7440‐22‐4 ☐ ☑ ☑ ☐ ☐ ☑
1385 Silver cyanide 506‐64‐9 ☐ ☑ ☑ ☐ ☐ ☑
1386 Silver nitrate 7761‐88‐8 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
394 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1387 Silvex (2,4,5‐TP) 93‐72‐1 ☐ ☑ ☑ ☐ ☐ ☑
1388 Simazine 122‐34‐9 ☐ ☑ ☑ ☐ ☐ ☑
1389 Sodium 7440‐23‐5 ☐ ☑ ☑ ☐ ☐ ☑
1390 Sodium arsenate 7631‐89‐2 ☐ ☑ ☑ ☐ ☐ ☑
1391 Sodium arsenite 7784‐46‐5 ☐ ☑ ☑ ☐ ☐ ☑
1392 SODIUM AZIDE 26628‐22‐8 ☐ ☑ ☑ ☐ ☑ ☑
1393 Sodium bichromate 10588‐01‐9 ☐ ☑ ☑ ☐ ☐ ☑
1394 Sodium bifluoride 1333‐83‐1 ☐ ☑ ☑ ☐ ☐ ☑
1395 Sodium bisulfite 7631‐90‐5 ☐ ☑ ☑ ☐ ☐ ☑
1396 Sodium cacodylate 124‐65‐2 ☐ ☑ ☑ ☐ ☐ ☑
1397 Sodium chlorate 7775‐09‐9 ☑ ☐ ☐ ☐ ☐ ☑
1398 SODIUM CHLORITE 7758‐19‐2 ☐ ☐ ☐ ☐ ☑ ☑
1399 Sodium chromate 7775‐11‐3 ☐ ☑ ☑ ☐ ☐ ☑
1400 Sodium cyanide 143‐33‐9 ☑ ☑ ☑ ☐ ☐ ☑
1401 Sodium dimethyldithiocarbamate 128‐04‐1 ☐ ☑ ☑ ☐ ☐ ☑
1402 Sodium dinitro‐o‐cresylate, dry 25641‐53‐6 ☑ ☐ ☐ ☐ ☐ ☑
1403 Sodium dithionite 7775‐14‐6 ☑ ☐ ☐ ☐ ☐ ☑
1404 Sodium dodecylbenzenesulfonate 25155‐30‐0 ☐ ☑ ☑ ☐ ☐ ☑
1405 Sodium fluoride 7681‐49‐4 ☐ ☑ ☑ ☐ ☐ ☑
1406 Sodium hydrosulfide 16721‐80‐5 ☐ ☑ ☑ ☐ ☐ ☑
1407 Sodium hydroxide 1310‐73‐2 ☐ ☑ ☑ ☐ ☐ ☑
1408 Sodium hypochlorite 7681‐52‐9 ☐ ☑ ☑ ☐ ☐ ☑
1409 Sodium hypochlorite 10022‐70‐5 ☐ ☑ ☑ ☐ ☐ ☑
1410 Sodium methylate 124‐41‐4 ☐ ☑ ☑ ☐ ☐ ☑
1411 Sodium nitrate 7631‐99‐4 ☑ ☐ ☐ ☐ ☐ ☑
1412 Sodium o‐phenylphenoxide 132‐27‐4 ☐ ☑ ☑ ☐ ☐ ☑
1413 Sodium pentachlorophenate 131‐52‐2 ☐ ☑ ☑ ☐ ☐ ☑
1414 Sodium phosphate, dibasic 10039‐32‐4 ☐ ☑ ☑ ☐ ☐ ☑
1415 Sodium phosphate, dibasic 10140‐65‐5 ☐ ☑ ☑ ☐ ☐ ☑
1416 Sodium phosphate, dibasic 7558‐79‐4 ☐ ☑ ☑ ☐ ☐ ☑
1417 Sodium phosphate, tribasic 10124‐56‐8 ☐ ☑ ☑ ☐ ☐ ☑
1418 Sodium phosphate, tribasic 7785‐84‐4 ☐ ☑ ☑ ☐ ☐ ☑
1419 Sodium phosphate, tribasic 10361‐89‐4 ☐ ☑ ☑ ☐ ☐ ☑
1420 Sodium phosphate, tribasic 7601‐54‐9 ☐ ☑ ☑ ☐ ☐ ☑
1421 Sodium phosphate, tribasic 10101‐89‐0 ☐ ☑ ☑ ☐ ☐ ☑
1422 Sodium phosphate, tribasic 7758‐29‐4 ☐ ☑ ☑ ☐ ☐ ☑
1423 Sodium phosphide (Na(H2P)) 24167‐76‐8 ☑ ☐ ☐ ☐ ☐ ☑
1424 Sodium phosphide (Na3P) 12058‐85‐4 ☑ ☐ ☐ ☐ ☐ ☑
1425 Sodium picramate, (Wet >20 water) 831‐52‐7 ☑ ☐ ☐ ☐ ☐ ☑
1426 Sodium selenite 10102‐18‐8 ☐ ☑ ☑ ☐ ☐ ☑
1427 Sodium selenite 7782‐82‐3 ☐ ☑ ☑ ☐ ☐ ☑
1428 Sodium tellurite 10102‐20‐2 ☐ ☑ ☑ ☐ ☐ ☑
1429 Stannane, acetoxytriphenyl‐ 900‐95‐8 ☐ ☑ ☑ ☐ ☐ ☑
1430 STILBENEDIOL, alpha,alpha'‐ 56‐53‐1 ☐ ☑ ☑ ☐ ☑ ☑
DIETHYL‐, 4 ,4‐
1431 Strontium chromate 7789‐06‐2 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 395

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1432 STRONTIUM PHOSPHIDE 12504‐13‐1 ☑ ☐ ☐ ☐ ☐ ☑
1433 Strychnine 57‐24‐9 ☐ ☑ ☑ ☐ ☐ ☑
1434 Strychnine, sulfate 60‐41‐3 ☐ ☑ ☑ ☐ ☐ ☑
1435 Styrene 100‐42‐5 ☐ ☑ ☑ ☑ ☑ ☑
1436 Styrene oxide 96‐09‐3 ☐ ☑ ☑ ☑ ☐ ☑
1437 SULFONE, METHYL VINYL 3680‐02‐2 ☐ ☐ ☐ ☐ ☑ ☑
1438 Sulfoxide, 3‐chloropropyl octyl 3569‐57‐1 ☐ ☑ ☑ ☐ ☐ ☑
1439 Sulfur dichloride 10545‐99‐0 ☑ ☐ ☐ ☐ ☐ ☑
1440 Sulfur dioxide 7446‐09‐5 ☑ ☑ ☑ ☐ ☐ ☑
1441 Sulfur monochloride 10025‐67‐9 ☑ ☐ ☐ ☐ ☐ ☑
1442 Sulfur monochloride 12771‐08‐3 ☐ ☑ ☑ ☐ ☐ ☑
1443 Sulfur tetrafluoride 7783‐60‐0 ☑ ☑ ☑ ☐ ☐ ☑
1444 Sulfur trioxide 7446‐11‐9 ☑ ☑ ☑ ☐ ☐ ☑
1445 Sulfuric acid 7664‐93‐9 ☐ ☑ ☑ ☐ ☐ ☑
1446 Sulfuric acid, fuming 8014‐95‐7 ☑ ☑ ☑ ☐ ☐ ☑
1447 Sulfuric acid, fumin g 7783‐05‐3 ☑ ☐ ☐ ☐ ☐ ☑
1448 Sulfuryl chloride 7791‐25‐5 ☑ ☐ ☐ ☐ ☑ ☑
1449 Sulfuryl fluoride 2699‐79‐8 ☑ ☑ ☑ ☐ ☐ ☑
1450 Tabun 77‐81‐6 ☑ ☑ ☑ ☐ ☐ ☑
1451 TANNIC ACID 1401‐55‐4 ☐ ☐ ☐ ☐ ☑ ☑
1452 TECRAETHYL 3689‐24‐5 ☐ ☑ ☑ ☐ ☑ ☑
DITHIOPYROPHOSPHATE
1453 Tellurium hexafluoride 7783‐80‐4 ☑ ☑ ☑ ☐ ☐ ☑
1454 Temephos 3383‐96‐8 ☐ ☑ ☑ ☐ ☐ ☑
1455 Terbufos 13071‐79‐9 ☐ ☑ ☑ ☐ ☐ ☑
1456 tert‐Amyl acetate 625‐16‐1 ☐ ☑ ☑ ☐ ☐ ☑
1457 tert‐Butyl acetate 540‐88‐5 ☐ ☑ ☑ ☐ ☐ ☑
1458 tert‐Butyl alcohol 75‐65‐0 ☐ ☑ ☑ ☐ ☐ ☑
1459 tert‐Butylamine 75‐64‐9 ☐ ☑ ☑ ☐ ☐ ☑
1460 Tetrabromobisphenol A 79‐94‐7 ☐ ☑ ☑ ☐ ☐ ☑
1461 Tetrachloroethylene 127‐18‐4 ☐ ☑ ☑ ☑ ☑ ☑
(Perchloroethylene)
1462 Tetrachlorosilane 10026‐04‐7 ☑ ☐ ☐ ☐ ☐ ☑
1463 Tetracycline hydrochloride 64‐75‐5 ☐ ☑ ☑ ☐ ☐ ☑
1464 Tetraethyltin 597‐64‐8 ☐ ☑ ☑ ☐ ☐ ☑
1465 Tetrafluoroethylene 116‐14‐3 ☑ ☑ ☑ ☐ ☐ ☑
1466 Tetramethyllead 75‐74‐1 ☑ ☑ ☑ ☐ ☐ ☑
1467 Tetramethylsilane 75‐76‐3 ☑ ☑ ☑ ☐ ☐ ☑
1468 Tetranitroaniline 53014‐37‐2 ☑ ☐ ☐ ☐ ☐ ☑
1469 Tetranitromethane 509‐14‐8 ☑ ☑ ☑ ☐ ☑ ☑
1470 Tetraphosphoric acid, hexaethyl 757‐58‐4 ☑ ☑ ☑ ☐ ☐ ☑
1471 TETRETHYL PYROPHOSPHATE 107‐49‐3 ☐ ☑ ☑ ☐ ☑ ☑
1472 Thallic oxide 1314‐32‐5 ☐ ☑ ☑ ☐ ☐ ☑
1473 Thallium 7440‐28‐0 ☐ ☑ ☑ ☐ ☐ ☑
1474 Thallium chloride TlCl 7791‐12‐0 ☐ ☑ ☑ ☐ ☐ ☑
1475 Thallium sulfate 10031‐59‐1 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
396 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1476 Thallium(I) acetate 563‐68‐8 ☐ ☑ ☑ ☐ ☐ ☑
1477 Thallium(I) carbonate 6533‐73‐9 ☐ ☑ ☑ ☐ ☐ ☑
1478 Thallium(I) nitrate 10102‐45‐1 ☐ ☑ ☑ ☐ ☐ ☑
1479 Thallium(I) sulfate 7446‐18‐6 ☐ ☑ ☑ ☐ ☐ ☑
1480 Thallous malonate 2757‐18‐8 ☐ ☑ ☑ ☐ ☐ ☑
1481 Thiabendazole 148‐79‐8 ☐ ☑ ☑ ☐ ☐ ☑
1482 THIAZOLE, 2‐AMINO‐5‐NITRO‐ 121‐66‐4 ☐ ☐ ☐ ☐ ☑ ☑
1483 Thiocarbazide 2231‐57‐4 ☐ ☑ ☑ ☐ ☐ ☑
1484 Thiodicarb 59669‐26‐0 ☐ ☑ ☑ ☐ ☐ ☑
1485 Thiofanox 39196‐18‐4 ☐ ☑ ☑ ☐ ☐ ☑
1486 Thionyl chloride 7719‐09‐7 ☑ ☐ ☐ ☐ ☐ ☑
1487 Thiophanate‐methyl 23564‐05‐8 ☐ ☐ ☐ ☐ ☐ ☑
1488 THIOPHENE, 2,3,4,5‐ 6012‐97‐1 ☐ ☑ ☑ ☐ ☑ ☑
TETRACHLORO‐
1489 THIOPHOSPHORYL CHLORIDE 3982‐91‐0 ☐ ☑ ☑ ☐ ☑ ☑
1490 Thiosemicarbazide 79‐19‐6 ☐ ☑ ☑ ☐ ☐ ☑
1491 Thiourea, (2‐chlorophenyl)‐ 5344‐82‐1 ☐ ☑ ☑ ☐ ☐ ☑
1492 Thiourea, (2‐methylphenyl)‐ 614‐78‐8 ☐ ☑ ☑ ☐ ☐ ☑
1493 Thiram 137‐26‐8 ☐ ☑ ☑ ☐ ☐ ☑
1494 Thorium dioxide 1314‐20‐1 ☐ ☑ ☑ ☐ ☐ ☑
1495 Titanium(IV) chloride 7550‐45‐0 ☑ ☑ ☑ ☑ ☑ ☑
1496 Toluene 108‐88‐3 ☐ ☑ ☑ ☑ ☐ ☑
1497 Toluene 2,6‐diisocyanate 91‐08‐7 ☑ ☑ ☑ ☐ ☐ ☑
1498 Toluene diisocyanate 26471‐62‐5 ☑ ☑ ☑ ☐ ☐ ☑
1499 Toluene‐2,4‐diisocyanate 584‐84‐9 ☑ ☑ ☑ ☑ ☑ ☑
1500 TOLUIDINE, 4‐(o‐TOLYLAZO)‐, o‐ 97‐56‐3 ☐ ☑ ☑ ☐ ☑ ☑
1501 TOLUIDINE, 5‐NITRO‐, o‐ 99‐55‐8 ☐ ☑ ☑ ☐ ☑ ☑
1502 Toxaphene (chlorinated camphene) 8001‐35‐2 ☐ ☑ ☑ ☑ ☑ ☑
1503 trans‐1,3‐Dichloropropene 10061‐02‐6 ☐ ☑ ☑ ☐ ☐ ☑
1504 trans‐2‐Butene 624‐64‐6 ☑ ☑ ☑ ☐ ☐ ☑
1505 Triallate 2303‐17‐5 ☐ ☑ ☑ ☐ ☐ ☑
1506 Triamiphos 1031‐47‐6 ☐ ☑ ☑ ☐ ☐ ☑
1507 TRIAZIN‐2(lH)‐ONE, 4‐AMINO‐1‐ 320‐67‐2 ☐ ☐ ☐ ☐ ☑ ☑
beta‐D‐RIBOFURANOSYL‐, s‐
1508 TRIAZINE, 2,4,6‐TRIFLUORO‐,s‐ 675‐14‐9 ☐ ☑ ☑ ☐ ☑ ☑
1509 TRIAZINE, 2,4,6‐TRIS 101‐37‐1 ☐ ☐ ☐ ☐ ☑ ☑
(ALLYLOXY)‐, s‐
1510 TRIAZINE, 2‐CHLORO‐4‐ 1912‐24‐9 ☐ ☑ ☑ ☐ ☑ ☑
ETHYLAMINO‐6‐
ISOPROPYLAMINO‐, s‐
1511 Triazofos 24017‐47‐8 ☐ ☑ ☑ ☐ ☐ ☑
1512 TRIAZOLE, 3‐AMINO‐, s‐ 61‐82‐5 ☐ ☑ ☑ ☐ ☑ ☑
1513 Tributyltin fluoride 1983‐10‐4 ☐ ☑ ☑ ☐ ☐ ☑
1514 Tributyltin methacrylate 2155‐70‐6 ☐ ☑ ☑ ☐ ☐ ☑
1515 Trichloro(chloromethyl)silane 1558‐25‐4 ☐ ☑ ☑ ☐ ☐ ☑
1516 Trichloro(cyclohexyl)silane 98‐12‐4 ☑ ☐ ☐ ☐ ☐ ☑
1517 Trichloro(dichlorophenyl)silane 27137‐85‐5 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 397

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1518 Trichloro(octadecyl)silane 112‐04‐9 ☑ ☐ ☐ ☐ ☐ ☑
1519 Trichloro(propyl)silane 141‐57‐1 ☑ ☐ ☐ ☐ ☐ ☑
1520 TRICHLOROACETYL CHLORIDE 76‐02‐8 ☐ ☑ ☑ ☐ ☑ ☑
1521 Trichloroethylene 79‐01‐6 ☐ ☑ ☑ ☑ ☑ ☑
1522 Trichloroethylsilane 115‐21‐9 ☑ ☑ ☑ ☐ ☐ ☑
1523 Trichloromethanesulfenyl chloride 594‐42‐3 ☑ ☑ ☑ ☐ ☑ ☑
1524 Trichloronate 327‐98‐0 ☐ ☑ ☑ ☐ ☐ ☑
1525 Trichlorophenol 25167‐82‐2 ☐ ☑ ☑ ☐ ☐ ☑
1526 Trichlorosilane 10025‐78‐2 ☑ ☑ ☑ ☐ ☐ ☑
1527 Trichlorovinylsilane 75‐94‐5 ☑ ☐ ☐ ☐ ☐ ☑
1528 TRICHOTHEC‐9‐ENE‐3‐alpha,4‐ 21259‐20‐1 ☐ ☐ ☐ ☐ ☑ ☑
beta,8‐alpha, 15‐TETROL,12,13‐
EPOXY‐
1529 Triclopyr triethylammonium salt 57213‐69‐1 ☐ ☑ ☑ ☐ ☐ ☑
1530 Triethanolamine 102‐71‐6 ☑ ☐ ☐ ☐ ☐ ☑
1531 Triethanolamine dodecylbenzene 27323‐41‐7 ☐ ☑ ☑ ☐ ☐ ☑
sulfonate
1532 Triethanolamine hydrochloride 637‐39‐8 ☑ ☐ ☐ ☐ ☐ ☑
1533 Triethoxysilane 998‐30‐1 ☐ ☑ ☑ ☐ ☐ ☑
1534 Triethyl phosphite 122‐52‐1 ☑ ☐ ☐ ☐ ☐ ☑
1535 Triethylamine 121‐44‐8 ☐ ☑ ☑ ☑ ☐ ☑
1536 TRIETHYLAMINE, 2,2',2``‐ 817‐09‐4 ☐ ☐ ☐ ☐ ☑ ☑
TRICHLORO‐, HYDROCHLORIDE
1537 Trifluoroacetyl chloride 354‐32‐5 ☑ ☐ ☐ ☐ ☐ ☑
1538 Trifluralin 1582‐09‐8 ☐ ☑ ☑ ☑ ☐ ☑
1539 Trimethyl phosphite 121‐45‐9 ☑ ☐ ☐ ☐ ☐ ☑
1540 Trimethylamine 75‐50‐3 ☑ ☑ ☑ ☐ ☐ ☑
1541 Trimethylolpropane phosphite 824‐11‐3 ☐ ☑ ☑ ☐ ☐ ☑
1542 Trimethyltin chloride 1066‐45‐1 ☐ ☑ ☑ ☐ ☐ ☑
1543 Trinitronaphthalene 55810‐17‐8 ☑ ☐ ☐ ☐ ☐ ☑
1544 Triphenyltin chloride 639‐58‐7 ☐ ☑ ☑ ☐ ☐ ☑
1545 Triphenyltin hydroxide 76‐87‐9 ☐ ☑ ☑ ☐ ☐ ☑
1546 Tris(2,3‐dibromopropyl) phosphate 126‐72‐7 ☐ ☑ ☑ ☐ ☐ ☑
1547 Tris(2‐chloroethyl)amine 555‐77‐1 ☑ ☑ ☑ ☐ ☐ ☑
1548 Tris(2‐chlorovinyl)arsine 40334‐70‐1 ☑ ☐ ☐ ☐ ☐ ☑
1549 Tritonal 54413‐15‐9 ☑ ☐ ☐ ☐ ☐ ☑
1550 Trypan blue 72‐57‐1 ☐ ☑ ☑ ☐ ☐ ☑
1551 Tungsten hexafluoride 7783‐82‐6 ☑ ☐ ☐ ☐ ☐ ☑
1552 UCON 50‐HB‐5100 9038‐95‐3 ☐ ☐ ☐ ☐ ☑ ☑
1553 UNDECANOIC acid , 11‐AMINO 2432‐99‐7 ☐ ☐ ☐ ☐ ☑ ☑
1554 URACIL, 5‐(BIS(2‐CHLOROETHYL) 66‐75‐1 ☐ ☑ ☑ ☐ ☑ ☑
AMINO)‐
1555 URACIL, 5‐FLUORO‐ 51‐21‐8 ☐ ☑ ☑ ☐ ☑ ☑
1556 URACIL, 6‐PROPYL‐2‐THIO‐ 51‐52‐5 ☐ ☐ ☐ ☐ ☑ ☑
1557 Uranium hexafluoride 7783‐81‐5 ☑ ☐ ☐ ☐ ☐ ☑
1558 Uranyl acetate 541‐09‐3 ☐ ☑ ☑ ☐ ☐ ☑
1559 Uranyl nitrate 10102‐06‐4 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
398 Appendix 5: CAS RN Reportable Chemicals

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1560 Uranyl nitrate 36478‐76‐9 ☐ ☑ ☑ ☐ ☐ ☑
1561 Urea 57‐13‐6 ☑ ☐ ☐ ☐ ☐ ☑
1562 Urea nitrate, wetted 124‐47‐0 ☑ ☐ ☐ ☐ ☐ ☑
1563 UREA 1‐(2‐CHLOROETHYL)‐3 (4‐ 13909‐09‐6 ☐ ☐ ☐ ☐ ☑ ☑
METHYLCYCLOHEXYL)‐l‐
NITROSO‐
1564 UREA, 1‐(2‐CHLOROETHYL)‐3‐ 13010‐47‐4 ☐ ☐ ☐ ☐ ☑ ☑
CYCLOHEXYL‐1‐NITROSO‐
1565 UREA, 2‐THIO‐ 62‐56‐6 ☐ ☑ ☑ ☐ ☑ ☑
1566 UREA, 3‐(p‐CHLOROPHENYL)‐1,1‐ 150‐68‐5 ☐ ☑ ☑ ☐ ☑ ☑
DIMETHYL‐
1567 UREA, l‐ETHYL‐1‐NITROSO‐ 759‐73‐9 ☐ ☑ ☑ ☐ ☑ ☑
1568 UREA,1,1‐DIMETHYL‐3‐ (alpha, 2164‐17‐2 ☐ ☑ ☑ ☐ ☑ ☑
alpha,alpha‐TRIFLUORO‐m‐TOLYL)‐
1569 VALINOMYCIN 2001‐95‐8 ☐ ☑ ☑ ☐ ☑ ☑
1570 Vanadium pentoxide 1314‐62‐1 ☐ ☑ ☑ ☐ ☐ ☑
1571 Vanadyl sulfate 27774‐13‐6 ☐ ☑ ☑ ☐ ☐ ☑
1572 Vandium (except when contained in an 7440‐62‐2 ☐ ☑ ☑ ☐ ☐ ☑
alloy)
1573 Vinyl acetate 108‐05‐4 ☑ ☑ ☑ ☑ ☐ ☑
1574 Vinyl acetylene 689‐97‐4 ☑ ☑ ☑ ☐ ☐ ☑
1575 Vinyl bromide 593‐60‐2 ☐ ☑ ☑ ☑ ☑ ☑
1576 Vinyl chloride 75‐01‐4 ☑ ☑ ☑ ☑ ☑ ☑
1577 Vinyl fluoride 75‐02‐5 ☑ ☑ ☑ ☐ ☐ ☑
1578 Warfarin sodium 129‐06‐6 ☐ ☑ ☑ ☐ ☐ ☑
1579 XANTHEN‐7‐ONE, 7H‐FURO 10048‐13‐2 ☐ ☐ ☐ ☐ ☑ ☑
(3',2'4,5)FURO(2,3‐c)
1580 Xylenes (isomers and mixture) 1330‐20‐7 ☐ ☑ ☑ ☑ ☐ ☑
1581 Xylenol 1300‐71‐6 ☐ ☑ ☑ ☐ ☐ ☑
1582 XYLIDINE, 2,6 87‐62‐7 ☐ ☑ ☑ ☐ ☑ ☑
1583 Xylylene dichloride 28347‐13‐9 ☐ ☑ ☑ ☐ ☐ ☑
1584 Zinc 7440‐66‐6 ☐ ☑ ☑ ☐ ☐ ☑
1585 Zinc acetate 557‐34‐6 ☐ ☑ ☑ ☐ ☐ ☑
1586 Zinc ammonium chloride 52628‐25‐8 ☐ ☑ ☑ ☐ ☐ ☑
1587 Zinc ammonium chloride 14639‐97‐5 ☐ ☑ ☑ ☐ ☐ ☑
1588 Zinc ammonium chloride 14639‐98‐6 ☐ ☑ ☑ ☐ ☐ ☑
1589 Zinc borate 1332‐07‐6 ☐ ☑ ☑ ☐ ☐ ☑
1590 Zinc bromide 7699‐45‐8 ☐ ☑ ☑ ☐ ☐ ☑
1591 Zinc carbonate 3486‐35‐9 ☐ ☑ ☑ ☐ ☐ ☑
1592 Zinc chloride 7646‐85‐7 ☐ ☑ ☑ ☐ ☐ ☑
1593 Zinc cyanide 557‐21‐1 ☐ ☑ ☑ ☐ ☐ ☑
1594 Zinc dithionite 7779‐86‐4 ☑ ☑ ☑ ☐ ☐ ☑
1595 Zinc fluoride 7783‐49‐5 ☐ ☑ ☑ ☐ ☐ ☑
1596 Zinc formate 557‐41‐5 ☐ ☑ ☑ ☐ ☐ ☑
1597 Zinc nitrate 7779‐88‐6 ☐ ☑ ☑ ☐ ☐ ☑
1598 Zinc phenolsulfonate 127‐82‐2 ☐ ☑ ☑ ☐ ☐ ☑
1599 Zinc phosphide 1314‐84‐7 ☐ ☑ ☑ ☐ ☐ ☑
(continued)
Appendix 5: CAS RN Reportable Chemicals 399

(continued)
ID Chemical Name CAS DHS EPCRA SARA HAPS PHC OSHA
1600 Zinc silicofluoride 16871‐71‐9 ☐ ☑ ☑ ☐ ☐ ☑
1601 Zinc sulfate 7733‐02‐0 ☐ ☑ ☑ ☐ ☐ ☑
1602 ZINC, BIS 137‐30‐4 ☐ ☑ ☑ ☐ ☑ ☑
(DIMETHYLDITHIOCARBAMATO)‐
1603 Zinc, dichloro(4,4‐dimethyl‐5 58270‐08‐9 ☐ ☑ ☑ ☐ ☐ ☑
((((methylamino)carbonyl)oxy)imino)
pentanenit
1604 Zirconium nitrate 13746‐89‐9 ☐ ☑ ☑ ☐ ☐ ☑
1605 Zirconium picramate 63868‐82‐6 ☑ ☐ ☐ ☐ ☐ ☑
1606 Zirconium Potassium fluoride 16923‐95‐8 ☐ ☑ ☑ ☐ ☐ ☑
1607 Zirconium sulfate 14644‐61‐2 ☐ ☑ ☑ ☐ ☐ ☑
1608 Zirconium tetrachloride 10026‐11‐6 ☐ ☑ ☑ ☐ ☐ ☑
Appendix 6
Material Safety Data

MSD 6.1. Safety Data Sheets (SDS)

Related Links
MSDSonline
Advantor (Mallinckrodt Baker)
Fisher Scientific
Sigma Aldrich
VWR Scientific Prod.
Vermont SIRI
SDS Guide (PDF)
Safety Data Sheets (SDS) and hazard communication labels are the first place to
look for information concerning hazardous properties of chemical products.
The OSHA Hazard Communication Standard requires that all chemical manufac-
turers and importers supply an appropriate SDS to their customers. Chemical
manufactures typically develop their own SDS. All users should be able to access
an SDS for all hazardous chemicals used.

SDS Management at MU

The University of Missouri is taking a two-pronged approach to SDS Management.

Colleges, Departments and Units can choose to manage SDSs electronically (either
on their own or through the MU-Sponsored method) or with physical paper copies.
The MU-Sponsored Method is a commercial product which has been purchased
called MSDSonline. Complete information about this program is available on the
MSDSonline portal page
Users that wish to create their own solution should probably include links to the
common manufacturers found in their workspace such as Fisher Scientific,
Sigma-Aldrich, & Mallinckrodt/ Baker. These sites, plus other useful links, can be
found in the “Related Links” box on this page.

© US Government (outside the USA) 2018 401

D.S. Viswanath et al., Emerging Energetic Materials: Synthesis, Physicochemical,
and Detonation Properties, https://doi.org/10.1007/978-94-024-1201-7
402 MSD 6.1. Safety Data Sheets (SDS)

User that prefer to manage paper copies (aka “hard copies”) of SDSs may
continue to do so. However, keep in mind that the more chemicals you are
managing, the more difficult it becomes to keep your hard copies current. You may
decide to only keep the most frequently used or most hazardous chemicals used in
hard copies, while also participating in one of the electronic solutions described
above.

What does an SDS Contain?

Most modern SDS contain 16 sections. In the “Related Links” box, you can access
the SDS Guide, a PDF that describes SDSs in detail. If you need this information in
another format, please don't hesitate to contact EHS by phone at (573) 882-7018 or
by e-mail [email protected].
https://www.osha.gov/Publications/OSHA3514.html
https://www.osha.gov/Publications/HazComm_QuickCard_SafetyData.html
https://www.osha.gov/dsg/hazcom/
https://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=
standards&p_id=10103
https://www.msdsonline.com/resources/ghs-answer-center/ghs-101-safety-data-
sheets-sds
NIOSH—On-line chemical safety information: www.cdc.gov/niosh/npg/
CDC—NIOSH Pocket Guide to Chemical Hazards (NPG): www.cdc.gov/
niosh/npg/

SDS Requirements

Johns Hopkins staff, including Supervisors, Principal Investigators and Laboratory

Managers, are responsible for ensuring their employees have access to Safety Data
Sheets for all hazardous chemicals used in the workplace or laboratory. The
information in the Safety Data Sheets information must be accessible for employees
during all shifts, including laboratory personnel. Access to SDSs can mean access
to paper copies or electronic access via the Internet.
HSE strongly recommends paper copies be kept in the workplace or laboratory;
however, having SDS websites bookmarked is acceptable as long as all employees
in the workplace know where to find the SDS information online.
Keep in mind that any accidents involving a chemical will require an SDS being
provided to emergency personnel and to the attending physician so proper treatment
can be administered.
MSD 6.1. Safety Data Sheets (SDS) 403

• Emergency contact information is available at: http://www.hopkinsmedicine.

org/hse/emergency/
• For more information about our chemical and safety policies, see: http://www.
hopkinsmedicine.org/hse/policies/index.html

How to Obtain an SDS

Our recommended guidelines for obtaining an SDS are as follows:

1. Keep and use the SDS which is shipped to you with a chemical, or use the SDS
which is forwarded to you or your department from HSE.
2. Use the Internet access to find an SDS for a chemical or product.
3. If you still can't locate an SDS, you may request one from our office or by using
the “Right-to-Know Chemical Information Request Form.”

GHS 101 Safety Data Sheets (SDS)

Role of Safety Data Sheets in the Harmonized System

Safety Data Sheets are an essential component of the GHS and are intended to
provide comprehensive information about a substance or mixture for use in
workplace chemical management.
In the GHS, they serve the same function that the Material Safety Data Sheet or
MSDS does in OSHA's HazCom Standard.
They are used as a source of info about hazards, including environmental haz-
ards, and to obtain advice on safety precautions.
The SDS is normally product related and not specific to workplace; nevertheless,
the information on an SDS enables the employer to:
1. Develop an active program of worker protection measures, including training,
which is specific to the workplace.
2. Consider measures necessary to protect the environment.
404 MSD 6.1. Safety Data Sheets (SDS)

Criteria for Determining Whether an SDS Should be Produced

An SDS should be produced for substances and mixtures which meet the har-
monized criteria for physical, health, or environmental hazards under the GHS and
for all mixtures which contain ingredients that meet the criteria for carcinogenic,
toxic to reproduction or specific target organ toxicity in concentrations exceeding
the cut-off limits for SDS specified by the criteria for mixtures.
Competent authorities may also requires SDSs for mixtures not meeting the
criteria for classification but containing hazardous ingredients in certain
concentrations.
SDS Format
Information in the SDS should be presented using the following 16 headings in
the order given below
1. Identification
2. Hazard(s) identification
3. Composition/information on ingredients
4. First-aid measures
5. Fire-fighting measures
6. Accidental release measures
7. Handling and Storage
8. Exposure controls/personal protection
9. Physical and chemical properties
10. Stability and reactivity
11. Toxicological information
12. Ecological information
13. Disposal considerations
14. Transport information
15. Regulatory information
16. Other information

Brief

Brief
Hazard Communication Standard: Safety Data Sheets
The Hazard Communication Standard (HCS) (29 CFR 1910.1200(g)), revised in
2012, requires that the chemical manufacturer, distributor, or importer provide
Safety Data Sheets (SDSs) (formerly MSDSs or Material Safety Data Sheets) for
each hazardous chemical to downstream users to communicate information on these
hazards. The information contained in the SDS is largely the same as the MSDS,
MSD 6.1. Safety Data Sheets (SDS) 405

except now the SDSs are required to be presented in a consistent user-friendly,

16-section format. This brief provides guidance to help workers who handle haz-
ardous chemicals to become familiar with the format and understand the contents of
the SDSs.
The SDS includes information such as the properties of each chemical; the
physical, health, and environmental health hazards; protective measures; and safety
precautions for handling, storing, and transporting the chemical. The information
contained in the SDS must be in English (although it may be in other languages as
well). In addition, OSHA requires that SDS preparers provide specific minimum
information as detailed in Appendix D of 29 CFR 1910.1200. The SDS preparers
may also include additional information in various section(s).
Sections 1 through 8 contain general information about the chemical, identifi-
cation, hazards, composition, safe handling practices, and emergency control
measures (e.g., fire fighting). This information should be helpful to those that need
to get the information quickly. Sections 9 through 11 and 16 contain other technical
and scientific information, such as physical and chemical properties, stability and
reactivity information, toxicological information, exposure control information, and
other information including the date of preparation or last revision. The SDS must
also state that no applicable information was found when the preparer does not find
relevant information for any required element.
The SDS must also contain Sections 12 through 15, to be consistent with the UN
Globally Harmonized System of Classification and Labeling of Chemicals (GHS),
but OSHA will not enforce the content of these sections because they concern
matters handled by other agencies.
A description of all 16 sections of the SDS, along with their contents, is pre-
sented below:

Section 1: Identification
This section identifies the chemical on the SDS as well as the recommended uses. It
also provides the essential contact information of the supplier. The required
information consists of:
• Product identifier used on the label and any other common names or syn nyms
by which the substance is known.
• Name, address, phone number of the manufacturer, importer, or other respon-
sible party, and emergency phone number.
• Recommended use of the chemical (e.g., a brief description of what it actually
does, such as flame retardant) and any restrictions on use (including recom-
mendations given by the supplier). 1

Section 2: Hazard(s) Identification

This section identifies the hazards of the chemical presented on the SDS and the
appropriate warning information associated with those hazards. The required
information consists of:
406 MSD 6.1. Safety Data Sheets (SDS)

• The hazard classification of the chemical (e.g., flammable liquid, category1).

• Signal word.
• Hazard statement(s).
• Pictograms (the pictograms or hazard symbols may be presented as graphical
reproductions of the symbols in black and white or be a description of the name
of the symbol (e.g., skull and crossbones, flame).
• Precautionary statement(s).
• Description of any hazards not otherwise classified.
• For a mixture that contains an ingredient(s) with unknown toxicity, a statement
describing how much (percentage) of the mixture consists of ingredient(s) with
unknown acute toxicity. Please note that this is a total percentage of the mixture
and not tied to the individual ingredient(s).
Section 3: Composition/Information on Ingredients
This section identifies the ingredient(s) contained in the product indicated on the
SDS, including impurities and stabilizing additives. This section includes infor-
mation on substances, mixtures, and all chemicals where a trade secret is claimed.
The required information consists of:

Substances
• Chemical name.
• Common name and synonyms.
• Chemical Abstracts Service (CAS) number and other unique identifiers.
• Impurities and stabilizing additives, which are themselves classified and which
contribute to the classification of the chemical.
Mixtures
• Same information required for substances.
• The chemical name and concentration (i.e., exact percentage) of all ingredients
which are classified as health hazards and are:
• Present above their cut-off/concentration limits or
• Present a health risk below the cut-off/concentration limits.
• The concentration (exact percentages) of each ingredient must be specified
except concentration ranges may be used in the following situations:
• A trade secret claim is made,
• There is batch-to-batch variation, or
• The SDS is used for a group of substantially similar mixtures.
Chemicals where a trade secret is claimed
• A statement that the specific chemical identity and/or exact percentage
(concentration) of composition has been withheld as a trade secret is required.
MSD 6.1. Safety Data Sheets (SDS) 407

Section 4: First-Aid Measures

This section describes the initial care that should be given by untrained responders
to an individual who has been exposed to the chemical. The required information
consists of:
• Necessary first-aid instructions by relevant routes of exposure (inhalation, skin
and eye contact, and ingestion).
• Description of the most important symptoms or effects, and any symptoms that
are acute or delayed.
• Recommendations for immediate medical care and special treatment needed,
when necessary.
Section 5: Fire-Fighting Measures
This section provides recommendations for fighting a fire caused by the chemical.
The required information consists of:
• Recommendations of suitable extinguishing equipment, and information about
extinguishing equipment that is not appropriate for a particular situation.
• Advice on specific hazards that develop from the chemical during the fire, such
as any hazardous combustion products created when the chemical burns.
• Recommendations on special protective equipment or precautions for
firefighters.
Section 6: Accidental Release Measures
This section provides recommendations on the appropriate response to spills, leaks,
or releases, including containment and cleanup practices to prevent or minimize
exposure to people, properties, or the environment. It may also include recom-
mendations distinguishing between responses for large and small spills where the
spill volume has a significant impact on the hazard. The required information may
consist of recommendations for:
• Use of personal precautions (such as removal of ignition sources or providing
sufficient ventilation) and protective equipment to prevent the contamination of
skin, eyes, and clothing.
• Emergency procedures, including instructions for evacuations, consulting
experts when needed, and appropriate protective clothing.
• Methods and materials used for containment (e.g., covering the drains and
capping procedures).
• Cleanup procedures (e.g., appropriate techniques for neutralization, decontam-
ination, cleaning or vacuuming; adsorbent materials; and/or equipment required
for containment/clean up)
Section 7: Handling and Storage
This section provides guidance on the safe handling practices and conditions for
safe storage of chemicals. The required information consists of:
• Precautions for safe handling, including recommendations for handling
incompatible chemicals, minimizing the release of the chemical into the
408 MSD 6.1. Safety Data Sheets (SDS)

environment, and providing advice on general hygiene practices (e.g., eating,

drinking, and smoking in work areas is prohibited).
• Recommendations on the conditions for safe storage, including any incompat-
ibilities. Provide advice on specific storage requirements (e.g., ventilation
requirements)
Section 8: Exposure Controls/Personal Protection
This section indicates the exposure limits, engineering controls, and personal
protective measures that can be used to minimize worker exposure. The required
information consists of:
• OSHA Permissible Exposure Limits (PELs), American Conference of
Governmental Industrial Hygienists (ACGIH) Threshold Limit Values (TLVs),
and any other exposure limit used or recommended by the chemical manufac-
turer, importer, or employer preparing the safety data sheet, where available.
• Appropriate engineering controls (e.g., use local exhaust ventilation, or use only
in an enclosed system).
• Recommendations for personal protective measures to prevent illness or injury
from exposure to chemicals, such as personal protective equipment (PPE) (e.g.,
appropriate types of eye, face, skin or respiratory protection needed based on
hazards and potential exposure).
• Any special requirements for PPE, protective clothing or respirators (e.g., type
of glove material, such as PVC or nitrile rubber gloves; and breakthrough time
of the glove material).
Section 9: Physical and Chemical Properties This section identifies physical and
chemical properties associated with the substance or mixture. The minimum
required information consists of:
• Appearance (physical state, color, etc.);
• Upper/lower flammability or explosive limits;
• Odor;
• Vapor pressure;
• Odor threshold;
• Vapor density;
• pH;
• Relative density;
• Melting point/freezing point;
• Solubility(ies);
• Initial boiling point and boiling range;
• Flash point;
• Evaporation rate;
• Flammability (solid, gas);
• Partition coefficient: n-octanol/water;
• Auto-ignition temperature;
• Decomposition temperature; and
• Viscosity.
MSD 6.1. Safety Data Sheets (SDS) 409

The SDS may not contain every item on the above list because information may
not be relevant or is not available. When this occurs, a notation to that effect must
be made for that chemical property. Manufacturers may also add other relevant
properties, such as the dust deflagration index (Kst) for combustible dust, used to
evaluate a dust's explosive potential

Section 10: Stability and Reactivity

This section describes the reactivity hazards of the chemical and the chemical
stability information. This section is broken into three parts: reactivity, chemical
stability, and other. The required information consists of:
Reactivity
• Description of the specific test data for the chemical(s). This data can be for a
class or family of the chemical if such data adequately represent the anticipated
hazard of the chemical(s), where available.
Chemical stability
• Indication of whether the chemical is stable or unstable under normal ambient
temperature and conditions while in storage and being handled.
• Description of any stabilizers that may be needed to maintain chemical stability.
• Indication of any safety issues that may arise should the product change in
physical appearance.
Other
• Indication of the possibility of hazardous reactions, including a statement
whether the chemical will react or polymerize, which could release excess
pressure or heat, or create other hazardous conditions. Also, a description of the
conditions under which hazardous reactions may occur.
• List of all conditions that should be avoided (e.g., static discharge, shock,
vibrations, or environmental conditions that may lead to hazardous conditions).
• List of all classes of incompatible materials (e.g., classes of chemicals or specific
substances) with which the chemical could react to produce a hazardous
situation.
• List of any known or anticipated hazardous decomposition products that could
be produced because of use, storage, or heating. (Hazardous combustion
products should also be included in Section 5 (Fire-Fighting Measures) of the
SDS.)
Section 11: Toxicological Information
This section identifies toxicological and health effects information or indicates that
such data are not available. The required information consists of:
• Information on the likely routes of exposure (inhalation, ingestion, skin and eye
contact). The SDS should indicate if the information is unknown.
• Description of the delayed, immediate, or chronic effects from short- and
long-term exposure.
410 MSD 6.1. Safety Data Sheets (SDS)

• The numerical measures of toxicity (e.g., acute toxicity estimates such as the
LD50 (median lethal dose))—the estimated amount [of a substance] expected to
kill 50% of test animals in a single dose.
• Description of the symptoms. This description includes the symptoms associ-
ated with exposure to the chemical including symptoms from the lowest to the
most severe exposure.
• Indication of whether the chemical is listed in the National Toxicology Program
(NTP) Report on Carcinogens (latest edition) or has been found to be a potential
carcinogen in the International Agency for Research on Cancer (IARC)
Monographs (latest editions) or found to be a potential carcinogen by OSHA
Section 12: Ecological Information (non-mandatory)
This section provides information to evaluate the environmental impact of the
chemical(s) if it were released to the environment. The information may include:
• Data from toxicity tests performed on aquatic and/or terrestrial organisms, where
available (e.g., acute or chronic aquatic toxicity data for fish, algae, crustaceans,
and other plants; toxicity data on birds, bees, plants).
• Whether there is a potential for the chemical to persist and degrade in the
environment either through biodegradation or other processes, such as oxidation
or hydrolysis.
• Results of tests of bioaccumulation potential, making reference to the
octanol-water partition coefficient (Kow) and the bioconcentration factor (BCF),
where available.
• The potential for a substance to move from the soil to the groundwater (indicate
results from adsorption studies or leaching studies).
• Other adverse effects (e.g., environmental fate, ozone layer depletion potential,
photochemical ozone creation potential, endocrine disrupting potential, and/or
global warming potential).
Section 13: Disposal Considerations (non-mandatory)
This section provides guidance on proper disposal practices, recycling or recla-
mation of the chemical(s) or its container, and safe handling practices. To minimize
exposure, this section should also refer the reader to Section 8 (Exposure
Controls/Personal Protection) of the SDS. The information may include:
• Description of appropriate disposal containers to use.
• Recommendations of appropriate disposal methods to employ.
• Description of the physical and chemical properties that may affect disposal
activities.
• Language discouraging sewage disposal.
• Any special precautions for landfills or incineration activities
Section 14: Transport Information (non-mandatory)
This section provides guidance on classification information for shipping and
transporting of hazardous chemical(s) by road, air, rail, or sea. The information may
include:
MSD 6.1. Safety Data Sheets (SDS) 411

• UN number (i.e., four-figure identification number of the substance)1.

• UN proper shipping name1.
• Transport hazard class(es)1.
• Packing group number, if applicable, based on the degree of hazard2.
• Environmental hazards (e.g., identify if it is a marine pollutant according to the
International Maritime Dangerous Goods Code (IMDG Code)).
• Guidance on transport in bulk (according to Annex II of MARPOL 73/783 and
the International Code for the Construction and Equipment of Ships Carrying
Dangerous Chemicals in Bulk (International Bulk Chemical Code (IBC Code)).
• Any special precautions which an employee should be aware of or needs to
comply with, in connection with transport or conveyance either within or out-
side their premises (indicate when information is not available).
Section 15: Regulatory Information (non-mandatory)
This section identifies the safety, health, and environmental regulations specific for
the product that is not indicated anywhere else on the SDS. The information may
include:
• Any national and/or regional regulatory information of the chemical or mixtures
(including any OSHA, Department of Transportation, Environmental Protection
Agency, or Consumer Product Safety Commission regulations)
Section 16: Other Information
This section indicates when the SDS was prepared or when the last known revision
was made. The SDS may also state where the changes have been made to the
previous version. You may wish to contact the supplier for an explanation of the
changes. Other useful information also may be included here.
Employer Responsibilities
Employers must ensure that the SDSs are readily accessible to employees for all
hazardous chemicals in their workplace. This may be done in many ways. For
example, employers may keep the SDSs in a binder or on computers as long as the
employees have immediate access to the information without leaving their work
area when needed and a back-up is available for rapid access to the SDS in the
case of a power outage or other emergency. Furthermore, employers may want to
designate a person(s) responsible for obtaining and maintaining the SDSs. If the
employer does not have an SDS, the employer or designated person(s) should
contact the manufacturer to obtain one.

1
Chemical, as defined in the HCS, is any substance, or mixture of substances.
2
Found in the most recent edition of the United Nations Recommendations on the Transport of
Dangerous Goods.
3
MARPOL 73/78 means the International Convention for the Prevention of Pollution from Ships,
1973, as modified by the Protocol of 1978 relating thereto, as amended
412 MSD 6.1. Safety Data Sheets (SDS)

References
OSHA, 29 CFR 1910.1200(g) and Appendix D. United Nations Globally
Harmonized System of Classification and Labelling of Chemicals (GHS), third
revised edition, United Nations, 2009. These references and other information
related to the revised Hazard Communication Standard can be found on OSHA's
Hazard Communication Safety and Health Topics page, located at:http://www.
osha.gov/dsg/hazcom/index.html.

Disclaimer: This brief provides a general overview of the safety data sheet
requirements in the Hazard Communication Standard (see 29 CFR 1910.1200
(g) and Appendix D of 29 CFR 1910.1200). It does not alter or determine
compliance responsibilities in the standard or the Occupational Safety and
Health Act of 1970. Since interpretations and enforcement policy may change
over time, the reader should consult current OSHA interpretations and
decisions by the Occupational Safety and Health Review Commission and the
courts for additional guidance on OSHA compliance requirements. Please
note that states with OSHA-approved state plans may have additional
requirements for chemical safety data sheets, outside of those outlined above.
For more information on those standards, please visit: http://www.osha.gov/
dcsp/osp/statestandards.html.

This is one in a series of informational briefs highlighting OSHA programs,

policies or standards. It does not impose any new compliance requirements. For a
comprehensive list of compliance requirements of OSHA standards or regulations,
refer to Title 29 of the Code of Federal Regulations. This information will be made
available to sensory-impaired individuals upon request. The voice phone is
(202) 693-1999; teletypewriter (TTY) number: (877) 889-5627.
For assistance, contact us. We can help. It's confidential

U.S. Department of Labor

www.osha.gov (800) 321 OSHA (6742)
DSG BR-3514 2/2012
MSD 6.2. Hexanitrohexaazaisowurtzitane (HNIW, CL-20) 413

MSD 6.2. Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Section 3. Hazards Identification

Exposure Limits: Not applicable.

Effects of Exposure: .
414 MSD 6.2. Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Inhalation: Not known. Explosives similar to CL-20 may

sensitizesusceptible individuals, causing
asthma-like allergic reactions.
Eyes: Not known.
Skin: Not known.
Ingestion: Not known. May be highly toxic if ingested.
Existing conditions .
which may be aggravated:

Section 4. First AI Measures

Inhalation: Contact physician, Give oxygen or artificial respiration if needed.

For thermal burns contact physician.
Eyes: Flush immediately with water for least 15 min. Contact physician.
Skin: Wash with soap and water. Contact physician.
Ingestion: Contact physician

Section 5. Fire-Fighting Measures

Extinguishing Media: Do not attempt to fight CL-20 explosive fires.
Special Fire Fighting Procedures: Do not fight fires involving this CL-20
explosive. If ignited, this explosive may detonate. Thrust and overpressure
created while burning may give this CL-20 explosive uncontrollable ballistic
properties. Fire fighting should be limited to evacuating an area proportional to
the amount of CL-20 explosive which may detonate or bum, and preventing
the spread of fire beyond the isolated area.
Unusual Fire and Explosions Hazards: Static discharge, impact, friction and
pinch points between hard surfaces may initiate a conflagration or detonation.
Overpressures associated with rapidly burning CL-20 explosive can be
explosive-like, creating fireballs and shock waves.

Section 6. Accidental Release Measures

Precautions if Container is Damaged or Material Spilled: CL-20 explo-
sive must be protected from sources of ignition (see Section 7). If ignited
accidentally, a detonation should be anticipated, causing a shock wave,
spreading burning material over a wide area, and producing toxic decom-
position fumes. Contact appropriate authorities.
MSD 6.2. Hexanitrohexaazaisowurtzitane (HNIW, CL-20) 415

Section 7. Handling and Storage

Buildings and transporting equipment must be protected from lightning and
other forms of static discharge. Protect CL-20 explosive from ignition
sources, static charge buildup, mechanical shock, friction. Burning charac-
teristics may only be predicted when the environmental history is known,
and aging and temperature limits set by design and aging studies have not
been exceeded. CL-20 should be shipped wet-packed to minimize
sensitivity.
Other Precautions: CL-20 explosive is federally controlled, CL-20 explosive
should be controlled and handled only by personnel properly trained and
authorized to handle explosive materials.

Section 8. Exposure Controls—Personal Protection

Ventilation: Provide sufficient mechanical (general and/or exhaust ventila-
tion to limit vapor inhalation.
Respiratory Protection: A NIOSH/MSHA approve air supplied respirator is
advised in the absence of proper environmental control. Engineering and/or
administrative controls may be implemented to reduce exposure.
Protective Gloves: Wear nonporous gloves such as natural rubber or neo-
prene for handling.
Eye Protection: Protect from exposure to dust. Chemical monogoggles
should be worn for most applications, Workers who risk exposure should
have access to an eye fountain and safety shower.
Other Protective Equipment: Clothing combinations which may create
static discharges must be avoided. Workers handling this explosive should
be grounded, wearing conductive shoes or equivalent on a clean conductive
floor. Flame resistant clothing is advised. CL-20 explosive should be con-
tained in conductive containers, Glassware, metal tools, and grainy or gritty
surfaces should be avoided.

Section 9. Physical and Chemical Properties

Vapor Density: N/A

Specific Gravity: >1.8 g/cc
Solubility in Water: NIL
Vapor Pressure: N/A
Evaporation Rate: N/A
Melting Point: Decomposes.
416 MSD 6.2. Hexanitrohexaazaisowurtzitane (HNIW, CL-20)

Bouing Point: Decomposes.

Appearance and Color: White crystalline solid.
Detection Methods: N/A
pH: N/A
Flashpoint: Not applicable

Section 10. Stability and Reactivity

Stability: Unstable, if heated.
Conditions to Avoid: Shock, impact, friction, and static charge buildup and
high temperatures.
Incompatibility (Materials to Avoid): Not known.
Hazardous Decomposition Products:
Hazardous Polymerization: Will not occur.
Other Hazards:

Section 11. Tomocological Information

Acute Effects: See Section 3.
Chronic Effects: May sensitize susceptible individuals causing asthma-like
allergic reactions.
Target Organ(s): Unknown.

Section 12. Ecological Information

No data available.

Section 13. Disposal Considerations

Dispose of in accordance with federal, state, and local regulations. This
material is an explosive and may detonate,
Section 14. Transportation Information
Transport in accordance with federal, state, and local regulations. See 49
CPR—Rules governing transportation.

CL-20 Dry
MSD 6.2. Hexanitrohexaazaisowurtzitane (HNIW, CL-20) 417

Proper Shipping Names: Substances, explosive, n.o.s., (Hexanitro

hexaazaisowurtzitane)
Hazard Class: 1.1D
I.D. Number: UN0475
Packing Group: II
Label: Explosive 1.1 D
Packing Method: E-5 49 CFR 173.62(C)
EX-Number: EX-9410242

CL-2O.Wetted with 15% Water

Proper Shipping Names: Substances, explosive, n.o.s., (Hexanitr

hexaazaisowurtzitane)
Hazard Class: 1.ID
Number: UN0475
Packing Group: Hl
Label: Explosive 1.1 D
Packing Method: (E-6 (a)(i)), (E-6(a)(ii)) 49 CFR 173.62(C)
EX-Number: EX-9405294

Section 15. Regulatory Information

Toxic Substances Control Act (TSCA)
NOTICE: CL-20 is not registered on the TSCA Inventory and therefore this
chemical material is for Research and Development Use Only under the
supervision of a technically qualified individual.

Section 16 Other Information

For R&D use only. To the best of our knowledge the information contained
herein is correct. All chemicals may present unknown health hazards and must
be used with caution. Although certain hazards are described herein, we cannot
guarantee that these are the only hazards which exist. Final determination of the
suitability of the chemical is the sole responsibility of the user. Users of any
chemical should satisfy themselves that the conditions and methods of use
assure that the chemical is used safely.
NO REPRESENTATIONS OR WARRANTIES, EITHER EXPRESS OR
IMPLIED, TO INCLUDE WARRANTIES OF MERCHANTABILITY,
FITNESS FOR A PARTICULAR PURPOSE OR ANY OTHER NATURE
ARE MADE HEREUNDER WITH RESPECT TO THE INFORMATION
CONTAINED HEREIN OR THE CHEMICAL TO WHICH
THE INFORMATION REFERS.
418 MSD 6.3. 1,1-diamino-2,2-dinitroethylene (DADN; FOX-7)

MSD 6.3. 1,1-diamino-2,2-dinitroethylene (DADN; FOX-7)

MSD 6.4. 2,4-Dinitroanisole (DNAN) 419

MSD 6.4. 2,4-Dinitroanisole (DNAN)

420 MSD 6.4. 2,4-Dinitroanisole (DNAN)
MSD 6.4. 2,4-Dinitroanisole (DNAN) 421
422 MSD 6.4. 2,4-Dinitroanisole (DNAN)
MSD 6.4. 2,4-Dinitroanisole (DNAN) 423
424 MSD 6.4. 2,4-Dinitroanisole (DNAN)
MSD 6.4. 2,4-Dinitroanisole (DNAN) 425
426 MSD 6.5. 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

MSD 6.5. 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

OSHA REGULATORY STATUS: This material is considered hazardous by

the OSHA Hazard
Communications Standard (29 CFR 1910.1200).
MSD 6.5. 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO) 427

Potential Health Effects:

Effects of a Single (Acute) Overexposure
Inhalation. Overexposure may irritate the mucous membranes, sinuses,
pharynx, and bronchia, with pain, headache, cyanosis, irregular respiration,
choking, dizziness, and possibly pulmonary edema. Pulmonary symptoms
may be delayed from 5 to 72 h. High concentrations of vapor may cause
pain, choking, bronchoconstriction, reflex slowing of the heart, and possibly
asphyxiation. Lack of oxygen can kill.
Skin Contact. Severe irritant; may cause burns. Prolonged or widespread
skin contact may result in absorption of harmful amounts of nitrogen
dioxide.
Swallowing. A highly unlikely route of exposure; this product is a gas at
normal temperature and pressure. May cause burns of the mouth, esophagus,
and stomach.
Eye Contact. May cause severe conjunctivitis, seen as marked excess red-
ness and
swelling of the conjunctiva, and corneal injury with opacification.
Effects of Repeated (Chronic) Overexposure. Repeated inhalation may cause
bronchitis or emphysema; repeated skin contact may cause dermatitis.
Other Effects of Overexposure. None known.
Medical Conditions Aggravated by Overexposure. Inhalation may aggravate
asthma and inflammatory or fibrotic pulmonary disease. Skin irritating properties
may aggravate dermatitis.
Carcinogenicity: Nitrogen dioxide is not listed by NTP, OSHA, or IARC.
Potential Environmental Effects: None known. For further information, see
section 12, Ecological Information.

3. Composition/Information on Ingredients

See section 16 for important information about mixtures

Component CAS number Concentration
Nitrogen Dioxide 10102-44-0 >99%a
Dinitrogen Tetroxide 10544-72-6 Trace
a
The symbol > means “greater than”

4. First Aid Measures

Inhalation: Remove to fresh air. If not breathing, give artificial respiration.

WARNING:
428 MSD 6.5. 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Rescuer could receive chemical burns from giving mouth-to-mouth. Rescuer

should avoid breathing air exhaled by victim. If breathing is difficult, qualified
personnel may give oxygen. Keep patient warm. Call a physician immediately.
Keep under medical observation. Symptoms may be delayed.
Skin Contact: Immediately flush skin with plenty of water for at least 15 min
whileremoving contaminated clothing and shoes. Discard clothing and shoes. Call a
physician.
Swallowing: An unlikely route of exposure. This product is a gas at normal
temperature and pressure.
Eye Contact: Immediately flush eyes thoroughly with water for at least 15 min.
Hold the eyelids open and away from the eyeballs to ensure that all surfaces are
flushed thoroughly. See a physician, preferably an ophthalmologist, immediately.
Notes to Physician: In case of overexposure, keep patient under medical
observation for at least 72 h to observe for pulmonary edema. Patient may have a
second acute pulmonary reaction 2–6 weeks after the first. The hazards of this
material are due chiefly to its severe irritant and corrosive properties on the skin and
mucosal surfaces. There is no specific antidote. Treatment of overexposure should
be directed at the control of symptoms and the clinical condition of the patient.
Contact the Poison Control Center in your area for additional information on
patientmanagement and follow-up.

5. Fire Fighting Measures

Flammable Properties: Oxidizing agent; may accelerate combustion. Contact

with flammable materials may cause fire or explosion.
Suitable Extinguishing Media: Oxidizing agent; may accelerate combustion.
Use media appropriate for surrounding fire.
Products of Combustion: Not applicable. Decomposition due to heating may
produce toxic fumes. (See section 10.)
Protection of Firefighters: Danger! Poisonous, corrosive, oxidizing liquid
and gas under pressure. Evacuate all personnel from danger area. Do not
approach area without self-contained breathing apparatus and protective clothing.
Immediately spray cylinders with water from maximum distance until cool; then
move them away from fire area if without risk. Remove ignition sources if without
risk. If cylinders are leaking, reduce vapors with water spray or fog. Do not spray
water directly onto leak; this may only increase the leak. Reverse flow into cylinder
may cause it to rupture. Shut off leak if without risk. On-site fire brigades must
comply with OSHA 29 CFR 1910.156.
Specific Physical and Chemical Hazards. Heat of fire can build pressure in
cylinder and cause it to rupture. To provide maximum containment up to cylinder
burst pressure, nitrogen dioxide cylinders are not equipped with a pressure-relief
device. No part of a cylinder should be subjected to a temperature higher than 125 °
F (52 °C). Vapors are irritating; contact may cause skin and eye burns.
MSD 6.5. 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO) 429

Protective Equipment and Precautions for Firefighters. Firefighters should

wear selfcontained breathing apparatus and full fire-fighting turnout gear.

6. Accidental Release Measures

Steps to be taken if Material is Released or Spilled:

Danger! Poisonous, corrosive, oxidizing liquid and gas under pressure.
Personal Precautions. Immediately evacuate all personnel from danger area.
Use selfcontained breathing apparatus and protective clothing where needed.
Reduce vapors with fog or fine water spray. Reverse flow into cylinder may cause it
to rupture. Shut off flow if without risk. Ventilate area or move leaking cylinder to
well-ventilated area. Toxic, corrosive vapors may spread from spill. Before entering
area, especially confined areas, check atmosphere with an appropriate device.
Environmental Precautions. Prevent waste from contaminating the surround-
ing environment. Keep personnel away. Discard any product, residue, disposable
container, or liner in an environmentally acceptable manner, in full compliance with
federal, state, and local regulations. If necessary, call your local supplier for
assistance.

7. Handling and Storage

Precautions to be taken in Handling: May be fatal if inhaled. Do not breathe

gas. Do not get vapors or liquid in eyes, on skin, or on clothing. Keep away from
oxidizing agents and from other flammables. Have safety showers and eyewash
fountains immediately available. Protect cylinders from damage. Use a suitable
hand truck to move cylinders; do not drag, roll, slide, or drop. All piped systems
and associated equipment must be grounded. Electrical equipment must be
non-sparking or explosion-proof. Leak check with soapy water; never use a flame.
Never attempt to lift a cylinder by its cap; the cap is intended solely to protect the
valve. Never insert an object (e.g., wrench, screwdriver, pry bar) into cap openings;
doing so may damage the valve and cause a leak. Use an adjustable strap wrench to
remove over-tight or rusted caps. Open valve slowly. Close valve after each use;
keep closed even when empty. If valve is hard to open, discontinue use and contact
your supplier. For other precautions in using nitrogen dioxide, see section 16.
Precautions to be taken in Storage: Store and use with adequate ventilation,
away from oil, grease, and combustibles. Firmly secure cylinders upright to keep
them from falling or being knocked over. Nitrogen dioxide cylinders designed to
accept a valve protection cap must be provided with a cap. Screw cap firmly in
place by hand. Store only where temperature will not exceed 125°F (52°C). Store
full and empty cylinders separately. Use a first-in, first-out inventory system to
prevent storing full cylinders for long periods.
430 MSD 6.5. 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

Recommended Publications: For further information on storage, handling, and

use, see Praxair publication P-14-153, Guidelines for Handling Gas Cylinders and
Containers. Obtain from your local supplier.

8. Exposure Controls/Personal Protection

Component OSHA PEL ACGIH TLV-TWA (2007)

Nitrogen Dioxide Dinitrogen Tetroxide 5 ppm (c)a 3 ppm; 5 ppm, 15 min STEL
Values above are for equilibrium mixture
a
(c)—ceiling. Ceiling values are not Time-Weighted-Average (TWA)

TLV-TWAs should be used as a guide in the control of health hazards and not as
fine lines between safe and dangerous concentrations.
IDLH = 20 ppm
Engineering Controls:
Local Exhaust. Use a corrosion-resistant local exhaust system.
Mechanical (General). Inadequate. See SPECIAL.
Special. Use only in a closed system. A corrosion-resistant, forced-draft fume
hood preferred.
Other. None
Personal Protective Equipment:
Skin Protection. Wear work gloves when handling cylinders; neoprene gloves
where contact with product may occur. Metatarsal shoes for cylinder handling,
protective clothing where needed. Select in accordance with OSHA 29 CFR
1910.132 and 1910.133. Regardless of protective equipment, never touch live
electrical parts.
Eye/Face Protection. Select in accordance with OSHA 29 CFR 1910.133
Respiratory Protection. Use an air-supplied respirator or a full-face, positive-
breathing apparatus. Respiratory protection must conform to OSHA 29 CFR
1910.134. Select per OSHA 29 CFR 1910.134 and ANSI Z88.2.

9. Physical and Chemical Properties

Appearance: Reddish-brown gas

Odor: Irritating
Odor Threshold: Not available.
Physical State: Gas at normal temperature and
pressure
MSD 6.5. 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO) 431

pH: Acid when dissolved in H2O.

Melting Point at 1 atm: 11.8 °F (−11.2 °C)
Boiling Point at 1 atm: 70.16 °F (21.20 °C)
Flash Point (test method): Not applicable.
Evaporation Rate (Butyl Acetate = 1): High
Flammability: Nonflammable.
Flammable Limits in Air, % by volume: Lower: Not applicable.
Upper: Not applicable.
Vapor Pressure at 70 °F (21.1 °C): 14.7 psia (101.4 kPa abs)
Vapor Density at 70 °F (21.1 °C) and 1 atm: Not available.
Specific Gravity (H2O = 1) at 68°/39.9 °F .
(20°/4 °C): 1.448
Specific Gravity (Air = 1) at 70 °F (21.1 °C) .
and 1 atm: 2.62
Solubility in Water: Reacts; forms nitric and nitrous
acids.
Partition Coefficient: n-octanol/water: Not available.
Autoignition Temperature: Not applicable.
Decomposition Temperature: >320 °F (160 °C)
Percent Volatiles by Volume: 100
Molecular Weight: NO2 = 46.0055, N2O4 = 92.0011
Molecular Formula: NO2 & N2O4 in equilibrium

10. Stability and Reactivity

Chemical Stability: ❑ Unstable ⌧ Stable

Conditions to Avoid: None known.
Incompatible Materials: Water, bases, flammable and combustible materials,
copper, aluminum. Very corrosive to metals when wet. Explosions may occur on
contact with ammonia, boron trichloride, carbon disulfide, cyclohexane, fluor-
ine, formaldehyde, nitrobenzene, toluene, incompletely halogenated hydrocar-
bons, propylene, alcohols, and ozone.
Hazardous Decomposition Products: Above 320 °F (160 °C), nitrogen dioxide
decomposes to form nitric oxide and oxygen. Nitrogen dioxide reacts with water
to form nitric acid and nitric oxide.
Possibility of Hazardous Reactions: ⌧ May Occur ❑ Will Not Occur
Explosions may occur on contact with ammonia, boron trichloride, carbon
disulfide, cyclohexane, fluorine, formaldehyde, nitrobenzene, toluene, incom-
pletely halogenated hydrocarbons, propylene, alcohols, and ozone. Nitrogen
dioxide reacts with water to form nitric acid and nitric oxide.
432 MSD 6.5. 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

11. Toxicological Information

Acute Dose Effects: LC50, 1 hr, rat = 115 ppm

Study Results: Nitrogen dioxide has been shown to cause mutations in bacteria
and to cause mutations, sister-chromatid exchanges, and chromasomal aberra-
tions in mammalian cells.

12. Ecological Information

Ecotoxicity: No known effects.

Other Adverse Effects: Nitrogen dioxide does not contain any Class I or Class II
ozonedepleting chemicals.

13. Disposal Considerations

Waste Disposal Method: Do not attempt to dispose of residual or unused

quantities. Return cylinder to supplier.

14. Transport Information

DOT/IMO Shipping Name: Dinitrogen tetroxide

Hazard Packing Group/Zone: Identification number: Product RQ: 10 lb
Class: 2.3 NA*/A UN1067 (4.54 kg)
SHIPPING LABEL(s): POISON GAS, OXIDIZER, CORROSIVE**
PLACARD (when required): POISON GAS, OXIDIZER, CORROSIVE**
*NA = Not available
**The words in the POISON GAS diamond are INHALATION HAZARD
Special Shipping Information: Cylinders should be transported in a secure posi tion, in a
well-ventilated vehicle. Cylinders transported in an enclosed, nonventilated compartment of a
vehicle can present serious safety hazards
Additional Marking Requirement: Inhalation Hazard
Shipment of compressed gas cylinders that have been filled without the owner’s consent is a
violation of federal law [49 CFR 173.301(b)]
Marine Pollutants: Nitrogen dioxide is not listed as a marine pollutant by DOT
MSD 6.5. 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO) 433

15. Regulatory Information

The following selected regulatory requirements may apply to this product. Not
all such requirements are identified. Users of this product are solely responsible for
compliance with all applicable federal, state, and local regulations.

40 CFR 68: Risk Management Program for Chemical Accidental Release

Prevention: Requires development and implementation of risk management pro-
grams at facilities that manufacture, use, store, or otherwise handle regulated
substances in quantities that exceed specified thresholds.
Nitrogen dioxide is not listed as a regulated substance.
TSCA: Toxic Substances Control Act: Nitrogen dioxide is listed on the TSCA
inventory.
OSHA: Occupational Safety and Health Administration:
29 CFR 1910.119: Process Safety Management of Highly Hazardous Chemicals:
Requires facilities to develop a process safety management program based on
Threshold Quantities (TQ) of highly hazardous chemicals.
Nitrogen dioxide is listed in Appendix A as a highly hazardous chemical in
quantities of 250 lb (113.5 kg) or greater.
State Regulations:
434 MSD 6.5. 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO)

California: Nitrogen dioxide is not listed by California under the SAFE

DRINKING
Water and Toxic Enforcement Act of 1986 (Proposition 65).
Pennsylvania: Nitrogen dioxide is subject to the Pennsylvania Worker and
Community Right-to-Know act (35 P.S. Sections 7301–7320).

16. Other Information

Be sure to read and understand all labels and instructions supplied with all
containers of this product.
Other Hazardous Conditions of Handling, Storage, and Use: Poisonous, cor-
rosive, oxidizing liquid and gas under pressure. Store and use with adequate
ventilation at all times. Use only in a closed system constructed only of
corrosion-resistant materials. Use with equipment cleaned for oxygen service. Use
piping and equipment adequately designed to withstand pressures to be encoun-
tered. Prevent reverse flow. Reverse flow into cylinder may cause rupture. Use a
check valve or other protective device in any line or piping from the cylinder.
Never work on a pressurized system. If there is a leak, close the cylinder valve.
Blow the system down in an environmentally safe manner in compliance with all
federal, state, and local laws; then repair the leak. When returning cylinder to
supplier, be sure valve is closed; then install valve outlet cap or plug leak-tight.
Never place a compressed gas cylinder where it may become part of an elec-
trical circuit.
Note: Prior to using any plastics, confirm their compatibility with nitrogen
dioxide.
Mixtures. When you mix two or more gases or liquefied gases, you can create
additional, unexpected hazards. Obtain and evaluate the safety information for each
component before you produce the mixture. Consult an industrial hygienist or other
trained person when you evaluate the end product. Remember, gases and liquids
have properties that can cause serious injury or death.
Recommended Equipment: In semiconductor process gas and other suitable
applications, Praxair recommends the use of engineering controls such as gas
cabinet enclosures, automatic gas panels (used to purge systems on cylinder
changeout), excess-flow valves throughout the gas distribution system, double
containment for the distribution system, and continuous gas monitors.

Hazard rating systems

NFPA ratings: HMIS ratings:
Health = 3 Health = 3
Flammability = 0 Flammability = 0
Instability = 0 Physical hazard = 1
Special = OX
MSD 6.5. 5-Nitro-2,4-Dihydro-3H-1,2,4-Triazole-3-One (NTO) 435

Standard Valve Connections for U.S. and Canada:

Threaded: CGA-660
Pin-Indexed Yoke: Not applicable.
Ultra-High-Integrity Connection: Not applicable

Use the proper CGA connections. Do Not Use Adapters. Additional

limited-standard connections may apply. See CGA pamphlet V-1 listed below.
Ask your supplier about free Praxair safety literature as referred to in this MSDS
and on the label for this product. Further information can be found in the following
materials published by the Compressed Gas Association, Inc. (CGA), 4221 Walney
Road, 5th Floor, Chantilly, VA 20151-2923, Telephone (703) 788–2700, http://
www.cganet.com/Publication.asp.
AV-1 Safe Handling and Storage of Compressed Gases
P-1 Safe Handling of Compressed Gases in Containers
P-39 Oxygen-Rich Atmospheres
SB-2 Oxygen-Deficient Atmospheres
V-1 Compressed Gas Cylinder Valve Inlet and Outlet Connections
— Handbook of Compressed Gases, Fourth Edition

Praxair asks users of this product to study this MSDS and become aware of
product hazards and safety information. To promote safe use of this product, a user
should (1) notify employees, agents, and contractors of the information in this
MSDS and of any other known product hazards and safety information, (2) furnish
this information to each purchaser of the product, and (3) ask each purchaser to
notify its employees and customers of the product hazards and safety information.
The opinions expressed herein are those of qualified experts within Praxair, Inc.
We believe that the information contained herein is current as of the date of this
Material Safety Data Sheet. Since the use of this information and the conditions of
use of the product are not within the control of Praxair, Inc., it is the user’s
obligation to determine the conditions of safe use of the product.
Praxair MSDSs are furnished on sale or delivery by Praxair or the independent
distributors and suppliers who package and sell our products. To obtain current
MSDSs for these products, contact your Praxair sales representative or local dis-
tributor or supplier, or download from www.praxair.com. If you have questions
regarding Praxair MSDSs, would like the form number and date of the latest
MSDS, or would like the names of the Praxair suppliers in your area, phone or write
the Praxair Call Center (Phone: 1- 800-PRAXAIR; Address: Praxair Call Center,
Praxair, Inc., PO Box 44, Tonawanda, NY 14151-0044).
Praxair and the Flowing Airstream design are trademarks or registered trade-
marks of Praxair Technology, Inc. in the United States and/or other countries.
Praxair, Inc.
39 Old Ridgebury Road, Danbury, CT 06810-5113
436 MSD 6.6. Hexanitrostilbene (HNS)

MSD 6.6. Hexanitrostilbene (HNS)

MSD 6.6. Hexanitrostilbene (HNS) 437
438 MSD 6.6. Hexanitrostilbene (HNS)
MSD 6.6. Hexanitrostilbene (HNS) 439
440 MSD 6.6. Hexanitrostilbene (HNS)

MSD 6.6. Hexanitrostilbene (HNS)

MSD 6.7. N-Methy-4-nitroaniline (MNA) 441

MSD 6.7. N-Methy-4-nitroaniline (MNA)

SIGMA-ALDRICH sigma-aldrich.com
SAFETY DATA SHEET
Version 3.8
Revision Date 07/01/2014
Print Date 11/07/2014

1. PRODUCT AND COMPANY IDENTIFICATION

1.1 Product identifiers

Product name : Epoxy embedding medium, hardener MNA

Product Number : 45347
Brand : Fluka
CAS-No. : 25134-21-8

1.2 Relevant identified uses of the substance or mixture and uses advised against
Identified uses : Laboratory chemicals, Manufacture of substances

1.3 Details of the supplier of the safety data sheet

Company : Sigma-Aldrich
3050 Spruce Street
SAINT LOUIS MO 63103
USA
Telephone : +1 800-325-5832
Fax : +1 800-325-5052

1.4 Emergency telephone number

Emergency Phone # : (314) 776-6555

2. HAZARDS IDENTIFICATION

2.1 Classification of the substance or mixture

GHS Classification in accordance with 29 CFR 1910 (OSHA HCS)

Acute toxicity, Oral (Category 4), H302
Skin corrosion (Category 1C), H314
Serious eye damage (Category 1), H318
Respiratory sensitisation (Category 1), H334
Skin sensitisation (Category 1), H317
442 MSD 6.7. N-Methy-4-nitroaniline (MNA)

For the full text of the H-Statements mentioned in this Section, see Section 16.

2.2 GHS Label elements, including precautionary statements

Pictogram

Signal word Danger

Hazard statement(s)
H302 Harmful if swallowed.
H314 Causes severe skin burns and eye damage.
H317 May cause an allergic skin reaction.
H334 May cause allergy or asthma symptoms or breathing difficulties
if in haled.
Precautionary statement(s)

P261 Avoid breathing dust/ fume/ gas/ mist/ vapours/ spray.

P264 Wash skin thoroughly after handling.
P270 Do not eat, drink or smoke when using this product.
P272 Contaminated work clothing should not be allowed out of the
workplace.
P280 Wear protective gloves/ protective clothing/ eye protection/
face
P301 + P312 IF SWALLOWED: Call a POISON CENTER or doctor/ phy-
sician if you feel unwell.
P301 + P330 + P331 IF SWALLOWED: rinse mouth. Do NOT induce vomiting.
P303 + P361 + P353 IF ON SKIN (or hair): Remove/ Take off immediately all con-
taminated clothing. Rinse skin with water/ shower.
P304 + P340 IF INHALED: Remove victim to fresh air and keep at rest in a
position comfortable for breathing.
P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes.
Remove contact lenses, if present and easy to do. Continue
rinsing.
P310 Immediately call a POISON CENTER or doctor/ physician.
P321 Specific treatment (see supplemental first aid instructions on
this label).
P333 + P313 If skin irritation or rash occurs: Get medical advice/ attention.
P363 Wash contaminated clothing before reuse.
P405 Store locked up.
P501 Dispose of contents/ container to an approved waste disposal
plant.
MSD 6.7. N-Methy-4-nitroaniline (MNA) 443

2.3 Hazards not otherwise classified (HNOC) or not covered by GHS – none

3. COMPOSITION/INFORMATION ON INGREDIENTS

3.1 Substances
Synonyms : Methyl nadic anhydride
Methyl-5-norbornene-2,3-dicarboxylic anhydride
Epon® MNA substitute
Methylnorbornene-2,3-dicarboxylic acid anhydride
MNA

Formula : C10H10O3
Molecular Weight : 178.18 g/mol
CAS-No. : 25134-21-8
EC-No. : 246-644-8

Hazards Components

Component Classification Concentration

Methyl-5-norbornene-2,3-dicarboxylicanhydride
Acute Tox. 4; Skin Corr. 1C; -
Eye Dam. 1; Resp. Sens. 1;
Skin Sens. 1; H302, H314,
H317, H334
For the full text of the H-Statements mentioned in this Section, see Section 16
.
4. FIRST AID MEASURES

4.1 Description of first aid measures

General advice
Move out of dangerous area.Consult a physician. Show this safety data sheet to the
doctor in attendance.
If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial resp ration.
Consult a physician.
In case of skin contact
Take off contaminated clothing and shoes immediately. Wash off with soap and
plenty of water. Consult a physician.
In case of eye contact
Rinse thoroughly with plenty of water for at least 15 minutes and consult a phys
cian.Continue rinsing eyes during transport to hospital.
444 MSD 6.7. N-Methy-4-nitroaniline (MNA)

If swallowed
Do NOT induce vomiting. Never give anything by mouth to an unconscious person.
Rinse mouth with water. Consult a physician.

4.2 Most important symptoms and effects, both acute and delayed
The most important known symptoms and effects are described in the labelling (see
section 2.2) and/or in section 11

4.3 Indication of any immediate medical attention and special treatmenneeded

no data available

5. FIREFIGHTING MEASURES

5.1 Extinguishing media

Suitable extinguishing media

Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.

5.2 Special hazards arising from the substance or mixture

Carbon oxides

5.3 Advice for firefighters

Wear self contained breathing apparatus for fire fighting if necessary.

5.4 Further information

no data available

6. ACCIDENTAL RELEASE MEASURES

6.1 Personal precautions, protective equipment and emergency procedures

Use personal protective equipment. Avoid breathing vapours, mist or gas. En
sure adequate ventilation. Evacuate personnel to safe areas.
For personal protection see section 8.

6.2 Environmental precautions

Do not let product enter drains.

6.3 Methods and materials for containment and cleaning up

Soak up with inert absorbent material and dispose of as hazardous waste. Keep
in suitable, closed containers for disposal.

6.4 Reference to other sections

For disposal see section 13.
MSD 6.7. N-Methy-4-nitroaniline (MNA) 445

7. HANDLING AND STORAGE

7.1 Precautions for safe handling

Avoid contact with skin and eyes. Avoid inhalation of vapour or mist.
For precautions see section 2.2.

7.2 Conditions for safe storage, including any incompatibilities

Keep container tightly closed in a dry and well-ventilated place. Containers which are
opened must be carefully resealed and kept upright to prevent leakage.

7.3 Specific end use(s)

Apart from the uses mentioned in section 1.2 no other specific uses are stipulated

8. EXPOSURE CONTROLS/PERSONAL PROTECTION

8.1 Control parameters

Components with workplace control parameters
Contains no substances with occupational exposure limit values.

8.2 Exposure controls

Appropriate engineering controls
Handle in accordance with good industrial hygiene and safety practice. Wash hands be-
fore breaks and at the end of workday.

Personal protective equipment

Eye/face protection
Tightly fitting safety goggles. Faceshield (8-inch minimum). Use equipment for
eye protection tested and approved under appropriate government standards such
as NIOSH (US) or EN 166(EU).

Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove re-
moval technique (without touching glove's outer surface) to avoid skin contact with
this product. Dispose of contaminated gloves after use in accordance with applica-
ble laws and good laboratory practices. Wash and dry hands.

Full contact
Material: Nitrile rubber
Minimum layer thickness: 0.4 mm
Break through time: 480 min
Material tested:Camatril® (KCL 730 / Aldrich Z677442, Size M)
446 MSD 6.7. N-Methy-4-nitroaniline (MNA)

Splash contact
Material: Nitrile rubber
Minimum layer thickness: 0.11 mm
Break through time: 30 min
Material tested:Dermatril® (KCL 740 / Aldrich Z677272, Size M)

data source: KCL GmbH, D-36124 Eichenzell, phone +49 (0)6659 87300, e-mail
[email protected], test method:
EN374
If used in solution, or mixed with other substances, and under conditions which
differ from EN 374, contact the supplier of the CE approved gloves. This recom-
mendation is advisory only and must be evaluated by an industrial hygienist and
safety officer familiar with the specific situation of anticipated use by our custom-
ers. It should not be construed as offering an approval for any specific use scenario.

Body Protection
Complete suit protecting against chemicals, The type of protective equipment must
be selected according to the concentration and amount of the dangerous substance
at the specific workplace.

Respiratory protection
Where risk assessment shows air-purifying respirators are appropriate use a full-
face respirator with multipurpose combination (US) or type ABEK (EN 14387)
respirator cartridges as a backup to engineering controls. If the respirator is the sole
means of protection, use a full-face supplied air respirator. Use respirators and
components tested and approved under appropriate government standards such as
NIOSH (US) or CEN (EU).

Control of environmental exposure

Do not let product enter drains.

9. PHYSICAL AND CHEMICAL PROPERTIES

9.1 Information on basic physical and chemical properties

a) Appearance Form: viscous liquid

Colour: light yellow
b) Odour no data available
c) Odour Threshold no data available
d) pH no data available
e) Melting point/freezing no data available
point
f) Initial boiling point and
boiling range no data available
MSD 6.7. N-Methy-4-nitroaniline (MNA) 447

g) Flash point 135 °C (275 °F)

h) Evapouration rate no data available
i) Flammability (solid, gas) no data available
j) Upper/lower
flammability or
explosive limits no data available
k) Vapour pressure no data available
l) Vapour density no data available
m) Relative density 1.232 g/mL at 25 °C (77 °F)
n) Water solubility no data available
o) Partition coefficient:
o-noctanol/water no data available
p) Auto-ignition
temperature no data available
q) Decomposition
Temperature no data available
r) Viscosity no data available
s) Explosive properties no data available
t) Oxidizing properties no data available

9.2 Other safety information

no data available

10. STABILITY AND REACTIVITY

10.1 Reactivity
no data available

10.2 Chemical stability

Stable under recommended storage conditions.

10.3 Possibility of hazardous reactions

no data available

10.4 Conditions to avoid

no data available

10.5 Incompatible materials

no data available

10.6 Hazardous decomposition products

Other decomposition products - no data available
In the event of fire: see section 5
448 MSD 6.7. N-Methy-4-nitroaniline (MNA)

11. TOXICOLOGICAL INFORMATION

11.1 Information on toxicological effects

Acute toxicity
LD50 Oral - rat - 914 mg/kg
Remarks: Behavioral:Somnolence (general depressed activity). Kidney, Ureter,
Bladder:Hematuria. Nutritional and

Gross Metabolic:Weight loss or decreased weight gain.

Inhalation: no data available

LD50 Dermal - rat - 4,290 mg/kg

Remarks: Behavioral:Somnolence (general depressed activity). Lungs, Thorax,
or Respiration:Other changes.

no data available

Skin corrosion/irritation
no data available

Serious eye damage/eye irritation

no data available

Respiratory or skin sensitisation

Prolonged or repeated exposure may cause allergic reactions in certain sensitive in-
dividuals.

Germ cell mutagenicity

no data available

Carcinogenicity

IARC: No component of this product present at levels greater than or equal to

0.1% is identified as probable, possible or confirmed human carcinogen
by IARC.
ACGIH: No component of this product present at levels greater than or equal to
0.1% is identified as a carcinogen or potential carcinogen by ACGIH.
NTP: No component of this product present at levels greater than or equal to
0.1% is identified as a known or anticipated carcinogen by NTP.
OSHA: No component of this product present at levels greater than or equal to
0.1% is identified as a carcinogen or potential carcinogen by OSHA.
MSD 6.7. N-Methy-4-nitroaniline (MNA) 449

Reproductive toxicity
no data available

no data available

Specific target organ toxicity - single exposure

no data available

Specific target organ toxicity - repeated exposure

no data available

Aspiration hazard
no data available

Additional Information
RTECS: RB9100000

To the best of our knowledge, the chemical, physical, and toxicological proper
ties have not been thoroughly investigated.

12. ECOLOGICAL INFORMATION

12.1 Toxicity
no data available

12.2 Persistence and degradability

no data available

12.3 Bioaccumulative potential

no data available

12.4 Mobility in soil

no data available

12.5 Results of PBT and vPvB assessment

PBT/vPvB assessment not available as chemical safety assessment not r quired/not con-
ducted

12.6 Other adverse effects

no data available
450 MSD 6.7. N-Methy-4-nitroaniline (MNA)

13. DISPOSAL CONSIDERATIONS

13.1 Waste treatment methods

Product
Offer surplus and non-recyclable solutions to a licensed disposal company. Contact a
censed professional waste disposal service to dispose of this material. Dissolve or mix
the material with a combustible solvent and burn in a chemical incinerator equipped with
an afterburner and scrubber.

Contaminated packaging
Dispose of as unused product.

14. TRANSPORT INFORMATION

DOT (US)
UN number: 3265 Class: 8 Packing group: III
Proper shipping name: Corrosive liquid, acidic, organic, n.o.s. (Methyl-5-norbornene-
2,3-dicarboxylicanhydride) Reportable Quantity (RQ):
Marine pollutant: No
Poison Inhalation Hazard: No

IMDG
UN number: 3265 Class: 8 Packing group: III EMS-No: F-A, S-B
Proper shipping name: CORROSIVE LIQUID, ACIDIC, ORGANIC, N.O.S. (Methyl-5-
norbornene-2,3-dicarboxylicanhydride)
Marine pollutant: No

IATA
UN number: 3265 Class: 8 Packing group: III
Proper shipping name: Corrosive liquid, acidic, organic, n.o.s. (Methyl-5-norbornene-
2,3-dicarboxylicanhydride)

15. REGULATORY INFORMATION

SARA 302 Components

SARA 302: No chemicals in this material are subject to the reporting requirements of
SARA Title III, Section 302.

SARA 313 Components

SARA 313: This material does not contain any chemical components with known CAS
numbers that exceed the
threshold (De Minimis) reporting levels established by SARA Title III, Section 313.
MSD 6.7. N-Methy-4-nitroaniline (MNA) 451

SARA 311/312 Hazards

Acute Health Hazard

Massachusetts Right To Know Components

No components are subject to the Massachusetts Right to Know Act.

Pennsylvania Right To Know Components

Methyl-5-norbornene-2,3- CAS-No. Revision Date

Dicarboxylicanhydride 25134-21-8 1989-12-01

New Jersey Right To Know Components

Methyl-5-norbornene-2,3- CAS-No. Revision Date

dicarboxylicanhydride 25134-21-8 1989-12-01

California Prop. 65 Components

This product does not contain any chemicals known to State of California to cause can-
cer, birth defects, or any other reproductive harm.

16. OTHER INFORMATION

Full text of H-Statements referred to under sections 2 and 3.

Acute Tox. Acute toxicity

Eye Dam. Serious eye damage
H302 Harmful if swallowed.
H314 Causes severe skin burns and eye damage.
H317 May cause an allergic skin reaction.
H318 Causes serious eye damage.
H334 May cause allergy or asthma symptoms or
breathing difficulties if inhaled.
Resp. Sens. Respiratory sensitisation
Skin Corr. Skin corrosion

HMIS Rating
Health hazard: 3
Chronic Health Hazard: *
Flammability: 1
Physical Hazard 0
452 MSD 6.7. N-Methy-4-nitroaniline (MNA)

NFPA Rating
Health hazard: 3
Fire Hazard: 1
Reactivity Hazard: 0

Further information
Copyright 2014 Sigma-Aldrich Co. LLC. License granted to make unlimited pa-
per copies for internal use only. The above information is believed to be correct
but does not purport to be all inclusive and shall be used only as a guide. The in-
formation in this document is based on the present state of our knowledge and is
applicable to the product with regard to appropriate safety precautions. It does
not represent any guarantee of the properties of the product. Sigma-Aldrich Cor-
poration and its Affiliates shall not be held liable for any damage resulting from
handling or from contact with the above product. See www.sigma-aldrich.com
and/or the reverse side of invoice or packing slip for additional terms and condi-
tions of sale.

Preparation Information

Product Safety ó Americas Region

1-800-521-8956

Version: 3.8 Revision Date: 07/01/2014 Print Date: 12/01/2014

MSD 6.8. 1-azido-2-nitro-2-azapropane (ANAP) 453

MSD 6.8. 1-azido-2-nitro-2-azapropane (ANAP)

ARTEC CHEMICAL CO., LTD

Material Safety Data Sheet

1. IDENTIFICATION OF THE SUBSTANCE AND THE COMPANY INFORMATION

Product Name: ANAP
Supplier: Artec Chemical Co., Ltd.
1401-03, Crocodile House 2, 55 Connaught Rd. Cen-
tral, Hong Kong
Emergency Phone No.: 852-25432233 / 25422082
Fax: 852-25431883 / 25451036

2. COMPOSITION / INFORMATION ON INGREDIENTS

INCI Name: 1-NAPHTHOL

CAS No.: 90-15-3
ENIECS No.: 201-969-4
C.I. NO.: 76605
Molecular Formula: C10H8O

3. HAZARD IDENTIFICATION

Most Important Hazards:

DANGER! May cause respiratory tract irritation. Harmful if absorbed through the skin.
Corrosive. Light sensitive. Air sensitive. May be harmful if swallowed. Cause digestive
tract irritation. Cause eye and skin burns. May cause liver and kidney damage. May cause
reproductive and fetal effects. May cause blood abnormalities.
454 MSD 6.8. 1-azido-2-nitro-2-azapropane (ANAP)

Potential Health Effects:

Eye: Cause eye burns. May cause eye injury.
Skin: Harmful is absorbed through the skin. Cause skin burns.
Inhalation: May cause severe irritation of the upper respiratory tract with pain,
burns and inflammation. May cause effects similar to those described
for ingestion.
Ingestion: May be harmful if swallowed. Overexposure may result in hemolytic
anemia, leading to kidney failure. Symptoms include diarrhea,
headache, perspiration, listlessness and confusion

4. First Aid Measures

Eye Contact: Rinse immediately with plenty of water for at least 15 min. Get
medical aid immediately. Do not allow victim to rub or keep eyes
closed
Skin Contact: Get medical aid immediately. Flush skin with soap and water for at
least 15 min. Discard contaminated clothing.
Skin Contact: Get medical aid immediately. Flush skin with soap and water for at
least 15 min. Discard contaminated clothing.
Ingestion: Move to fresh air, get medical help immediately. If breathing is
difficult, give oxygen.
Inhalation: Do not induce vomiting. Do not give anything by mouth to an
unconscious person. Get immediate medical attention

5. Fire Fighting Measures

Extinguishing Media:
Carbon dioxide, dry chemical, chemical foam or water spray recommended.
Special Equipment for Firefighters:
Self-contained breathing apparatus and full protective gear recommended.

6. Accidental Release Measures

Personal Precautions:
Wear self-contained breathing apparatus, appropriate protective gloves and
clothing.
Methods for Cleaning Up:
Take up mechanically and collect in suitable container for disposal. Ventilate
area and wash off with plenty of water.
Environmental Precautions:
Do not flush into surface water or sanitary sewer system.
MSD 6.8. 1-azido-2-nitro-2-azapropane (ANAP) 455

7. Handling and Storage

Handling:
Avoid contact with skin and eyes, wear personal protective equipment.
Avoid ingestion and inhalation. Use with adequate ventilation.
Storage:
Keep container tightly closed in a dry and well-ventilated place. Keep away
from heat.
8. Exposure Controls/Personal Protection
Engineering Control:
Ensure adequate local ventilation to control airborne level.
Personal Protection:
NIOSH approved dust respirators are recommended when handling in areas
of organic chemical dusting. Safety glasses are also recommended.
Impervious clothing should be worn when gross contact is likely, such as
cleaning up spills of large amounts.

9. Physical and Chemical Properties

Appearance: Off-white flakes

Melting Point: 95–96 °C
Boiling Point: 278–280 °C @760.00 mm Hg
Molecular Weight: 144.2

10. Stability and Reactivity

Stability:
Stable under normal temperatures and pressures. Substance undergoes color
change upon exposure to light and air.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide, acid smoke and fumes.
Incompatibilities:
Strong oxidizing agents, strong bases, acid chlorides, acid anhydrides,
halogens.

11. Toxicological Information

Carcinogenicity:
Mutation has been observed in cases where 1-naphthol was administered to
microorganisms and E. Coli and Bacillus subtilis bacteria.
456 MSD 6.8. 1-azido-2-nitro-2-azapropane (ANAP)

12. Ecological Information

No data available.

13. Disposal Consideration

Waste from Residue/Unused Products:
Dispose of as special waste in compliance with local and national
regulations.
Contaminated Packaging:
Triple rinse containers. Dispose of as special waste in compliance with local
and national regulations.

14. Transport Regulations

UN- number: 2811
ADR/RID:
Shipping Name: Toxic Solid, Organic, N.O.S.
Class: 6.1
Packing Group: III
IMO:
Shipping Name: Toxic Solid, Organic, N.O.S.
Class: 6.1
Packing Group: III
ICAO:
Shipping Name: Toxic Solid, Organic, N.O.S.
Class: 6.1
Packing Group: III

15. Regulatory Information

Classification according to European directive on classification of hazardous preparations
90/492/EEC
Hazard Symbol Xn—Harmful
(s):
Risk Phrase(s): R21/22- Harmful in contact with skin and if swal lowed
R37/38- Irritating to respiratory system and skin
R41- Risks of serious damage to eyes
(continued)
MSD 6.8. 1-azido-2-nitro-2-azapropane (ANAP) 457

(continued)
Classification according to European directive on classification of hazardous preparations
90/492/EEC
Safety Phrase S22- Do not inhale dust
(s): S26- In case of contact with eyes, rinse immediately with plenty of water
and seek medical advice
S37/39- Wear suitable gloves and eye/face protection
Water Hazard Class 1 (German Regulation): slightly hazardous for water
Class:

16. Other Information

The information provided in this material safety data sheet is correct to the best
of our knowledge. No warranty is expressed or implied regarding the accuracy of
these data or the results to be obtained from the use thereof. Artec Chemical Co.,
Ltd. assumed no responsibility for any personal injury or property damage caused
by the materials. Users assume all risks associated with the use of the materials.
458 MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB)

MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB)

SIGMA-ALDRICH sigma-aldrich.com
SAFETY DATA SHEET
Version 5.10
Revision Date 11/04/2014
Print Date 11/07/2014

1. PRODUCT AND COMPANY IDENTIFICATION

1.1 Product identifiers

Product name : 4,4′ ,4″-s-Triazine-2,4,6-triyl-tribenzoic acid

Product Number : 741175

Brand : Aldrich

CAS-No. : 61414-16-2

1.2 Relevant identified uses of the substance or mixture and uses advised against

Identified uses : Laboratory chemicals, Manufacture of substances

1.3 Details of the supplier of the safety data sheet

Company : Sigma-Aldrich
3050 Spruce Street
SAINT LOUIS MO 63103
USA
Telephone : +1 800-325-5832
Fax : +1 800-325-5052

1.4 Emergency telephone number

Emergency Phone # : (314) 776-6555

2. HAZARDS IDENTIFICATION

2:1 Classification of the substance or mixture

GHS Classification in accordance with 29 CFR 1910 (OSHA HCS)
Acute toxicity, Oral (Category 4), H302
MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) 459

Skin irritation (Category 2), H315

Eye irritation (Category 2A), H319
Reproductive toxicity (Category 1B), H360
Specific target organ toxicity—single exposure (Category 3), Respiratory
system, H335
Chronic aquatic toxicity (Category 4), H413
For the full text of the H-Statements mentioned in this Section, see
Section 16.
2:2 GHS Label elements, including precautionary statements
Pictogram
Signal word Danger

Hazard statement(s)
H302 Harmful if swallowed.
H315 Causes skin irritation.
H319 Causes serious eye irritation.
H335 May cause respiratory irritation.
H360 May damage fertility or the unborn child.
H413 May cause long lasting harmful effects to aquatic life

Precautionary statement(s)
P201 Obtain special instructions before use.
P202 Do not handle until all safety precautions have been read
and understood.
P261 Avoid breathing dust/ fume/ gas/ mist/ vapours/ spray.
P264 Wash skin thoroughly after handling.
P270 Do not eat, drink or smoke when using this product.
P271 Use only outdoors or in a well-ventilated area.
P273 Avoid release to the environment.
P280 Wear protective gloves/ eye protection/ face protection.
P301 + P312 IF SWALLOWED: Call a POISON CENTER or doctor/
physician if you feel unwell.
P302 + P352 IF ON SKIN: Wash with plenty of soap and water.
P304 + P340 IF INHALED: Remove victim to fresh air and keep at rest
in a position comfortable for breathing.
P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several
minutes. Remove contact lenses, if present and easy to do.
Continue rinsing.
460 MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB)

P308 + P313 IF exposed or concerned: Get medical advice/ attention.

P321 Specific treatment (see supplemental first aid instructions
on this label).
P330 Rinse mouth.
P332 + P313 If skin irritation occurs: Get medical advice/ attention.
P337 + P313 If eye irritation persists: Get medical advice/ attention.
P362 Take off contaminated clothing and wash before reuse.
P403 + P233 Store in a well-ventilated place. Keep container tightly
closed.
P405 Store locked up.
P501 Dispose of contents/ container to an approved waste
disposal plant

2:3 Hazards not otherwise classified (HNOC) or not covered by GHS

Rapidly absorbed through skin.

3. COMPOSITION/INFORMATION ON INGREDIENTS
3:1 Substances
Formula : C24H15N3O6
Molecular weight : 441.39 g/mol
CAS-No.: 61414-16-2
Hazardous Components
Component Classification Concentration
4,4′,4′′-s-Triazine-2,4,6-triyl-tribenzoic acid
Skin Irrit. 2; Eye Irrit. 2A; <=100%
STOT SE 3; Aquatic Chronic 4; H315, H319, H335, H413
N,N-Dimethylformamide Included in the Candidate List of Substances of Very High Concern
(SVHC) according to Regulation (EC) No. 1907/2006 (REACH)
Flam. Liq. 3; Acute Tox. 4; Eye >=30–<50%
Irrit. 2A; Repr. 1B; H226, H312 + H332, H319, H360
For the full text of the H-Statements mentioned in this Section, see Section 16
MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) 461

4. FIRST AID MEASURES

4.1 Description of first aid measures

General advice
Consult a physician. Show this safety data sheet to the doctor in attendance.Move out of
dangerous area.

If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial respiration. Con-
sult a physician.

In case of skin contact

Wash off with soap and plenty of water. Consult a physician.

In case of eye contact

Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.
Aldrich - 741175 Page 3 of 8

If swallowed
Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult
a physician.

4.2 Most important symptoms and effects, both acute and delayed
The most important known symptoms and effects are described in the labelling (see sec-
tion 2.2) and/or in section 11

4.3 Indication of any immediate medical attention and special treatment needed
No data available

5. FIREFIGHTING MEASURES

5.1 Extinguishing media

Suitable extinguishing media

Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.
462 MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB)

5.2 Special hazards arising from the substance or mixture

Carbon oxides, Nitrogen oxides (NOx)

5.3 Advice for firefighters

Wear self-contained breathing apparatus for firefighting if necessary.

5.4 Further information

No data available

6. ACCIDENTAL RELEASE MEASURES

6.1 Personal precautions, protective equipment and emergency procedures

Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist
or gas. Ensure adequate
ventilation. Evacuate personnel to safe areas. Avoid breathing dust.
For personal protection see section 8.

6.2 Environmental precautions

Prevent further leakage or spillage if safe to do so. Do not let product enter drains.

6.3 Methods and materials for containment and cleaning up

Pick up and arrange disposal without creating dust. Sweep up and shovel. Keep in suit-
able, closed containers for
disposal.

6.4 Reference to other sections

For disposal see section 13.

7. HANDLING AND STORAGE

7.1 Precautions for safe handling

Avoid contact with skin and eyes. Avoid formation of dust and aerosols.
Provide appropriate exhaust ventilation at places where dust is formed.
For precautions see section 2.2.

7.2 Conditions for safe storage, including any incompatibilities

Keep container tightly closed in a dry and well-ventilated place.

7.3 Specific end use(s)

Apart from the uses mentioned in section 1.2 no other specific uses are stipulated
MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) 463

8. Exposure Controls/Personal Protection

8:1 Control parameters

Components with workplace control parameters
Component CAS-No. Value Control Basis
parameters
N, 68-12-2 TWA 10 ppm USA. ACGIH Threshold
N-Dimethylformamide Limit Values (TLV)
Remarks Liver damage Substances for which there is a
Biological Exposure Index or Indice (see BEI®
section) Not classifiable as a human carcinogen
Danger f cutaneous absorption
TWA 10 ppm, USA. OSHA—TABLE
30 mg/m3 Z-1 Limits for Air
Contaminants—
1910.1000
Skin notation
TWA 10 ppm USA. Occupational
30 mg/m3 Exposure Limits
(OSHA)—Table Z-1
Limits for Air
Contaminants
Skin designation
The value in mg/m3 is approximate
TWA 10 ppm USA. NIOSH
30 mg/m3 Recommended
Exposure Limits
Potential for dremal absorption
Biological occupational exposure limits
Component CAS-No. Parameters Value Biological Basis
specimen
N, 68-12-2 N-Methylformamide 150,000 In urine ACGIH—
NDimethylformamide mg/l Biological
Exposure
Indices
(BEI)
Remarks End of shift (As soon as possible after exposure ceases)
N-Acetyl-S- 40.0000 In urine ACGIH—
(Nmethylcarba mg/l Biological
moyl)cysteine Exposure
Indices
(BEI)
Prior to last shift of workweek
464 MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB)

8:2 Exposure controls

Appropriate engineering controls
Handle in accordance with good industrial hygiene and safety practice.
Wash hands before breaks and at the end of workday.
Personal protective equipment
Eye/face protection
Safety glasses with side-shields conforming to EN166 Use equipment for
eye protection tested and approved under appropriate government stan-
dards such as NIOSH (US) or EN 166(EU).
Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper
glove removal technique (without touching glove's outer surface) to avoid
skin contact with this product. Dispose of contaminated gloves after use in
accordance with applicable laws and good laboratory practices. Wash and
dry hands.
Body Protection
Impervious clothing, The type of protective equipment must be selected
according to the concentration and amount of the dangerous substance at
the specific workplace.
Respiratory protection
Where risk assessment shows air-purifying respirators are appropriate use a
full-face particle respirator type N100 (US) or type P3 (EN 143) respirator
cartridges as a backup to engineering controls. If the respirator is the sole
means of protection, use a full-face supplied air respirator. Use respirators
and components tested and approved under appropriate government stan-
dards such as NIOSH (US) or CEN (EU).
Control of environmental exposure
Prevent further leakage or spillage if safe to do so. Do not let product enter
drains.
MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) 465

9. PHYSICAL AND CHEMICAL PROPERTIES

9.1 Information on basic physical and chemical properties

a) Appearance Form: solid

b) Odour No data available
c) Odour Threshold No data available
d) pH No data available
e) Melting point/freezing
point Melting point/range: 83 - 88 °C (181 - 190 °F)
f) Initial boiling point and
boiling range No data available
g) Flash point No data available
h) Evaporation rate No data available
i) Flammability (solid, gas) No data available
j) Upper/lower
flammability or
explosive limits No data available
k) Vapour pressure No data available
l) Vapour density No data available
m) Relative density No data available
n) Water solubility No data available
o) Partition coefficient:
noctanol/water log Pow: 4.412
p) Auto-ignition
temperature No data available
q) Decomposition
temperature No data available
r) Viscosity No data available
s) Explosive properties No data available
t) Oxidizing properties No data available

9.2 Other safety information

No data available
466 MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB)

10. STABILITY AND REACTIVITY

10.1 Reactivity
No data available
10.2 Chemical stability
Stable under recommended storage conditions.
10.3 Possibility of hazardous reactions
No data available
10.4 Conditions to avoid
No data available
10.5 Incompatible materials
Strong oxidizing agents
10.6 Hazardous decomposition products
Other decomposition products - No data available
In the event of fire: see section 5

11. TOXICOLOGICAL INFORMATION

11.1 Information on toxicological effects

Acute toxicity

No data available
Inhalation: No data available
Dermal: No data available
No data available

Skin corrosion/irritation
No data available
MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) 467

Serious eye damage/eye irritation

No data available

Respiratory or skin sensitisation

No data available

Germ cell mutagenicity

No data available

Carcinogenicity
IARC: 3 - Group 3: Not classifiable as to its carcinogenicity to humans (N,N-
Dimethylformamide)
NTP: No component of this product present at levels greater than or equal to
0.1% is identified as a known or anticipated carcinogen by NTP.
OSHA: No component of this product present at levels greater than equal to 0.1%
is identified as a carcinogen or potential carcinogen by OSHA.

Reproductive toxicity
No data available

No data available

Specific target organ toxicity - single exposure

Inhalation - May cause respiratory irritation.

Specific target organ toxicity - repeated exposure

No data available

Aspiration hazard
No data available

Additional Information
RTECS: Not available

Warning: intolerance for alcohol can occur up to 4 days after dimethylformamide ex-
posure. N,N-dimethylformamide is considered to be a potent liver toxin., Vomiting, Diar-
rhoea, Abdominal pain, To the best of our knowledge, the chemical, physical, and toxico-
logical properties have not been thoroughly investigated
To the best of our knowledge, the chemical, physical, and toxicological properties have
not been thoroughly investigated.
468 MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB)

12. ECOLOGICAL INFORMATION

12.1 Toxicity
No data available

12.2 Persistence and degradability

No data available

12.3 Bioaccumulative potential

No data available

12.4 Mobility in soil

No data available

12.5 Results of PBT and vPvB assessment

PBT/vPvB assessment not available as chemical safety assessment not required/not
conducted

12.6 Other adverse effects

No data available

13. DISPOSAL CONSIDERATIONS

13.1 Waste treatment methods

Product
Offer surplus and non-recyclable solutions to a licensed disposal company. Contact a li-
censed professional waste disposal service to dispose of this material.

Contaminated packaging
Dispose of as unused product.

14. TRANSPORT INFORMATION

DOT (US)
Not dangerous goods

IMDG
Not dangerous goods

IATA
Not dangerous goods
MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) 469

15. REGULATORY INFORMATION

SARA 302 Components

No chemicals in this material are subject to the reporting requirements of SARA Title
III, Section 302.

SARA 313 Components

The following components are subject to reporting levels established by SARA Title
III, Section 313:

CAS-No. Revision Date

N,N-Dimethylformamide 68-12-2 2007-07-01

SARA 311/312 Hazards

Acute Health Hazard, Chronic Health Hazard

Massachusetts Right To Know Components

CAS-No. Revision Date
N,N-Dimethylformamide 68-12-2 2007-07-01

Pennsylvania Right To Know Components

CAS-No. Revision Date
4,4′ ,4′ ′ -s-Triazine-2,4,6-triyl-tribenzoic acid 61414-16-2
N,N-Dimethylformamide 68-12-2 2007-07-01

New Jersey Right To Know Components

CAS-No Revision Date
4,4′ ,4′ ′ -s-Triazine-2,4,6-triyl-tribenzoic acid 61414-16-2
N,N-Dimethylformamide 68-12-2 2007-07-01

California Prop. 65 Components

This product does not contain any chemicals known to State of California to cause can-
cer, birth defects, or any other reproductive harm.

16. Other Information

Full text of H-Statements referred to under sections 2 and 3.
Acute Tox. Acute toxicity
Aquatic Chronic Chronic aquatic toxicity
Eye Irrit. Eye irritation
Flam. Liq. Flammable liquids
470 MSD 6.9. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB)

H226 Flammable liquid and vapour.

H302 Harmful if swallowed.
H302 Harmful if swallowed.
H312 + H332 Harmful in contact with skin or if inhaled
H315 Causes skin irritation.
H319 Causes serious eye irritation.
H335 May cause respiratory irritation.
H360 May damage fertility or the unborn child.
H413 May cause long lasting harmful effects to aquatic life.
Repr. Reproductive toxicity
Skin Irrit. Skin irritation
STOT SE Specific target organ toxicity—single exposure

HMIS Rating
Health hazard: 2
Chronic Health Hazard: *
Flammability: 0
Physical Hazard 0

NFPA Rating
Health hazard: 2
Fire Hazard: 0
Reactivity Hazard: 0

Further information
Copyright 2014 Sigma-Aldrich Co. LLC. License granted to make unlimited
paper copies for internal use only. The above information is believed to be correct
but does not purport to be all inclusive and shall be used only as a guide. The
information in this document is based on the present state of our knowledge and is
applicable to the product with regard to appropriate safety precautions. It does not
represent any guarantee of the properties of the product. Sigma-Aldrich Corporation
and its Affiliates shall not be held liable for any damage resulting from handling or
from contact with the above product. See www.sigma-aldrich.com and/or the
reverse side of invoice or packing slip for additional terms and conditions of sale.
Preparation Information
Sigma-Aldrich Corporation
Product Safety—Americas Region
1-800-521-8956
Version: 5.10 Revision Date: 11/04/2014 Print Date: 12/09/2014
MSD 6.10. Triacetone triperoxide (TATP) 471

MSD 6.10. Triacetone triperoxide (TATP)

ChemSpectra, Inc.
2599 Still Meadow Lane
Lancaster, CA 93536
(661) 860-9014

Section 1—Identity

Product Name: YELLOW CAPPED SOLUTION

Test Mix for Peroxide, TATP, HMTD, and Chlorate

Section 2—Typical Composition

Componenta CAS # % (by wt)

Ethyl Alcohol 64-17-5 40–70%
Water 7732-18-5 30–60%
a
Carcinogenic components <0.1% and non-carcinogenic components <1% not considered
hazardous and not listed

Section 3—Health Hazards

Warning Statement
Caution: Flammable liquid. May irritate eyes. May cause birth defects.
Routes of Absorption
Accidental ingestion, inhalation of vapor of aerosol, contact with the skin and
eye.
Eye
May irritate eyes.
Skin
May dehydrate and/or defat skin.
Acute Toxicity
Ethyl Alcohol: Oral rat, LD50: 7060 mg/kg; Inhalation rat, LC50: 20,000
ppm/10-hour.
472 MSD 6.10. Triacetone triperoxide (TATP)

Organ System Toxicity

Ethyl Alcohol: May cause CNS depression, liver toxicity.
Reproductive and Developmental Toxicity
Ethyl Alcohol: May cause birth defects (fetal alcohol syndrome).
Carcinogenicity and Mutagenicity
None of the components are listed as a carcinogen under NTP, OSHA, or IARC.
Occupational Exposure Limits
Ethyl alcohol: OSHA Permissible Exposure Limits (PEL)—1000 ppm.
American Conference of Governmental Industrial Hygienists (ACGIH)
Threshold Limit Values (TLV)—1000 ppm.

Section 4—First Aid Precautions

Eye Contact
Flush eyes thoroughly with water for at least 15 min; notify medical personnel
and supervisor if redness or irritation develops.
Skin Contact
Wash thoroughly with soap and water for 15 min; notify medical personnel and
supervisor if redness or irritation develops.
Inhalation
Remove from exposure source; notify medical personnel and supervisor if
breathing difficulties develop.
Ingestion
Rinse mouth thoroughly with water; notify medical personnel and supervisor to
determine if vomiting should be induced.

Section 5—Fire Protection

Flammability/Explosivity
Product is considered a flammable liquid with flammable vapors (based on 70%
ethyl alcohol content). Above its flash point (21 °C or 70 °F), vapor-air mix-
tures of alcohol between 3.3% by volume (the Lower Explosive Limit or LEL)
and 19% by volume (the Upper Explosive Limit or UEL) are explosive in the
presence of an ignition source.
Extinguishing Media
For packaging material, use water fog or fire extinguishing media suitable for
Class B fires (e.g., dry chemical, carbon dioxide or foam).
Special Fire Fighting Procedures
Wear appropriate personal protective equipment. Decontaminate all equipment
after use.
MSD 6.10. Triacetone triperoxide (TATP) 473

Section 6—Spill and Release Measures

If material is released or spilled, cordon off spill area. Limit the spread of the
liquid with absorbent materials. Dispose of collected material in accordance
with applicable waste disposal regulations.

Section 7—Handling and Storage

Avoid contact with skin, eyes or clothing. Store in accordance with material
specifications. Wash thoroughly after handling.

Section 8—Exposure Control/Personal Protection

Eye Protection
Use safety glasses if eye contact is possible. Base the choice of protection on the
job activity and potential for contact with eyes or face.
Respiratory Protection
Required use of respiratory protective equipment is not anticipated when pro-
duct is used in a room with adequate mechanical ventilation.
Skin Protection
Use gloves if skin contact is possible. Wear lab coat or other protective
over-garment if splashing is possible. Base the choice of protection on the job
activity and potential for skin contact.
Engineering Controls
Use of local exhaust ventilation or a laboratory hood to mitigate exposure to
volatile components of the mixture (principally ethyl alcohol) is not anticipated
if adequate general room ventilation is available.
Other
Wash hands, face and other potentially exposed areas immediately in the event
of physical contact with contents.
474 MSD 6.10. Triacetone triperoxide (TATP)

Section 9—Physical/Chemical Properties

For Ethyl Alcohol:

Appearance and Odor: Clear, colorless liquid; mild pleasant whiskey-like
odor.
Solubility: Miscible in water.
Density: 0.79 g/mL @ 20 °C/4 °C
pH: No information found.
% Volatiles (v @ 21 °C): 100
Boiling Point: 78 °C (172 °F)
Melting Point: −114 °C (−173 °F)
Vapor Density (Air = 1): 1.6 g/L
Vapor Pressure (mm Hg): 40 @ 19 °C (66 °F)
Evaporation Rate: *1.4 (CCl4 = 1)

Section 10—Stability/Reactivity

Stability: Stable chemically

Hazardous Polymerization: Will not occur
Hazardous Decomposition Products: Carbon monoxide, carbon dioxide
Conditions to Avoid: Heat, flames, ignition sources

Section 11—Toxicological Information

Section 12—Environmental Information

Persistence and Degradability

Ethyl Alcohol: Expected to readily degrade.
Aquatic Toxicity
Ethyl Alcohol: Not expected to be toxic to aquatic life; 96-h LC50 values in fish
exceeded 100 mg/L
MSD 6.10. Triacetone triperoxide (TATP) 475

Section 13—Waste Disposal Methods

All wastes containing the product should be properly labeled. Dispose of wastes
in accordance to prescribed federal, state, and local guidelines, e.g., appropri-
ately permitted chemical waste incinerator. Rinse waters resulting from spill
cleanups should be discharged in an environmentally safe manner, e.g.,
appropriately permitted municipal or on-site wastewater treatment facility.

Section 14—Transportation Information

In addition to the identity label, containers of this material should have affixed
the following:
UN1170, Ethanol Solution, 3, II

Section 15—Labeling/Regulatory Information

European Union (EU) Risk and Safety Phrases

R10: Flammable
R36: Irritating to the eyes
R61: May cause harm to the unborn child
California Proposition 65
None of the components are listed.

Section 16—Other Information

No additional information.
—–
The above information is offered in good faith and with the belief that it is
accurate. As of the date of issuance, we are providing all information relevant to
the foreseeable handling of the material. However, in the event of an adverse
incident associated with this product, this Material Safety Data Sheet is not, and
is not intended to be, a substitute for consultation with appropriately trained
personnel.
Date of Issue: November 11, 2010
MSD 6.11. 1,3,3-Trinitroazetidine (TNAZ)

MATERIAL SAFETY DATA SHEET

MSDS D0582
Issue 1
Latest Revision: February 19, 2003

ATK Thiokol Propulsion Emergency Phone No. (435) 863-8545

P.O. Box 707 Product Information (435) 863-3325
Brigham City, UT 84302-0707

Section 1. CHEMICAL PRODUCT IDENTIFICATION

NAME: 1,3,3-Trinitroazetidine
SYNONYMS: TNAZ

NOTICE: Under TSCA regulations this chemical material is for Research

and Development Use Only under the supervision of a technically qualified
individual.

Section 2. COMPOSITION AND INFORMATION ON INGREDIENTS

Ingredients CAS # Percent PEL (TWA) STEL TLV
1,3,3- 97645-24-4 100 NE NE NE
Trinitroazetidine
NE: Not Established

Section 3. HAZARDS IDENTIFICATION

Exposure Limits: Have not been established for this material.
Inhalation: Unknown. Avoid inhalation or breathing particulate. May be
toxic if inhaled.
Eyes: Unknown. Avoid eye contact. May cause eye irritation.
Skin: Unknown. Avoid skin contact. May cause skin irritation.
Ingestion: Unknown. Avoid ingestion. May be toxic if ingested.
Existing conditions that may be aggravated:

Section 4. FIRST AID MEASURES

Inhalation: Move to fresh air. Administer artificial respiration or oxygen. Con-
tact physician.
Eyes: Flush with water for 15 minutes while holding eyelids open.
Skin: Remove contaminated clothing and wash with soap and water.
Contact physician.
Ingestion: Induce vomiting if conscious. Contact poison control center or
physician immediately.

Section 5. FIREFIGHTING MEASURES

SPECIAL FIRE FIGHTING PROCEDURES: DOT 1.1, Explosive! Do not at-
tempt to fight fire. If ignited, this material may detonate. If this material detonates,
thrust and overpressure may result with uncontrollable ballistic property. Fire
Fighting should belimited to evacuating an area proportional to the amount of ex-
plosive that may burn or detonate, and to preventing the spread of fire beyond the
isolated area.
EXTINGUISHING MEDIA: Use sprinkler or deluge system where available to
prevent the spread of fire to other areas.
MSD 6.11. 1,3,3-Trinitroazetidine (TNAZ) 477

UNUSUAL FIRE AND EXPLOSIONS HAZARDS: Material liberates toxic prod-

ucts when subjected to fire or heat. Material carries 1.1 explosive classification;
may deflagrate or detonate and containers may rupture in a fire.

Section 6. ACCIDENTAL RELEASE MEASURES

Precautions if Container is Damaged or Material Spilled: Avoid open
flame,sparks, heat, impact, shock, friction, and temperatures above 100°C (212°F).
If acc de tally ignited, a detonation should be anticipated, causing a shock wave
and spreading of burning material with the release of toxic decomposition gases.
Contact proper authorities.

Section 7. HANDLING AND STORAGE

Avoid eye contact. Store material in an approved container in a cool, dry place.
Building and transportation equipment must be protected from lightning and other
forms of static discharge. Do not store at temperatures above 100°C.

Section 8. EXPOSURE CONTROLS - PERSONAL PROTECTION

VENTILATION: Provide sufficient mechanical ventilation to limit material inha-
lation.
RESPIRATORY PROTECTION: In the absence of adequate mechanical venti-
lation, an approval NIOSH particulate respirator (P100) may be necessary when
handling this material.
PROTECTIVE GLOVES: Use impervious gloves such as neoprene.
EYE PROTECTION: Chemical goggles.
OTHER PROTECTIVE EQUIPMENT: flame resistant clothing and conductive
safety shoes.

Section 9. PHYSICAL AND CHEMICAL PROPERTIES

VAPOR DENSITY: <1
SPECIFIC GRAVITY: 1.83
SOLUBILITY IN WATER: Low
VAPOR PRESSURE: <0.01
EVAPORATION RATE: <1
MELTING POINT: 101 ° C
BOILING POINT: >200 ° C
APPEARANCE AND COLOR: White solid, no odor.
DETECTION METHODS: NE
pH: NE
FLASHPOINT: NE

Section 10. STABILITY AND REACTIVITY

STABILITY: Stable under normal conditions of storage and use.
Conditions to Avoid: Open flame, sparks, heat, impact, shock, friction, and
temperatures above 100°C.
INCOMPATIBILITY (Materials to Avoid): Strong caustic
HAZARDOUS DECOMPOSITION PRODUCTS: Dinitrogen tetroxide, oxides
of nitrogen (NOX).
HAZARDOUS POLYMERIZATION: Will not occur.
OTHER HAZARDS: Unknown.
478 MSD 6.11. 1,3,3-Trinitroazetidine (TNAZ)

Section 11. TOXICOLOGICAL INFORMATION

ACUTE EFFECTS: Moderately toxic orally, TNAZ caused transitory irritation to
the conjuctive of the eye.
CHRONIC EFFECTS: Not known. May affect internal organ systems.
TARGET ORGAN(s): Not known

Section 12. ECOLOGICAL INFORMATION

Data not available.

Section 13. DISPOSAL CONSIDERATIONS

Dispose of in accordance with federal, state, and local regulations.

Section 14. TRANSPORTATION INFORMATION

Transport in accordance with federal, state, and local regulations. See 49 CFR –
rules governing transportation.

TNAZ can only be shipped in 25 gram quantities or less in accordance with DOT-
E 8451 until an Interim Hazard Classification (IHC) from a DoD or DOE agency or
an EX number from the USDOT Competent Authority for the United States is ob-
tained for this material. This material can be transported for developmental testing in
accordance with the requirements set forth in 49 CFR 173.56(e).

Section 15. REGULATORY INFORMATION

1,3,3-Trinitroazetidine (TNAZ) is a “new chemical” as defined by the Toxic Sub-
stance Control Act (TSCA) and is not listed on the TSCA Inventory. It is “For Re-
search and Development Use Only” and can only be used by or under the supervi-
sion of a Technically Qualified Individual (TQI).
NOTICE: Under TSCA regulations this chemical material is for Research and
Development Use Only under the supervision of a technically qualified individ-
ual.

Section 16. OTHER INFORMATION

For R&D use only. To the best of our knowledge the information contained herein is
correct. All chemicals may present unknown health hazards and must be used
withcaution. Although certain hazards are described herein, we cannot guarantee
that these are the only hazards that exist. Final determination of the suitability of the
chemical is the sole responsibility of the user. Users of any chemical should satisfy
themselves that the conditions and methods of use assure that the chemical is used
safely.

NO REPRESENTATIONS OR WARRANTIES, EITHER EXPRESS OR

IMPLIED, TO INCLUDE WARRANTIES OF MERCHANTABILITY, FITNESS
FOR A PARTICULAR PURPOSE, OR ANY OTHER NATURE ARE MADE
HEREUNDER WITH RESPECT TO THE INFORMATION CONTAINED
HEREIN OR THE CHEMICAL TO WHICH THE INFORMATION REFERS.