Robert Matyáš · Jiří Pachman

Primary Explosives
Primary Explosives
.
Robert Matyáš • Jiřı́ Pachman

Primary Explosives
Robert Matyáš Jiřı́ Pachman
Faculty of Chemical Technology Faculty of Chemical Technology
University of Pardubice University of Pardubice
Pardubice Pardubice
Czech Republic Czech Republic

ISBN 978-3-642-28435-9 ISBN 978-3-642-28436-6 (eBook)

DOI 10.1007/978-3-642-28436-6
Springer Heidelberg New York Dordrecht London
Library of Congress Control Number: 2012945904

# Springer-Verlag Berlin Heidelberg 2013

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or
information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed. Exempted from this legal reservation are brief excerpts
in connection with reviews or scholarly analysis or material supplied specifically for the purpose of being
entered and executed on a computer system, for exclusive use by the purchaser of the work. Duplication
of this publication or parts thereof is permitted only under the provisions of the Copyright Law of the
Publisher’s location, in its current version, and permission for use must always be obtained from
Springer. Permissions for use may be obtained through RightsLink at the Copyright Clearance Center.
Violations are liable to prosecution under the respective Copyright Law.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt
from the relevant protective laws and regulations and therefore free for general use.
While the advice and information in this book are believed to be true and accurate at the date of
publication, neither the authors nor the editors nor the publisher can accept any legal responsibility for
any errors or omissions that may be made. The publisher makes no warranty, express or implied, with
respect to the material contained herein.

Printed on acid-free paper

Springer is part of Springer Science+Business Media (www.springer.com)

Preface

Primary explosives, or initiators, represent a small subset of those chemical

compounds called explosives and are used for the purpose of initiating explosions.
Simply said, they can be found in various initiation devices where it is necessary to
use a mechanical, thermal, or electrical stimulus to prime the combustion or
detonation of the main explosive.
We are currently confronted with an overwhelming volume of negative news
about the use and abuse of explosives for criminal activities or terrorist bomb
attacks, such that the word explosive itself has acquired a rather pejorative conno-
tation and is often replaced with the more neutral, but rather meaningless, term
energetic material. Leaving aside the Orwellian Newspeak, it is fair to say—
without any exaggeration—that, although not generally known, explosives are
part and parcel of everyday life, much more so now than in the past. If one just
considers a small group of explosives used for initiation—primary explosives—we
find that most of us are in contact with them on a daily basis, in the form of initiators
or pyrotechnic devices in air bag systems, for example. Given this, it seems rather
surprising that there has been nothing published in English summarizing the vast
knowledge of their properties, preparation, or usage.
Of course, claiming that no information is available on primary explosives
would not be entirely true. However, it is common for primary explosives to be
discussed in a chapter or a paragraph in publications dealing with explosives in
general or in a wider picture (e.g., in T. Urbański’s “Chemistry and Technology of
Explosives” or David’s “The Chemistry of Powder and Explosives”). Another
significant source of information are the hundreds or thousands of specialized
articles in technical periodicals and papers published in conference publications,
which are far too focused on a particular substance or phenomenon and do not allow
an easy grasp of the function of primary explosives in the wider context. A fair
amount of information is also included in encyclopedias on explosives (of which
the most famous and comprehensive are Fedoroff, Shefield and Kaye’s
“Encyclopaedia of Explosives and Related Items” or Meyer’s “Explosives”). How-
ever, information included in these publications is usually rather brief and generally
omits many essential details. Very comprehensive and valuable sources of

v
vi Preface

information on primary explosives are the many publications written in non-

English languages, which, despite today’s translation capabilities, often remain
inaccessible for the majority of potential readers due to the language barrier. This
is really regrettable as there are numerous comprehensive and high-quality sources
produced in Russian or the Czech language. Here, one should note Bagal’s 500-
page publication “Khimiya i tekhnologiya initsiiruyushchikh vzryvshchatykh
veshchestv” (Chemistry and Technology of Primary Explosives) written in Russian
or Hanus’s Czech publication “Méně známé třaskaviny” (Lesser Known Primary
Explosives).
Given all the above, the authors of this publication decided to summarize the
information on primary explosives included in the sources mentioned above. The
information given is not restricted to the traditional primary explosives used in
numerous applications, but there is also information on the latest trends and
substances which are currently the subject of research and development projects,
which are regarded as being potentially useful in the future. The publication also
contains some information on primary explosives which are frequently produced
illegally by nonprofessionals. Their inclusion represents the authors’ intention to
provide accurate information on this group of substances, for which the general
public, and even the experts, find rather fanciful, distorted, and false information in
the mass media and on the Internet. Being chemical engineers, we could not resist
the temptation to include also a few substances which are unlikely to be used
practically in the future but whose properties are so interesting that omitting them
would be unforgiveable.
The publication has been written for the general public interested in the field of
explosive chemical compounds, but especially for chemistry students and teachers,
researchers working in the field of explosives, police officers, criminologists,
forensic analysts, soldiers, engineers working in the production of initiators, rock
blasters, and others who are likely to come across primary explosives in their
various forms in their professional lives. A basic knowledge of chemistry at a
secondary school level may be of great benefit to the reader; however, even a
complete layman may learn a lot about the properties, methods of preparation, or
use of individual substances. Ideally, the publication should assist in achieving a
deeper understanding of the role of primary explosives, helping to demystify their
extreme sensitivity and dangerousness, and providing precise definitions, enhanc-
ing understanding of the historical context of their development and outlining the
potential future use of this group of substances.
With the exception of the first two chapters dealing with general performance
and sensitivity properties of primary explosives, the structure of the publication is
rather simple, each chapter covering a group of substances. The chapters which
follow are consistently subdivided and include information on the discovery of the
substance, sometimes including a few anecdotal or historical pieces of information,
followed by a summary of physical, chemical, and explosive properties, a brief
description of methods of preparation and a final part giving information on its
usage. We have not sought to discuss special properties in great detail. We aimed to
summarize what we consider to be most important and we paid special attention to
Preface vii

thorough referencing to enable the reader easily to find detailed information in the
available literature sources. Detailed instructions are not provided for individual
syntheses; methods resulting in individual substances are highlighted. In places,
where necessary, the topic has been discussed in more detail; in others, it has
been simplified. However, it is always rather easy to find the original source,
including all details, using the references. To make the rather technical text more
user-friendly, we decided to accompany it with photographs of a number of the
substances discussed. In most cases, these are the authors’ unpublished photographs
of products made or supplied by the authors and which cannot therefore be found in
the available literature.
In conclusion, let us express our gratitude and thanks to all who supported the
development of this project. Without their help, its creation would not have been
possible. We would like to thank especially Prof. How-Ghee Ang, director of the
Energetics Research Institute, Nanyang Technological University in Singapore,
who had the original idea to create such a work and who generously supported
the writing of the book throughout the first year of its preparation. We would also
like to thank Prof. Svatopluk Zeman, director of the Institute of Energetic Materials,
University of Pardubice, Czech Republic for his support in the second stage of its
development, especially for creating an inspiring environment for completing the
publication. Further, thanks to Mr. Jiřı́ Strnad, in memoriam, for providing valuable
and unpublished information, which significantly enhanced the chapter on Explo-
sive Properties of Primary Explosives.
We would also like to express our thanks to Jiřı́ Nesveda and Pavel Valenta for
providing expert consultation and for supplying samples of a number of primary
explosives, to Lenka Murcková for her ability to obtain even the unobtainable, to
Monika Šubrtová for her infinite patience when producing graphs, and to Jakub
Šelešovský, Zdeněk Jalový and John Svoboda for the first review of this publica-
tion. We would especially like to thank Prof. Stanisław Cudziło from Wojskowa
Akademia Techniczna in Warszawa for reviewing the manuscript.
This work was created as part of two projects: project of the Ministry of
Education, Youth and Sports of the Czech Republic No. MSM-0021627501 and
project of the Ministry of Interior of the Czech Republic No. VG 20102014032.
.
Contents

1 Introduction to Initiating Substances . . . . . . . . . . . . . . . . . . . . . . . 1

1.1 Primary Explosives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2 Priming Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3 Environmental Hazards: Emergence of Green Initiating Substances 6
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2 Explosive Properties of Primary Explosives . . . . . . . . . . . . . . . . . . 11
2.1 Influence of Density on Detonation Parameters . . . . . . . . . . . . . 11
2.2 Initiating Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2.1 Influence of Density and Compacting Pressure . . . . . . . . 13
2.2.2 Influence of Specific Surface . . . . . . . . . . . . . . . . . . . . . 19
2.2.3 Influence of the Charge Diameter . . . . . . . . . . . . . . . . . . 20
2.2.4 Influence of Confinement . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2.5 Influence of Secondary Charge Type . . . . . . . . . . . . . . . 22
2.2.6 Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.3 Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.3.1 Impact Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.3.2 Friction Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.3.3 Sensitivity to Electrostatic Discharge . . . . . . . . . . . . . . . 31
2.3.4 Sensitivity to Flame . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3 Fulminates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1.1 Fulminic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1.2 Mercury Fulminate . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.1.3 Silver Fulminate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.1.4 Other Fulminates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

ix
x Contents

4 Azides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.1 Azoimide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.2 Lead Azide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4.2.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 72
4.2.2 Chemical Reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
4.2.3 Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
4.2.4 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 78
4.2.5 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
4.2.6 Spontaneous Explosions During Crystal Growth . . . . . . 85
4.2.7 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4.3 Other Substances Derived from Lead Azide . . . . . . . . . . . . . . . 87
4.3.1 Basic Lead Azide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.3.2 Lead (IV) Azide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4.4 Silver Azide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4.4.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 89
4.4.2 Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
4.4.3 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.4.4 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.4.5 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.5 Copper Azides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.5.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 97
4.5.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 98
4.5.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
4.5.4 Undesired Formation of Copper Azides . . . . . . . . . . . . . 102
4.5.5 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
4.6 Other Metallic Azides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
4.6.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 105
4.6.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 106
4.6.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
4.6.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
4.7 Organic Azides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
4.8 Cyanuric Triazide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4.8.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 112
4.8.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4.8.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.8.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.9 4,40 ,6,60 -Tetra(azido)hydrazo-1,3,5-triazine and 4,40 ,6,60 -Tetra
(azido)azo-1,3,5-triazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.9.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 116
4.9.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.9.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.9.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
4.10 1,3,5-Triazido-2,4,6-trinitrobenzene . . . . . . . . . . . . . . . . . . . . . 118
4.10.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . 118
4.10.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . 119
Contents xi

4.10.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120

4.10.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.11 2,3,5,6-Tetraazido-1,4-benzoquinone . . . . . . . . . . . . . . . . . . . . 121
4.11.1 Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.11.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . 122
4.11.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.11.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
5 Salts of Polynitrophenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
5.1 Salts of Picric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
5.1.1 Normal Lead Picrate . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
5.1.2 Basic Lead Picrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
5.2 Salts of Dinitroresorcinol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
5.2.1 Lead salts of 2,4-Dinitroresorcinol . . . . . . . . . . . . . . . . . 133
5.2.2 Lead Salts of 4,6-Dinitroresorcinol . . . . . . . . . . . . . . . . . 135
5.3 Salts of Trinitroresorcine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
5.3.1 Lead Styphnate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
5.3.2 Basic Lead Styphnate . . . . . . . . . . . . . . . . . . . . . . . . . . 145
5.3.3 Double Salts of Lead Styphnate . . . . . . . . . . . . . . . . . . . 148
5.3.4 Barium Styphnate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.3.5 Other Salts of Styphnic Acid . . . . . . . . . . . . . . . . . . . . . 152
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
6 Diazodinitrophenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
6.2 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
6.3 Physical and Chemical Properties . . . . . . . . . . . . . . . . . . . . . . . 159
6.4 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
6.5 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
6.6 Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
7 Salts of Benzofuroxan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
7.2 Salts of 4,6-Dinitrobenzofuroxan . . . . . . . . . . . . . . . . . . . . . . . . 168
7.2.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . . 169
7.2.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
7.2.3 Preparation of 4,6-Dinitrobenzofuroxan . . . . . . . . . . . . . 172
7.2.4 Preparation of 4,6-Dinitrobenzofuroxan Salts . . . . . . . . . 173
7.2.5 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
7.3 Potassium Salt of 7-Hydroxylamino-4,6-dinitro-4,7-
dihydrobenzofuroxan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
7.4 Potassium Salt of 7-Hydroxy-4,6-dinitrobenzofuroxan . . . . . . . . 176
7.4.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . . 176
7.4.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
xii Contents

7.4.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177

7.4.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
7.5 Salts of Bis(furoxano)-2-nitrophenol . . . . . . . . . . . . . . . . . . . . . 179
7.5.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . . 180
7.5.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
7.5.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
7.5.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
8 Tetrazoles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
8.1 Tetrazene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
8.1.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 190
8.1.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 191
8.1.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
8.1.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
8.2 5-Aminotetrazole Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
8.2.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 194
8.2.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 195
8.2.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
8.2.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
8.3 5-Nitrotetrazole Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
8.3.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 197
8.3.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 199
8.3.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
8.3.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
8.4 5-Chlorotetrazole Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
8.4.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 207
8.4.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 207
8.4.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
8.4.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
8.5 5-Azidotetrazole Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
8.5.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 209
8.5.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 209
8.5.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
8.5.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
8.6 5,50 -Azotetrazole Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
8.6.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . 213
8.6.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 214
8.6.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
8.6.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
8.7 Tetrazoles with Organic Substituent . . . . . . . . . . . . . . . . . . . . . 217
8.7.1 5-Picrylaminotetrazole . . . . . . . . . . . . . . . . . . . . . . . . . 218
8.7.2 1-(1H-Tetrazol-5-yl)guanidinium Nitrate . . . . . . . . . . . . 219
Contents xiii

8.8 Organic Derivatives of 5-Nitrotetrazole . . . . . . . . . . . . . . . . . . 221

8.9 Organic Derivatives of 5-Azidotetrazole . . . . . . . . . . . . . . . . . 222
8.9.1 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 222
8.9.2 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
9 Tetrazole Ring-Containing Complexes . . . . . . . . . . . . . . . . . . . . . . 227
9.1 Cobalt Perchlorate Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . 228
9.1.1 Pentaamine(5-cyano-2H-tetrazolato-N2)cobalt(III)
perchlorate (CP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
9.1.2 CP Analogs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
9.1.3 1,5-Cyclopentamethylenetetrazole Complexes . . . . . . . . . 238
9.1.4 Tetraammine-cis-bis(5-Nitro-2H-tetrazolato-N2)
cobalt(III) perchlorate (BNCP) . . . . . . . . . . . . . . . . . . . . 241
9.1.5 BNCP Analogs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
9.1.6 Perchlorate Complexes of 1,5-Diaminotetrazole . . . . . . . 245
9.1.7 Other Perchlorate-Based Complexes . . . . . . . . . . . . . . . . 247
9.2 Perchlorate-Free Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
9.2.1 Iron- and Copper-Based 5-Nitrotetrazolato-N2
Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
9.2.2 Perchlorate-Free CP Analogs . . . . . . . . . . . . . . . . . . . . . 250
9.3 Other Transition Metal-Based 5-Nitrotetrazolato-N2
Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
10 Organic Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
10.1 Peroxides of Acetone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
10.1.1 Diacetone Diperoxide . . . . . . . . . . . . . . . . . . . . . . . . . 256
10.1.2 Triacetone Triperoxide . . . . . . . . . . . . . . . . . . . . . . . . 262
10.1.3 Tetraacetone Tetraperoxide . . . . . . . . . . . . . . . . . . . . 274
10.2 Hexamethylene Triperoxide Diamine . . . . . . . . . . . . . . . . . . . . 275
10.2.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . 275
10.2.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . 278
10.2.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
10.2.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
10.3 Tetramethylene Diperoxide Dicarbamide . . . . . . . . . . . . . . . . . 280
10.3.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . 281
10.3.2 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
10.3.3 Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
xiv Contents

11 Nitrogen Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289

11.1 Nitrogen Trichloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
11.1.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . 289
11.1.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . 290
11.1.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
11.1.4 Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
11.2 Nitrogen Tribromide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
11.2.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . 294
11.2.2 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
11.3 Nitrogen Triiodide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
11.3.1 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
11.3.2 Physical and Chemical Properties . . . . . . . . . . . . . . . . 297
11.3.3 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . 298
11.3.4 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
11.3.5 Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
12 Acetylides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
12.1 Silver Acetylides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
12.1.1 Silver Acetylide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
12.1.2 Silver Acetylide–Silver Nitrate . . . . . . . . . . . . . . . . . . 308
12.1.3 Silver Acetylide–Silver Hexanitrate . . . . . . . . . . . . . . 312
12.1.4 Other Salts of Silver Acetylide–Silver Nitrate . . . . . . . 312
12.2 Cuprous Acetylide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
12.2.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . 313
12.2.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . 314
12.2.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
12.2.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
12.3 Cupric Acetylide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
12.3.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . 316
12.3.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . 317
12.3.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
12.3.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
12.4 Mercuric Acetylide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
12.4.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . 318
12.4.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . 319
12.4.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
12.4.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
12.5 Mercurous Acetylide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
Contents xv

12.6 Aurous Acetylide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321

12.6.1 Physical and Chemical Properties . . . . . . . . . . . . . . . . 321
12.6.2 Explosive Properties . . . . . . . . . . . . . . . . . . . . . . . . . 321
12.6.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
13 Other Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
13.1 Salts of Nitramines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
13.2 Organophosphates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
13.3 Hydrazine Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
.
List of Abbreviations

2,4-DNR 2,4-Dinitroresorcinol; 2,4-dinitrobenzene-1,3-diol

2,4-LDNR Lead salt of 2,4-dinitroresorcinol; lead salt of 2,4-dinitrobenzene-
1,3-diol
4,6-DNR 4,6-Dinitroresorcinol; 4,6-dinitrobenzene-1,3-diol
4,6-LDNR Lead salt of 4,6-dinitroresorcinol; lead salt of 4,6-dinitrobenzene-
1,3-diol
5-ATZ 5-Amino-1H-tetrazole
5-PiATZ 5-(2,4,6-Trinitrophenylamino)-1H-tetrazole
Å om (1010 m)
Ångstr€
APCP Pentaammin-aqua cobalt(III) perchlorate
ATZ 5-Amino-1H-tetrazole
AzTZ 5,50 -Azo-1H-tetrazole
b.p. Boiling point
BAM Bundesanstalt f€ur Materialforschung und pr€ufung
BaS Barium styphnate; barium salt of 2,4,6-trinitrobenzene-1,3-diol
BFNP Bis(furoxano)-2-nitrophenol
BNCP Tetraammine-cis-bis(5-nitro-2H-tetrazolato-N2)cobalt(III)
perchlorate
CL-14 5,7-Diamino-4,6-dinitrobenzofuroxan
CL-20 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitan (HNIW)
CMC Carboxymethyl cellulose
CoHN Cobalt hydrazine nitrate
CP Pentaamine(5-cyano-2H-tetrazolato-N2)cobalt(III) perchlorate
CPCN Pentaammine-carbonato cobalt(III) nitrate
CTCN Tetraamine-carbonato cobalt(III) nitrate
D Detonation velocity
DADP Diacetone diperoxide; 3,3,6,6-tetramethyl-1,2,4,5-tetroxane
DAHA 4,4,6,6,8,8-Hexaazido-1,3,5,7,2l5,4l5,6l5,8l5-tetrazatetrapho-
sphocine-2,2-diamine
DANT 4,6-Diazido-N-nitro-1,3,5-triazine-2-amine
DDNP 2-Diazo-4,6-dinitrophenol

xvii
xviii List of Abbreviations

DDT Deflagration-to-detonation transition

Dinol 2-Diazo-4,6-dinitrophenol
DNBF 4,6-Dinitrobenzofuroxan
DNR Dinitroresorcinol; 1,3-dihydroxybenzene
DSC Differential scanning calorimetry
DTA Differential thermal analysis
DTG Differential thermogravimetry
E Energy
E50 Energy causing initiation in 50 % of the trials
EDNA N,N-dinitromethylenediamide
Emin Minimal energy causing initiation
en 1,2-Ethylenediamine; ethane-1,2-diamine
ENTA 7,7,9,9-Tetraazido-1,4-dinitro-1,4,6,8,10-pentaaza-5l5,7l5,9l5-
triphospha-spiro[4.5]deca-5,7,9-triene
ERDE Explosives Research and Development Establishment
ESD Electrostatic discharge
Et2O Diethylether
F of I Figure of insensitivity (explosives having a 50 % initiation drop
height equal to that of RDX are given a F of I of 80)
FOX-7 2,2-Dinitroethene-1,1-diamine
GNGT Tetrazene
h10 Impact height causing initiation in 10 % of the trials with particular
hammer mass
h50 Impact hight causing initiation in 50 % of the trials with particular
hammer mass
hmin Minimal impact hight causing initiation with particular hammer mass
HMTD Hexamethylene triperoxide diamine; 1,6-diaza-3,4,8,9,12,13-
hexaoxabicyclo[4,4,4]tetradecane
HMX 1,3,5,7-Tetranitro-1,3,5,7-tetrazocane (octogen)
HNT 5-Nitro-1H-tetrazole
IR Infrared spectroscopy
IUPAC International Union of Pure and Applied Chemistry
KBFNP Potassium salt of bis(furoxano)-2-nitrophenol
KDNBF Potassium salt of 2,4-dinitrobenzofuroxan
KDNP 7-Hydroxy-4,6-dinitrobenzofuroxan
LA Lead azide
LD50 Median lethal dose
LDDS Double lead salts of styphnic acid with 1,3-di(5-tetrazoyl)triazene
LS Lead styphnate; lead salt of 2,4,6-trinitrobenzene-1,3-diol
m- Meta
m.p. Melting point
Me Metal
MF Mercury fulminate
MO Molecular orbital
nc/na Molar ratio of catalyst to acetone
List of Abbreviations xix

NC Nitrocellulose
NG Nitroglycerine
NHN Nickel hydrazine nitrate
NKT Pentaamine (5-nitro-2H-tetrazolato-N2)cobalt(III) perchlorate
NMR Nuclear magnetic resonance
NT 5-Nitro-1H-tetrazole
o- Ortho
P Pressure
p- Para
PAC Pentaamine(1,5-cyclopentamethylene-tetrazolato-N 3) cobalt(III)
perchlorate
PbNATNR Double lead salt of styphnic acid and 5-nitraminotetrazole
PBX Plastic bonded explosives
PDT Plate dent test
PETN Pentaerytritol tetranitrate
PiC Picrylchloride; 1-chloro-2,4,6-trinitrobenzene
pKa The negative logarithm of the acid dissociation constant
prob. Probability
PVA Polyvinylalcohol
PVP-1 Detonation transition element in oil well perforators
RC Reinforcing cap
RDX 1,3,5-Trinitro-1,3,5-triazinane (hexogen)
SA Silver azide
SEM Scanning electron microscopy
SF Silver fulminate
SII Simple initiating impulse
STANAG NATO abbreviation for Standardization Agreement
T Temperature
TAAT 4,40 ,6,60 -Tetra(azido)azo-1,3,5-triazine
TAHT 4,40 ,6,60 -Tetra(azido)hydrazo-1,3,5-triazine
TATNB 1,3,5-Triazido-2,4,6-trinitrobenzene
TATP Triacetone triperoxide; 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxonane
Tdec Decomposition temperature
TeATeP 3,3,6,6,9,9,12,12-Octamethyl-1,2,4,5,7,8,10,11-
octaoxacyclododecane
TeAzQ 2,3,5,6-Tetraazido-1,4-benzoquinone
Tetryl N-methyl-N,2,4,6-tetranitroaniline
TMD Theoretical maximum density
TMDD Tetramethylene diperoxide dicarbamide; 1,2,8,9-tetraoxa-4,6,11,13-
tetraazacyclotetradecane-5,12-dione
TNR Trinitroresorcinol; 2,4,6-trinitrobenzene-1,3-diol
TNT 2,4,6-Trinitrotoluene
UV Ultraviolet
DHf Heat of formation
r Density
Chapter 1
Introduction to Initiating Substances

Initiating substances (primaries) are chemical compounds/mixtures used in igniters

or detonators to bring about burning or detonation of energetic material. The
vocabulary regarding initiators is rather vast, often divided by the type of input
and output of the element or its application. In general, igniters (containing a
priming composition) are used to provide flame, while detonators (containing the
primary explosive) are designed to create a shock wave which starts the detonation
reaction in a secondary explosive. Combinations of both are seen, for example, in
detonators in which the igniter is first initiated and the resulting flame starts the
detonator [1].
The successful initiation of explosives begins with a small external stimulus
called the simple initiating impulse (SII). The SII is a nonexplosive type of impulse
such as flame, heat, impact, stab, friction, electric spark, etc. The choice depends on
the type of material to be initiated and on the desired output effect. The energy
provided by this impulse is sufficient enough to initiate the burning of a priming
mixture—a sensitive mixture sometimes called prime (in pyrotechnics the term
prime is used for the first layer enabling successful ignition). The energy from the
combustion of the priming composition needs to be magnified or delayed by a
sequence of elements, such as delay, transfer, and output charges. The entire
sequence is called an explosive train and is simplified in Fig. 1.1.
The term primer in Fig. 1.1 represents the first element in the explosive train with
flame as a desired output (e.g., percussion primer, pyrotechnic prime, electric
fusehead, safety fuse, etc.). It needs to be stressed here that consistency in termi-
nology does not exist regarding the term primer which is often used for primary
explosives and boosters, but also for a charge consisting of detonating cord,
detonator, and transfer charge made of secondary explosive, for detonator fused
booster charges or more commonly for percussion-sensitive pyrotechnic mixtures
loaded in small metal caps used in ammunition cartridges. Regarding Fig. 1.1, the
primer is, as stated, the first element in the explosive train sensitive to the SII. All
such elements contain a priming composition, which is typically a pyrotechnic
mixture designed specifically for each particular application from a variety of
substances (the topic is briefly described in later parts of this chapter). The transfer

R. Matyáš and J. Pachman, Primary Explosives, 1

DOI 10.1007/978-3-642-28436-6_1, # Springer-Verlag Berlin Heidelberg 2013
2 1 Introduction to Initiating Substances

Detonator
non-explosive
impulse
Transfer Output
Primer charge
element

Igniter
non-explosive
impulse
Output
Primer
charge

flame

shock wave

Fig. 1.1 Schematic representation of the two most common types of explosive trains

element in Fig. 1.1 represents any element used in the detonation train to augment
or delay the initial impulse. The materials for such an element may range from a
primary explosive (column of lead azide or 2-diazo-4,6-dinitrophenol—dinol) or
pyrotechnic mixtures (e.g., FeSiCr/Pb3O4) to black powder. The output charges are
secondary explosives, pyrotechnic mixtures, or propellants depending on the type
of application.
In the following text, we have decided to adopt an approach in which we divide
the vast group of sensitive condensed energetic materials according to various
criteria (Fig. 1.2). The first criterion we used is their usefulness in real applications.
We further divide those that have found a use depending upon the type of the desired
function into two groups: (a) detonating substances (primary explosives) and
deflagrating substances or mixtures (priming mixtures, primes). The term primary
explosive is generally used for individual substances (not mixtures) which are
further divided based on their response to flame into those which detonate practically
immediately after ignition and those that require some distance/time for developing
stable detonation. The former are sometimes referred to as detonants in Anglo-
American literature, whereas in Czech literature these are called primary explosives
belonging to the group of lead azide, while the latter belong to the group of mercury
fulminate. In Russian literature, the latter are denominated as pseudo primary
explosives because they must undergo so-called deflagration to detonation transi-
tion, which is a process of accelerating the burning reaction zone to a point where the
propagation mechanism changes from being heat transfer driven to being shock
wave driven.
1 Introduction to Initiating Substances 3

Sensitive condensed
energetic materials

used not used as intiating

Initiating substances substances

nitrogen halides (NI3,NCI3)

detonating deflagrating
sensitive and unstable azides
(TNTAB,CuN3,N3I)
acetylides (Ag,Cu)
fulminates (Ag,Cd,Cu)
primary explosives priming compositions nitrides (Ag,Au,Ti,Hg)
many tetrazoles,tetrazines,
and their complexes and salts

containing primary without primary

undergoing DDT detonating immediately
explosives explosives

mercury fulminate lead azide pyrotechnic

MF based
lead tricinate silver azide mixtures
SINOXID
tetracene silver fulminate
SINTOX
DDNP
NONTOX
CP, BNCP
Clean Fire
TATP improvised primary
HMTD explosives

Fig. 1.2 Subdivisions of sensitive energetic materials with some common examples

It is difficult, if not impossible, to draw a clear line between substances used for
igniters and those used for detonators. These two groups overlap in many
compositions. Mercury fulminate, for example, is a well-known primary explosive
used in the past, capable of detonation, but which found a use in priming compositions
much earlier than it did in detonators. It should therefore be understood that any type
of partitioning of initiating substances is rather artificial and cannot be considered
rigorous or definitive. Whether a substance finds a use as a primary explosive in a
detonator, as part of a priming mixture or does not find any use at all depends on a large
number of criteria which we have tried to introduce in Chap. 2. Many substances are
disqualified from practical application due to their inability to meet these stringent
criteria. Some examples include substances that are too sensitive for practical
application (e.g. fulminating silver, silver acetylide, nitrogen triiodide), substances
with low initiating efficiency (e.g. nitrogen triiodide, tetrazene), chemically unstable
substances (e.g. 1,6-diaza-3,4,8,9,12,13-hexaoxabicyclo[4,4,4]tetradecane—HMTD),
etc. Further, there are substances that are sensitive but are not expected to explode in
their typical application (diazonium intermediate products in the dye industry,
dibenzoyl and other peroxides used as catalysts of radical reactions, etc.), substances
used in the entertainment world for creating sound or light effects, etc.
Further we have included some of those that we believe may attract attention in
the future although they are not used at the moment (tetrazole salts and complexes).
4 1 Introduction to Initiating Substances

The main focus of this monograph is on the individual primary explosives

that have been used or reported as promising candidates for potential use. The
only exception we included is nitrogen triiodide, which we believe will never
find any use. The priming compositions are covered only briefly in this chapter
to give more space to discussing the use of primary explosives in a broader
perspective.

1.1 Primary Explosives

Primary explosives are sensitive mixtures/compounds that can be easily detonated

by an SII—nonexplosive means such as flame, heat, impact, friction, electric spark,
etc. They are mainly used in applications where it is desired to produce shock for
initiation of a less sensitive explosive (secondary explosive). The ability to initiate
detonation of secondary explosives is the characteristic that makes primary
explosives useful in detonators and blasting cups or caps (detonators used for
mining). In order for this to work, primary explosives must detonate shortly after
the nonexplosive initiation. The fast transition from SII to detonation (sometimes
referred to as acceleration) is the most important distinction between primary and
secondary explosives.
Another important use of primary explosives lies in their application as
sensitizers in priming compositions. The purpose of such mixtures is to provide
reliable ignition and the role of the primary explosives in such mixtures is to make
them sensitive enough to be easily ignited. The detonation of such a mixture is
undesirable and must be prevented by careful selection of the ingredients and their
quantities for a particular application.
The first substance ever used as a primary explosive was mercury fulminate (MF).
It was patented for use in priming mixtures in 1807 and it took another 60 years
before Nobel realized that it was possible to use MF in “Fulminate Blasting Caps”—
practically the first detonators—for initiation of detonation of nitroglycerine. The
price of mercury and the toxicity of decomposition products led to the search for
suitable replacements. Even though lead azide (LA) was tested before 1900 as a
replacement for MF in detonators, production of MF continued to grow and peaked
during World War I. The toxicity of MF, which was even at that time considered a
problem in priming mixtures, was not seen as a big issue in the case of detonators.
The real replacement of MF in detonators was a lengthy process closely related to
improvements in manufacturing of a suitable form of LA.
Apart from the already mentioned lead azide and mercury fulmiate, the classic
examples of primary explosives include lead styphnate (LS), silver azide (SA), dinol
(DDNP), and tetrazene (GNGT). Primary explosives (individual components) are
often mixed and used in the form of compositions rather than as single component
energetic materials. Mixtures may consist of either individual primary explosives
(astryl-MF/SA [2]) or primary explosives plus some nonexplosive additive (LA/LS/
dextrine or ASA composition—LA/LS/Al).
1.2 Priming Compositions 5

Table 1.1 Example of Substance Amount (wt%)

typical historical priming
composition [1] Mercury fulminate 13.7
Potassium chlorate 41.5
Antimony sulfide 33.4
Powdered glass 10.7
Gelatin glue 0.7

Table 1.2 Example of Substance Amount (wt%)

typical historical priming
compositions without MF 40 50 36
potassium chlorates [3] Barium nitrate 40 – –
Lead chromate – 24 –
Lead dioxide – 20 –
Mercury chromate – – 40
Antimony sulfide 14 – 20
Glass powder 6 6 4

1.2 Priming Compositions

Priming compositions or priming mixtures are sensitive explosive mixtures that are
designed to produce a flame in a particular application. They are most often
mixtures containing a primary explosive as one of the components in such a form
and amount that ensures the inability to initiate detonation of the mixture. The role
of the primary explosive is to sensitize the mixture to external stimuli, not to make it
detonatable. Priming mixtures are used in percussion caps for ignition of gun
powder, on electric fuseheads, delay elements, etc.
The typical examples of priming mixtures used almost exclusively in the nine-
teenth century include mercury fulminate, potassium chlorate, antimony sulfide,
glass powder, and gum Arabic. The priming mixtures widely used for small arms in
the USA in the early 1900s were based on MF. The composition of the most typical
one is summarized in Table 1.1.
At the time of black powder, weapons had to be carefully cleaned after use. The
combustion products of priming mixtures therefore did not present such a crucial
problem since they were in any case removed together with the black powder residues
during cleaning. The problem of corrosive products became apparent when black
powder was replaced by smokeless powder which meant much less careful cleaning of
weapons. Potassium chlorates as a part of the priming composition have therefore
been abandoned and replaced by other oxidizers. Some of the compositions from that
time can be seen in Table 1.2 [3].
The use of alternative oxidizers led to mixtures that were not corrosive but
contained MF, which liberated toxic mercury vapors during firing. To overcome
the problem of toxicity, Edmund von Herz proposed replacing MF in priming
compositions with lead hypophosphite nitrate (1913) and later by the lead salt of
trinitroresorcine (1914). The more important of these two MF substitutes was the
6 1 Introduction to Initiating Substances

priming compositions

primary secondary
fuel oxidizer binder sensitizer
explosive explosive

PETN Sb2S3 KClO3 Gum acacia Glass

MF
NC Al Ba(NO3)2 NC powder
LS
NG B KNO3
GNGT Ti KClO4
DDNP CaSi2 ZnO2
KDNBF CuO
MnO2

Fig. 1.3 Typical examples of components found in priming compositions

latter—the lead salt of trinitroresorcine; so-called lead styphnate, lead tricinate, or

simply just tricinate. This substance, however, does not possess sufficient percussion
sensitivity and therefore did not find wider use until the introduction of tetrazene
by Rathsburg in 1921 [3]. Some patented compositions contained both MF and
tricinate [4].
Typical primary mixtures contain some of the following: lead styphnate,
tetrazene, aluminum, antimony sulfide, calcium silicate, lead peroxide, boron,
metals, barium nitrate, secondary explosive, binder, sensitizer, etc. (Fig. 1.3).
Variations in the ingredients and their relative amounts result in compositions
which possess sensitivity and ignition properties tailored to specific requirements.
The replacement of mercury was a significant improvement with respect to the
toxicity of the combustion products. It led, however, to the introduction of tricinate
which also presents health problems due to its lead content. Concerns over envi-
ronmental hazards resulted in the search for lead-free or, more generally, heavy
metal-free compositions which would eliminate the health threat while maintaining
performance and other important properties at least to the level of lead-containing
predecessors [5].

1.3 Environmental Hazards: Emergence of Green Initiating

Substances

The problem of toxicity, as it is seen today, is caused mainly by lead which is

present in primary explosives in form of lead azide and in priming mixtures mostly
as lead styphnate. The evolution in the initiating materials is therefore heading
toward lead-free, environmentally friendly, “green” initiating substances or more
specifically “green primary explosives” and “green priming compositions.”
1.3 Environmental Hazards: Emergence of Green Initiating Substances 7

Fig. 1.4 Evolution of primary explosives and priming mixtures from the perspective of toxicity

The term “green” is “science marketing” more than anything else and is quite
confusing as it describes compositions not containing lead, as well as compositions
without heavy metals such as Hg, Pb, Ba, and Sb or more recently also
compositions that do not contain any toxicologically potentially hazardous
substances such as DDNP (often found in green compositions today). Further, the
term “green initiating substances” or sometimes “green primaries” usually covers
substances used as primary explosives as well as substances used in priming
mixtures. This may be even more confusing and we will therefore try to distinguish
only between “green primary explosives” and “green priming mixtures” with the
first ones being the replacement for LA in blasting caps and detonators while the
second is a replacement for LS in priming compositions.
Historically the oldest toxic initiating substance is MF. It has to all intents and
purposes been replaced in both igniting and detonating initiating devices by lead
alternatives. Today these lead-based alternatives coexist with the more modern
lead-less compounds or compositions containing other, less toxic, heavy metals.
The efforts in finding suitable priming compositions were more successful and led
to mixtures not containing lead such as SINTOX, NONTOX, WINCLEAN [5], CCI
Clean Fire [6], etc. [7–9]. Future research is therefore aimed toward completely
nontoxic alternatives. Results from the search for lead-free primary explosives were
not particularly good, and a suitable replacement of lead azide practically does not
exist today. The emergence in recent years of a new class of transition metal
complexes is a direct response to the toxicity of heavy metals and environmental
concerns. From recently published works, one of the more promising possibilities is
found in complexes with high nitrogen content such as tetrazoles with nontoxic
cations such as sodium, ammonium, and iron [10]. The evolution of the initiating
substances and compositions with respect to toxicity is schematically summarized
in Fig. 1.4.
In Fig. 1.4 “toxic” refers to the classical compositions with toxic heavy metals,
“less toxic” substances relate to those not containing toxic heavy metals but still
containing some problematic ingredients, and “green” to nontoxic substances.
The search for suitable replacements of LA and LS should not be seen as a search
for one universal substance. It would obviously be nice to have one substance
8 1 Introduction to Initiating Substances

Table 1.3 Target properties of green explosives and priming mixtures

Green primary explosive Green priming mixture
Criteria (blasting caps, detonators) (electric pills, percussion caps)
Chemically stable under light, X X
moisture, and in presence of
carbon dioxide
Sufficient thermal stability X X
Low toxicity (no heavy metals, X X
DDNP, ClO4 )
Sensitivity within useful limits X X
High initiation efficiency X
Resistant to dead-pressing good X
compatibility with construction
materials
Fast DDT X Unwanted
High flame temperature X
Low barrel erosion/corrosion X
Low antilubricating effect X
Low cost X X

replacing both lead salts in both applications but with respect to their different
function it should not be the ultimate goal due to different requirements for suitable
replacements. High initiation efficiency, very important in primary explosives,
is not at all important in primers and suitable properties with respect to barrel
corrosion, very important in primers, are practically meaningless in detonators.
Six criteria for “green primaries” have been proposed including [10]:
1. Lack of sensitivity to light and moisture.
2. Sensitivity to initiation in suitable limits (sensitive enough to be initiated by
nonexplosive stimulus but not too sensitive to make handling and transport
unnecessarily risky).
3. Thermally stable to at least 200  C.
4. Chemically stable for an extended period.
5. Devoid of toxic metals such as lead, mercury, silver, barium, or antimony.
6. Free of perchlorate which may be a possible teratogen and have an adverse effect
on thyroid function.
These criteria are in our opinion relatively broad and cover both primary
explosives as well as priming mixtures but do not include some important
properties specific to each group. We are therefore proposing criteria summarized
in Table 1.3.
It should be also pointed out that the toxicity of combustion products of classical
priming mixtures today is mainly concerned with air born lead. It must therefore be
stressed that using a lead-free priming mixture would have a somewhat question-
able effect if a lead bullet without at least an enclosed bottom were to be used. More
1.3 Environmental Hazards: Emergence of Green Initiating Substances 9

Table 1.4 Some compositions of priming compositions without heavy metals

Composition (%)
Substance Reported by Kusak FA956 SINTOX NONTOX
DDNP 35.0 29.8 40.0 37.0  5 Unreported amount –
Tetrazene 8.0 19.8 20.0 4.0  1 Unreported amount Unreported amount
PETN – – – 5.0  1 – Unreported amount
CuO – 29.8 – – – –
MnO2 – – 10.0 – – –
Ba(NO3)2 38.0 – – 32.0  5 – –
KNO3 – – – – – Unreported amount
ZnO2 – – – – Unreported amount –
Sb2S3 12.0 – – 15.0  2 – –
B – – – – – Unreported amount
Al 7.0 9.8 – 7.0  1 – –
Ti – – – – Unreported amount –
Glass – 9.8 28.0 – – Unreported amount
Binder – 1.0 2.0 0.2 Unreported amount Unreported amount
References [11] [11] [11] [1] [3] [8]

suitable in this case are either fully encapsulated bullets or bullets made from metals
other than lead.
Various new energetic materials have been designed and tested as potential
candidates for replacement of the lead substances. The green priming mixtures
for percussion caps of small arms ammunition for indoor shooting usually use
DDNP or tetrazene (or both) as a replacement for tricinate. DDNP, although better
than lead salts, is reported to cause some allergic reactions [10]. Example
compositions without heavy metals are summarized in Table 1.4.
A suitable replacement for lead azide in detonators still does not exist even though
new candidates, mostly based on tetrazole complexes, have been proposed and to a
certain limited extent even employed. There are also some alternative approaches
which eliminate toxic metals from the detonator by eliminating the primary explosive
but they have not yet succeeded in replacing lead azide detonators.
Environmental friendliness is of course only one important aspect to be consid-
ered. Explosives that show extraordinary properties such as stability, sensitivity,
initiation efficiency, compatibility, or other properties can find their application in
some special cases even though they will not meet the green criteria. Typical
examples of such explosives may be the mercury salt of tetrazole or cirkon
(cadmium(II)tris-carbonohydrazide) perchlorate used in Russia [12, 13].
An enormous amount of work has been done in Russia on perchlorate coordi-
nation complexes. A very interesting initiative to find “green” primary explosives
among the cobalt perchlorate complexes has been reported by Ilyushin et al. [14].
The differences in perception of toxicity in various parts of the world make direct
comparison misleading. Perchlorates, which are not seen as a problem in
many countries, are considered unsuitable from the long-term perspective in the
USA [10].
10 1 Introduction to Initiating Substances

References

1. Fedoroff, B.T., Sheffield, O.E., Kaye, S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, Dover, NJ (1960–1983)
2. Krauz, C.: Technologie výbušin. Vědecko-technické nakladatelstvı́, Praha (1950)
3. Hagel, R., Redecker, K.: Sintox – a new, non-toxic primer composition by Dynamit Nobel AG.
Propell. Explos. Pyrotech 11, 184–187 (1986)
4. Burns, J.E.: Priming mixture. US Patent 1,880,235, 1932
5. Mei, G.C., Pickett, J.W.: Lead-free priming mixture for percussion primer. US Patent
5,417,160, 1995
6. Bjerke, R.K., Ward, J.P., Ells, D.O., Kees, K.P.: Primer composition. US Patent 4,963,201, 1990
7. Brede, U., Hagel, R., Redecker, K.H., Weuter, W.: Primer compositions in the course of time:
from black powder and SINOXID to SINTOX compositions and SINCO booster. Propell.
Explos. Pyrotech 21, 113–117 (1996)
8. Nesveda, J., Brandejs, S., Jirásek, K.: Non toxic and non-corrosive ignition mixtures. Patent
WO 01/21558, 2001
9. Oommen, Z., Pierce, S.M.: Lead-free primer residues: a qualitative characterization of Winchester
WinClean, Remington/UMC LeadLess, Federal BallistiClean, and Speer Lawman CleanFire
handgun ammunition. J. Forensic Sci. 51, 509 (2006)
10. Huynh, M.V., Coburn, M.D., Meyer, T.J., Wetzer, M.: Green primaries: environmentally
friendly energetic complexes. Proc. Natl. Acad. Sci. USA 103, 5409–5412 (2006)
11. Kusák, J., Klecka, J., Lehký, L., Svachouček, V., Pechouček, P.: Základy konstrukce munice.
Edičnı́ středisko University Pardubice, Pardubice (2003)
12. Danilov, J.N., Ilyushin, M.A., Tselinskii, I.V.: Promyshlennye vzryvchatye veshchestva;
chast I Iniciiruyushchie vzryvshchatye veshchestva. Sankt-Peterburgskii gosudarstvennyi
tekhnologicheskii institut, Sankt-Peterburg (2001)
13. Andreev, V.V., Neklyudov, A.G., Pozdnyakov, S.A., Fogelzang, A.E., Sinditskii, V.P.,
Serushkin, V.V., Egorshev, V.Y., Kolesov, B.I.: Kapsyul-detonator (varianty). Patent RU
2,104,466, 1996
14. Ilyushin, M.A., Tselinskii, I.V., Sudarikov, A.M.: Razrabotka komponentov vysokoenergeti-
cheskikh kompozitsii. SPB:LGU im. A. S. Pushkina - SPBGTI(TU), Sankt-Peterburg (2006)
Chapter 2
Explosive Properties of Primary Explosives

The main requirements for primary explosives are sensitivity within useful limits, high
initiating efficiency, reasonable fluidity, resistance to dead-pressing, and long-term
stability. Useful limits mean that the substance must be sensitive enough to be initiated
by an SII but not too sensitive as to be unsafe for handling or transportation. The
initiating efficiency, perhaps the most important parameter, determines the ability of a
primary explosive to initiate secondary explosives. The reasonable free flowing
properties are important for manufacturing where the primary explosives are
often loaded volumetrically. Primary explosives must not undergo desensitization
when pressed thereby yielding a dead-pressed product. The long-term stability and
compatibility with other components, even at elevated temperatures, are essential
because primary explosives are often embedded inside more complex ammunition
and are not expected to be replaced during their service life. They must also be
insensitive to moisture and atmospheric carbon dioxide. Parameters important for
secondary explosives such as brisance, strength, detonation velocity, or pressure are of
lesser importance to primary explosives although they are of course related to the
above properties.

2.1 Influence of Density on Detonation Parameters

Primary explosives are generally prepared in the form of crystalline or powdery

material with low bulk densities and large specific surface. This form is hardly ever
suitable for direct application and therefore it has to be further processed. For use in
detonators they must be compacted by pressing to the detonator caps in a way that
assures the best initiation properties.
When higher pressures are used to achieve higher densities, a phenomenon called
“dead-pressing” may occur, leading to a material which is hard to ignite and which,
if ignited, only burns without detonation [1]. Pressing a primary explosive to a point
where it loses its capability to detonate is therefore not desirable.
The phenomenon of dead pressing is not common to all primary explosives.
Many azides, including lead azide, cannot be easily dead-pressed. On the other

R. Matyáš and J. Pachman, Primary Explosives, 11

DOI 10.1007/978-3-642-28436-6_2, # Springer-Verlag Berlin Heidelberg 2013
12 2 Explosive Properties of Primary Explosives

Fig. 2.1 Influence of density on detonation velocity: top: mercury fulminate [3–11] and bottom:
lead azide [4–9, 12–16]. Two samples with specific surface 706 cm2 g 1 and 5,802 cm2 g 1 were
listed in [9]

hand MF, DDNP and peroxides can be dead-pressed very easily. The pressure
needed for dead-pressing MF is highly dependent on its crystal size [2].
The compaction process reflects in the density, which influences practically all
of the other explosive properties. On the following two charts (Fig. 2.1), the
relationship between detonation velocity and density for MF and LA is presented.
2.2 Initiating Efficiency 13

The values have been compiled from various literature sources and hence obtained
under a variety of conditions. Rigorous conclusions based on such data are not
possible but they provide a surprisingly good idea of the shape of the relationship.
The values in Fig. 2.1 show that the detonation velocity of both MF and LA
increases with increasing density, as expected. In general, one would further expect
that it is desirable to press explosives to densities as close to the theoretical
maximum density (TMD) as possible. This is, however, not exactly the case for
primary explosives in a detonator where it is more important to have good initiation
efficiency rather than high detonation velocity.

2.2 Initiating Efficiency

Initiating efficiency, sometimes referred to as initiating power, strength, or priming

force, is the ability of a primary explosive to initiate detonation in a secondary
explosive adjacent to it. It is usually reported as a minimum amount of primary
explosive necessary to cause detonation of the adjacent high explosive with 100%
probability.
The initiating efficiency is not a material constant for a particular primary
explosive. It depends on many factors including: pressure used for compression,
type of ignition, type of confinement, presence of reinforcing cap and its material,
type of the secondary explosive, size of the contact surface between primary and
secondary explosive, etc. The values of initiation efficiency reported in the literature
are therefore difficult to compare due to a variation in these conditions. We have
collected initiation efficiencies of some primary explosives with respect to TNT and
summarized them in Fig. 2.2.
These values show variations in the minimal amount based on a combination of
these factors which are generally not provided in the references. This makes
comparison of various results quite a troublesome task. It is important to understand
that a single number reported without further specification (as shown in Fig. 2.2)
has very low information value. The effects of the most important factors are
therefore addressed in the following sections.

2.2.1 Influence of Density and Compacting Pressure

The influence of compacting pressure cannot really be separated from the influence of
density as these two parameters are related. Higher compacting pressure leads to
material of higher density. This is shown in Fig. 2.3 for MF, LA, and DDNP. The
reason why we address both of these factors here is purely practical—the lack of data.
Primary charges (for testing of initiating efficiency) are prepared in the form of powder
compressed either (a) directly onto an already compressed secondary explosive in a
metal cap or (b) into a reinforcing cap which is then pressed onto the secondary charge.
14 2 Explosive Properties of Primary Explosives

Fig. 2.2 Initiation efficiencies of some primary explosives for TNT (previously unused acronyms:
SF silver fulminate, SA silver azide, TATP triacetone triperoxide) [4, 5, 17–22]

Fig. 2.3 Density of MF, LA, and DDNP as a function of compacting pressure, by kind permission
of Dr. Strnad [9]
2.2 Initiating Efficiency 15

Fig. 2.4 The influence of compacting pressure and specific surface on initiation efficiency of
dextrinated LA (acceptor 0.35 g of TNT compressed by 76.5 MPa without reinforcing cap) by kind
permission of Dr. Strnad [9]

In both cases it is difficult to determine the exact density before the experiment.
The only known (or reported) parameter is therefore compacting pressure.
Very rare results have been obtained by Strnad [9] who used MF, LA, and DDNP
of various specific surfaces, compressed them with defined pressures, and experimen-
tally measured the resulting densities (Fig. 2.3). This allowed him to study the
influence of the resulting density on the initiation efficiency. More on this issue will
be addressed in detail later in this chapter but, to summarize, it can be stated that, in the
case of MF, LA, and DDNP, an increase in density first leads to a decrease in the
minimal necessary amount of explosive—and what happens subsequently is material
specific. Some substances (e.g., DDNP, MF) start to lose their ability to initiate
secondary explosives, which is reflected in higher amounts needed for successful
initiation, while other substances work in the same way, no matter how hard they are
pressed (pure LA).
One important and, unfortunately, not so frequently considered parameter is
specific surface. Fine powder of the same primary explosive will behave differently
from coarse crystals. Figures 2.4, 2.5, 2.6, 2.7, 2.8, and 2.9 demonstrate that very
fine powders show worse initiating efficiency compared to their coarser form.
Nevertheless, it can be seen that gently compressing any primary explosive of
any specific surface leads to an increase of initiating efficiency.
The influence of compacting pressure on the mean minimal amount is shown in
Fig. 2.4 for LA, Fig. 2.5 for DDNP, and Fig. 2.6 for MF. All three exhibit a decrease
in the minimal amount by slight compression (9.8 MPa). Further increase of pressure
16 2 Explosive Properties of Primary Explosives

0.3

DEAD - PRESSED

0.25
Minimal amount (g)

0.2

0.15

6840 cm2/g
3360 cm2/g
0.1
2253 cm2/g
4750 cm2/g

0.05
0 10 20 30 40 50 60
Compacting pressure (MPa)

Fig. 2.5 The influence of compacting pressure and specific surface on initiation efficiency of
DDNP (acceptor 0.35 g of TNT compressed by 76.5 MPa with reinforcing cap), by kind
permission of Dr. Strnad [9]

0.6

DEAD-PRESSED

0.5

0.4
Minimal amount (g)

0.3

0.2

5570 cm2/g
0.1
8990 cm2/g
754 cm2/g

0
0 10 20 30 40 50 60
Compacting pressure (MPa)

Fig. 2.6 The influence of compacting pressure and specific surface on initiation efficiency of MF
(acceptor 0.35 g of TNT compressed by 76.5 MPa with reinforcing cap), by kind permission of
Dr. Strnad [9]
2.2 Initiating Efficiency 17

0.3

0.28 6840 cm2/g

2253 cm2/g
0.26 4750 cm2/g

0.24
Minimal amount (g)

0.22

0.2

0.18

0.16

0.14

0.12

0.1
0.08
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Density (g/cm3)

Fig. 2.7 Initiation efficiency of DDNP as a function of density and specific surface (acceptor
0.35 g of TNT compressed by 76.5 MPa with reinforcing cap), by kind permission of Dr. Strnad [9]

0.6

0.5
Minimal amount (g)

0.4

0.3

0.2

0.1 5570 cm2/g

2970 cm2/g
754 cm2/g
0
1.5 2 2.5 3 3.5 4
Density (g/cm3)

Fig. 2.8 Initiation efficiency of MF as a function of density and specific surface (acceptor 0.35 g
of TNT compressed by 76.5 MPa with reinforcing cap) by kind permission of Dr. Strnad [9]

has a negligible effect on LA but significant effects on both MF and DDNP.

The decrease of the initiation efficiency for these two depends on their specific
surface. Dead pressing occurs earlier for material with higher specific surface [9].
18 2 Explosive Properties of Primary Explosives

0.18

0.16
Minimal amount (g)

0.14

0.12

0.1
11760 cm2/g
8754 cm2/g
705 cm2/g
0.08 3640 cm2/g

1 1.5 2 2.5 3 3.5

Density (g/cm3)

Fig. 2.9 Initiation efficiency of LA as a function of density and specific surface (acceptor 0.35 g
of TNT compressed by 76.5 MPa without reinforcing cap) by kind permission of Dr. Strnad [9]

The compacting pressure in Figs. 2.4, 2.5, and 2.6 can be converted to densities
of the compacted material and the relationships then plotted as initiation efficiency
as a function of density (Fig. 2.7, 2.8, and 2.9). The highest initiation efficiency is
obtained for MF at 3.2 g cm 3 (72% of TMD) and for DDNP at 1.2–1.3 g cm 3
(73.6–80.2 TMD). Using higher pressures leads to an increase in the minimal
necessary amount of the explosive, and at density 3.6 g cm 3 MF and at
1.3–1.4 g cm 3 DDNP became dead-pressed. The density at which dead pressing
takes place is lower for material with higher specific surface.
LA shows minimal necessary amount at density 2.7 g cm 3 (58% of TMD).
Further increase in the compacting pressure does not have any significant effect on
the initiation efficiency. The only exception is LA with a very large specific surface
(~10,000 cm2 g 1) which has high minimal amounts that, after exceeding optimal
density, increase yet further (Fig. 2.9).
The graphs presented above clearly show that, in the case of primary explosives,
optimal rather than high density should be used. All the more so as unnecessarily high
pressures used for obtaining material of higher density are also more susceptible to
detonations during compression.
The compacting pressure is an important parameter not only for the primary but
also for the secondary explosive as it influences the densities of both. The values
tabulated in Table 2.1 refer to the amount of primary explosive causing detonation
of PETN in 10 out of 10 trials [23]. It can be clearly seen that the uncompressed
PETN requires much lower amounts of practically all primary explosives than
compressed PETN. The compression of the secondary charge may lead to such a
2.2 Initiating Efficiency 19

Table 2.1 Influence of processing pressure on the minimal amount of primary explosive needed
to detonate PETN in 10 out of 10 trials (copper detonator cap with internal diameter 6.2 mm
without reinforcing cap) [23]
Pressure on PETN (MPa) 0 196
Pressure on initiator (MPa) 0 0 49 98 147
Primary explosive Minimum initiating charge (g)
Tetrazene 0.16 0.25 Dead pressed
Mercury fulminate (white) 0.30 0.34 Dead pressed
Lead styphnate 0.55 Without detonation with 1 g
Lead azide 0.015 0.1 0.01 0.01 0.01
Silver azide 0.005 0.110 0.005 0.005 0.005

Table 2.2 Influence of the amount of unpressed lead azide on the probability of detonation of a
PETN charge pressed by 0 or 196 MPa [23]
PETN pressed by (MPa) Weight of LA (g) Result (+ detonation, failure)
0 0.01 ++++
0 0.015 ++++++++++
0 0.02 +++++
0 0.03 +++++
196 0.03
196 0.05 +++
196 0.09 +++
196 0.10 ++++++++++

desensitization of the secondary charge that it is impossible to initiate it by primary

explosives with lower initiation efficiency.
The amounts in Table 2.1 are the minimal amounts causing initiation in 10 out of
10 trials. This does not necessarily mean that lower amounts of primary explosives
do not initiate the secondary charge. In fact they do, but the probability of failure is
higher. This behavior is demonstrated by results for LA in Table 2.2.

2.2.2 Influence of Specific Surface

The influence of the specific surface of the primary explosives on their initiation
efficiency has already been included in the graphs above as reflected by their
compaction behavior. It was further studied in a standard detonator number 3 cap
with 0.35 g of TNT compressed by 76.5 MPa as a secondary charge [9]. LA was
compressed by 13.8 MPa without any reinforcing cap while MF and DDNP were
compressed by the same pressure with a reinforcing cap. The results are shown in
Fig. 2.10. Both DDNP and LA show a performance relatively independent of
specific surface with the best performance around 4,000 cm2 g 1. The behavior
of MF is however quite different, as its minimal necessary amount continually
increases with increasing specific surface (decreasing crystal size).
20 2 Explosive Properties of Primary Explosives

0.5
MF
DDNP
LA - dextrin.
0.4
Minimal amount (g)

0.3

0.2

0.1

0
0 2000 4000 6000 8000 10000 12000 14000
Specific surface (cm2/g)

Fig. 2.10 Initiation efficiency as a function of specific surface, LA without reinforcing cap,
DDNP and MF with reinforcing cap, compacting pressure 13.8 MPa, acceptor: 0.35 g of TNT
compressed by 76.5 MPa, by kind permission of Dr. Strnad [9]

2.2.3 Influence of the Charge Diameter

The detonation velocity is not influenced only by its density but, just as in secondary
explosives, also by the diameter of the charge. The fact that LA detonates practically
immediately without a predetonation zone does not mean that it always detonates with
the same detonation velocity irrespective of the charge size, as can be seen
from Fig. 2.11. In these experiments, the LA was measured in layers of varying
thickness [14].

2.2.4 Influence of Confinement

The initiating efficiency represented by the minimal initiating charge is further

influenced by the overall design of the detonator, especially by the material of the
detonator cap and the material of the reinforcing cap. This influence is more
significant in the case of primary explosives with a long predetonation zone
(DDNP, MF) but has only limited significance in the case of immediately
detonating substances (LA). In the cases where it plays a role (DDNP, MF), a
larger amount of primary explosive is required with aluminum detonator caps than
is required when copper is used.
The influence of the material of the reinforcing cap is shown in Fig. 2.12. The
initiation efficiency is in this case represented as a minimum amount of primary
2.2 Initiating Efficiency 21

4
Detonation velocity (km/s)

0
0 0.1 0.2 0.3 0.4 0.5 0.6
Thickness of slab (mm)

Fig. 2.11 Detonation velocity as a function of thickness of lead azide sheet (mean density
3.14 g cm 3) [14]

Fig. 2.12 Influence of reinforcing cap material on the minimal amount of primary explosive
necessary to detonate PETN with 50% probability [24]

explosive necessary for 50% initiation [24]. It can be seen that tougher confinement
significantly decreases the weight of the primary explosive required in the case of MF,
to a lesser extent in the case of DDNP, and has practically no effect on LA. This is
22 2 Explosive Properties of Primary Explosives

Fig. 2.13 Initiating efficiency of various primary explosives (lines are included just to help
understanding the chart) [17]

caused by the fact that LA detonates practically instantaneously after ignition

while both MF and DDNP detonate via DDT process. A careful optimization of the
detonator design with respect to the thickness of the reinforcing cap and the size of
the hole can further decrease the minimal necessary amount of some types of primary
explosives.

2.2.5 Influence of Secondary Charge Type

For initiation of various secondary explosives different minimum amounts of the

same primary explosive are needed. Using a secondary explosive less sensitive to
detonation results in the need for an increased amount of the same primary explosive.
An amount that works well for tetryl (relatively sensitive substance) is completely
insufficient for initiation of TNT (relatively insensitive substance). It is interesting to
note that MF, with its long predetonation zone, does not show a steep increase in the
necessary minimum amount when going from sensitive to insensitive secondary
acceptors (Fig. 2.13). The order of various primary explosives with respect to their
initiating efficiency varies with varying type of secondary explosive considered, as
can be seen from Fig. 2.13. Substances such as those in Fig. 2.13 are not used in
detonators today. They were replaced by PETN, RDX, and for applications requiring
high thermal stability by HNS.
2.3 Sensitivity 23

1.6

1.4

1.2

1
Initiation efficiency (g)

0.8

0.6

without reinforcing cap

0.4

0.2
with reinforcing cap

0
0 10 20 30 40 50 60 70 80 90 100
LS (%)

Fig. 2.14 Influence of amount of LS in LS/LA mixture on the initiating charge (values are for
detonators with tetryl as secondary charge) [25]

2.2.6 Mixtures

The initiating efficiency of mixtures of primary explosives does not necessarily

have to be between the values typical of its components. The classical mixture of
LA and LS in which LS serves as a substance sensitive to flame is a typical
example. Initiating efficiency of an LS and LA mixture is highly dependent on
the ratio of the two substances and the highest values are obtained for mixtures with
ratios around LS/LA 20/80 (Fig. 2.14). It is interesting to note that the initiation
efficiency of the mixture is higher than that of pure LA up to a 60/40 ratio [25].

2.3 Sensitivity

The usefulness of energetic materials is in their ability to explode when desired.

The energy of the stimulus that starts the explosion may range from a simple touch
of a feather (nitrogen triiodide) to the impact of a shock wave (in NONEL
detonators). Sensitivity of an energetic material can therefore be seen as an amount
of energy that the material needs to absorb to attain a certain probability of
developing an explosive reaction.
A distinction is sometimes made between the term sensitiveness and the term
sensitivity. The first is related to accidental initiation and the determination of
probabilities of initiation by various unwanted stimuli, while the second is related
24 2 Explosive Properties of Primary Explosives

to the reliability of the function. With this approach, impact and friction tests are
sensitiveness tests while the gap test is a sensitivity test [26]. In many sources, these
two concepts are, however, both referred to using the term sensitivity, and for the
sake of simplicity we decided to use this majority approach.
From the perspective of sensitivity, the most sensitive energetic materials are
primary explosives, less sensitive are secondary explosives, and very insensitive are
tertiary explosives. Rigorous limits between these groups do not exist and new
explosives are therefore related to the existing ones through a series of comparative
experiments. Some authors define primary explosives as substances being more
sensitive than PETN.
The problem of sensitivity is further complicated by the fact that it is influenced
by many factors. The most important are the type of initiation, the experimental
conditions, the state of the sample tested (crystallography, shape, size), and the
method of evaluating the results.
The presence of other materials in primary explosives (additives) also influences
the resulting sensitivity values. In some cases, hard particles (e.g., glass dust) are
added to increase the sensitivity of a primary explosive which would otherwise be
too insensitive for the desired method of initiation. A typical example is addition of
glass dust to the LA which increases the sensitivity of the mixture to a level desired
for application in stab and friction detonators. The opposite effect is observed after
addition of waxes or oils which lubricate the resulting mixture. This desensitizing
effect is often utilized when it would be too risky to transport the substance in
its pure form.
The tests used for determinating sensitivity of explosives have developed from the
historical ones to those that we use today. The progress in development was,
however, mainly on a national level and many different tests measuring generally
the same thing evolved. The results as absolute values are therefore highly dependent
on the country, or even the laboratory, carrying out the tests. Some testing
methodologies became standardized (STANAG, MIL-STD, GOST, ADR, BAM)
and provide to a certain degree the possibility of comparing results—absolute
values—of various researchers. However, the most reliable are still relative results
which compare newly referred substances to some well-defined standard. This
problem with reported values is not just typical of primary explosives but relates to
sensitivity testing of energetic materials in general.
One of the additional complications when trying to compare sensitivity data
from various sources is the unspecified methodology of the test. Not only the testing
instruments differ but in many cases it is not clear what method was used for the
acquisition and evaluation of the results. The most typical ones include 50% or
100% probability of initiation, minimal initiation energy as one positive out of 6 or
10 trials at the same level, at our institute the recently implemented probit analysis
[27], etc. Detailed specification of the variety of test methodologies is outside the
scope of this work and may be found in the literature [28, 29].
From an application perspective those materials that are easily initiated by rela-
tively small amounts of energy from a nonexplosive event (impact, spark, stab,
friction, flame, etc.) are used as the first members of an initiating sequence.
2.3 Sensitivity 25

The outcome of their reaction–flame or shock wave–then initiates less sensitive

substances which require more energy and are not as easily initiated by nonexplosive
stimuli. This leads to an initiation series in which the most sensitive substances
initiate the less sensitive ones which then initiate even less sensitive ones, etc. This
sequence is called the initiation train or, more specifically, the detonation or ignition
train, depending on the desired output. The reason for a sequence of initiation is
purely practical. The sensitive substances such as primary explosives are very
vulnerable to accidental initiation and do not have the desired performance
properties. They are therefore used only in small quantities enclosed in some type
of initiating device that prevents as much as possible an unwanted initiation. They
may further be stored and transported apart from the main secondary explosives
to ensure that an accidental explosion would not initiate the main charges. The
secondary explosives, on the other hand, are designed to fulfill specific performance
parameters and are used in much larger quantities than primary explosives. Their
sensitivity is much lower and they need to be initiated by primary explosives. The
even less sensitive tertiary explosives must be initiated by a charge of secondary
explosive (so-called booster) that amplifies the output effect of the detonator.
Let us look at a typical example of an explosion train, for example, in a surface
mining blasting application. How does it work practically? A hole is first drilled into
a rock; some booster with a detonator is inserted and filled with some explosive of
low sensitivity—for example, an emulsion explosive. Let us further assume that the
detonator is electric. What happens when the electric impulse is discharged into the
wires leading to the detonator? First the bridgewire heats up and ignites the pyro-
technic mixture of the fusehead. Flame from the fusehead ignites the delay compo-
sition if it is present, flame from the delay composition ignites the primary explosive
which undergoes deflagration to detonation transition, and the outgoing detonation
wave initiates the adjacent secondary explosive inside the detonator which amplifies
the shock wave. As the detonator is placed inside the booster (charge made from
secondary explosive) the shock wave, in combination with the kinetic energy of the
fragments of the metal cap, initiates it. The detonating booster initiates the detona-
tion reaction of the main explosive (the above-mentioned emulsion).

2.3.1 Impact Sensitivity

Impact sensitivity is probably the most common sensitivity test and, just like other
tests of explosive properties, it gives very different results depending on the
methodology used and the testing apparatus. Figure 2.15 shows data obtained by
various authors for the same substances. Although the idea behind this test is very
simple—hitting an explosive by a falling object—ball or hammer—the results
obtained show considerable scatter. It can be clearly seen that the values of impact
energy cannot easily be compared without exact specification of the test conditions.
An excellent summary of a large number of impact and friction tests of LA and
to a lesser extent of some other common explosives has been published by Avrami
26 2 Explosive Properties of Primary Explosives

4
Impact energy (J)

0
SF MF SA LA LS DDNP GNGT TATP HMTD PETN

References:
[1] [22] [35] [41] [47]
BoM [4] [30] [36] [42] [48]
PA [4] [31] [37] [43]
[18] [32] [38] [44]
[19] [33] [39] [45]
[20] [34] [40] [46]

Fig. 2.15 Impact sensitivity of individual primary explosives [1, 4, 18–20, 22, 32–50] (BoM
Bureau of mines, PA Picatinny Arsenal)

and Hutchinson [49]. The importance of methodology, additives, impurities,

methods of evaluation, temperature, and many other issues is discussed in great
detail especially for lead and copper azides, and will not be repeated here.
Despite the above-mentioned problems, most common primary explosives have
been compared and the order of their impact sensitivity has been evaluated by
various authors. The sensitivity of LA and SA is lower than that of MF and
comparable to that of PETN. The sensitivity of DDNP is mentioned as lower than
for MF [4, 18, 50]. 1-Amino-1-(tetrazol-5-yldiazenyl)guanidin (GNGT, tetrazene)
is sometimes reported as slightly more sensitive than MF [41] but slightly less
sensitive than MF by [33]. SF, often mentioned as a very sensitive substance, has an
impact sensitivity comparable to that of LA. Its high sensitivity to friction is
sometimes misleadingly attributed to impact. TATP is often reported as extremely
sensitive but, as indicated by the figures in Fig. 2.15, the results are relatively evenly
spread from about 0.2 to over 3 J. Of the usual primary explosives, LS shows the
lowest sensitivity to impact.
Impact sensitivity significantly depends on many aspects. Let us look at some of
these properties starting with crystal size of the material under test. Colloidal silver
azide prepared from concentrated solutions exhibits significantly lower sensitivity
(0.5 kg from 77.7 cm) than coarser crystals prepared from diluted solutions, which
required less than half the energy (0.5 kg from 28.5 cm). MF measured under the
same conditions for comparison required 12.7 cm with the 0.5 kg hammer [20]. It is
interesting to note that the impact sensitivity of SA (in fine powdery form), which is
considered very sensitive, is lower than that of MF. Similar investigations have
2.3 Sensitivity 27

100

90

80

70
Impact energy (kg/cm)

60

50

40

30

20

10

0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Crystal size (mm)

Fig. 2.16 Influence of crystal size on the impact sensitivity of lead azide (50% probability) [51]

been carried out with lead azide and the results are shown in Fig. 2.16 [51]. It can be
clearly seen that the fine particles are again much less sensitive.
Impact sensitivity is most often reported as 50% probability which gives a good
comparative value but it does not say anything about the steepness of the dependency.
An example of results covering the whole range from 10 to 100% probability of
initiation for cuprous azide is shown in Fig. 2.17. Results of this type are not very
common because it is a very time-consuming process to obtain them. Each point in
Fig. 2.17 represents probability calculated out of 15 trials, at various heights, totaling
300 shots. It can be clearly seen that the finer particles are less sensitive and that the
drop height more than doubles when going from 10 to 100% probability. In this
particular case, the probability curves exhibit roughly the same slope, and the order of
sensitivity is the same for all percentages. It will be shown later, in the part on friction
sensitivity, that the probability curves may even cross each other. One substance may
then appear more sensitive when looking at 10% probability of initiation and less
sensitive when evaluating 50% probability. It is therefore desirable to obtain the
entire sensitivity curve. Methods such as the probit analysis significantly reduce
the number of trials necessary. The steepness of the probability curves depends on
the particular explosive [52].
A good comparison of impact sensitivity for various explosives is presented in
Fig. 2.18. It shows probability of initiation at specific drop heights expressed as a
number of positive trials out of 5.
Impact sensitivity is further influenced to a very large extent by the thickness of
the layer of explosive tested. The sensitivity of the azides of silver, lead, and
mercury increases with the layer thickness, that of cadmium is almost constant,
28 2 Explosive Properties of Primary Explosives

Fig. 2.17 Impact sensitivity of cuprous azide [52]

4
Number of detonations out of 5 trials

3
GNGT
HMTD
MF
2 KDNBF
N2 S4
TATP
LA I
1
LA II
LA III
LA III
0
0 5 10 15 20 25 30 35 40 45 50
Drop height (cm)

Fig. 2.18 Impact sensitivity of various primary explosives determined as number of positive trials
out of five at specific drop heights (KDNBF-potassium salt of 4,6-dinitrobenzofuroxan, for other
abbreviations see previous text) [40]
2.3 Sensitivity 29

those of copper, manganese, zinc, and thallium decreased in sensitivity with

increasing thickness, and those of nickel, cobalt, calcium, barium, and strontium
increased to a maximum value with 0.02 g and then the sensitivity decreased [53].
Increasing the temperature significantly increases the impact sensitivity of LS.
It is therefore crucial to carefully control temperature and time of drying during
manufacture to prevent an unnecessary increase in manipulation risk.

2.3.2 Friction Sensitivity

Despite decades of friction testing, the phenomenon is still relatively poorly under-
stood. The quantitative interpretation of the results is problematic due to numerous
factors affecting the mechanism of “friction initiation.” In practice, the test is done
by placing the tested explosive between two inert surfaces, applying a defined load on
the sample and then sliding one or both of the surfaces in a direction normal to the
direction of the applied force. Ceramic plates are often the material of choice.
Only a small number of investigations comparing friction sensitivity of primary
explosives have been published to date. The most common approach is to synthesize a
new compound and compare it to one or two standards, commonly LA, MF, PETN or,
more recently, also LS. Comparison of sensitivity of various substances is therefore
difficult and mostly based on results gathered from various sources. One of the oldest
comparative works was done by Wallbaum [31] who found the following order of
decreasing sensitivity of primary explosives: SA > LA > LS > GNGT ~ MF. This
is practically identical with the order reported by Meyer [36] for at least one initiation
out of 6 trials. The order is consistent with our data of 50% probability of initiation
(from probit analysis) [54] which is shown in Fig. 2.19. Sensitivity of organic
peroxides (TATP and HMTD) is, however, reported to be very high by Meyer.
Measurements of Matyáš [37] indicate that TATP and HMTD are slightly more
sensitive to friction than MF. According to our recent results both peroxides, as well
as DADP, are less friction sensitive than LA. The results shown in Fig. 2.19 were
obtained at our institute under the same conditions and by the same operator.
Some primary explosives are reported to have extreme sensitivity. SF and SA are
two such substances. Extreme sensitivity of SF is reported in [33], very high
sensitivity (approximately 2–3 times higher than that of LA depending on the testing
surface) is reported for SA [55]. Such statements must be carefully considered and
evaluation based on solid data. Extreme sensitivity of SA is, for example, commonly
found in older sources and could be the result of the method of preparation. In the
early days, SA was prepared by direct precipitation of aqueous solutions of sodium
azide and the silver salt and such a method of preparation could have led to a more
sensitive product. Today’s industrial SA (product of BAE Systems) is reported to
have sensitivity lower than that of LA (determined by emery friction test) [56].
Comparing friction sensitivity of LA and MF based on published results can be
quite complicated. Some authors report LA to be more sensitive [23, 33, 36] than
MF while others refer to it being less sensitive [45, 57]. The reason for such
30 2 Explosive Properties of Primary Explosives

100
Meyer [36]
Matyas et al. [54]

10
Friction sensitivity (N)

0.1
0.28

0.30

0.50

0.82

1.45

1.50

2.22

2.99

6.48

7.47

8.57

12.4

24.7

51.7

93.0
Ag

Ag

C
de

cr nate

LS

TA

KD

D F

PE
u2
M

AD

D
N
ys

F
xt

TP NO 3

TN
N
2

N
G
TD LA
C2

C2

C2
w

br
ta d L
ri

P
T
hi

ow
llin A

.A

te
g
e

Fig. 2.19 Friction sensitivity of primary explosives—comparison of our data (50% probability of n
initiation from probit analysis) [54] and data from Meyer (min. one positive out of six trials) [36]

different results could be caused by many factors, e.g., different forms of LA. We
have measured dextrinated and crystalline a-LA and both white and brown MF
under the same conditions and found MF to be much less sensitive than LA, as can
be seen from Fig. 2.19.
A large batch-to-batch variation in surface roughness of porcelain plates used in
a BAM testing machine is a well-known problem. The relationship of the plate
surface roughness and the resulting friction sensitivity has been studied by Roux
[55]. He recommends using sandpaper with a well-defined roughness to obtain
better reproducibility and lower the measurement cost. The obtained order of
sensitivity of classical primary explosives is the same as the one obtained under
standard conditions which are mentioned above. Temperature has also been
reported to play an important role in the case of LS whereas in the case of LA,
SA, and GNGT it did not [31].
Sensitivity to friction is highly dependent on the method of measurement. The
most important factors influencing the final results include the material of the plate
surface and the peg, speed of the peg sliding, and humidity. These factors are very
difficult if not impossible to compare making results of various authors hardly ever
directly comparable.
Figure 2.20 demonstrates another issue regarding sensitivity of primary
explosives. Each point on the graph represents the probability of initiation from
15 trials at particular friction force. The curves were obtained by probit analysis
[27] for two samples—pure crystalline LA and dextrinated LA. The x-axis shows
the used friction force and the y-axis the probability of initiation. Interestingly, the
2.3 Sensitivity 31

100

80
Probability of ignition [%]

60

40

20

dextrinated LA
crystalline LA

0
0 0.5 1 1.5 2
Friction force [N]

Fig. 2.20 Friction sensitivity of dextrinated and crystalline a-LA [58]

sensitivity curves for crystalline LA cross with those for dextrinated LA showing it
to be more sensitive at higher friction forces and less sensitive at lower ones [58].

2.3.3 Sensitivity to Electrostatic Discharge

With sensitivity to electrostatic discharge the situation is even more complicated

than in the case of impact and friction sensitivities. The main problem is the variety
of testing instruments and testing modes of the discharge circuit (oscillating vs.
damped mode) [59]. Due to this variability, it is practically impossible to compare
values obtained by different authors. It should always be seen in relation to other
substances measured under the exact same conditions. We have therefore included
results of measurements of electrostatic discharge sensitivity of some primary
explosives measured at our institute, where we can be sure that they have been
obtained under the same conditions, and summarized them in Fig. 2.21 (Majzlik J
and Strnad J, unpublished work). We are aware of the fact that some published
results (e.g., [60]) may be as much as an order of magnitude different from ours due
to the variation in methodologies but the order of the individual substances should
remain the same. The complete methodology with the description of the measuring
device and conditions may be found in [59, 61, 62].
The electrostatic discharge sensitivity of LS is significantly higher than such
sensitivity in other primary explosives. This creates problems for the technology
used in its production and processing.
32 2 Explosive Properties of Primary Explosives

1000

65-115
100
Sensitivity to electric discharge (mJ)

26

10 8.8 6-12
5.6
2.7
1.8
1.3
1
0.51-0.62

0.1
0.04-0.14

0.01
LS MF SA DDNP GNGT TATP HMTD LA DADP PETN

Fig. 2.21 Electrostatic sensitivity of some primary explosives (Majzlik J and Strnad J, unpub-
lished work)

2.3.4 Sensitivity to Flame

Primary explosives differ in the way they respond when subjected to flame and, based
on this type of response, may be divided into two groups. The explosives in the first
group burn when initiated by flame and may, but do not have to, undergo transition to
detonation. The detonation then propagates further with stable detonation velocity if
such transition occurs. The typical substances in this group are MF, HMTD, TATP,
and DDNP. This group is sometimes called a “mercury fulminate group.”
The second group, the so-called lead azide group, does not exhibit a
predetonation zone under normal conditions. Initiation by flame results in practi-
cally instantaneous detonation. The typical members of this group include, besides
lead azide, also silver fulminate and silver azide. Explosives of both groups—MF
group as well as LA group—detonate when initiated by shock wave [24].
The sensitivity of primary explosives to flame varies based on their chemical
composition and manufacturing process. The pressure by which the material is
prepared again plays an important role. Of the classical primary explosives, the
most sensitive are LS and GNGT and the least sensitive is LA. The data comparing
flame sensitivity of primary explosives are relatively rare. The most compact
comparison of flame sensitivity of primary explosives is given by Bagal who
used a specially designed pendulum for investigating their ignition behavior
(Fig. 2.22) [21]. This pendulum test is, however, not widely used and sensitivity
to flame is more often determined by the “ease of ignition” (Bickford fuse) test
References 33

100

80
Probability of initiation (%)

60

MF 1000/1
LS 1000/1
40
GNGT 1000/1
LA 1000/1
MF 0/3
20 LS 0/3
GNGT 0/3
LA 0/3

0
0 2 4 6 8 10 12
Time in hydrogen/air flame (ms)

Fig. 2.22 Sensitivity of primary explosives to flame [21]—the first number refers to the
compacting pressure (MPa) and the second to the orifice diameter (mm)

where observations are made of the ease of ignition and type of response after the
action of a flame from a safety fuse. Such results, although they are easier to
achieve, do not provide a quantitative measure of the sensitivity.
It can be clearly seen from Fig. 2.22 that the sensitivity of LA to flame is lower
compared to other primary explosives. This is the reason why it is in some
applications mixed with other primary explosives with high flame sensitivity,
such as LS.

References

1. Urbański, T.: Chemie a technologie výbušin. SNTL, Praha (1959)

2. Krauz, C.: Technologie výbušin. Vědecko-technické nakladatelstvı́, Praha (1950)
3. Patry, M.: Combustion et detonation, Paris 1933 In: Urbański, T. Chemistry and Technology
of Explosives, vol. 3. PWN - Polish Scientific Publisher, Warszawa (1967)
4. Tomlinson, W.R., Sheffield, O.E.: Engineering Design handbook, Explosive Series, Properties
of Explosives of Military Interest, Report AMCP 706-177. U.S. Army Material Command,
Washington, DC (1971)
5. Muraour, H.: Sur la théorie des réactions explosives. Cas particulier des explosifs
d‘amourçage. Bull. Soc. Chim. Fr. 51, 1152–1166 (1932)
6. Kast, H., Haid, A.: Uber € die sprengtechnischen Eigenschaften der wichtigsten
Initialsprengstoffe. Zeitschrift f€
ur das angewandte Chemie 38, 43–52 (1925)
34 2 Explosive Properties of Primary Explosives

7. Jahresbericht VIII der chemisch-technischen Reichsanstalt. 8, 122 In: Urbański,

T. Chemistry and Technology of Explosives, vol. 3. PWN - Polish Scientific Publisher,
Warszawa (1967)
8. Cook, M.A.: An equation of state for gases at extremely high pressures and temperatures from
the hydrodynamic theory of detonation. J. Chem. Phys. 15, 518–524 (1947)
9. Strnad, J.: Iniciačnı́ vlastnosti nejpoužı́vanějšı́ch třaskavin a vývoj nových metodik jejich
měřenı́. Dissertation thesis, Vysoká škola chemicko-technologická, Pardubice (1972)
10. Kling, A., Florentin, D.: Action des basses températures sur les explosifs. Memorial des
poudres 17, 145–153 (1913)
11. Carl, L.R.: The rate of detonation of mercury fulminate and its mixtures with potassium
chlorate. Army Ordnance 6, 302–304 (1926)
12. Danilov, J.N., Ilyushin, M.A., Tselinskii, I.V.: Promyshlennye vzryvchatye veshchestva; chast
I. Iniciiruyushchie vzryvshchatye veshchestva. Sankt-Peterburgskii gosudarstvennyi tekhnolo-
gicheskii institut, Sankt-Peterburg (2001)
13. Stadler, R.: Analytische und sprengstofftechnische Untersuchungen an Azetylensilber.
Zeitschrift f€ur das gesamte Schiess- und Sprengstoffwesen 33, 302–305 (1938)
14. Bowden, F.P., McLaren, A.C.: Conditions of explosion of azides: effect of size on detonation
velocity. Nature 175, 631–632 (1955)
€
15. Friederich, W.: Uberh€ ohte Detonationsgeschwindigkeiten. Zeitschrift f€ ur das gesamte Schiess-
und Sprengstoffwesen 31, 253 (1936)
16. Baum, F.A., Stanjukovich, J.K., Sechter, B.I.: In: Fyzika vzryva, p. 290. Nauka, Moskva
(1959)
17. W€ohler, L., Martin, F.: Die Initialwirkung von Aziden und Fulminaten. Zeitschrift f€ ur das
Gesamte Schiess- und Sprengstoffwesen 30, 18–21 (1917)
18. Clark, L.V.: Diazodinitrophenol, a detonating explosive. J. Ind. Eng. Chem. 25, 663–669
(1933)
19. Taylor, C.A., Rinkenbach, W.H.: H.M.T.D. - a new detonating explosive. Army Ordnance 5,
463–466 (1924)
20. Taylor, C.A., Rinkenbach, W.H.: Silver azide: an initiator of detonation. Army Ordnance 5,
824–825 (1925)
21. Bagal, L.I.: Khimiya i tekhnologiya iniciiruyushchikh vzryvchatykh veshchestv.
Mashinostroenie, Moskva (1975)
22. Taylor, C.A., Buxton, E.P.: Silver fulminate, an initiator of detonation. Army Ordnance 6,
118–119 (1925)
23. Wallbaum, R.: Sprengtechnische Eigenschaften und Lagerbest€andigkeit der wichtigsten
Initialsprengstoffe. Zeitschrift f€ ur das Gesamte Schiess- und Sprengstoffwesen 34, 197–201
(1939)
24. Strnad, J.: Primary explosives and pyrotechnics - lecture notes. Katedra teorie a technologie
výbušin, Univerzita Pardubice (1999)
25. Grant, R.L., Tiffany, J.E.: Factors affecting initiating efficiency of detonators. J. Ind. Eng.
Chem. 37, 661–666 (1945)
26. Zukas, J.A., Walters, W.P.: Explosive Effects and Applications. Springer, New York (1998)
27. Šelešovský, J., Pachman, J.: Probit analysis in evaluation of explosive’s sensitivity. Cent. Eur.
J. Energ. Mater. 7, 269–277 (2010)
28. Krupka, M.: Testing of Energetic Materials. Univerzita Pardubice, Pardubice (2003)
29. Sućeska, M.: Test Methods for Explosives. Springer, New York, NY (1995)
30. Taylor, A.C., Rinkenbach, W.H.: Sensitivities of detonating compounds to frictional impact,
impact, and heat. J. Franklin Inst. 204, 369–376 (1927)
31. Wallbaum, R.: Sprengtechnische Eigenschaften und Lagerbest€andigkeit der wichtigsten
Initialsprengstoffe. Zeitschrift f€
ur das gesamte Schiess- und Sprengstoffwesen 34, 161–163 (1939)
32. Berthman, A.: Die Werkstoffrage bei der Herstellung der Explosivstoffe und Z€ undstoffe.
Chemische Apparatur 27, 243–245 (1940)
References 35

33. Fedoroff, B.T., Sheffield, O.E., Kaye, S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, Dover, NJ (1960–1983)
34. Phillips, A.J.: Technical report no 1202, Report. Picatinny Arsenal, Dover, NJ (1942)
35. Khmelnitskii, L.I.: Spravochnik po vzryvchatym veshchestvam. Voennaya ordena Lenina
i ordena Suvorova Artilleriiskaya inzhenernaya akademiya imeni F. E. Dzerzhinskogo,
Moskva (1962)
36. Meyer, R., K€ohler, J., Homburg, A.: Explosives. Wiley-VCH, Weinheim (2002)
37. Matyáš, R.:Výzkum vlastnostı́ vybraných organických peroxidů. Dissertation, Univerzita
Pardubice, Pardubice, Česká Republika (2005)
38. Mavrodi, G.E.: Improvements in or relating to explosives of the organic peroxide class.
GB Patent 620,498, 1949
39. Šelešovský, J.: Hodnocenı́ stability a životnosti vojenských výbušin. Diploma thesis,
Univerzita Pardubice, Pardubice, Česká Republika (2002)
40. Metz, L.: Die Pr€ufung von Z€ undh€ utchen (Initialsprengstoffen) aus Schlagempfindlichkeit und
Flammenwirkung. Zeitschrift f€ ur das gesamte Schiess- und Sprengstoffwesen 23, 305–308
(1928)
41. Rinkenbach, W.H., Burton, O.E.: Explosive characteristics of tetracene. Army Ordnance 12,
120–123 (1931)
42. Matyáš, R.: Influence of oil on sensitivity and thermal stability of triacetone triperoxide and
hexamethylenetriperoxide diamine. In: Proceedings of 8th Seminar on New Trends in
Research of Energetic Materials, pp. 674–679, Pardubice, Czech Republic (2005)
43. Marshall, A.: Explosives. Butler and Tanner, London (1917)
44. Ek, S., Menning D.: Purification and sensitivity of triacetone triperoxide (TATP). In: Proceedings
of 10th Seminar on New Trends in Research of Energetic Materials, pp. 570–574. Pardubice,
Czech Republic (2007)
45. Špičák, S., Šimeček, J.: Chemie a technologie třaskavin. Vojenská technická akademie
Antonı́na Zápotockého, Brno (1957)
46. Orlova, E.Y.: Khimiya i tekhnologiya brizantnykh vzryvchatykh vescestv. Khimiya,
Leningrad (1981)
47. Hiskey, M.A., Huynh, M.V.: Primary explosives, US Patent 2006/0030715A1, 2006
48. Yeager, K.: Trace Chemical Sensing of Explosives. Wiley, Hoboken, NJ (2007)
49. Avrami, A., Hutchinson, R.: Sensitivity to Impact and Friction In: Fair, H.D., Walker, R.F. (eds.)
Energetic materials 2.- Technology of the Inorganic Azides, vol. 2, pp. 111–162. Plenum,
New York, NY (1977)
50. Davis, T.L.: The Chemistry of Powder and Explosives. Wiley, New York, NY (1943)
51. Bowden, F.P., Singh, K.: Size effects in the initiation and growth of explosion. Nature 172,
378–380 (1953)
52. Singh, K.: Sensitivity of cuprous azide towards heat and impact. Trans. Faraday Soc. 55,
124–129 (1959)
53. W€ohler, L., Martin, F.: Azides; sensitiveness of. J. Soc. Chem. Ind. 36, 570–571 (1917)
54. Matyáš, R., Šelešovský, J., Musil, T.: Sensitivity to friction for primary explosives. J. Hazard.
Mater. 213–214, 236–241 (2012)
55. Roux, J.J.P.A.: The dependence of friction sensitivity of primary explosives upon rubbing
surface roughness. Propell. Explos. Pyrotech. 15, 243–247 (1990)
56. Millar, R.W.: Lead free initiator materials for small electro explosive devices for medium
caliber munitions: Final report 04 June 2003, report QinetiQ/FST/CR032702/1.1, QuinetiQ,
Farnborough, UK, 2003
57. Military explosives. Report TM-9-1300-214, Headquarters, Department of the Army,
1984
58. Šelešovský, J., Matyáš, R., Musil T.: Using of the probit analysis for sensitivity tests - sensitivity
curve and reliability. In: Proceediongs of 14th Seminar on New Trends in Research of Energetic
Materials, pp. 964–968. Univerzita Pardubice, Pardubice, Czech Republic (2011)
36 2 Explosive Properties of Primary Explosives

59. Strnad, J., Majzlı́k, J.: Technical Description of Apparatus ESZ KTTV, Report. Institute of
energetic materials, University of Pardubice, Pardubice (2001)
60. Talawar, M.B., Agrawal, A.P., Anniyappan, M., Wani, D.S., Bansode, M.K., Gore, G.M.:
Primary explosives: Electrostatic discharge initiation, additive effect and its relation to thermal
and explosive characteristics. J. Hazard. Mater. 137, 1074–1078 (2006)
61. Strnad, J., Majzlı́k, J.: Determination of electrostatic spark sensitivity of energetic materials.
In: Proceedings of 4th Seminar on New Trends in Research of Energetic Materials,
pp. 303–307. University of Pardubice, Pardubice, Czech Republic (2001)
62. Strnad, J., Majzlı́k, J.: Sample of energetic material as a consumer of electric impulse power
during the electrostatic discharge examination. In: Proceedings of 37th International Annual
Conference of ICT, pp. 58.1–58.11. Karlsruhe (2006)
Chapter 3
Fulminates

3.1 Introduction

The history of salts of fulminic acid goes back to the seventeenth century when
silver and mercury fulminate were discovered by the alchemists. The fulminates—
salts of fulminic acid—must not be confused with “fulminating” compounds—such
as fulminating silver, gold, or platinum which are most likely nitrides. Fulminating
metals are also primary explosives but are not used due to their high sensitivity.
They are formed by precipitating the corresponding metal solutions with ammonia.

3.1.1 Fulminic Acid

Fulminic acid is a gaseous, very toxic, and unstable substance with a hydrogen
cyanide-like odor but much more aggressive [1, 2]. Its melting point is
10  C with
decomposition [3]. The structure of fulminic acid is demonstrated above with the
left-hand structure being dominant.
In its pure form, fulminic acid polymerizes resulting in an indeterminate product
containing molecules with molecular weight about 1,500 g mol
1 [3]. In solution,
fulminic acid spontaneously polymerizes by a complex chain of chemical reactions
resulting in the di- and trimer. The first step of the polymerization is, according to
Danilov et al. [3], most probably a dimerization resulting in furoxane formation
followed by ring rupture and further reaction yielding the cyclic trimer called
“metafulminuric acid” (I) as a main product [3–6]. This “metafulminuric acid” is
not an explosive substance [7]. Other minor identified by-products of this sponta-
neous exothermic polymerization are the tetramer called “a-isocyanilic acid” (II)
and another trimer (III). Both trimer (I) and tetramer (II) form via unstable

R. Matyáš and J. Pachman, Primary Explosives, 37

DOI 10.1007/978-3-642-28436-6_3, # Springer-Verlag Berlin Heidelberg 2013
38 3 Fulminates

intermediates as shown in a reaction scheme below [4, 6]. Further detailed infor-
mation on the mechanism of polymerization may be found in [2].
+ -
H C N O

+ -
H C N O

N OH
H H H + - H C
+ - H C N O + -
C C C C N O C C N O
+ N
N N - N
O O
OH OH
H
+ -
C C N O
N
OH

HC N OH HO N CH HC N OH N O
HC C C C C
HC
+ + N OH
N N - N N -
O O O O
N
OH
III II I

The discovery of the chemical structure of fulminic acid is a long and interesting
story that is described in detail in separate scientific papers [8–11]. Fulminic acid
was originally regarded as a two-carbon compound (C2H2N2O2) owing to its origin
from ethanol [10, 12, 13]. At the turn of nineteenth and twentieth century, Nef
proposed fulminic acid as the monomeric oxime of carbon monoxide H
O
N¼C
[14]. Although other structures of fulminic acid were developed during the twentieth
century (the currently accepted structure of formonitrile oxide among others),
Nef’s formula was used in explosives-related literature throughout virtually the
whole of the twentieth century, and even for many years after it was refuted. For
example, the structure can be found in Bagal’s (1975) [15] or Urbański’s (1984) [16]
monographs. The currently accepted structure of fulminic acid (in the form of
formonitrile oxide H
CN+
O
) first appeared in technical literature as early as
1899 [10]. This structure was also proposed by Pauling and Hendrick on the basis of
calculated potential energies of all substances formed by combination of H, C, N,
and O atoms [17]. However, the structure was only fully accepted after it was
unequivocally confirmed by experiments using IR and microwave spectroscopy in
the 1960s [8, 10, 18].
The structure of fulminic acid was originally believed to be linear. Based on the
IR spectra and theoretical calculations, it was, however, proved that fulminic acid
does not have linear, but rather an unusual quasi-linear molecule with angle
between H
C
N of precisely 165.13 [8, 10, 11]. The isomers of fulminic acid
have attracted the attention of theoreticians and are even the topic of some recent
papers [8, 19]. A comprehensive review of fulminic acid and its salts was published
relatively recently by Wolfgang Beck [8].
3.1 Introduction 39

The structure of metallic salts of fulminic acid is usually presented by a

Pauling-like structure with metal bonded to carbon [3, 20–22]. This seems to be
a reasonable assumption even though some authors published studies supporting
bonding between metal and oxygen [23] or even the possibility of the existence of
both of these forms [24]. The issue still causes discussion and a report of a
theoretical study [22] and X-ray analysis [21], supporting the bonding between
metal and carbon, was recently published. The character of the metal to carbon
bond of alkaline and thallium fulminate is ionic, whereas fulminates of silver and
mercury are covalent [20, 25].

3.1.2 Mercury Fulminate

O
Nþ  C
Hg
C  Nþ
O

Mercury fulminate is one of the oldest known primary explosives probably having
been discovered by alchemists. The name of its discoverer is uncertain; however, the
discovery is most often ascribed to two alchemists—Cornelius Drebbel, a Dutchman
living at the beginning of seventeenth century as well as to the Swedish-German
alchemist Johannes Kunkel von L€ owenstern living in second half of seventeenth
century. The references confirming knowledge of mercury fulminate by these two
alchemists can be found in their books [10, 11, 21, 26–32]. Both of them probably
obtained this substance by treating mercury with nitric acid and alcohol. Neither of
them could, however, find a use for this explosive compound, and mercury fulminate
was forgotten until Edward Howard rediscovered it at the turn of the eighteenth
century, examined its properties and published his results in “Philosophical
Transactions of the Royal Society” [10, 33]. The discovery of mercury fulminate
is therefore in some older scientific resources attributed incorrectly to Howard
[34–38]. The first patent describing the use of mercury fulminate in initiators is
from 1807 and belongs to a Scottish clergyman, Alexander Forsyth [29, 34].

3.1.2.1 Physical and Chemical Properties

The mercury fulminate (MF) formula is Hg(CN+
O
)2 with a covalent bond

between the mercury and carbon atoms [20]. Its crystal density is reported to be
4.42–4.43 g cm
3 [29, 30, 39, 40], but recent results of X-ray analysis updated it to
4,467 g cm
3 [21]. Bulk density depends on crystal size and shape—it is reported to
be between 1.35 and 1.55 g cm
3 [38]. The heat of formation of MF is reported as
being between
268 and
273 kJ mol
1 [29, 41, 42]. The structure of the MF
molecule and its crystal was published recently by Beck et al. [21]. Pure and
ordinarily prepared mercury fulminate is, for all practical purposes, not hygroscopic,
but its hygroscopicity rapidly increases in presence of impurities (e.g., mercury
oxalate, calomel, mercuric chloride), which are generally present in the industrial
40 3 Fulminates

Fig. 3.1 The three common forms of mercury fulminate from left to right—gray, brown, and white

product [42, 43]. The presence of other substances can increase hygroscopicity as
well. For example, a mixture of MF with potassium chlorate (formerly used in
primers or blasting caps) is significantly more hygroscopic than each of the chemicals
itself. Kast suggested an explanation of this phenomenon by mutual reaction of MF
with potassium chlorate producing some hygroscopic substance [15, 43].
The taste of MF is described variously as a sweetish metallic taste by some
authors [38] or salty by Walke [12]. MF is, however, a very toxic substance [38].
MF is known to exist in various forms depending on the way of preparation.
Many authors mention two forms—white and gray [15, 28]. In reality there are
three forms—white, brown, and gray—obtained directly from the reaction mixture
(see Fig. 3.1) and other forms obtained by recrystallization from various solvents
(Pachman and Matyáš unpublished work).
The most common types of MF and the relations among them are schematically
summarized in Fig. 3.2. Some authors misleadingly refer to the brown form as
being gray [15, 28]. The white and brown forms are both desired products and are
purer than the gray form which is produced by improperly carrying out the reaction.
The brown form of MF is, contrary to general expectation, a little bit purer than the
white form [16, 44].
The brown product with a well-developed crystal structure (Fig. 3.3) is formed
when the reaction is carried out without any additives. Temperatures as well as
concentrations and amounts of reacting substances must be optimized.
The same procedure leads to the gray product if nitric acid contains more than
0.5 % of sulfuric acid or if it is too strong (density over 1.4 g cm
3) or too weak
(density below 1.38 g cm
3). The gray product is also obtained if the alcohol
temperature at the beginning of the reaction is too low or if its initial concentration
is lower than 95 %. Such product contains metallic mercury [42]. A preparation
route has, however, been published using 90 % ethanol [30].
The white form of MF is less pure than the brown form but purer than the gray
form. It is produced in presence of cupric chloride (or some other substances such as
KCl, ZnCl2, BaCl2, or Cu2Cl2). In practice copper and hydrochloric acid are added
to the dissolving tank containing mercury and nitric acid. Addition of hydrochloric
acid itself results in formation of white MF contaminated by oxalic acid.
The product is, however, not as clean-white looking and the crystals are not as
uniform in shape and size as in the case of combination of copper and hydrochloric
3.1 Introduction 41

ethanol UV light
brown heat dark brown to black
(99.7 -99.9%) on surface
ethanol
+
Cu + HCl (ZnCl2or BaCl2)
white
(98.8 -99.4%) UV light
heat gray
Hg + HNO3 on surface
acetaldehyde
white

improper conditions
gray
(MF with col. Hg)

recrystallization
recrystallization from pyridine
from water recrystallization from
NH3

light yellow white

pearl type surface light yellow crystals
fish bone crystals
(from NH3~ 99.9%)

Fig. 3.2 Preparation of various types of MF

Fig. 3.3 Brown MF crystal

acid [35, 38, 42, 45]. In presence of Cu(NO3)2 the brown form appears indicating
that not only copper but also chloride ions play a role in the formation of the white
product (Pachman and Matyáš unpublished work). According to Solonina (cited in
[38]) the purest white MF forms from addition of cuprous chloride.
Various theories trying to explain the nature of brown versus white MF have
been proposed. Probably, the most often cited one is a presence of colloidal
mercury in MF crystals [2, 15, 29, 41, 46]. This reasoning has been, however,
rejected by other scientists who have examined both color modifications and did not
42 3 Fulminates

Fig. 3.4 Ground brown MF (left) compared to white MF in “as prepared”

find metallic mercury in either form of MF (for example by Solonia cited by

Urbański). It has been proposed that the reason behind the colored mercury
fulminate is related to the presence of by-products [47] possibly resinous polymers
of fulminic acid [16, 48]. It has been further reported that grinding of brown MF in a
mortar under water produces practically white product [35]. The result of grinding
well-developed brown crystals (from Fig. 3.3) under water is presented in Fig. 3.4
and it is further compared to the white form (Pachman and Matyáš unpublished
work). The resulting product is a white powder.
Our own unpublished investigation shows that brown and white MF does not
contain metallic mercury visible by optical microscopy which is in agreement with
Krauz [35]. The gray form, however, does contain it. The presence of metallic
mercury in gray MF is clearly apparent from Fig. 3.5.
It is possible that the brown product with metallic mercury is obtained if reaction
conditions are not maintained within prescribed limits. Such product is, however,
not gray but brown with clearly visible mercury drops (Fig. 3.6).
It can be stated that the phenomenon of three basic colors of mercury
fulminates—white, brown, and gray—is even today not completely explained.
MF is a photosensitive substance and decomposes under UV light. Originally
nicely developed crystals become dark, break into pieces, and elementary mercury,
carbon monoxide, and nitrogen are formed [49]:

Figure 3.7 shows the effect of UV light on crystals of MF. The formation of
mercury inside the crystals is shown in Fig. 3.8.
The action of UV radiation on MF has also been published by Bartlett et al. They
observed that cracks on MF crystals after exposition on UV radiation can be removed
by treatment with moist ammonia vapor (but not with water vapor alone) [50].
3.1 Introduction 43

Fig. 3.5 Gray MF with visible metallic mercury

Fig. 3.6 Brown MF with visible metallic mercury

3.1.2.2 Solubility

MF is reported to crystallize in various forms depending on type of solvent used. The

resulting form is an anhydride using ethanol or a complex salt using pyridine [28, 29, 35].
Many scientific books that deal with explosives reported that MF crystallizes as a
hemihydrate from water [1, 28, 29, 35, 42]. However, this suggestion was disproved
44 3 Fulminates

Fig. 3.7 Influence of UV light on MF (left before, center after 10 min, right after 6 h under UV
lamp—12 cm distance, 254 nm—15 W, 198 nm—15 W)

Fig. 3.8 Formation of metallic mercury inside MF crystals after irradiation by UV

by Kast and Selle [15, 51] and by W€ ohler and Berthmann [46]. Solubility of MF in water
is presented in Table 3.1 [28, 52]. It should, however, be noted that MF is not stable in
aqueous solution. The decomposition is not significant at room temperature but becomes
observable at higher temperatures (in which case mercury oxide, hydroxylamine,
ammonia, and carbon dioxide form) [42, 53]. Despite this instability, purification of
MF by dissolving in boiling water followed by decanting supernatant liquid and cooling
is recommended by Walke. MF crystallizes in yellowish-white silky crystals [12]. The
method of heating of MF with a large volume of water under pressure has been
recommended for chemical decomposition of unwanted MF [38].
MF is soluble in many other solvents such as ammonia, pyridine, ethanolamines,
and in solutions of inorganic salts (cyanides, iodides), and slightly soluble in
ethanol and acetone. It is, however, not stable in these solutions (even in aqueous
solutions) and decomposes due to its high reactivity. The rate of decomposition
depends on the type of solvent, its concentration, and particularly on temperature.
The rate of decomposition can be rapid at high temperature (within several
3.1 Introduction 45

Table 3.1 Solubility of Temperature ( C) Solubility in 100 ml water (g)

mercury fulminate in water
[28, 52] 12 0.071
49 0.174
100 0.77

minutes). MF is very slightly soluble in hot ether and insoluble in chloroform,

glycerol, or benzene [15].
Aqueous ammonia is sometimes recommended for recrystallization of MF in
which it is very soluble. MF of very high purity can be obtained by dissolving it in
aqueous ammonia and, after filtration, the solution is neutralized with acetic or
nitric acid obtaining the white form of MF [2, 28, 39, 42, 54]. This procedure is
reported to increase the purity of MF from ~98.5 % to ~99.6 % [54]. Crystallization
from aqueous ammonia without neutralization is reported to give white crystals.
However, according to our own experience this yields large light yellow fishbone-
like crystals (Fig. 3.9). A partial decomposition of MF during recrystallization does
not affect the quality of the final product (solution darkens within several days at
laboratory temperature, metallic mercury slowly forms and a gaseous decomposi-
tion product is liberated [42, 54]). The rate of decomposition in aqueous ammonia
rapidly increases at higher temperature (60–65  C) and mercury oxide, urea,
guanidine, and other compounds are formed [1, 15].
Very good solubility is reported for ethanol and acetone saturated with ammo-
nia. The system ammonia/ethanol/water is often recommended as a suitable solvent
for preparation of nice well-formed pyramidal crystals (1–2 mm long) for crystal-
lographic and X-ray studies [21, 25, 55, 56].
Recrystallization from pyridine (solubility—1 g MF in 6.9 ml pyridine [15]) is
reported to produce complex salt crystals of unreported color [35, 39]. W€ohler and
Weber reported the formation of lustrous mica flakes obtained upon pouring the
pyridine solution of MF into ether [39]. The stability of MF in pyridine is reported
higher than in ammonium hydroxide but it decomposes during long standing or
boiling in the same way as it does in other solvents [15]. According to our
investigation both brown as well as white MFs dissolve in hot pyridine giving a
yellow to brown solution from which MF precipitates on slow cooling in the form
of large thin white rhomboids (Fig. 3.10, left). In the case of fast cooling and
stirring, these rhomboids break into shapes shown in Fig. 3.10, right. The precipi-
tation of MF back from its solution is possible by pouring it into water or into
diluted acid. A yellowish oil forms first which then turns into white crystals of MF
(by pouring into diluted acid). Recrystallization from pyridine is recommended by
Thorpe as the best method for purification of MF [38].
Mercury fulminate is also soluble in aqueous alkaline cyanides (e.g., KCN).
The solubility depends on the concentration of cyanide solution (up to one-to-
one ratio of MF to cyanide can be obtained) because the soluble double-salt
Hg(CNO)2·KCN forms [15]. The MF in its white form can be precipitated back
from this solution by addition of diluted nitric acid [3, 15, 57]. However, the
purification of MF by recrystallization from cyanide solution is not effective, as
the purity increases only slightly, e.g., from 98.39 to 98.60%. Boiling a cyanide
46 3 Fulminates

Fig. 3.9 Brown mercury fulminate recrystallized from ammonium hydroxide

Fig. 3.10 Brown mercury fulminate recrystallized from pyridine—left—fast cooling and agita-
tion, right—slow cooling

solution causes MF slowly to decompose. It is also soluble in alcoholic and

acetone solutions of alkaline cyanides [15].
The ethanolamines (mono, di, and tri) have been recommended as a solvent for
MF by Majrich (200 g MF/100 g monoethanolamine at 25  C, 40 g MF/100 g
diethanolamine at 30  C, and 28 g MF/100 g triethanolamine at 30  C). The MF,
however, rapidly decomposes with heat liberation and it is therefore recommended
to keep the solution below 30  C. The MF is precipitated back by pouring the
solution into water or by diluting it with acid. The precipitate forms as a white
powder [15]. MF is further soluble in many other solvents, e.g., aqueous potassium
iodide or potassium thiocyanide.
3.1 Introduction 47

3.1.2.3 Compatibility with Acids, Bases, and Metals

MF readily decomposes by action of many other chemical agents. It is relatively

resistant to the action of dilute acids, e.g., nitric acid. Concentrated nitric acid
decomposes it producing carbon monoxide, nitrogen(II) oxide, acetic acid, and mercuric
nitrate [1, 3, 35]. The reaction is fast when using fuming nitric acid [15]. Concentrated
hydrochloric acid decomposes MF according to the following equation [3]:
Hg(CNO)2 + 2 HCl HgCl2 + 2 HCNO

Cl
HCNO + HCl HC
N OH
Cl
HC + 2 H2 O NH2OH.HCl + HCOOH
N OH

Free fulminic acid is produced (with typical odor similar to hydrogen cyanide)
along with the product of the reaction of fulminic acid with hydrochloric acid
(N-hydroxyimidoformyl chloride). Concentrated sulfuric acid causes MF to
explode, whereas the dilute acid (1:5) decomposes it without explosion [37].
Significant decomposition does not occur in cold dilute sulfuric acid [15]. Further-
more, MF is decomposed even by organic acids (e.g., formic, acetic, or oxalic
acids) forming the corresponding mercuric salts [1].
MF also decomposes by the action of inorganic salts such as sulfides, or
thiosulfates. MF decomposes to mercuric sulfide by action of aqueous alkaline
sulfides. This method of decomposition is used for elimination of MF from waste
water [12, 42] or for decomposition of small quantities of solid MF in which case
warm ammonium sulfide solution is recommended [38]. The reaction of MF with
sulfides or hydrogen sulfide is fast when boiling the mixture, but slow at ambient
temperature. Alkaline thiocyanates give the MF double salts (e.g., Hg
(CNO)2·KSCN) [15]. The reaction with thiosulfates is very well documented
because it is sometimes used for quantitative analysis of MF [10, 15, 29, 35, 58]:

This reaction can also be used for chemical destruction of MF (on a lab scale).
The weight excess 3:1 of sodium thiosulfate in form of 20 % solution is
recommended. The decomposition in unsuitable conditions can lead to explosion
(e.g., when MF is enclosed in detonators or if carried out at high temperature) [59].
Some poisonous hydrogen cyanide may be produced during the reaction [30].
Concentrated nitric acid is recommended as the decomposition agent for MF and
hydrochloric acid as a decomposition agent on a laboratory scale [3]. The concen-
tration of acid has an impact on the rate of decomposition. A 5 % hydrochloric acid
mixture decomposes MF very slowly; the 18–20 % acid is faster but still safe and
hence more suitable [15].
48 3 Fulminates

Most ordinary bases decompose MF even in low concentrations [3] (e.g., in aqueous
ammonia solutions within several hours [1]). Decomposition of MF by boiling with
aqueous bases is sometimes recommended for destruction of unwanted MF in the
laboratory. The yellow form of mercury oxide forms during this decomposition [42].
Nesveda and Švejda proposed reduction of MF (pure or in priming mixtures) in
water suspension with metallic magnesium. The decomposition carried out in this
manner is suitable for recycling of mercury because the product of the reduction is
elementary metal in a form useable for further processing [60].
Dry mercury fulminate does not react with common metals, according to some
authors [3, 42] but other authors suggest the contrary (rapidly with aluminum,
slowly with copper, zinc, bronze, or brass) [29, 30]. According to Bagal, pure dry
MF does not react with metals, but metallic mercury present in the raw product
reacts forming amalgams [15]. MF reacts immediately, or rapidly, in presence of
low amounts of moisture [3, 42]. The moist MF form reacts with copper giving
basic copper fulminate Cu(CNO)2·Cu(OH)2 which is less sensitive to impact but
more sensitive to friction than MF itself. The presence of moisture is necessary for
the formation of basic cupric fulminate. Another side effect of the reaction with
copper is precipitation of mercury which forms an amalgam that may weaken a
copper cap in which MF is embedded [15, 42]. It is therefore necessary to prevent
contact of MF with copper in its applications by protective coating using lacquers or
nickeling of the copper surface [15, 29, 34, 35]. Unlike lead azide it rapidly reacts
with aluminum (over several hours) forming a large amount of Al2O3 and therefore
it cannot be used in direct contact with aluminum in its applications. On the other
hand, it does not react with nickel even when wet [42].

3.1.2.4 Thermal Stability

MF is significantly less thermally stable than LA. The weight loss of MF is about
7 % (vs. 0.3% for LA) within 45 days at 75  C [42]. Danilov et al. reported that MF
slowly decomposes at 60  C within 1 month [3]; Urbański reported that decompo-
sition of MF occurs even at 50  C [1]. The dependence of storage time at 50  C on
the purity of MF and the effect of purification by recrystallization on thermal
stability is shown in Fig. 3.11 [30].
MF slowly decomposes at moderate temperatures (as can be seen in Fig. 3.11).
The opinions about when MF loses its ignition efficiency differ. The following
durations were reported for the time it takes for MF to lose its ignition ability—
3 years at 35  C, 9–10 months at 50  C, and 10 days at 80  C [28, 54].
The stability of MF and its mixtures with other substances were measured using
a vacuum stability test by Farmer. He found that the presence of moisture
accelerates the decomposition of pure MF. The decomposition of dry MF is not
accelerated in mixtures with common metals and weak organic acids [61]. MF
thermally decomposes to gaseous products (mainly CO2, some N2, CO [61–65])
and a brown solid, insoluble and without explosive behavior, forms the remainder
of a not very well identified mixture of compounds. It contains HgO (free or in the
3.1 Introduction 49

120

100

80
Purity of MF (%)

60

40
Recrystallized MF, lotA
Recrystallized MF, lotB
20 Recrystallized MF, lotC
Uncrystallized MF

0
0 5 10 15 20 25 30
Storage time at 50°C (months)

Fig. 3.11 Effect of storage at 50  C on purity of MF [30]

complex salt HgCO3·2HgO), cyanide complexes, linear chain of CnNoOp, and

cluster of HgmCnNoOp [63, 66]. These solid decomposition products and impurities
accelerate the decomposition of MF [54, 61, 62].
The kinetics of the thermal decomposition of MF has been widely studied by
many scientists [50, 61–65, 67]. The decomposition conditions (temperature, pres-
sure, form of MF, weight of MF, etc.) have an impact on the process of decomposi-
tion. The decomposition is without explosion at lower temperatures, and the
probability of explosion increases with rising temperature. Most reports suggest
thermal decomposition up to 85  C [29] or up to 100  C [42] without danger of
explosion. Explosions are mentioned at temperatures of 100  C [61, 67, 68] and
higher (105–115  C [64, 65]). The exact temperature above which MF explodes
depends on the form of MF and conditions of measurement. Garner [65], and later
also Vaughan and Phillips [67], determined the dependence of induction period of
explosion on temperature. The white form of MF ignites at a temperature slightly
higher than for the brown form [1].
The storage of MF at higher temperatures can be hazardous. Carl reported
several spontaneous violent decompositions (probably deflagration) of MF during
long-term storage. The form of MF has an impact on the occurrence of this
phenomenon. The explosions occurred when MF was pressed as the pressure
increases the rate of decomposition [54].

3.1.2.5 Sensitivity

Mercury fulminate is more sensitive to impact than lead azide as was shown and
discussed in Chap. 2. Sensitivity to impact rapidly decreases by addition of water.
No detonation [35] or only partial detonations [48] were reported for small amounts
50 3 Fulminates

of MF containing 5 % of water. MF with more than 10 % of water decomposes on

impact without detonation [48]. Danilov et al. reported that MF becomes insensitive
to mechanical stimuli with water content higher than 30 % [3]. Paraffin, glycerin, or
oils could be used as desensitizing agents as well [3, 35, 40, 42]. On the other hand,
the presence of hard particles (such as sand, glass), even in low amounts, signifi-
cantly increases the sensitivity of MF to mechanical stimuli. Long exposure to
higher temperatures significantly increases its sensitivity to impact (e.g., by several
times when stored for several months even at 50  C [54]).
Sensitivity to friction is reported lower than for LA by some authors [42, 69] and
higher by others [29, 41]. Our own experiments indicate that MF is significantly less
sensitive than LA (see Fig. 2.19). The difference between the brown and white
modifications of MF is insignificant.
MF is highly sensitive to electrostatic discharge—ESD. The published values
show a significant spread, and range from 0.51 to 0.62 mJ (Majzlı́k and Strnad
unpublished work) [70] to 25 mJ [30]. The comparison of sensitivity to ESD with
other primary explosives is shown in Fig. 2.21. MF can be initiated by discharge of
static electricity generated from the human body [29].
Mercury fulminate is also sensitive to flame (see Fig. 2.22) and can be easily
ignited by a safety fuse.

3.1.2.6 Explosive Properties

The explosive decomposition of mercury fulminate is not clearly understood but is

often described as below [3, 38, 71, 72]:

with heat of explosion being 1,540 kJ kg
1 (Hg in gas phase), 1,803 kJ kg
1 (Hg in
liquid phase). On the basis of the analysis of the explosion products in a calorimet-
ric bomb, Kast [43] later corrected his previous work by following a more precise
equation for MF decomposition:

The heat of explosion calculated from the above equation is 1,543 kJ kg
1 (Hg in
gas phase) and the volume of liberated gases is 311 dm3 kg
1 [43]. A similar value
of 1,660 kJ kg
1 was published by W€ ohler and Martin who determined heat of
explosion in a calorimeter [57].
Dependence of detonation velocity on density is shown in Fig. 2.1. Mercury
fulminate belongs to the group of primary explosives with a long predetonation
zone. In other words, it means that it takes a long time, and uses significant amounts
of charge, before the decomposition reaction accelerates from simple initial
impulse to fully developed detonation (slow deflagration to detonation transition
3.1 Introduction 51

with respect to other primary explosives). This reflects in its lower initiating
efficiency compared to silver fulminate or lead azide (see Fig. 2.2). The exact
values depend heavily on the level of applied pressure, construction, and material of
the detonator (see Sect. 2.2). MF shows interesting behavior at lower temperatures.
The ignition efficiency of MF decreases with decreasing temperature (tested at
+25  C,
83  C, and
190  C) [73] but the detonation velocity does not change
[16]. Danilov reported that MF reliably initiates detonation down to
100  C [3].
Small amounts (several tenths of gram or grams) of unconfined and uncom-
pressed MF only deflagrate with a faint puff when initiated by flame [38]. The
burning speed markedly depends on the layer thickness; 0.5-mm-thick film burns
with velocity 0.05 m s
1 but 2.75 mm thick layer with 8.5 m s
1 [74]. At low
pressure, MF only burns. This process, as well as the pressure dependencies, has
been very carefully investigated, primarily by Russian scientists [75–80]. Large
amounts of MF, upon initiation by flame, detonate and can be safely destroyed by
burning in a mixture with oil. Ignition of slightly confined MF (even between sheets
of papers) leads to explosion [38].
The ability of MF to undergo deflagration to detonation transfer in detonators
depends significantly on many factors, primarily on the magnitude of pressure used
for pressing and the specific surface of MF. The initiation efficiency reaches its
maximum at densities around 3.2 g cm
3 after which it steeply decreases to a point
where it completely loses its capability to initiate secondary explosives at density
3.6 g cm
3 and above (it becomes dead pressed) [81]. The magnitude of applied
pressure needed for pressing of MF to this density depends on many factors including
the specific surface of MF (Fig. 2.6). The pressure values leading to dead pressed
material depend significantly on the construction and material of the detonator. They
are generally reported between 15 and 30 MPa [3, 44], although values as high
as 60 MPa [36], 68 MPa [54], or even 172 MPa [29] are sometimes mentioned.
The brisance of MF in a sand test is reported as 37.3–48 % TNT [29] or 49 %
TNT (vs. 39.6 % for LA) [30]. The power of MF measured by Trauzl test is 51 %
TNT (vs. 39 % TNT for LA) [30] or 37–50 % TNT [29]. Both brisance (measured
by sand test [29]) and power (measured by lead block test [71, 82]) of MF exceed
those for LA.
The ignition temperatures of MF by heating at heating rate 5 and 20  C are
summarized in Table 3.2. The temperature at which explosion takes place within 5 s
is 190  C [54], about 200  C [40], 205  C [71], or 215  C [83].

3.1.2.7 Preparation

As mentioned earlier, MF can be prepared in brown, gray, or white form. The gray
form is spoiled material, its formation unintentional, and it can be avoided by
maintaining optimized reaction conditions. The brown crystals form by dissolving
mercury in nitric acid and pouring the solution into ethanol. The crystals form in
solution after a short time. This method of preparation of MF is probably the only
one used in industrial production.
52 3 Fulminates

Table 3.2 Dependency of ignition temperature of MF on heating

Heating rate ( C min
1) Ignition temperature ( C) Reference
5 160–165 [35]
5 160–170 [42]
5 180–210 [3]
20 166–175 [71]

Acetaldehyde, or substances which are convertible into acetaldehyde (paralde-

hyde), can be used instead of ethanol but, unlike in the case of ethanol, yield the
white form. The reaction is more vigorous giving higher yields [28, 35, 84, 85].
If substances containing one (methanol, formaldehyde), 3, or 4 carbon atoms are
used, instead of ethanol or acetaldehyde, MF is not formed, according to Martin
[85]. Kibler, however, contradicts this and reported formation of the high purity
white form from propyl alcohol [84]. The Hg2+ and Ag+ cations probably catalyze
some of the reaction steps [35]. Without these cations [35], or without the presence
of nitrous oxides, fulminic acid is not formed [2, 86]. Due to oxidation processes in
the reaction mixture only the higher oxidation state of mercury can originate and
therefore mercurous fulminate is not formed in this way [57]. Metallic mercury can
be substituted for mercury compounds (e.g., mercury nitrate, basic mercury sulfate)
but the yield of MF is lower [9] and the reaction mixture can stand a long time at
higher temperature (even several days) before the reaction starts to proceed [54].
Wieland proposed the following mechanism for MF formation [87]:

(3.1)

CH3 CH O + HNO2 O N CH2 CH O + H2O ð3:2Þ

O N CH2 CH O HON CH CH O ð3:3Þ

HON CH CH O + HNO3 HON CH COOH ð3:4Þ

ð3:5Þ

ð3:6Þ

ð3:7Þ

ð3:8Þ

Ethanol is first oxidized by nitric acid to acetaldehyde (3.1). The nitrosation of

acetaldehyde proceeds in the second step to yield 2-nitrosoacetaldehyde (3.2),
3.1 Introduction 53

which then spontaneously isomerizes to the oxime (3.3). The aldehyde group is then
oxidized by nitric acid to the glyoxylic acid oxime (3.4). The glyoxylic acid oxime
is nitrated with nitric acid in the following step when nitroglyoxilic acid oxime is
formed (3.5). This a-nitrocarboxylic acid easily thermally decarboxylates at 80  C
yielding nitroformaldehyde oxime (3.6) which further yields fulminic acid (3.7).
The mercury fulminate forms in the last step of reaction (3.8) when fulminic acid
reacts with mercury nitrate. This Wieland reaction mechanism is still considered
correct. It is supported by the fact that ethanol can be replacedby the intermediates
of the reaction (acetaldehyde, glyoxylic acid oxime, nitroformaldehyde oxime) [2].
However, the reaction mechanism quoted here has been disputed by Dansi et al.
(cited in [16]) who claims (unlike source [2]) that MF cannot be prepared from pure
glyoxylic acid oxime [3].
The side products of the reaction include ethylnitrate, ethylnitrite, oxalic acid,
nitrogen oxides, and carbon dioxide. The raw MF ordinarily contains metallic
mercury, mercuric oxalate, calomel, and mother liquor enclosed in crystals [15].
Traces of free mercury can be removed from MF by evaporation by placing it in
vacuum desiccator for a few days [38]. The only industrially used method of
preparation of MF is the one described above. The technology is described in
great detail in the literature [3, 15, 35, 42, 48].
An alternative method of laboratory preparation of mercury fulminate is based
on decomposition of the mercury salt of nitromethane published by Nef [14].
The mercuric salt is prepared in the first step of a reaction when mercuric chloride
reacts with the sodium salt of nitromethane. The mercuric salt of nitromethane
decomposes in a second step by boiling with dilute hydrochloric acid to produce
MF [14]:
- - -
O O O
+ NaOH + + HgCl 2 +
2 CH3NO 2 2 H2C N+ Na H2C N+ N CH2
-
O O Hg O

- -
O O O N CH O Hg OH
+ HCl
H2C N+ N CH2 Hg(CNO)2 + 2 H 2O + Hg
DT
O Hg O O N CH O Hg OH

Unfortunately, the yield of MF is too low (only about 5 %) because the majority
of the mercuric salt of nitromethane is converted into a basic mercury salt of
formhydroxamic acid (also an explosive). This mercury salt cannot be converted
into MF [2]. The nitromethane itself can also be converted into fulminic acid by
nitrosation with nitrous acid to form nitroformaldehyde oxime. It further
decomposes (by heating in water or nitric acid) to fulminic acid which is trapped
with mercury nitrate as mercury fulminate [2].
54 3 Fulminates

- +
CH3NO 2 + HNO 2 HO N CH O N CH + HNO 2
NO 2

- +
2 O N CH + Hg(NO 3)2 Hg(CNO)2 + 2 HNO 3

Mercury fulminate also forms from malonic acid, mercury, and nitric acid.
The first intermediate (hydroxyiminomalonic acid) forms by nitrosation of the
starting malonic acid which then decarboxylates to glyoxylic acid oxime. The
following reaction is analogous to the Wieland mechanism presented above
[2, 16, 35, 88]:
COOH COOH COOH COOH
HNO2 - CO2 HNO3
H2C C NOH HC NOH C NOH

COOH COOH NO2

COOH H
DT - +
C NOH C NOH O N CH + HNO 2
- CO 2
NO2 NO2

- +
2 O N CH + Hg(NO3)2 Hg(CNO)2 + 2 HNO 3

According to Nef, metallic fulminates can also be synthesized by the reaction of

derivates of formaldehyde oxime with the relevant nitrate [15].
H
+ -
C N OH + 2 AgNO3 Ag C N O + AgR + 2 HNO3
R

R = Cl, HSO4 , HS

Other metallic fulminates cannot be synthesized directly by reaction of metal

with nitric acid and sequentially with ethanol in the same way as mercury or silver
fulminates (and probably also complex Na[Au(CNO)2]). They are therefore mostly
prepared by reaction of mercuric fulminate with the relevant amalgam.

3.1.2.8 Storage of MF

MF is highly sensitive when dry but can be safely stored under water at normal
temperature for a long time and even transported [29, 40]. Decomposition of MF is
very slow under water at normal temperatures. Ingraham reported that the purity of
MF decreases from 99.6 to 98.3 % within 5 years with 6 % decrease of brisance. Sea
water is not suitable for storage because MF decomposes faster than in fresh water
3.1 Introduction 55

(brisance decreases by 10 % after 2 years and 85 % after 3 years) [53]. At lower

temperatures, when the danger of water freezing comes into consideration, it is
possible to use a water–methanol mixture instead of water [28, 29].

3.1.2.9 Uses

In 1807, clergyman Alexander Forsyth patented the use of MF and shortly after it
found a very broad use in military applications. The first massive use of MF was as a
component in percussion priming mixtures. In the early percussion caps, MF was
used alone simply agglomerated by means of wax or an aqueous solution of gum,
and later in a mixture with other substances. However, the era of percussion
priming started in 1786 (before MF discovery) with the French chemist Berthollet
who discovered the possibility to initiate mixtures of potassium chlorate with
combustible substances by percussion. Purely pyrotechnic compositions such as
mixture of potassium chlorate and antimony sulfide were not very suitable for use
due to their low conversion rate and insufficient flame ignition temperature. The
next development therefore led to the incorporation of a primary explosive into the
priming mixture. The presence of a primary explosive such as MF helped to
overcome the problems of purely pyrotechnic mixtures. The compositions
containing MF, potassium chlorate, antimony sulfide, glass powder, and gum
Arabic were used exclusively for over 100 years until the beginning of the twentieth
century [38, 42, 89].
The production of mercury fulminate significantly increased from 1867 after
Alfred Nobel introduced his “Fulminate Blasting Caps.” These caps were effec-
tively the first detonators and were capable of reliably initiating detonation of
nitroglycerine. Prior to this invention, initiating the detonation of nitroglycerine
was done by fuses loaded with black powder with a very uncertain outcome [35].
Massive development of applications of MF in all types of initiating devices
followed Nobel’s invention. MF was practically the only primary explosive used
at that time and its application ranged from primers of small and artillery ammuni-
tion to fuses and detonators. In 1887, Hess used MF, desensitized by addition of
20 % of paraffin, to produce a detonating cord with detonation velocity of
5,200–5,300 m s
1. The use of MF in detonators was first modified by mixing it
with black powder, then with potassium nitrate, and later with potassium chlorate.
This last mixture was widely used and by 1910 had practically replaced pure MF in
detonators in USA. The usual amount of potassium chlorate in the mixture ranged
from 10 to 20 % [29, 35, 85, 90]. Such a mixture was cheaper than pure MF, but
more sensitive to moisture [28].
The explosion of MF/KClO3 77.7/22.3 mixture can be described by the follow-
ing equation:

with volume of liberated gases 183 dm3 kg
1, less than with MF alone [38].
MF/KClO3 mixtures are slightly more brisant than pure MF as shown in Fig. 3.12
56 3 Fulminates

60

50
Weight of pulverized sand (g)

40

30

20

10 MF
90/10 MF/KClO3
80/20 MF/KClO3
0
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2
Charge weight (g)

Fig. 3.12 Effect of amount of KClO3 on brisance determined by sand test bomb [28]

4400

4200

4000
Density (g/cm 3)

3800

3600

3400

3200 80/20
90/10
3000 100/0
MF
2800
1.6 1.8 2 2.2 2.4 2.6 2.8 3
Detonation velocity (m/s)

Fig. 3.13 Effect of density and the admixture of potassium chlorate on rate of detonation of MF [91]

by results of sand test [28, 29]. The detonation velocity of pure MF is higher than
that of the mixtures at low densities but lower at higher densities (Fig. 3.13) [91].
The initiating efficiency of MF/KClO3 exceeds that of pure MF (0.35 g alone MF
vs. 0.30 g for MF/KClO3 90/10 mixture and 0.275 g for MF/KClO3 80/20 mixture
for tetryl) [38]. Handling and loading of MF/KClO3 mixture was slightly safer than
3.1 Introduction 57

pure MF according to Davis [28] while Bethelot (cited in [38]) reported that
potassium chlorate renders the mixture very sensitive.
The idea of using a dual charge consisting of a small amount of primary
explosive pressed on top of a secondary explosive was introduced by Nobel. He
was investigating the possibility of lowering the cost of his detonators by replacing
at least part of the amount of expensive MF with other explosives. His new
detonator, described in French patent 184,129 from 1877, contained picric acid
on top of which MF was compressed. The combination of MF and secondary
explosive in the same body of the detonator was a great idea as it made the
detonators both much cheaper and more powerful. The detonators with picric
acid, however, had a major drawback in being sensitive to moisture. The picric
acid, in moist environments, immediately reacted with the copper tube of the
detonator, giving green cupric picrate. Such detonators were therefore not widely
used and practically coexisted side by side with “standard” single component MF
ones (sometimes referred to as plain detonators). The era of dominance of MF and
its mixtures in detonators ended at the beginning of twentieth century when
composite detonators with a partitioned charge (compound or composite caps)
started to use explosives other than picric acid as a secondary charge. In 1900,
W€ ohler and Bielefeld independently proposed to replace picric acid with nitro
aromatic substances. Many substances were tested and eventually lead to the
incorporation of TNT which was already available at that time and later tetryl.
Such detonators used only about 1/3 of the original amount of MF, were much safer
to handle, and had higher brisance, as shown in Fig. 3.14 [90]. About the same time,
a hollow cap pressed on top of the primary explosive started to be used. This simple
measure further increased manipulation safety, decreased the amount of MF
required, and increased the reliability of detonators [35, 42].
Although many other primary explosives were discovered, MF was used in a
wide variety of applications due to its desirable properties over a long time
(high density, flammability, stability, brisance, desired sensitivity, excellent
flowability, etc. [35]). Sensitivity of pure MF for applications in detonators
(stab or impact initiation) is sufficient for most applications as well as its
sensitivity to flame and it is not necessary to alter them by addition of other
substance [3]. The versatility of MF is due to its relatively long deflagration to
detonation transition under the application conditions. Its capability to defla-
grate with high temperature flame was exploited in primer compositions while
its capability of steady detonation designated it for the use in detonators and
detonating cords. The production of mercury fulminate increased during World
War I even though LA was already known. The total production of MF at that
time is unknown but in Germany alone production went from 104.8 tons in
1910 to 357 tons in 1917. Development of new primary explosives after World
War I slowly displaced MF in priming mixtures and later also in detonators
mainly due to its toxicity. As of today, MF is practically completely replaced
in detonators and blasting caps by lead azide and in primers by tricinate/
tetrazene or, most recently, by heavy metal-free compositions. [29, 34, 89]. It
58 3 Fulminates

200

180

160
Weight of crushed sand (g)

140

120

100

80

60

40 RDX
PETN
20 TETRYL
MF/KClO3 80/20
0
0.75 1 1.25 1.5 1.75 2 2.25 2.5 2.75 3 3.25
Weight of total explosive charge in detonator (g)

Fig. 3.14 Effect of base charge on initiating efficiency of detonators. The priming charge for all of
these detonators was 0.75 g of MF/KClO3 80/20 [90]

seems probable that MF may still be used in some applications in Russia and
China.

3.1.3 Silver Fulminate

The history of silver fulminate is just as long as the history of mercury fulminate.
It was probably also discovered by the alchemists Cornelius Drebbel and Johann
Kunckel von L€ owenstern in the seventeenth century [11, 26] even though some
other authors mention Brugnatelli in 1798 [29, 35, 92] or Edward Howard a few
years later [15, 35, 92, 93].

3.1.3.1 Physical and Chemical Properties

Silver fulminate (SF) is a white crystalline material with heat of formation

179 kJ mol
1 [15]. It crystallizes in the form of small rosettes or star-shaped clusters.
Two polymorphic forms have been reported—orthorhombic and trigonal. The
crystal shape depends on reaction conditions (temperature, concentration) during
silver fulminate preparation [94]. Recrystallization from ammonia leads to needles
and multiple growths of leaf-like habits [92]. Long (4–5 mm) needle-shaped crystals
were prepared by Singh and investigated by X-ray analysis. It was found that the
crystal is orthorhombic [95]. The crystal structure of SF was later investigated in
detail by Britton and Dunitz [96, 97] and their results were confirmed by Barrick
et al. [98]. Ammonium acetate solution (~20 %) is recommended as the solvent for
3.1 Introduction 59

Fig. 3.15 Silver fulminate crystals

preparation of SF in the form of thin plate crystals to be used for crystallographic

studies [25]. The crystal shape we have obtained at 80  C starting from AgNO3 and
using NaNO2 as a source of NOx is shown in Fig. 3.15.
Britton and Dunitz observed that SF prepared from an ammoniacal solution after
ammonia evaporation is a mixture of needles and multiple growths which tended to a
leaf-like habit. The X-ray examination showed that there were two polymorphic forms
present, one orthorhombic and the other trigonal, but both forms occurred as needles
and as part of the leaf-like clusters. The crystal density determined by X-ray is
4.107 g cm
3 for the orthorhombic crystals and 3.796 g cm
3 for the trigonal crystals
[96, 97]. The density of SF determined formerly by W€ohler and Weber is 4.09 g cm
3
[39] or 3.938 g cm
3 according to Singh [95]; both determined it by pycnometry.
Silver fulminate is a very poisonous substance. According to Walke it has a
strong bitter metallic taste [12].
Just like other silver salts, SF darkens when exposed to light. It is practically
insoluble in cold water and can therefore be re-crystallized from hot water with
high yields [35]. The solubility of silver fulminate in water at various temperatures
is given in Table 3.3 [28, 29]. Solubility of SF in water is considerably higher than
silver halogenides.
Silver fulminate is soluble in ammonia and solutions of alkali chlorides forming
complex salts NH4[Ag(CNO)2] and K[Ag(CNO)2], respectively. An interesting
complex—Ag[Ag(CNO2)]—forms from more concentrated aniline solutions [2].
It is further soluble in alkali cyanides, pyridine, and potassium iodide. Thiosulphate
decomposes SF in a similar manner to that of mercury fulminate and may be used for
nonexplosive decomposition of this substance. SF is insoluble in nitric acid [28, 35].
Alike MF, silver fulminate reacts with concentrated hydrochloric acid. This
60 3 Fulminates

Table 3.3 Solubility of silver Temperature ( C) Solubility in 100 ml water (g)

fulminate in water [28, 29]
13 0.0075
30 0.018
100 0.25

decomposition is of nonexplosive nature; dry SF decomposes only with hissing noise

[99]. Silver fulminate immediately explodes on touch with concentrated sulfuric acid
or in contact with chlorine and bromine but not in contact with iodine [28, 35, 100].
The reaction with concentrated sulfuric acid has been used for chemical initiation of
explosion [28, 35]. The silver fulminate prepared by precipitation from an aqueous
solution of zinc fulminate (prepared by reaction of MF with metallic zinc in water) is
more sensitive to chlorine and bromine than commonly prepared SF. It explodes even
in presence of 1 % of chlorine [100]. According to Bagal this behavior is probably
caused by a small amount of zinc fulminate in SF [15]. Silver fulminate is not
hygroscopic and it can remain for years under water at ordinary temperatures without
decomposing. It has been reported that SF did not lose its explosive properties even
after 37 years under water [93, 101].

3.1.3.2 Sensitivity

Silver fulminate is considered as an extremely dangerous primary explosive to handle

due to its high sensitivity, particularly to electric discharge and friction. It is more
sensitive than MF with respect to both of these initiation stimuli. The sensitivity to
electric discharge is extreme, particularly when it is dry [92]. The sensitivity of silver
fulminate depends on its crystal form; the amorphous form is less sensitive to impact
than the crystalline form. However, since it is practically impossible to produce purely
amorphous material without any crystals the whole mass might be nearly as sensitive
as the crystalline form itself [29]. Taylor and Buxton published preparation of SF in
form of fine crystals with an impact sensitivity significantly lower than MF (no
explosion from 32.7 cm for 1/2 kg hammer vs. only 12.7 cm for MF) approaching
values typical for lead azide [93]. Comparison of impact sensitivity of SF with other
common primary explosives is shown in Fig. 2.15.
Silver fulminate can explode when moist or even under water [12, 35]. It is known
as one of the trickiest primary explosives. A number of accidental initiations have been
reported during preparation or handling of SF. Unsuspected explosions have been
reported by Liebig who had many years’ experience with handling even large
amounts—up to 100 g (!) [8]. Collins and Holloway [92] describe an explosion
when turning a thermometer in the reaction mixture during SF preparation, when a
small wet sample of SF was placed on the glass slide for microscopic examination, and
even during filtration under suction. The most probable cause of the last two
explosions was an electric discharge. The first was not fully explained but it is believed
to be related to the increased rate of nucleation of SF crystals on addition of water
(which decreases the solubility of SF in the reaction mixture) [92]. Taylor and
Rinkenbach described explosion during filtration and washing of SF after its
3.1 Introduction 61

preparation [94]. Ignition of silver fulminate by exposure to light has been reported by
Berchtold and Eggert [102]; Walke reported that extremely sensitive silver fulminate
(exploded upon the slightest touch) forms when dried in sunlight after synthesis [12].

3.1.3.3 Explosive Properties

Silver fulminate is a more effective initiating agent than MF although it has nearly
the same brisance by sand test [29]. The presence of moisture does not affect its
brisance [15]. The initiating efficiency is very high being 2–3 times higher compared
to that of MF (0.14 g SF vs. 0.35 g MF without reinforcing cap, 0.07 g SF vs. 0.24 g
MF with reinforcing cap both for 0.4 g of TNT in num. 6 detonator capsule [93]).
The only value of detonation velocity the current authors were able to find is
1,700 m s
1 reported for 0.5 mm thick unconfined film initiated by hot wire [103].
SF is reported to become dead pressed by loads above 33 MPa in an amount of
120 mg in 1.5 gr type detonator (1 gr ¼ 0.0648 g). For preparation of 100 mg
charges it was necessary to press the material in two increments to avoid dead
pressing [92].
The 5-s explosion temperature of SF is 170  C compared to 217  C for MF and
327  C for LA [83]. Silver fulminate explodes at 236–241  C at high heating rates
(10–20  C min
1) and 186–193  C at slow heating rate (0.2  C min
1) (Pachman
and Matyáš unpublished work). The heat of explosion of SF is 1,970 kJ mol
1
(determined in calorimeter [57]).

3.1.3.4 Preparation

Preparation of silver fulminate is similar to the preparation of MF. Silver is dissolved

in nitric acid after which the solution is poured into ethanol [14, 29, 33, 35, 93].
The reaction mechanism is the same as in the case of MF and the overall reaction
may be simplified by the following equation:

Silver in the above-mentioned reaction may be replaced by silver nitrate. In this

case it is dissolved in water, and nitric acid is added followed by ethanol. Temper-
ature is one of the key factors of the reaction. According to Taylor and Rinkenbach
it is necessary to heat the reaction mixture to 80–90  C. When the temperature of
reaction mixture is below 30  C, product does not form even when standing for
weeks and only a low yield is obtained after 1 month at 30–34  C [94]. Addition of
small amounts of sodium nitrite to the reaction mixture is often recommended to
generate nitrogen oxides necessary for the reaction. These nitrogen oxides form by
reaction of nitrite with nitric acid [35, 42, 92, 94, 95]. The reaction conditions affect
the size and shape of SF crystals; highly sensitive needle crystals or relatively
insensitive fine powder are the two possible forms. The large highly sensitive
62 3 Fulminates

needle crystals were prepared, e.g., by Liebig [15]. The preparation of fine crystal-
line and relatively insensitive SF was published by Taylor and Buxton [15, 93].
Silver fulminate also forms when passing nitrogen oxide gas through an ethanol
solution of silver nitrate [35, 42]. Other methods of SF preparation are almost
analogous to preparation of MF (see Sect. 3.1.2.7).

3.1.3.5 Uses

A combination of the high cost of silver and the extreme sensitiveness of silver
fulminate has prevented its wider use in commercial and military applications.
Detonators containing silver fulminate (first used by Turpin in 1885 for initiation of
picric acid) were apparently used only by the Italian Navy [35, 48]. It was also used
in small quantities in fireworks and pyrotechnic toys such as “snaps,” or “pull-
crackers” for making noise [12, 13, 28, 36, 38, 104, 105].

3.1.4 Other Fulminates

3.1.4.1 Physical and Chemical Properties

In contrast to mercury and silver fulminates, most other metallic fulminates are too
sensitive, or physically or chemically unstable. Further, their preparation is too
expensive and demanding for practical use. Many fulminates are hygroscopic;
stable when dry but decompose in presence of carbon dioxide when moist (cad-
mium, copper(I), copper(II), thallium) [15, 29, 57, 106].
Alkaline fulminates—sodium and potassium—are soluble in methanol, not
soluble in acetone and ethanol, and insoluble in ether and benzene [39, 107].
Sodium fulminate explosively decomposes by action of sulfuric acid in the
same way as MF and SF do [15]. The spontaneous explosion is reported even
during drying above sulfuric acid [108]. The density of alkali fulminates is
similar to alkali azides; sodium fulminate 1.92 g cm
3 and potassium fulminate
1.80 g cm
3 [39]. Sodium fulminate forms an anhydride or monohydrate
depending on preparation procedure. Alkaline fulminates can be stored for a
long time in the form of methanol solutions in the dark. These fulminates are
hygroscopic; they are not stable in contact with moisture and quickly decom-
pose when wet (white color changes to yellow and brown with loss of explosive
properties) [15, 107]. Toxicity of sodium fulminate is about the same as that of
sodium cyanide [2].
Thallium fulminate is photosensitive; it turns yellow under light. It very slowly
becomes brown and loses explosive properties on exposure to air (unless sealed in
air tight container). Thallium fulminate is hygroscopic; it explosively decomposes
by action of sulfuric and nitric acid. It slowly decomposes to a nonexplosive
substance on long-term heating [15, 57, 109].
3.1 Introduction 63

Cadmium fulminate forms white crystals that are soluble in alcohol. It is

hygroscopic but dry cadmium fulminate is stable (in desiccator above CaCl2) [15].
As briefly mentioned in the previous chapter, fulminates are capable of forming
a variety of complexes with metals [8, 39]. The first of the fulminato(metal)
complexes (complexes with fulminate ligands) was K[Ag(CNO)2]. This compound
was obtained by Liebig from the reaction of SF and potassium chloride [8].
Ammonium fulminate NH4CNO has not yet been synthesized. A complex salt
containing the ammonium cation NH4[Ag(CNO)2] can be easily prepared by the
reaction of the ammonium salt with SF in methanol [39].
The simple gold (I and III) fulminate has not yet been prepared. Complex
Na[Au(CNO)2], however, exists and is formed by the reaction of sodium fulminate
with gold chloride or by direct reaction of AuCl3 with nitric acid and ethanol. The
compound is slightly soluble in water, stable at room temperature, and relatively
stable against concentrated nitric and hydrochloric acid [39, 110].
Some of the fulminato(metal) complexes are stable only with water of crystal-
lization present and decompose on drying. Examples of such complexes
are Na4[Fe(CNO)6]∙18H2O or Na4[Fe(CN)5CNO]·H2O. Whether such complexes
exhibit explosive properties is unknown to the authors. Anionic (fulminato)metal
complexes of alkali and alkaline earth metals were reported by W€ohler as “highly
explosive.” Explosive properties have also been reported for Na2[Hg(CNO)4].
The possibility to stabilize fulminate complexes of transition metals by “diluting”
energy-rich metal fulminate groups with large cations (AsPh4+, PPh4+, NR4+) or
with large neutral ligands (PPh3) has been investigated by Beck [8].

3.1.4.2 Sensitivity

As opposed to alkaline azides which do not have properties of explosives, alkaline

fulminates are mostly reported as highly sensitive and explosive substances [8, 107,
108] even though one source mentioned sodium fulminate as not so sensitive
(impact sensitivity for NaCNO to be 32 cm with 0.5 kg hammer compared to
7.5–10 cm MF under the same conditions) [27]. Sensitivity of these fulminates is
reported as extreme and handling a hazardous operation [8, 107, 108]. Extreme
sensitivity is further reported for the rubidium and cesium salts. Alkaline fulminates
undergo explosion when initiated by flame, even in small amounts, whereas mer-
cury fulminate only deflagrates. The exact sensitivity data are, however, not
reported in this work [107]. Sensitivity of cadmium fulminate to impact is about
the same as that of MF; sensitivity of thallium fulminate is higher [15, 57].

3.1.4.3 Explosive Properties

Cupric fulminate and particularly cadmium fulminate are powerful primary

explosives. The initiating efficiency of cadmium fulminate is even higher than
that of silver fulminate. The initiating temperature and initiation efficiency of
64 3 Fulminates

some fulminates are summarized in Table 3.4. The ignition efficiency of thallium
fulminate is significantly lower than for MF. W€ohler and Martin reported that it is
about 20 times lower than LA [57]. In a lead block test, sodium fulminate acts with
power of 58 % of MF [112].
The explosive properties of complex fulminates depend on composition. For
example, NH4[Ag(CNO)2] is explosive but less explosive than SF; Mg[Ag(CNO)2]
detonates violently whereas pyridine complexes only deflagrate or burn [39].
Na[Au(CNO)2] explodes by action of flame with “sharper” detonation than other
complex fulminates [39, 110].

3.1.4.4 Preparation

Fulminates other than those of Hg and Ag (and also complex Na[Au(CNO)2] from
AuCl3 [110]) cannot be prepared directly by reaction of the metal with nitric acid
and subsequently with ethanol like MF or SF [15, 33]. Several reasons exist that
make direct formation of other fulminates impossible. W€ohler and Martin reported
that solubility of most fulminates in the reaction mixture is a reason why only MF
and SF can form directly. Most other fulminates are soluble and unstable in the
reaction mixture, in which they decompose [57]. Another reason is that the fulminic
acid too readily forms complex salts and therefore simple fulminates cannot be
isolated [35]. A catalytic effect of noble metals (Hg, Ag) on some of the reaction
steps of fulminate formation was reported by Krauz. He mentioned the analogy of
the catalytic effect of mercuric ions on hydrocarbons that are oxidized to the
relevant nitrophenols in dilute nitric acid [35].
The preparation of alkaline fulminates and fulminates of alkaline earth metals
was not successful for a long time. The reaction of MF or SF with relevant salts was
not successful due to the formation of double salts. The first successful preparation
of sodium fulminate was published by Carstanjen and Ehrenberg only in 1882;
about 80 years after the discovery of MF [15, 113].
The majority of fulminates (except those of SF and MF) are prepared by reaction
of relevant amalgam of less noble metal with mercury (or silver) fulminate in
methanol or ethanol and precipitated by diethyl ether [29, 39, 57, 106, 107, 114].

Alkaline fulminates form the anhydride while fulminates of alkaline earths

(Ca, Sr, Ba) contain one molecule of alcohol (from alcoholic reaction environ-
ment). The alcohol cannot be removed from the molecule without its decomposi-
tion [15, 39]. The sodium fulminate can also be prepared in an aqueous
environment but product forms as the monohydrate [8, 15, 113]. The fulminate
turns yellow during evaporation of water [15, 113].
The preparation in an aqueous environment is not recommended for the majority
of fulminates due to low stability of the reaction mixture. The hydrolytic dissocia-
tion results in free fulminic acid which tends to polymerize [15, 57]. Preparation of
3.1 Introduction 65

Table 3.4 The explosive parameters of metallic fulminates

Initiation efficiency
Initiating temperature ( C) [111]
Heat of explosion [57] Explosiona Explosion at
(kJ g
1) [83] heating [107] Tetryl (g) TNT (g)
NaCNO – 215 210–220 – –
KCNO – 225 200 – –
RbCNO – – 195 – –
CsCNO – – 220–225 – –
Cd(CNO)2 1.97 215 – 0.008 0.11
Cu(CNO)2 2.13 205 – 0.025 0.15
TlCNO 0.933 120 – 0.300 –
a
Explosion within 5 s, weight 0.02 g

the sodium salt in aqueous environment is also not convenient for another reason—
the product formed is not pure and is highly sensitive. A pure and more stable
sodium salt forms using ethanol, or preferably methanol, as a reaction environment
instead of water [2]. The use of a protective atmosphere of inert gas is
recommended during preparation and vacuum drying for moisture sensitive
fulminates (e.g., cadmium fulminate) [15, 57].
Significant purification of alkaline fulminates after preparation is recommended
especially in case of rubidium and cesium ones (dissolving in methanol and
re-precipitated by addition of diethylether). The importance of purification is to
avoid the formation of double salts with MF that are more sensitive than the original
fulminates themselves (mentioned double salts spontaneously detonate at 45  C)
[107].
The other way of preparation of fulminates is via the sodium salt. For example,
thallium fulminate forms as a fine powder by reaction of sodium fulminate with
thallium acetate in methanol [25].

Some metallic fulminates also form directly by reaction of powdered metal with
MF in a water suspension while boiling (e.g., Zn, Al, Cu) [15, 48, 105]. The
preparation of thallium fulminate without use of an amalgam starting from MF
and thallium is a good example, described by Hawley [109]:

The (fulminato)metal complexes are prepared from aqueous sodium fulminate

solutions and transition metal salts followed by addition of tetraphenylarsonium
chloride [8]. The aqueous solutions of sodium fulminate can be directly prepared
from MF and sodium amalgam in water [8].
66 3 Fulminates

3.1.4.5 Uses

Metallic fulminates (except mercury and silver) have never been practically used as
explosives due to the difficulties with their preparation and generally low physical
and chemical stability. However, the sodium salt can be used for many applications
in organic chemistry. This salt is more suitable for this application than the more
easily accessible mercury or silver salts due to their tendency to form complexes in
solutions. For example, the sodium salt is useable in the preparation of free fulminic
acid by acidification of its solution with dilute sulfuric acid [2].

References

1. Urbański, T.: Chemistry and Technology of Explosives. PWN — Polish Scientific Publisher,
Warszawa (1967)
2. Grundmann, C., Grunanger, P.: The Nitrile Oxides, Versatile Tools of Theoretical and
Preparative Chemistry. Springer, Berlin (1971)
3. Danilov, J.N., Ilyushin, M.A., Tselinsky, I.V.: Promyshlennye vzryvchatye veshchestva;
chast I. Iniciiruyushchie vzryvshchatye veshchestva. Sankt-Peterburgskii gosudarstvennyi
tekhnologicheskii institut, Sankt-Peterburg (2001)
4. Sarlo, F., Guarna, A., Brandi, A., Goti, A.: The chemistry of fulminic acid. Tetrahedron 41,
5181–5185 (1985)
5. Wieland, H., Baumann, A.: Zur Kenntnis der polymeren Knalls€auren. Justus Liebigs Annalen
der Chemie 392, 196–213 (1912)
6. Wieland, H., Baumann, A., Reisenegger, C., Scherer, W., Thiele, J., Will, J., Haussmann, H.,
Frank, W.: Die Polymerisation der Knalls€aure. Isocyanils€aure und Erythro-cyanils€aure.
Justus Liebigs Annalen der Chemie 444, 7–40 (1925)
7. Ulpiani, C.: Per la costituzione degli acidi fulminurici. Sulľacido metafulminurico. Gazzetta
Chimica Italiana 46, 1–48 (1916)
8. Beck, W.: The first chemical achievements and publications by Justus von Liebig
(1803–1873) on metal fulminates and some further developments in metal fulminates and
related areas of chemistry. Eur. J. Inorg. Chem. 4275–4288 (2003)
9. Kurzer, F.: The life and work of Edward Charles Howard FRS. Ann. Sci. 56, 113–141 (1999)
10. Kurzer, F.: Fulminic acid in the history of organic chemistry. J. Chem. Educ. 77, 851–856
(2000)
11. Winnewisser, M., Winnewisser, B.P.: Proč trvalo objasňovánı́ struktury třaskavé kyseliny
174 let. Chemické listy 70, 785–807 (1976)
12. Walke, W.: Lectures on Explosives. Wiley, New York (1897)
13. Wisser, J.P.: Explosive Materials – The Phenomena and Theories of Explosion. D. Van
Nostrand, New York (1907)
14. Nef, J.U.: Ueber die Constitution der Salze der Nitroparaffine. Justus Liebigs Annalen der
Chemie 280, 263–342 (1894)
15. Bagal, L.I.: Khimiya i tekhnologiya iniciiruyushchikh vzryvchatykh veshchestv.
Mashinostroenie, Moskva (1975)
16. Urbański, T.: Chemistry and Technology of Explosives. Pergamon, Oxford (1984)
References 67

17. Pauling, L., Hendricks, S.B.: The prediction of the relative stabilities of isosteric ions and
molecules. J. Am. Chem. Soc. 48, 641–651 (1926)
18. Beck, W., Feldl, K.: Die Struktur der Knalls€aure HCNO. Angew. Chem. 746 (1966)
19. Shapley, W.A., Bacskay, G.B.: A gaussian-2 quantum chemical study of CHNO: Isomeriza-
tion and molecular dissociation reactions. J. Phys. Chem. A 103, 6624–6631 (1999)
20. Sarlo, F., Brandi, A., Fabrizi, L., Guarna, A., Niccolai, N.: Multinuclear magnetic resonance
study of organomercury fulminates. The structure of mercury fulminate in solution. Org.
Magn. Reson. 22, 372–375 (1984)
21. Beck, W., Evers, J., G€ obel, M., Oehlinger, G., Klap€otke, T.M.: The crystal and molecular
structure of mercury fulminate (knallquecksilber) [1]. Zeitschrift f€ ur anorganische und
allgemeine Chemie 633, 1417–1422 (2007)
22. Beck, W., Klap€ otke, T.M.: Mercury fulminate: ONC–Hg–CNO or CNO–Hg–ONC – a DFT
study. J. Mol. Struct. THEOCHEM 848, 94–97 (2008)
23. T€urker, L., Erkoç, S.: Density functional theory calculations for mercury fulminate. J. Mol.
Struct. THEOCHEM 712, 139–142 (2004)
24. Bottaro, J.: Ideas to Expand Thinking About New Energetic Materials, pp. 473–501. World
Scientific Publishing, New Jersey (2005)
25. Iqbal, Z., Yoffe, A.D.: Electronic structure and stability of the inorganic fulminates. Proc. R.
Soc. Lond. A Math. Phys. Sci. 302, 35–49 (1967)
26. Nielsen, A.H.T.: Knaldkviksølvets og knaldsølvets opdagelseshistorie. Dansk kemi 12,
17–21 (1996)
27. Marshall, A.: Explosives. Butler and Tanner, London (1917)
28. Davis, T.L.: The Chemistry of Powder and Explosives. Wiley, New York (1943)
29. Fedoroff, B.T., Sheffield, O.E., Kaye, S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, New Jersey (1960–1983)
30. Tomlinson, W.R., Sheffield, O.E.: Engineering Design Handbook, Explosive Series of
Properties Explosives of Military Interest, report AMCP 706-177 (1971)
31. Davis, T.L.: Kunckel and the early history of phosphorus. J. Chem. Educ. 4, 1105–1113
(1927)
32. Davis, T.L.: Kunckel’s discovery of fulminate. Army Ordnance 7, 62–63 (1926)
33. Howard, E.: On a new fulminating mercury. Philos. Trans. R. Soc. Lond. 90, 204–238 (1800)
34. Brede, U., Hagel, R., Redecker, K.H., Weuter, W.: Primer compositions in the course of time:
from black powder and SINOXID to SINTOX compositions and SINCO booster. Propellants
Explosives Pyrotechnics 21, 113–117 (1996)
35. Krauz, C.: Technologie výbušin. Vědecko-technické nakladatelstvı́, Praha (1950)
36. Blechta, F.: Dnešnı́ stav otázky náhražek třaskavé rtuti. Chemický obzor 3, 330–336 (1928)
37. MacDonald, G.W.: The discovery of fulminate of mercury (1800). Arms Explosives 19,
24–25 (1911)
38. Thorpe, E.: A Dictionary of Applied Chemistry, pp. 79–84. Longmans, Green, London
(1928)
39. W€ohler, L., Weber, A.: Neue Salze der Knalls€aure. Berichte der deutschen chemischen
Gesellschaft 62, 2742–2758 (1929)
40. Zhukov, B.P.: Energeticheskie kondesirovannye sistemy. Izdat, Yanus-K, Moskva (2000)
41. Meyer, R., K€ohler, J., Homburg, A.: Explosives. Wiley-VCH Verlag GmbH, Weinheim
(2002)
42. Špičák, S., Šimeček, J.: Chemie a technologie třaskavin. Vojenská technická akademie
Antonı́na Zápotockeho, Brno (1957)
43. Kast, H.: Weitere Untersuchungen € uber die Eigenschaften der Initialsprengstoffe. Zeitschrift
f€ur das gesamte Schiess- und Sprengstoffwesen 21, 188–192 (1926)
44. Strnad, J.: Iniciačnı́ vlastnosti nejpoužı́vanějšı́ch třaskavin a vývoj nových metodik jejich
měřenı́. Institute of Chemical Technology, Dissertation thesis, Pardubice (1972)
45. Batrnett, B.: Explosives. D. van Nostrand, New York (1919)
46. W€ohler, L., Berthmann, A.: Uber € Verunreinigungen und einige Eigenschaften des
technischen Knallquecksilbers. Zeitschrift f€ ur das angewandte Chemie 43, 59–63 (1930)
68 3 Fulminates

47. Langhans, A.: Graues und weißes Knallquecksilber. Zeitschrift f€ ur das gesamte Schiess- und
Sprengstoffwesen 15, 23–24 (1920)
48. Urbański, T.: Chemie a technologie výbušin. SNTL, Praha (1959)
49. Borocco, A.: Contribution à l’étude de l’action des rayons ultraviolets sur le fulminate de
mercure. Comptes rendues de l’Académie des sciences 207, 166–168 (1938)
50. Bartlett, B.E., Tompkins, F.C., Young, D.A.: The decomposition of mercury fulminate. J.
Chem. Soc. 3323–3330 (1956)
€
51. Kast, H., Selle, H.: Uber den angeblichen Krystallwasser-Gehalt des Knallquecksilber.
Berichte der deutschen chemischen Gesellschaft 59, 1958–1962 (1926)
52. Holleman, A.F.: Notices sur les fulminates. Recueil des Travaux Chimiques des Pays-Bas 15,
159–160 (1896)
53. Ingraham, W.T.: The deterioration of mercury fulminate when stored under water. Army
Ordnance 10, 201–202 (1929)
54. Carl, L.R.: Mercury fulminate, its autocatalytic reactions and their relation to detonation. J.
Franklin Inst. 240, 149–169 (1945)
55. Miles, F.D.: The formation and characteristic of crystals of lead azide and of some other
initiating explosives. J. Chem. Soc. 2532–2542 (1931)
56. Singh, K.: Initiation of explosion in crystals of mercury fulminate. Trans. Faraday Soc. 52,
1623–1625 (1956)
€
57. W€ohler, L., Martin, F.: Uber neue Fulminate und Azide. Berichte der deutschen chemischen
Gesellschaft 50, 586–596 (1917)
58. Khmelnitskii, L.I.: Spravochnik po vzryvchatym veshchestvam. Voennaya ordena Lenina i
ordena Suvorova Artilleriiskaya inzhenernaya akademiya imeni F. E. Dzerzhinskogo,
Moskva (1962)
59. Dupré, F.H., Dupré, P.V.: Notes on the reactions of fulminate of mercury with sodium
thiosulfate. Analyst 46, 42–49 (1921)
60. Nesveda, J., Švejda, M.: Způsob zı́skávánı́ kovové rtuti z třaskavé rtuti a zařı́zenı́ k prováděnı́
tohoto způsobu. CS Patent 267,047, 1990
61. Farmer, R.C.: The velocity of decomposition of high explosives in a vacuum. III. Mercuric
fulminate. J. Chem. Soc. Trans. 121, 174–187 (1922)
62. Vaughan, J., Phillips, L.: Thermal decomposition of explosives in the solid phase. III. The
kinetics of thermal decomposition of mercury fulminate in a vacuum. J. Chem. Soc.
2741–2745 (1949)
63. Boddington, T., Iqbal, Z.: Decomposition of inorganic fulminates. Trans. Faraday Soc. 65,
509–518 (1969)
64. Narayana, P.Y.: The thermal decomposition of mercuric fulminate. Curr. Sci. 13, 313–315
(1944)
65. Garner, W.E., Hailes, H.R.: Thermal decomposition and detonation of mercury fulminate.
Proc. R. Soc. Lond. A Math. Phys. Eng. Sci. 139, 576–595 (1933)
66. Zhulanova, V.P., Bannov, S.I., Pugachev, V.M., Ryabykh, S.M.: Products of the radiation-
chemical and thermal decomposition of mercury fulminate. High Energy Chem. 35, 26–32
(2001)
67. Vaughan, J., Phillips, L.: Thermal decomposition of explosives in the solid phase. II. The
delayed explosion of mercury fulminate. J. Chem. Soc. 2736–2740 (1949)
68. Miszczak, M., Milewski, E., Kostrow, R., Goryca, W., Terenowski, H.: An analysis of the test
and assessment methods on physicochemical stability of primary explosives. In: Proceedings
of 10th Seminar on New Trends in Research of Energetic Materials, pp. 805–811, Pardubice,
Czech Republic, (2007)
69. Military Explosives. Report TM-9-1300-214, Headquarters, Department of the army, (1984)
70. Matyáš, R.: Investigation of properties of selected organic peroxides. University of
Pardubice, dissertation, Pardubice, Czech Republic (2005)
71. Kast, H., Haid, A.: Uber € die sprengtechnischen Eigenschaften der wichtigsten
Initialsprengstoffe. Zeitschrift f€
ur das angewandte Chemie 38, 43–52 (1925)
72. Muraour, H.: Sur la theorie des reactions explosives. Cas particulier des explosifs
d‘amourcage. Mémories présentés a la Société chimique 51, 1152–1166 (1932)
References 69

73. Kling, A., Florentin, D.: Action des basses températures sur les explosifs. Mémorial des
poudres 17, 145–153 (1913)
74. Evans, B.L., Yoffe, A.D.: The burning and explosion of single crystals. Proc. R. Soc. Lond.
A238, 325–333 (1956)
75. Belyaev, A.F., Belyaeva, A.E.: Issledovanie goreniya gremuchei rtuti. Zhurnal fizicheskoi
khimii 20, 1381–1389 (1946)
76. Belyaev, A.F., Belyaeva, A.E.: O normalnoi skorosti i kharaktere “goreniya” nekotorykh
initsiirujushchikh vzryvchatykh veshchestv. Doklady akademii nauk SSSR 52, 507–509
(1946)
77. Belyaev, A.F., Belyaeva, A.E.: Zavisimost skorosti gorjeniya initsiirujushchikh
vzryvchatykh veshchestv ot davleniya. Doklady akademii nauk SSSR 56, 491–494 (1947)
78. Belyaev, A.F., Belyaeva, A.E.: Uber € das Brennen von Knallquecksilber bei einem
Unterdruck. Doklady akademii nauk SSSR 33, 41–44 (1941)
79. Urbański, T., Stanuch, J.: Decomposition of initiating explosives under reduced pressure.
Archiwum Procesów Spalania 4, 5–12 (1973)
80. Andreev, K.K.: O zavisimosti skorosti goreniya vtorichnykh i iniciiruyushchikh
vzryvchatykh veshchestv ot davleniya. Doklady akademii nauk SSSR 51, 29–32 (1946)
81. Strnad, J.: Primary Explosives and Pyrotechnics—Lecture Notes. Institute of Energetic
Materials, University of Pardubice, Pardubice (1999)
82. Wallbaum, R.: Sprengtechnische Eigenschaften und Lagerbest€andigke der wichtigsten
Initialsprengstoffe. Zeitschrift f€
ur das gesamte Schiess- und Sprengstoffwesen 34, 197–201
(1939)
83. W€ohler, L., Martin, F.: Azides; Sensitiveness of. J. Soc. Chem. Ind. 36, 570–571 (1917)
84. Kibler, A.L.: Synthesis of mercury fulminate from propyl alcohol. Orig. Commun. 8th Int.
Congr. Appl. Chem. 25, 239–243 (1913)
85. Martin, G., Barbour, W.: Manual of Chemical Technology; III. Industrial Nitrogen
Compounds and Explosives. Crosby Lockwood and son, London (1915)
86. Hodgkinson, W.R.: Fulminate of mercury. J. Soc. Chem. Ind. 37, 190t (1918)
87. Wieland, H.: Eine neue Knalls€auresynthese. Uber € den Verlauf der Knalls€aurebildung aus
Alkohol und Salpeters€aure. Berichte der deutschen chemischen Gesellschaft 40, 418–422
(1907)
88. Adam, D., Karaghiosoff, K., Klap€ otke, T.M., Hioll, G., Kaiser, M.: Triazidotrinitro benzene:
1,3,5-(N3)3-2,4,6-(NO2)3C6. Propellants Explosives Pyrotechnics 27, 7–11 (2002)
89. Hagel, R., Redecker, K.: Sintox – a new, non-toxic primer composition by Dynamit Nobel
AG. Propellants Explosives Pyrotechnics 11, 184–187 (1986)
90. Grant, R.L., Tiffany, J.E.: Factors affecting initiating efficiency of detonators. Ind. Eng.
Chem. 37, 661–666 (1945)
91. Carl, L.R.: The rate of detonation of mercury fulminate and its mixtures with potassium
chlorate. Army Ordnance 6, 302–304 (1926)
92. Collins, P.H., Holloway, K.J.: A reappraisal of silver fulminate as a detonant. Propellants
Explosives 3, 159–162 (1978)
93. Taylor, C.A., Buxton, E.P.: Silver fulminate, an initiator of detonation. Army Ordonance 6,
118–119 (1925)
94. Taylor, C.A., Rinkenbach, W.H.: A sensitive form of silver fulminate. Army Ordonance 6,
448 (1926)
95. Singh, K.: Crystal structure of silver fulminate. Acta Crystallogr. 12, 1053 (1959)
96. Britton, D.: A redetermination of the trigonal silver fulminate structure. Acta Crystallogr.
C 47, 2646–2647 (1991)
97. Britton, D., Dunitz, J.D.: The crystal structure of silver fulminate. Acta Crystallogr. 19,
662–668 (1965)
98. Barrick, J.C., Canfield, D., Giessen, B.C.: A redetermination of the silver fulminate structure.
Acta Crystallogr. B 35, 464–465 (1979)
99. Divers, E., Kawakita, M.: On the decomposition of silver fulminate by hydrochloric acid.
J. Chem. Soc. Trans. 47, 69–77 (1885)
70 3 Fulminates

100. Davy, E.: An account of a new fulminating silver, and its application as a test for chlorine.
Trans. R. Irish Acad. 17, 265–274 (1837)
101. Peter, A.M.: On the stability of silver fulminate under water. J. Am. Chem. Soc. 38, 486
(1916)
€
102. Berchtold, J., Eggert, J.: Uber die Z€undf€ahigkeit von Sprengstoffen dur Stahlung hoher
Intensit€at. Naturwissenschaften 40, 55–56 (1953)
103. Bowden, F.P., Williams, R.J.E.: Initiation and propagation of explosion in azides and
fulminates. Proc. R. Soc. Lond. A Math. Phys. Sci. A208, 176–188 (1951)
104. Stettbacher, A.: Explosive toys. Chem. Abstr. 14, 17792 (1920)
105. Cundill, J.P., Thomson, J.H.: A Dictionary of Explosives. Eyre and Spottiswoode, London
(1895)
106. Hanus, M.: Méně známé třaskaviny. Synthesia a.s, VÚPCH, Pardubice (1996)
107. Hackspill, L., Schumacher, W.: Contribution à l’étude des fulminates alcalins. Rocznik
Akademji Nauk Technicznych w Warszawie 3, 84–89 (1936)
108. Ehrenberg, A.: Ueber Natriumfulminat. Journal f€ ur praktische Chemie 32, 230–234 (1885)
109. Hawley, L.F.: Contributions to the chemistry of thallium. I. J. Am. Chem. Soc. 29, 300–304
(1907)
110. Bos, W., Bour, J.J., Steggerda, J.J., Pignolet, L.H.: Reaction of gold(I) compounds with
carbon monoxide to form gold clusters and fulminates. Inorg. Chem. 24, 4298–4301 (1985)
111. W€ohler, L., Martin, F.: Die Initialwirkung von Aziden und Fulminaten. Zeitschrift f€ ur das
gesamte Schiess- und Sprengstoffwesen 12, 18–21 (1917)
112. W€ohler L., Matter, O.: Beitrag zur Wirkung der Initialz€unding von Sprengstoffen. Zeitschrift
f€ur das gesamte Schiess- und Sprengstoffwesen 244–247 (1907)
113. Carstanjen, E., Ehrenberg, A.: Ueber Knallquecksilber. Journal f€ ur praktische Chemie 25,
232–248 (1882)
114. W€ohler, L.: Neue Salze der Knalls€aure und Stickstoffwasserstoffs€aure und die explosiven
Eigenschaften von Fulminaten und Aziden. Zeitschrift f€ ur das angewandte Chemie 27,
335–336 (1914)
Chapter 4
Azides

Azides are substances containing the N
3 group. They exist as inorganic salts,
organic compounds, organo-metals, or complexes. For the purpose of this book, we
have decided to include the inorganic and organic compounds. Some organic
substances that contain the azido group are included in other chapters (e.g.,
tetrazoles, other substances). We have also decided to separate out complex
compounds containing the azido group and place them into a separate chapter
with other complexes.

4.1 Azoimide
HN3
Azoimide (or hydrazoic acid) was discovered by Curtius in 1890 and in pure form
was first prepared by Curtius and Radenhauser in 1891 [1, 2]. It is a colorless liquid
with a strong odor which boils without decomposition at 37  C and freezes at

80  C [3–5]. Azoimide, even in gaseous form, is highly toxic with a very strong
unpleasant odor [4]. The pure liquid form is dangerous to handle as it explodes with
a blue-colored flash with the slightest mechanical or thermal shock. One of its
discoverers was wounded by the explosion when he removed a test tube with
azoimide from the cooling mixture [2, 6]; explosion can occur even by friction of
an azoimide bubble (at boiling point of azoimide) against a sharp glass edge [4].
An aqueous solution containing as little as 17% azoimide can explode [7]. Pure
liquid azoimide may be stored but, after months of storage, it has a tendency to
undergo spontaneous explosion [5]. It is dangerous in gaseous form in which it may
also spontaneously explode. The probability of explosion is higher at higher
pressures. Azoimide explosively decomposes to nitrogen and hydrogen:

Heat of formation of azoimide is 300.25 kJ mol
1 [3] and density is 1.13 g cm
3
(from 0 to 20  C) [5]. The detonation velocity is 8,100 m s
1 according to Urbański [8]

R. Matyáš and J. Pachman, Primary Explosives, 71

DOI 10.1007/978-3-642-28436-6_4, # Springer-Verlag Berlin Heidelberg 2013
72 4 Azides

or 7,000–7,500 m s
1 according to Danilov [3]. On contact with flames, it explodes

with a blue flash. Azoimide is weakly acidic and may be liberated from its salts using
acids [4, 6]. Aqueous solutions react with common metals such as iron, copper, or
aluminum even when quite diluted (7% m/m). More concentrated solutions react also
with silver or gold. A mixture with hydrochloric acid dissolves gold and platinum.
Platinum black decomposes azoimide to ammonia and nitrogen. Inorganic salts of
azoimide have chemical properties similar to those of halides [4].

4.2 Lead Azide

PbðN3 Þ2
The discovery of lead azide (LA) is attributed to Curtius who first prepared this
substance and characterized its explosive properties in 1891 [2]. In 1893, some
experiments with lead, silver, and mercury were carried out in Spandau in Prussia.
However, an unexpected explosion occurred during testing of azides with fatal
results, which caused termination of further experiments. They were not re-started
until 1907 when W€ ohler drew attention to azides once again as he saw it as a
possible substitute for expensive MF [5].
The real era of LA started in 1908 after Hyronimus patented its use as “a primer
for mines and fire-arms consisting of charge of trinitride of lead” [9]. In 1911,
W€ohler proposed the use of LA as a substitute for MF in military applications.
Problems with industrial application of LA, mostly related to its high sensitivity,
were overcome in the 1920s and, despite the previous tragic accidents and numer-
ous doubts about its practical utilization, lead azide gradually superseded mercury
fulminate as a primary explosive [8]. The manufacture of LA probably began in
Germany around 1914 following the extensive investigations by W€ohler. Science
itself was, however, not persuasive enough to convince the armies to use LA. The
development of the course of World War I played a key role in the incorporation of
LA into munitions. The Italian advance upon Gorizia brought the Austrian mercury
mines within their range. This created a problem as the mercury was used for
preparation of MF. Central powers had no choice but to replace MF with LA where
possible. Since 1920, the use of LA has developed considerably and other nations
followed the Germans [4, 10, 11]. Significant production of LA is reported from
Russia since 1929 [3].

4.2.1 Physical and Chemical Properties

Lead azide forms white or yellowish crystals. It is known to form four allotropic
modifications: a, b, g, and d (older literature refers only to the first two of them).
The orthorhombic a-form with crystal density reported from 4.68 to 4.716 g cm
3
[12–14] is the main product of precipitation, with traces of other forms present, and
is the only form acceptable for technical applications [15]. A variety of crystal
4.2 Lead Azide 73

Fig. 4.1 Crystals of lead azide: left a-form, right b-form

structure modifiers was tested for modification of the crystal form of precipitated
LA. The most commonly noted ones include dextrin, carboxymethyl cellulose, and
PVA. The presence of dextrin promotes formation of the a-form [16] while the
presence of organic dyes (eosin, erythrosin, or neutral red) at precipitation time
enhances the formation of the b-form [15]. The crystals of b lead azide are formed
in the shape of long needles (Fig. 4.1).
The dry monoclinic b-form has a crystal density reported from 4.87 to
4.93 g cm
3 [12, 13] and is stable. In older literature, the b-form is referred to as
extremely sensitive to mechanical stimuli with the formation of long needles that
may explode simply by the breaking of a single crystal [11]. Crystals 1 mm in
length were reported liable to explode spontaneously because of the internal
stresses within them [17]. This extreme sensitivity of the b-form was, however,
later disproved and shown to be a common myth (more in part on sensitivity of LA).
The other two allotropic forms can be obtained from pure reagents by
maintaining the pH in the range 3.5–7.0 for monoclinic g and 3.5–5.5 for triclinic
d. They usually precipitate from the solution simultaneously [8]. The g-form is also
created in presence of polyvinyl alcohol [18]. A method of exclusive preparation of
a particular polymorph (g, d) was not known to Fair who recommended hand
selection under the microscope as the only possible way, since the crystals differ
in shape and size [15]. g-LA may be prepared reproducibly by using PVA (degree
of polymerization does not play a role) which is free from unhydrolyzed polyvinyl
acetate [19].
The a-form is the most stable of all four versions. For example, the enthalpy of
formation of the g-form is higher by 1.25 kJ mol
1 than the a-form [3]. Thermal
decomposition of both the a-form and b-form has been studied and various results
were reported. At temperatures around 160  C, the b-form transforms irreversibly
to the a-form [20].
LA is practically insoluble in cold water, ammonia, and in most common organic
solvents. It decomposes in boiling water liberating azoimide [6, 8]. LA is soluble in
solutions of sodium or ammonium acetate (see Sect. 2.6), acetic acid, and ethanol-
amine (Table 4.1).
Lead azide is photosensitive and its crystals turn yellow and later gray in daylight.
Lead and nitrogen form during photodecomposition. Decomposition, accompanied by
74 4 Azides

Table 4.1 Solubility of lead Solubility in 100 ml solvent (g)

azide [16, 21] 
Temperature ( C) Water Conc. aqueous sodium acetate
18 0.023 1.54
70 0.090 –
80 – 2.02

the change of color, takes place only in the outer layer and does not propagate
throughout the crystal. The decomposition of the surface layer is not reflected notice-
ably in any deterioration of explosive properties of the bulk material [3, 5, 15, 22].
Lead azide can be ignited by high-intensity light (argon flash) [23]. LA decomposes
even when illuminated under water in which case basic lead azide forms.1 W€ohler and
Krupko described this reaction by the following sequence of equations [24]:

Thermal stability of dry LA in absence of moisture is quite good and degradation

at 60  C after 12 months or at 80  C after 1 month is scarcely detectable. The
presence of water plays the most important role in decomposition of this substance
and it has been reported that heating periods at 250  C in vacuum, and hence
excluding moisture, had to be increased 80 times to produce the same reduction of
detonation velocity compared to the same trials under moist air [25, 26]. Gray and
Waddington published heat of formation of LA 484 kJ mol
1 [27]; however,
according to Yoffe its decomposition is reported to release 443 kJ mol
1 [28].

Metallic lead, formed during thermal decomposition of LA, may react with
oxygen from the air and form lead oxides [29]. LA is a weak photoconductor [7].

4.2.2 Chemical Reactivity

Lead azide decomposes by action of acids liberating azoimide and the relevant lead
salt. It easily reacts even with weak acids (such as acetic acid, carbonic acid,

1
Basic forms of lead azide are described by various formulas most often as PbO·Pb(N3)2 or
Pb(OH)N3.
4.2 Lead Azide 75

atmospheric CO2, or even lead styphnate) liberating azoimide. An example of such

decomposition is its reaction with nitric acid which decomposes LA into azoimide
and lead nitrate [3].

The too narrow blank in comparison with others liberation of poisonous

azoimide limits the use of acids themselves for decomposition of LA. This problem
can be overcome simply by addition of sodium nitrite which eliminates azoimide,
since the reaction changes in the following way [3, 5]:

2 Pb(N3)2 + 6 HNO 3 + 2 NaNO 2 2 Pb(NO3)2 + 2 NaNO 3

+ N 2O + 6 N 2 + 3 H 2O

It is therefore recommended to add sodium nitrite solution before using acid for
destruction of unwanted LA (or also sodium azide) residues in the laboratory or
even in industrial applications [3, 5, 21]. Urbański recommends the use of 8 %
solution of sodium nitrite and 15 % nitric acid for LA [30], whereas 92 % sulfuric
acid is recommended for sodium azide [5]. Many other reactions have been
proposed for the decomposition of LA, including reaction with sodium polysulfide
[21] or dissolving LA in ammonium acetate and adding sodium or potassium
bichromate until no more lead chromate precipitates [5].
Lead azide is stable in air under normal conditions when dry. However, it slowly
decomposes in presence of moist air containing carbon dioxide. Detailed analysis of
the reactions of LA with water and carbon dioxide has been presented by Lamnevik
[31]. According to this author, basic lead azide forms and gaseous azoimide is
liberated by reaction of LA with moisture:

If the partial pressure of carbon dioxide is lower than 1.2 kPa azoimide, basic
lead azide forms in a similar way as with water (see above). At higher carbon
dioxide partial pressures, dibasic lead carbonate and also azoimide form according
to the following equation:

Both reactions are in equilibrium and reach that state at very low partial pressure of
azoimide. For example, the equilibrium pressure of azoimide in the first reaction is
5.3 Pa (at 25  C). To give an idea, this pressure can be reached by the reaction of
0.6 mg of LA with 0.04 mg water in space with volume of 1 l. Therefore, the normal
moisture content of LA is more than sufficient to establish equilibrium conditions. The
deterioration of LA due to these reactions is therefore not significant as only a very
76 4 Azides

small amount reacts before reaching equilibrium. When the system with lead azide is
not well sealed azoimide diffuses into atmosphere and equilibrium conditions are not
obtained. The consequence is gradual conversion of LA to basic lead azide or basic
lead carbonate. This is one of the reasons why detonators with LA must be hermeti-
cally sealed. The other problem related to degradation of LA due to azoimide
consumption, and hence impossibility of reaching equilibrium, is the reaction of LA
with some components of the system mainly with some metals like copper and its
alloys or zinc commonly used in construction of detonators. The reaction of azoimide
with metals, especially copper, is without question the biggest drawback of LA.
Various copper azides that form as a result of this reaction exhibit differing degrees
of sensitivity, some being more sensitive than lead azide itself. It is therefore necessary
to prevent lead azide coming into contact with copper in its applications. Aluminum,
stainless steel, tin, and lead do not react with lead azide even in presence of water. The
preferred material for applications containing LA is therefore aluminum [5, 8, 32–34].
Lead azide is also incompatible with many polymeric substances [35].
It was originally assumed that the deterioration of LA in a detonator, because of
its decomposition by carbon dioxide and the formation of basic lead azide or basic
lead carbonate, would decrease its initiation efficiency and hence decrease overall
ability of the detonator to perform with the desired strength. Danilov et al., however,
published that the lead carbonate that forms during the reaction of LA with carbon
dioxide creates a surface layer which protects LA from further decomposition [3].
The mechanism of deterioration of LA depends upon hydrolysis conditions.
According to Blay and Rapley, if the hydrolysis is not accelerated by abnormal
conditions, the deterioration does not proceed beyond an acceptable level in service
detonators [36]. The same thinking was reported in 1975 by Lamnevik who did not
notice any loss of function in an LA detonator due to LA degradation [3, 31].
Bases only decompose the surface layer, which turns to lead oxide and the
relevant azide. The lead oxide protects LA from further attack by the base [3]:

Other possible reactions are described for decomposing LA by hydroxides. The

two reactions below are such examples. The first takes place with a sodium
hydroxide solution concentration of 10 % while the second takes place with the
concentration at 20 % [8]. Some authors even suggest the formation of basic salts
Pb(N3)2·xPbO [15, 34].

Lead azide easily reacts with many inorganic salts. Its reaction with cerium(IV)
sulfate [21, 34] or with ammonium cerium(IV) nitrate [3, 5] is used for quantitative
analysis or decomposition of unwanted LA:
4.2 Lead Azide 77

Table 4.2 Sensitivity of LA polymorphs to impact, friction and electrostatic discharge (EDS) [37]
Service LAa b-LAb g-LA
Impact (50 %) (cm) 15.24 15.04 7.35
Friction (50 %) (m s
1) 1.36 1.32 1.92
ESD (mJ) 2 1.2 1.1
a
Service lead azide refers to “British military service LA” whose manufacture is based on
nucleation by 2.5 % of lead carbonate (formed from sodium carbonate and lead acetate) [38].
b
Crystals were broken up by a rubber spatula and therefore were of mixed particle size.

Table 4.3 Sensitivity of LA polymorphs to impact, friction, and electrostatic discharge (ESD) [19]
90 % Service LA 90 % Service LA
Service LAa 10 % b-LA 10 % g-LA
Impact (50 %) (cm) 15.24 11.91 10.31
Friction (50 %) (m s
1) 1.36 1.10 1.09
a
Service lead azide refers to “British military service LA” whose manufacture is based on
nucleation by 2.5 % of lead carbonate (formed from sodium carbonate and lead acetate) [38].

4.2.3 Sensitivity

The sensitivity of lead azide depends on its crystalline form. Experimental values of
the sensitivities of a, b, and g-forms published by Wyatt are summarized in
Table 4.2. The g modification of LA is more sensitive to impact but less sensitive
to friction than the a and b forms. The electrostatic discharge sensitivity is about the
same for all three polymorphs according to the author. The difference between
1.2 mJ and 2.0 mJ was claimed to be not too significant. On the other hand, the
sensitivity of the g-form to mechanical stimuli and electrostatic discharge is
reported not to be significantly higher than that of the a and b forms according to
Taylor and Thomas [18].
Table 4.3 shows that the addition of both b- and g-LA to the service LA
increases its sensitivity to friction and impact. It was further reported that crystal
size does not influence sensitivity of a-LA [19].
The a-form of lead azide is less sensitive to impact than MF and approaches
PETN (see Fig. 2.15). Sensitivity to friction is reported lower than for MF by some
authors [3, 4, 21, 39] and higher by others [5, 40]. This inconsistency in published
results is most likely due to a different crystal form of samples tested [34].
According to our own results (see Fig. 2.19) is LA significantly more sensitive to
friction than MF and its sensitivity exceeds other commonly used primary
explosives (e.g., LS, GNGT, DDNP). The sensitivity of pure LA and dextrinated
one is about the same [41, 42]. The sensitivity of LA to mechanical stimuli is
generally influenced by several factors: by its method of preparation, by crystal size
78 4 Azides

(see Fig. 2.16), and by the presence of side products with particles softer than LA
(e.g., basic lead carbonate decreases its sensitivity) [4, 21]. The presence of water
does not decrease its sensitivity as significantly as it does in the case of MF [6].
Other authors even report the sensitivity for wet and dry LA to be the same [17].
The sensitivity to mechanical stimuli may be diminished, just as with MF, by
addition of desensitizing substances such as paraffin, glycerin, or oils [21].
Dextrinated lead azide is generally considered less sensitive to mechanical stimuli
than pure LA [31]. Mixtures with harder particles (e.g., glass) are significantly more
sensitive than LA [4].
An interesting finding was published by Clark et al. They observed that a
mixture of LA with tetryl is more sensitive to impact (maximum at about 10 %
content of LA) than pure LA even though tetryl crystals are considerably softer than
crystals of LA. A reasonable explanation of this phenomenon is a chemical reaction
between LA and tetryl. Tetryl decomposes to picric acid, which happens readily on
heating or impact. The picric acid so formed further reacts with lead azide to
produce a minute amount of highly sensitive lead picrate. However, no accident
as a consequence of this reaction was observed [43].
LA has relatively low sensitivity to flame which is one of its biggest drawbacks.
This low sensitivity is further lowered by formation of basic lead carbonate on its
surface. This layer of carbonate isolates LA and makes the initiation by flame
difficult, and as mentioned earlier, the formation of carbonate is favored in a humid
and CO2-rich atmosphere (e.g., in mines). In order to introduce and maintain good
ignitability by flame, LA is mixed with some other primary explosive sensitive to
flame (particularly lead salts of di- or trinitroresorcine).
LA also shows very low sensitivity to stab initiation. This problem is usually
solved by adding harder particles or tetrazene to the mixture.

4.2.4 Explosive Properties

Lead azide explosively decomposes to nitrogen and metallic lead. The volume of
gaseous products is only 231 dm3 kg
1 [3]. Dependence of detonation velocity on
density is shown in Fig. 2.1. Danilov et al. [3] published equation for determination
of detonation velocity of LA in dependence on its density:

and detonation pressure:

The detonation velocity, D0, of LA is 3,880 m s
1 at density 2 g cm
3 and it is

slightly higher than for SA (3,830 m s
1 at the same density) [3]. Lead azide easily
detonates in thin layers with high detonation velocity. The detonation velocity for
4.2 Lead Azide 79

Table 4.4 Properties of pure, dextrinated and gelatined (G.A.M) LA [44]

Pure LA Dextrinated LA G.A.M
Bulk density (g cm
3) 1.6–1.8 2.1–2.3 1.3–1.5
Particle size (mm) – 60–100 200–400
Detonation velocity (m s
1)a 4,550 3,850 3,750
Ignition efficiency to PETN (g)a 0.02 0.03 0.04
Ignition efficiency to RDX (g)a 0.04 0.06 0.07
a
Measured in 6 mm copper tube; pressed at the same pressure.

0.45-mm-thick sheet is 5,500 m s
1 [26]. The dependence of LA’s detonation

velocity on thickness is shown in Fig. 2.11. The detonation velocity in slim line
diameters (10–200 mm) was recently measured by Jung [22]. He observed acceler-
ative reaction of LA after ignition (depends on sample diameter) before reaching
steady detonation velocity. The steady detonation velocity was in the range of
2,670–3,440 m s
1 for diameters from 50 to 200 mm.
Initiation efficiency of LA is significantly higher than that of MF. Unlike
mercury fulminate, LA belongs to the group of primary explosives with a short
predetonation zone, so-called detonants—substances with a fast deflagration to
detonation transition with respect to other primary explosives. This is reflected in
its high initiating efficiency compared to MF. The method of LA preparation, its
composition, density, confinement, physical dimensions—all influence initiation
efficiency. Even the presence of a crystal structure modifier during LA preparation
has an impact on initiation efficiency. The efficiency of pure LA is superior to LA
prepared in presence of a colloid agent. According to Lamnevik, approximately
twice the amount of dextrinated LA must be used compared to pure LA to get the
same output from a secondary explosive in a detonator [31]. Gelatin was one of the
modifying agents tested in the 1960s and at first it was regarded as less favorable
than dextrin. Later it was found that electrostatic sensitivity was excellent but
cohesion was poor. This was overcome by addition of a small amount of molybde-
num disulfide. LA precipitated in presence of gelatin and molybdenum disulfide is
known as G.A.M. Although it had excellent electrostatic and friction sensitivity its
flowability was not as good as that of dextrinated LA and was influenced by gelatin
type [44]. The comparison of initiation efficiency of pure LA with azide prepared in
presence of a colloid agent is presented in Table 4.4.
In practice, the quantity of LA used in detonators is generally several times
higher than the minimum amount required to cause detonation of the secondary
explosive. This ensures satisfactory performance for a number of years [44].
The brisance and initiating efficiency of LA enclosed in standard detonators is not
significantly affected by decomposition of LA following the reaction with water and
carbon dioxide in the air during long-term storage. In the cases when there appears
risk of function loss, the humidity inside the detonator should be checked. Aging of
detonators was investigated by Lamnevik who found that detonators which failed
after more than 20 years of storage functioned properly after being dried [31].
The power of LA (measured by Trauzl block) is relatively low, 36.7 % TNT [40]
or 39 % TNT [45], which is lower than for MF [46–48].
Lead azide is a primary explosive with exceptionally high thermal stability.
The ignition temperature of LA is relatively high, 330  C at a heating rate of
80 4 Azides

pure LA
4

Temperature difference (°C)

3
dextrinated LA

50 100 150 200 250 300 350 400 450

Temperature (°C)

Fig. 4.2 Graph DTA thermogram of pure and dextrinated a-LA showing exceptional thermal
stability of the dextrinated product (heating 5  C min
1, 5 mg samples, static air atmosphere, open
test tube)

5  C min
1 (LA type RD 1333) [35]; 357–384  C at a heating rate of 40  C min
1

[43]. The 5-s explosion temperature of LA is 340  C [49]. LA has been found not to
have changed after being stored for 4 years at 80  C. The thermal stability threshold
is, according to Danilov, 200  C at which temperature it keeps its explosive
properties for 6 h. It is therefore used in thermostable detonators TED-200 with
maximum application temperature 200  C [3]. We have tested various types of lead
azides at our laboratory and found that standard industrial dextrinated LA (product
of Austin Detonator) is surprisingly even more thermally stable than pure crystal-
line product. The decomposition of both types (pure and dextrinated) of LA under
the same conditions is shown in Fig. 4.2.
LA also does not lose brisance at low temperatures [50] and can be used as
an initiating substance at temperatures as low as the boiling point of oxygen
(
183  C) [3].
As opposed to mercury fulminate, pure LA cannot be dead-pressed in normal
circumstances (even by a pressure of 200 MPa). However, LA prepared in presence
of a crystal structure modifier (dextrin, carboxymethyl cellulose, and others) or
desensitized (e.g., paraffin) can be dead-pressed; dextrinated LA cannot be dead-
pressed below 118 MPa and paraffined below 78 MPa [3].

4.2.5 Preparation

The first preparation of LA, by Curtius, was based on addition of lead acetate to a
solution of sodium or ammonium azide [51]. This has not changed and, even today,
4.2 Lead Azide 81

Fig. 4.3 Comparison of lead azide prepared with the colloid agents—dextrin and PVA

preparation of lead azide is based on the reaction of sodium azide and lead nitrate or
acetate followed by precipitation of the insoluble lead azide:

A summary of published LA preparation methods before the 1930s is presented

in Audrieth’s review [11]. Preparation and technology of LA production is
described in many books that deal with explosives in detail [3, 5, 8, 15, 21, 30, 46].

The pure a-form of LA can be grown from a solution of LA in ammonium

acetate or acetic acid [7]. In the early years, the main problem in the manufacture of
LA using the above reaction was the formation of a very sensitive product—desired
a-LA mixed with other forms. Re-crystallization was industrially unacceptable and
this problem was therefore solved by addition of a colloid, fast agitation, and use of
diluted solutions. The colloid agent is added to the reaction mixture to prevent
growth of large crystals and to support formation of the a-form with suitable shape
and size. With the colloid present, crystals of LA form agglomerates (consisting of
small crystals Fig. 4.3) with better flowability than the pure crystalline form
(compare with Fig. 4.1). Furthermore, the colloid decreases the sensitivity of the
LA product. The first colloids used in this application were gelatin and dextrin [5,
44, 52]. Some other tested surface active agents include polyvinyl alcohol and the
sodium salt of carboxymethylcellulose [8].
Dextrin does not cover the formed crystals but is rather entrapped inside. The
dependency of the amount of dextrin inside the crystals of LA on the concentration
of the dextrin in the solution is shown in Fig. 4.4.
It is evident that the absorption of colloid at first increases rapidly with the
concentration in the reacting solution, but less and less rapidly as the concentration
rises. The curve for 60  C becomes almost level more rapidly than the others and tends
to reach much lower limiting absorption. The data for 20  C show that when the acidity
of the dextrin was not neutralized, the limit of absorption was more readily reached.
At 60  C the influence of this acidity was found to be very small [16]. When
dextrin is added to already developed crystals it adsorbs on the surface. The amount
82 4 Azides

10

8
Colloid in crystal (%)

4
neutralized dextrin at 20°C
3 ordinary dextrin 20°C
neutralized dextrin at 60°C
2
0 1 2 3 4 5 6 7
Colloid in solution (g/100 cm3)

Fig. 4.4 Absorption of dextrin by crystals of LA [16]

adsorbed on the crystal surface in the solution with concentrations in range from 0.2
to 2.17 % was from 0.151 to 0.174 % calculated on the weight of azide [16].
The type of agitator, concentration, pH, and order of adding the reactants all have a
significant influence on the size and shape of LA crystals and their composition. Sodium
azide and lead nitrate aqueous solutions used for preparation in today’s technologies are
considerably diluted and the reaction mixture is intensively stirred during reaction. The
reason for this is to prevent the formation of large sensitive crystals that form from
saturated solutions when using slow diffusion of both reaction agents. Spontaneous
explosions of reaction mixtures occur under these conditions (see Sect. 2.6).
In the 1960s, production of a spheroidal form of the dextrinated azide was
developed [8, 53]. The technology is not covered here as it is described in great
detail in the easily obtainable literature [6, 8, 21, 46].
The order of adding of reactants is an important factor. Even though simulta-
neous addition exists [8], a solution of sodium azide is most often added to a
solution of lead nitrate (in discontinuous technology) [3, 5, 6, 8, 21, 30, 50]. The
main reason for this order is to eliminate potential hydrolysis in aqueous sodium
azide and the formation of basic lead azide (basic reaction of sodium azide) which
would occur if the order of adding were reversed (Valenta Private Communication).
The product formed by addition of aqueous sodium azide into a solution of lead salt
is easy crumbled into a free flowing powder. If the order of reactant mixing is
reversed, a hard and scarcely pulverizable product forms. The process of grinding
of such product is dangerous and therefore its formation is undesirable [50].
The a-form (Fig. 4.5) is the only one that is really acceptable in any
manufactured product. However, the b, g, and d forms are also sometimes created
if the manufacturing process is not carried out in a correct and consistent manner.
Their presence in the product is not acceptable as it increases the overall sensitivity.
In industrial production each batch is checked and if it contains any of these other
modifications the whole batch is destroyed [3].
4.2 Lead Azide 83

Fig. 4.5 Agglomerates of the dextrinated a-form of lead azide prepared by batch process (left)
and the same prepared without addition of crystal structure modifier (right) (by kind permission of
Pavel Valenta, Austin Detonator)

water

crystallization of β-form
of lead azide

solution of lead nitrate

solution of sodium azide

Fig. 4.6 Method for preparing b-form of lead azide [46]

The b-form is not a desirable commercial product as it increases the sensitivity

of the final product but, if needed, it may be prepared by so-called diffusion method
[46]. In this method, a small beaker filled to about one half with a 10 % solution of
sodium azide is placed into a bigger beaker. The space between the smaller beaker
and the larger one is filled with 5 % solution of lead nitrate to the level of sodium
azide in the smaller beaker. Both beakers are then carefully filled with water up to
the level where the smaller beaker is completely immersed under the water surface.
In a few hours, crystals form on the edges of the smaller beaker (Fig. 4.6) and after
15–20 h the beaker fills up with nice long crystals of the b-form of lead azide.
It is also possible to fill both beakers with pure water to the level when the
smaller one is completely immersed. Then, using a funnel, a few crystals of sodium
azide are dropped into the smaller one and a few crystals of lead nitrate into the
bigger one. The salts dissolve, diffuse, and needles of the b-form of lead azide
appear [46]. Another method uses a big dish into which two small beakers are
placed and one is filled with sodium azide and the other with lead nitrate. The big
dish is then carefully filled with water in such a way that the two solutions do not
84 4 Azides

Fig. 4.7 Needles of the

b-form of lead azide prepared
by the diffusion process
captured by optical
microscopy

mix. The crystals of the b-form of lead azide form between the beakers [13].
Figure 4.7 shows the needle crystals formed by the diffusion process. Evans reports
another way of preparing the b-form of lead azide by a different type of diffusion
process, in which azide and nitrate solutions are separated by sodium nitrate. Haze
forms in the nitrate layer close to the original azide boundary just before crystals of
b-LA begin to grow out from the walls of the container into the solution [7].
Another method for preparing the b-form is based on the reaction of lead nitrate
and sodium azide, at room temperature and in the presence of organic dyes. When
solutions of lead nitrate (20 %) and of sodium azide were run continuously into
water at 20  C only a-LA was observed, but if even as little as 0.02 % of eosin or
other organic dye is present in the reaction mixture, the b-form appears. The
crystals are best handled as single specimens as they are sensitive; breaking one
will set off the whole batch [16].
The g and d forms form together by precipitation from an unstirred diluted
aqueous solution of sodium azide and lead nitrate in presence of nitric acid (in
molar ratio 2:2:1) at room temperature. The reaction mixture is admixed and
swirled once after mixing of the nitric acid and lead nitrate with solution of sodium
azide. Both forms appear after 3 days in an unstirred mixture; the crystals need to be
collected and separated by hand [15].
The pure g-form of lead azide may be prepared by simultaneous slow addition of
solutions of sodium azide and lead acetate into a stirred solution of PVA containing
a small amount of sodium azide at a temperature not exceeding 15  C. The
temperature must be kept low as with temperatures above 25  C mainly a-LA
forms. The g-LA may also be prepared by action of hydrazoic acid on a lead acetate
solution containing 0.2 % of PVA. The final product may be recrystallized from
ammonium acetate to give crystals of better quality. The g-form may also be
prepared from a- or b-LA by recrystallization from a 5 % aqueous solution of
ammonium acetate containing PVA. The solution is left standing at temperatures
below 40  C. The preparation of the g-form of LA without the use of additives
requires employment of a buffer of hydrazoic acid/sodium azide at pH 3.0–5.0 [19].
4.2 Lead Azide 85

Table 4.5 Time to explosion for LA dissolved in 5 % aqueous ammonium acetate at 70  C and
allowed to cool down to room temperature without disturbance [18, 54]
Concentration of LA (%)
1.0 0.9 0.8 0.7 0.6 0.5 0.4
Time to explosion 40 75 80 210 225 7 explosions out of 0 explosions out of
(min) 50 65 85 220 255 10 experiments 4 experiments in
in 18 h 4 days

4.2.6 Spontaneous Explosions During Crystal Growth

Spontaneous explosions of LA occur without apparent reason during the course of

its crystallization. This phenomenon is known but not very well understood. These
explosions are not exclusive to azides of lead but have been observed also in the
case of cadmium, cupric, and mercuric [15]. In the case of lead azide, it has been
frequently attributed to the formation of b-lead azide or the growth of large crystals
to a point where internal stresses become important [12, 18, 34]. Both of these
theories have little or no experimental support [18].
The experimental results show conclusively that the suppression of spontaneous
explosion during crystallization by metathesis from solutions of soluble lead salt
(usually lead acetate or nitrate) and soluble azide (usually sodium azide) is obtained
by (a) rapid and thorough mixing of the solutions and (b) the use of certain additives
especially hydrophilic colloids (PVA, dextrin, eosin). Amounts as small as 0.02 %
of PVA completely suppressed spontaneous explosions [18].
It has been further shown that explosions still occur when lead nitrate is replaced
by lead acetate and sodium azide with calcium azide [12]. The explosions are
reported to occur at room temperature as well as at 0  C and 60  C [12].
With the reduction of mixing efficiency during crystallization by metathesis the
probability of explosion increases. When mixing was reduced until the solutions
merely diffused as is usual in the method for preparation of the b-form (!), the
incidence of explosions increased greatly—up to a 50 % probability [18].
The most reliable way to produce explosions of LA is recrystallization from
ammonium acetate. A reasonable explosion control time is possible by carefully
controlling the concentration, temperature, and conditions of cooling. Table 4.5
gives results of a series of experiments with times to explosion from concentrations
from 0.6 to 1.0 % LA. The frequency of explosions decreases below 0.6% and falls
to nil at 0.4 %. An interesting observation was made that intact crystals of LA could
be found after the vessel had been shattered by an explosion [18].
An experiment has been reported where a solution of 0.7 % LA was made in
exactly the same way as is reported in Table 4.5 and allowed to cool down from
70  C. After approximately 190 min (220 min was the expected time of explosion!)
a number of large crystals had formed and these were filtered off and separated from
the mother liquor. Thirty minutes later the mother liquor, still free of crystals,
exploded shattering the vessel. The separated crystals remained intact. This leads to
86 4 Azides

the conclusion that spontaneous explosions in LA crystallization originate from the

mother liquor and not from the crystals already formed [18].
The capability of the LA/ammonium acetate solution to propagate explosions
was tested. It proved unable to propagate explosions in a variety of conditions [18].
Aqueous ammonium acetate is recommended as the solvent for preparing large
crystals of LA (a-form, size 0.5–1 cm) for further studies. The growing solution
must have a near neutral pH. This prevents the formation of basic salts of LA (at
higher pH) or high concentrations of azoimide (at low pH). Ammonium acetate is a
suitable solvent since the hydrolysis products (acetic acid and ammonium hydroxide)
have equal dissociation constants and therefore buffer the solution at a neutral pH
value. LA is dissolved in a hot solution of ammonium acetate (70  C) and very slowly
cooled (e.g., 0.5  C per day). LA slowly crystallized from the solution and it was
isolated by filtration when the temperature reached 40  C. If the cooling continues
below 35–40  C, explosions occur! The collection of LA crystals is a critical step. If
the growing solution is not immediately washed from the crystals’ surfaces it will
saturate by evaporation and cause spontaneous explosion. The remaining LA
dissolved in the solution must be destroyed, e.g., by ceric solution. The second method
of preparing large crystals of LA is based on the reaction of stoichiometric
concentrations of ammonium azide and lead acetate to give LA solution in aqueous
ammonium acetate. The details are in the literature [55, 56].

4.2.7 Uses

Lead azide is today one of the most widely produced primary explosives. It has
almost completely replaced mercury fulminate in some of that product’s former
applications, primarily in detonators (a summary of published patents up to the
1930s is presented in Audrieth’s review [11]) due to its high initiation efficiency
and extremely short predetonation zone in normal conditions. High initiating
efficiency, high density, low cost, reasonably good stability, ability to withstand
high pressures without becoming dead pressed, and long-term experience are the
main reasons for its extensive application as a charge for detonating secondary
explosive in flash, stab, electric, and other types of detonators.
Lead azide is used in many applications accompanied by other substances that
compensate for its drawbacks, particularly its low sensitivity to flame and stab. The
most common additive in detonators is lead styphnate which improves the inflam-
mability of resulting mixture. A typical composition of this binary mixture is 30 %
LS and 70 % LA. It is sometimes presented that lead styphnate can serve as a
protective layer against access of water and carbon dioxide to LA surface [3, 4].
However, lead styphnate increases the level of acidity and accelerates the rate of
hydrolysis of LA in presence of moisture [35, 49]. Regardless of this fact a
combination of LA/LS is still used in detonators.
4.3 Other Substances Derived from Lead Azide 87

Probably, the most commonly known LA/LS mixture for detonators is the ASA
composition. It contains 68 % dextrinated LA, 29 % LS, and 3 % aluminum. The
small amount of aluminum was added to overcome the tendency of the LA/LS
mixture to build up on the punches during pressing. On the other hand, aluminum
unfortunately has a sensitizing effect on the composition. The possible problems
with this mixture caused by static discharge between the leading wires and the tube
of electric detonators have been discussed in detail by Medlock and Leslie [44].
These problems led to a number of accidents in the past [44]. The ASA mixture has
been subsequently discontinued.
A single step method of preparing an LA and LS mixture by precipitation of the
two salts together in one solution has been reported by Herz [57, 58]. In this
method, a solution of sodium azide and a soluble styphnate salt (e.g., magnesium)
is allowed to slowly flow into the solution of lead nitrate. This mixture, however,
also suffers from the above-mentioned incompatibility [35].
LA is further not very sensitive to stab initiation. In compacted form it requires
an initiation energy as high as 1 J. However, addition of only 2 % of GNGT lowers
the required initiation energy to 3 mJ [59].
Despite all its strengths and manageable weaknesses, its toxicity, caused by the
presence of lead, resulted in the search for nontoxic primary explosives which could
fully replace LA.

4.3 Other Substances Derived from Lead Azide

There exists a variety of other substances which are formed from lead, azide, and
other ions. Such substances mostly do not have sufficient explosive properties to be
considered as initiating explosives but may form in the process of production or
aging of normal lead azide.

4.3.1 Basic Lead Azide

Basic lead azides were in the early days believed to have varying content of (OH)

groups. The monobasic lead azide was sometimes abbreviated by the formula
PbN3(OH) [15, 19] and other times as Pb(N3)2·PbO [60]. Todd and Tasker [61]
have carried out X-ray diffraction analysis and infrared analysis of gamma modification
of basic LA and concluded that the product is oxyazide containing neither
hydroxide nor water of crystallization. Other reported forms include: 3Pb(N3)2·5PbO,
Pb(N3)2·2PbO to Pb(N3)2·3PbO, 2Pb(N3)2·7Pb(OH)2, Pb(N3)2·4PbO to Pb(N3)2·9PbO
[5]. Fourteen types of basic lead azides are reported by Todd and Tasker [61], and
twelve by Sinha [62].
Basic LA sometimes appears in service lead azide in trace amounts [19]. This
substance may be prepared by recrystallization of a-LA from a 5 % ammonium
acetate solution containing free ammonia to a pH of 8.7. The product takes the form
88 4 Azides

of well-formed white crystals on pellets of a-LA [19]. A pure form of basic lead
azide—Pb(N3)2·PbO may be prepared by the following methods:
1. Bubbling of carbon dioxide-free air through a boiling suspension of lead azide in
water until the calculated amount of azoimide is evolved [24]
2. Heating an aqueous suspension of Pb(N3)2 and Pb(OH)2 in molar ratio 1:1 in a
sealed tube at 140  C for 12–15 h [24]
3. Heating the desired amounts of Pb(N3)2 and Pb(OH)2 on a water bath for 20 h [24]
During slow cooling of the tube, the second method tends to give long needle
crystals which tend to detonate. W€ ohler recommended the third method as the most
suitable one (out of the first three) [24].
Reacting stoichiometric quantities of lead nitrate solution with mixed
solution of sodium azide/sodium hydroxide (molar ratio 2:1) at 35  C leads to
pure 3Pb(N3)2·2PbO [63]. Varying molar ratio and acidity of the reaction mixture
lead to 12 different types of basic LA. It was observed that only one type of basic
LA forms, if mixture of sodium azide and sodium hydroxide is added to the solution
of lead nitrate. The opposite way of reactants mixing leads to formation of mixture
of basic azides. It indicates that in neutral or acidic reaction mixture only one type
of compound forms while from basic medium mixture of azides emerge [62].
Basic lead azide—3Pb(N3)2·2PbO—is much less sensitive to mechanical stimuli
than LA but it keeps relatively acceptable explosive properties. It explodes vio-
lently when heated, with an explosion temperature of 350  C at heating rate
5  C min
1. Basic lead azide is not attacked by moisture like LA at 30  C and
90 % humidity during 3 months. Ignition efficiency is 0.07 g for tetryl, and bulk
density 1.177 g cm
3 or 1.25 g cm
3 if prepared in presence of 0.02 % of
carboxymethyl cellulose. Sinha et al. suggested basic lead azide as an LA replace-
ment despite its lower initiating efficiency [63]. Agrawal [64] reported identical
explosion temperature and initiation efficiency; however, deviates from the report
of Sinha et al. [63] in bulk density by reporting 2.00  0.2 g cm
3.
Substances analogous to basic lead azide having the assumed OH
group
replaced with a halogen have also been reported. One example of such substance
is PbN3Cl which may be prepared from lead nitrate and azide/chloride mixtures.
This substance has inferior explosive properties compared to normal lead azide.

4.3.2 Lead (IV) Azide

The compound that would correspond to the overall formula Pb(N3)4 is not stable.
Attempts to prepare it from PbO2 and hydrazoic acid in an aqueous medium failed, as
the resulting red solution or dark red needles quickly decomposed to yield LA and
nitrogen [15]. Different lead azides form when using Pb3O4 and aqueous HN3. The
yellow to red solution contains compounds with overall formula PbN9 to almost PbN12
based on the reaction conditions. These aqueous solutions are unstable and decompose
evolving nitrogen and LA [5].
4.4 Silver Azide 89

Fig. 4.8 Silver azide

prepared by diffusion process

4.4 Silver Azide

AgN3

Silver azide (SA) was first prepared by Curtius in 1890 by passing azoimide into a
silver nitrate solution [1].

4.4.1 Physical and Chemical Properties

Silver azide forms a white crystalline compound presented in Fig. 4.8. It forms
orthorhombic crystals with reported crystal density 4.81 g cm
3 [5, 21] or
5.1 g cm
3 [3, 5, 14, 40, 45]. Heat of formation of SA is 311 kJ mol
1 [27].
Silver azide is nonhygroscopic [8, 65] and its chemical properties are similar to
silver chloride; silver azide is practically insoluble in water (0.765 mg/100 g at
25  C) and common organic solvents; soluble in pyridine and ammonia with which
it forms complexes [1, 8, 15, 65–67]. Pure silver azide may be precipitated back
from its solution in the form of orthorhombic crystals [5, 8]. Recrystallization of
silver azide from its aqueous ammonia solution, by evaporation while standing,
yields needles up to 20 mm long and 0.3 mm thick. This needle form of SA is
reported to be extremely sensitive and with a tendency to explode by breaking even
under water [2, 6, 15, 68]. Solonina (cited by Bagal), however, reported that these
crystals do not explode when broken or even cut by a steel knife. He further
reported an accident during which a bottle with SA needles fell to the floor, all
crystals broke, the glass bottle shattered, but no explosion occurred [46].
Unlike lead azide SA does not react with water in presence of carbon dioxide [6, 69]
or, more precisely, it yields very low partial pressure of azoimide, too low for formation
of copper azides in applications with copper or brass [70].
90 4 Azides

Silver azide is often reported as being compatible with most usual metals, even
though it reacts with the two most common ones—copper and aluminum. Taylor
does not mention aluminum and reports that among common metals only copper
reacts under moist conditions [71]. Blay and Rapley reported that copper azides
form when SA comes into contact with copper in moist conditions [36]. They
further reported that SA reacts with aluminum as well. The corrosion of aluminum
is quite fast but requires water in liquid phase in direct contact with both SA and
aluminum. This is not the situation that would normally be found inside a detonator
and, if it were the case, then the presence of liquid water would cause the detonator
to fail for other reasons than corrosion. A humid environment itself is not sufficient
to cause any significant degree of reaction and the use of SA in aluminum
detonators has not presented a problem [36]. The decomposition products of SA
are not hazardous substances and mainly contain metallic silver [36].
The incompatibility of SA with sulfur or its compounds (e.g., Sb2S3 present in
many stab priming mixtures) leading to a silver sulfide [72] is a well known and
often mentioned issue [3, 36, 73, 74]. SA slowly decomposes when it is in contact
with some plastics and rubbers (possibly due to sulfur content). Silver azide is
compatible with common explosives such as HMX, RDX, or the lead salt of
dinitroresorcine [36]. According to Bates and Jenkins, it is incompatible with
GNGT [74], which is supported by findings of Blay and Rapley, who reported
that explosions may occur during storage of SA/GNGT mixtures [36]. SA, unlike
silver chloride, dissolves in nitric acid with decomposition and evolution of
azoimide [6, 15]. Suspensions of silver azide decompose in boiling water in a
similar way to that during photodecomposition [15].
It is more difficult to decompose SA chemically than LA for two reasons. First, it
is more resistant to hydrolysis and secondly the reaction with sodium nitrite
solution results in soluble silver salt which gives a flocculent yellow precipitate
of silver nitrite which is insoluble in the reaction mixture. It is therefore
recommended to use nitric acid for acidifying the solution rather than acetic acid
as used in the destruction of LA. Nitric acid first reacts with SA yielding silver
nitrite which then dissolves in the excess of nitric acid. The rate of nitric acid
addition must be carefully controlled. It is important not to add the acid too quickly
as that would result in reaction with unreacted SA and liberation of azoimide [71].
Silver azide is photosensitive (but much less than a halogen silver salt [75]); it
turns violet at first and finally black, as colloidal silver is formed on exposure to
light (and nitrogen is released) [7, 76]. The photolysis takes place only on the
crystal surface and the material does not lose its explosive properties [6, 8, 15, 77,
78]. Photodecomposition is faster than in the case of LA and is quite rapid when SA
is irradiated by ultraviolet light [22] and, if sufficiently intense, it may cause
initiation. The critical light absorption for initiation of a crystal of silver azide
corresponds to a total energy input of 0.19 mJ into each square millimeter of the
crystal [77]. The initiation of decomposition is photochemical and the growth to
explosion is thermal. The mechanism of the decomposition has been suggested by
4.4 Silver Azide 91

Evans and Yoffe [7, 76, 79]. The complete equation of SA decomposition is given
by the following equation:

Yoffe published a different value of reaction heat for the above-mentioned equa-
tion, 568 kJ [28]. Earlier papers described the photochemical mechanism of initiation
as thermal, meaning that light absorbed by the thin surface layer of the crystal is
converted to heat, and very quickly (less than 1/50 ms) results in ignition [7, 30, 77].
Silver azide is exceptionally thermally stable exceeding the stability of other
common primary explosives. Unlike most of them, silver azide melts when heated.
By heating a small amount of silver azide it first begins to turn slightly violet at
about 150  C, the color increasing somewhat in intensity until, at a temperature
somewhat above 250  C, the compound melts giving a blackish looking liquid
which begins to liberate gas or vapor at about 254  C. It decomposes rapidly above
melting point to silver and nitrogen gas—so quickly that it looks as if the liquid is
boiling [65, 76, 80]. Yoffe reported that the explosion temperature depended on
ambient pressure, the mass of SA, and the thermal conductivity of the vessel. SA
does not explode even at 400  C if it is heated in a vacuum but it explodes at 340  C
in a nitrogen atmosphere at 26.7 kPa with a white flash [28].
Temperature of ignition highly depends on heating rate and on the testing
methodology. Millar [81] reported it as 390  C (by STANAG) but onset of
decomposition on DSC thermogram is 303  C (heating rate 10  C min
1). Taylor
and Rinkenbach [82] reported 273  C (hot iron dish method, which determines the
temperature at which material explodes instantaneously or within 1 s); Hitch gave
300–301  C [80], and W€ ohler and Martin 297  C (explosion within 5 s) [83]. The
rate of decomposition of SA depends not only on sample purity, sample size, or
heating rate, but on the sample history as well. Particularly whether or not SA has
been exposed to light, because metallic silver nuclei are believed to influence the
rate of decomposition [81].
Ionizing radiations generally decompose azides without explosion, which how-
ever may occur if the intensity is high enough owing to the crystals heating up
during decomposition by irradiation [79].

4.4.2 Sensitivity

Sensitivity of silver azide to impact is several times lower than that of mercury
fulminate. Comparison with lead azide is reported a little bit higher than LA by some
authors [45] (Bureau of Mines) [82], same as LA [45] (Picatinny Arsenal Apparatus),
or lower than LA by others [21, 81] (see Fig. 2.15). The sensitivity of SA highly
depends on crystal size and shape. Colloidal silver azide prepared from concentrated
solutions exhibits significantly lower sensitivity (0.5 kg from 77.7 cm) than coarser
crystals prepared from diluted solutions which required less than half the energy (0.5 kg
92 4 Azides

Table 4.6 The sensitivity of SA to mechanical stimuli [81]

Impact sensitivity Friction sensitivity Sensitivity to ESD
Ball and Disc test Rotter test Emergency paper friction test Advanced test no. 7
Compound (h50, cm) (F of I) 50 % prob. (m s
1) (mJ)
a
SA 47.4 30 2.6 0.21 ign., 0.118 not
LAb 19 29 1.2 2.5
a
RD 1374, producer BAE system.
b
RD 1343, precipitated from sodium carboxymethylcellulose/sodium hydroxide.

from 28.5 cm) [65]. Values for impact sensitivity of SA (commercial product) deter-
mined by Millar are summarized in Table 4.6 in comparison with values for LA.
Silver azide is generally considered to be highly sensitive to friction and much
more than other common primary explosives including LA [21, 84] and, just as with
impact, friction sensitivity depends considerably on its crystalline form [65]. The
values reported by Millar [81] for two specific kinds of LA (RD 1343) and SA (RD
1374) are presented in Table 4.6. It follows from the results that the sensitivity of at
least some commercially produced SA is lower than that of LA. Sensitivity of SA to
electrical discharge is higher than that of LA (Table 4.6), while sensitivity to flame
is about the same as that of mercury fulminate [6, 21].

4.4.3 Explosive Properties

Silver azide has a very small critical diameter. Needles of SA having a diameter of
25 mm still explode. Rapid combustion (about 7 m s
1) was observed when the
diameter was decreased to approx. 10 mm [85]. The values of detonation velocity
usually range from about 1,000 m s
1 for very thin layers (~0.1 mm thick) to about
5,000 m s
1 for layers with dimensions ensuring ideal detonation [7]. Bowden
published an average detonation velocity of 1,500 m s
1 for 0.5-mm-thick uncon-
fined films (initiated by hot wire) and 1,700 m s
1 for confined product, initiated by
impact [86]. A detonation velocity of 1,500 m s
1 was determined for crystals with
diameter 0.3–0.4 mm and length about 1 cm by Deb (cited as unpublished work in
[76, 87]). Detonation velocity in capillaries and micro-capillaries (10–200 mm) has
been relatively recently measured by Jung [22]. He observed an accelerating
reaction of SA after ignition (depends on sample diameter). Steady detonation
velocity was in the range from 1,880 to 2,400 m s
1 for diameters from 50 to
200 mm. The density of SA was not determined.
Danilov et al. [3] found the detonation velocity of SA to be 3,830 m s
1 at density
2 g cm
3 and 4,400 m s
1 at maximum obtainable density. For the dependence of
detonation velocity on density of SA, they proposed the following equation:

and for detonation pressure:

4.4 Silver Azide 93

Table 4.7 Results of sand Weight of crushed sand (g)

test for SA and MF [65] Charge weight (g)
SA MF
0.05 1.4 0
0.1 3.3 0
0.2 6.8 4.2
0.3 10.4 8.9
0.5 18.9 16.0
0.75 30.0 26.1
1 41.1 37.2

The initiating efficiency is very high; it surpasses mercury fulminate (several

times) and even LA [48, 71, 88] (see Table 2.1). Taylor and Rinkenbach measured
brisance of SA by the sand test [65]. They observed that brisance of SA is not that
much greater than that to be expected for MF. Values for both primary explosives
are summarized in Table 4.7.

The power of SA measured by the Trauzl test is a relatively low 115 cm
3 for
10 g SA (38.3 % TNT, 88 % MF). Volume of gaseous products of detonation is
244 dm3 kg
1 [3, 40, 45]. Silver azide cannot be dead-pressed [3].

4.4.4 Preparation

Preparation of silver azide is based on precipitation of silver azide from a sodium

azide solution after addition of a solution of silver nitrate:

The extremely high friction sensitivity of the crystalline form of SA prohibited

its usefulness in the early days. Taylor and Rinkenbach found that mixing fairly
concentrated solutions of silver nitrate and sodium azide yielded silver azide in a
form of colloidal aggregates. This form of SA is less sensitive than crystals [5, 65].
Another method of decreasing the sensitivity of SA is based on the addition of an
inert absorbent material to the solution of SA. In this way, individual crystals are
separated from each other by the inert material [89]. The presence of some
substances (e.g., cyanamide ion) during precipitation of SA can, however, increase
the decomposition rate and decrease its explosion temperature [90].
A technologically interesting way of preparation of silver azide is based on
mixing a solution of sodium azide with some explosive (MF, tetryl, TNT, picric
acid, etc.) before adding silver nitrate. Silver azide then forms a thin film on the
surface of the added substance [5].
The initiating efficiency of the mixture of MF with approximately 3–5 % of SA
is several times higher than for pure MF and practically the same as for pure SA.
94 4 Azides

350

300
Initiation efficiency (mg) pure MF
250

200

150

100

2.5% silver azide

50
5% silver azide
0
0 50 100 150 200 250 300 350

Processing pressure (kg)

Fig. 4.9 Effect of silver azide addition on initiation efficiency of MF (conditions—tetryl as

acceptor charge, detonator number 6, varying processing pressures) [6]

Figure 4.9 [6] also shows that addition of SA prevents dead pressing of such
mixture in the pressure range concerned. This mixture, prepared by mixing moist
SA with MF, was named Astryl and was used in blasting caps [5, 91, 92].
The mixture described above may raise a question as to why one should not mix
MF with LA which is cheaper and accelerates MF in the same way as silver azide
does. There are two reasons why such a mixture has been rejected. The first one is
the very high sensitivity of LA/MF mixture (higher than SA/MF) and the second
reason is its incompatibility with both aluminum and copper [6].
The main historical obstacle for the practical use of pure silver azide (apart from
its price) was its unsuitable form—unsuitable free flowing properties for volumetric
loading and pressing into detonators. This problem was successfully solved by the
development of a process for production of granular silver azide. An example of
commercially manufactured spherical shaped crystals of silver azide is presented in
Fig. 4.10 [22].
Silver azide prepared by direct reaction of sodium azide and the soluble silver
salt forms as a fine powder with a low bulk density. This is caused by its extremely
low solubility and a tendency to nucleate profusely which results in extensive
nucleations and very small crystals. Several processes have been developed for
preparation of a product with a more suitable crystal structure.
The most commonly known historical technique is based on the simultaneous
addition of sodium azide and silver nitrate solutions to a vigorously stirred solution
of sodium hydroxide. The product obtained, in the form of small granules made of
very small crystals, had good sensitivity but low initiating ability. Larger crystals
were obtained by substituting sodium hydroxide with ammonium hydroxide, which
increased the solubility of SA but created two problems (a) low yield and
(b) dangerous waste (ammoniacal silver solution). Simultaneous addition of nitric
acid to provide a nearly neutral solution solved the two problems and yielded a
4.4 Silver Azide 95

Fig. 4.10 Micrograph of

Sandia produced silver
azide [22]. Image courtesy of
Sandia Corporation

product commonly known as RD 1336 [71]. This product forms as a free-flowing

irregular aggregate approximately 0.1 mm in size (individual crystals in aggregates are
approximately 0.02 mm in size) and has a bulk density about 1 g cm
3 [71, 93, 94].
The possibility of neutralization of ammonia by carbon dioxide (rather than by nitric
acid) has also been patented [94].
The RD 1336 process leads to a SA with relatively low bulk density. Technologies
leading to a product with not only good flowability but also higher bulk density are
based on the modification of the RD 1336 process. They differ from each other only in
partial technological steps as all of them are based on increasing the solubility of silver
azide in aqueous medium by addition of other complex-forming substances such as
ammonia, pyridine, cyanides, thiosulfates, thiourea, etc. [69, 95].
A method of preparing a reduced sensitivity SA introduced in USA is called the
“Costain” process after Thomas Costain who improved the original procedure for RD
1336 developed in England in the ERDE laboratories shortly after World War II [96]. In
the Costain process, aqueous solutions of silver nitrate and sodium azide are added to
the dilute aqueous ammonia (or an aqueous solution of sodium azide is added to an
aqueous solution of silver nitrate and ammonia). The reaction mixture is then heated
and part of the ammonia is distilled from the solution. When the first silver azide
precipitate appears, a small amount of acid (e.g., acetic acid) is added to induce crystal
seeding and results in profuse nucleation (“shock crystallization”). The distillation of
ammonia then continues and the precipitation of silver azide is total. Costain reported
several improvements for his product, first of all bulk density 1.4 g cm
3 [96]. Hirlinger
and Bichay later reported a further improvement leading to a product with density
1.6 g cm
3 [97] (vs. 1.0 g cm
3 for original ERDE silver azide). Further, concentration
and addition parameters are not as critical as for the ERDE process [96]. Not much has
been published about the Costain process but some details have been published in [98].
Three years after publication of the Costain process in the USA, McGuchan
published a conference paper summarizing areas of primary explosives research at
PERME in UK which included production of improved SA—product RD 1376
[95]. The increased solubility of SA by addition of ammonia was confirmed as a
best option (all other substances performed worse). The neutralization of the
ammoniacal solution of SA was recognized as a major aspect. The type of acid
was found to affect the nucleation process and even weak acids (e.g., acetic acid)
96 4 Azides

were found to cause the nucleation at a rate which was too quick, yielding small
crystals. It was recognized that the process needed to be modified by addition of
crystal modifiers (e.g., carboxymethylcellulose) and controlled rate of product
nucleation. The technical operations such as stirring, temperature regime, rate of
reactant feeding, and method used for ammonia evaporation have a significant
impact on the properties of the final product [8, 69, 95, 96].
One of the oldest but least known methods for obtaining silver azide (unfortu-
nately in the form of nice white needles) is based on addition of a cold saturated
aqueous solution of silver nitrite to a cold saturated solution of hydrazine sulfate
[46]. A modification of this method (developed in the KHTOSA LTI department in
Lensoveta [3]) uses hydrazine sulfate (or hydrazine), silver nitrate, and sodium
nitrite. Careful adjustment of the reaction conditions can result in an optimized
method giving yields up to 90 % of the theoretical maximum [46, 99].

Some rather unusual situations in which silver azide forms may be found in the
literature. One such case is the formation of SA during electrolysis of solutions of
sodium or ammonium azides with a silver anode [100].

4.4.5 Uses

The only remaining problem preventing wider use of SA was the high cost which
limited the use of pure silver azide only to special applications. The first occurrence
in non-American ammunition is reported from 1945 [45]. Urbański published the
use of silver azide in small and strong detonators in USA, Great Britain, Germany,
and some other countries [8]. In industrial applications, silver azide was used
practically exclusively in the form of a mixture with other substances. The first
reported use of silver azide in detonators for underground mining is from 1932 [92].
Even today, SA is used particularly in small size detonators. For these applications
it is more suitable than LA because of its high brisance, being superior to LA. It is
also used in applications requiring a thermally stable primary explosive [3].

4.5 Copper Azides

Copper forms several azides including cuprous CuN3, cupric Cu(N3)2, and a few
basic azides. The only copper azide that used to have at least some practical
application was cupric azide. Even though the practical application is rather
limited, it is important to understand the formation of various copper azides because
their formation represents significant risk for munitions containing lead azide.
4.5 Copper Azides 97

Fig. 4.11 Amorphous form

of cupric azide

Some of the copper azides are extremely sensitive and may form wherever copper
comes into contact with lead azide in presence of weak acids. Even carbonic acid
forming from moisture and carbon dioxide has the ability to decompose lead azide
liberating azoimide. Copper and its alloys react with liberated azoimide and,
depending on conditions, form various copper azides.
This process may lead to an increase of sensitivity of the original ammunition
resulting in higher manipulation risks. Furthermore, copper azides form many
complex compounds that will not be covered in this monograph.

4.5.1 Physical and Chemical Properties

Cuprous azide CuN3 is a white crystalline solid easily oxidized by atmospheric

oxygen, as a result of which it is usually obtained as a gray-green powder [15]. Heat
of formation is 281 kJ mol
1 [27]. CuN3 is photosensitive and changes color to deep
red with a violet tinge in sunlight while decomposing into copper and nitrogen
[5, 15, 78]. On heating, the surface turns slightly red at 205  C, then black, then
melts to a viscous blob and explodes [76]. It can explode when irradiated with an
intense light flash [76]. Photoconductivity of CuN3 has not been observed [7, 76]. It
is practically insoluble in water and most common organic solvents [5, 15, 21] and
decomposes in acids and bases at higher temperatures [21].
Cupric azide Cu(N3)2 forms a dark black-brown crystalline solid with a red tinge
(Fig. 4.11). The color depends on the way it is prepared [101].
Cupric azide Cu(N3)2 is not reported to be light sensitive [15]. It is slightly soluble
in water, insoluble in most common solvents except those that form complex
compounds [5, 6, 15]. It undergoes hydrolysis in boiling water transforming to CuO
[6, 102]. Cupric azide Cu(N3)2 is decomposed by mineral acids liberating HN3 [46].
Cu(N3)2 is slowly converted to basic cupric azide in the presence of water or after a
98 4 Azides

Table 4.8 Color of various copper azides (unless stated otherwise [15])
Formula Density (g cm
3) DHf (kJ mol
1) Color
Cuprous azide CuN3 3.26 (pycnometer) 281 [27, 103] White
3.34 (X-ray) [104]
Normal cupric azide Cu(N3)2 2.2–2.25 [5] 587 [27] Black-brown
2.58 [105]
Basic cupric azides Cu(N3)2·Cu(OH)2 Yellow-brown
Cu(N3)2·2Cu(OH)2 Yellow-green
Cu(N3)2·3Cu(OH)2 Green
Cu(N3)2·8CuO Blue-green

long exposure to the air [46, 101]. Hydrazine and hydroxylamine reduce Cu(N3)2 to
white CuN3 [102]:

Cupric azide Cu(N3)2 forms several basic salts that are described in Table 4.8
[15]. Basic cupric azides are insoluble in water and undergo hydrolysis above
80  C. They are soluble in acids and bases [5, 15].

The basic cupric azides form in principle by partial hydrolysis of cupric azide or
by partial reaction of azoimide with Cu(OH)2 [15].

It has been stated that copper azide easily forms when copper or brass is in direct
contact with lead azide. Ammunition containing lead azide is therefore tested for
the presence of copper azide using a 30 % solution of ferric chloride (Swedish
copper azide test). A positive test results in the appearance of an intense red color
[70]. A solution of lower concentration—only 1 % was reported to be sufficient—
was further recommended, as it does not attack the tested metal’s surface. It is also
possible to use ammonium hexanitrato cerate (NH4)2Ce(NO3)6 which is a much
more sensitive reagent capable of detection of the “invisible layer” formed in the
early stages of corrosion [106].

4.5.2 Explosive Properties

Cuprous and cupric azides are very sensitive to impact and friction [15, 21, 101,
102]. Sensitivity of cuprous azide CuN3 depends on the crystal size (Fig. 2.17). The
larger crystals of CuN3 (~3 mm) may explode even by the touch of a feather [5].
4.5 Copper Azides 99

Table 4.9 Sensitivity of normal and basic cupric azide to impact in comparison with lead azide
and mercury fulminate
0.5 kg 0.13 kg ball 0.13 kg ball
1 kg (cm) (cm, 50 % prob.) (cm, 50 % prob.) (cm/% prob.)
[5] [46] [49] [107]
CuN3 – 16 10 10/40
12.5/80
Cu(N3)2—crystals 1 9a – –
Cu(N3)2—amorphous 2 – – –
Cu(N3)2·Cu(OH)2 7–8 – 10 10/60; 12.5/78
Cu(N3)2·2Cu(OH)2 – – 70 no fire 70/0
Pb(N3)2 4 – 20 20/50
Hg(CNO)2 – 14 – –
a
Unspecified crystal form.

Table 4.10 Sensitivity of Load (g) Probability of explosion (%)

normal and basic cupric azide
to friction in comparison with CuN3 30 50
lead azide [107] 40 80
Cu(N3)2·Cu(OH)2 120 75
150 100
Cu(N3)2·2Cu(OH)2 60 15
120 60
Pb(N3)2 80 50

Moist Cu(N3)2 cannot be ignited by flame and is rather insensitive to friction and
shock [101]. Unfortunately, discrepancies in the literature exist and other authors
mention high sensitivity even when wet [5]. Cu(N3)2 explodes with a green flame
and red smoke [101].
The sensitivity of normal and basic cupric azides to impact varies significantly.
The impact sensitivity is represented in Table 4.9 showing that cuprous and cupric
azides are more sensitive than LA. Monobasic cupric azide is reported to be more
sensitive than LA according to Kabik and Urman [49] and Lamnevik [107] while
Fedoroff’s encyclopedia reports its sensitivity lower than LA [5]. Basic cupric
azides with two or more bases are less sensitive to impact than LA [107].
The friction sensitivity of various copper azides is often generalized as “very
high.” The values measured by Lamnevik [107] (Table 4.10), however, show that
such generalization cannot be accepted.
From the above data it can be seen that copper azides are not significantly more
sensitive than LA to mechanical stresses with just one exception—cuprous azide.
This, however, does not apply to sensitivity to electrostatic discharge where copper
azides are shown to be in most cases below the lowest possible limit obtainable with
standard apparatus. The estimations of initiation energies by Lamnevik are 1–10 mJ
[107], Holloway obtained 0.1–0.2 mJ for both CuN3 and Cu(N3)2 [108].
The thermal stability of copper azides is not very high. The 5 s explosion
temperature of cuprous azide is around 216  C compared to 340  C for LA [49].
100 4 Azides

Table 4.11 Response of Behavior

copper azides to open
flame [107] CuN3—both forms Detonates
Cu(N3)2 Detonates
Cu(N3)2·Cu(OH)2 Detonates
Cu(N3)2·2Cu(OH)2 Flashes like a black powder
Cu(N3)2·3Cu(OH)2 Burns rapidly
Cu(N3)2·3Cu(OH)2 Burns rapidly
CuxZn1
x(OH)N3 Burns rapidly

Lamnevik reports copper azides as “rather heat sensitive with explosion

temperatures at ca. 180  C” [107]. The response of various copper azides to open
flame is summarized in Table 4.11.

4.5.3 Preparation

CuN3 forms as an intermediate product during the reaction of hydrazoic acid with
copper.

Cuprous azide is further oxidized by atmospheric oxygen to Cu(N3)2 [15, 102] or

Cu(N3)2·Cu(OH)2 [107]. The second stage of the reaction is slow and usually takes
about a month [107].

Turrentine and Moore reported different reaction; the metallic copper reduces
hydrazoic acid and yields cupric azide, ammonium azide, and nitrogen as its
reduction products [109].

The common method for preparing CuN3 is by reaction of a cuprous salt with
sodium azide. Aqueous solution of cupric salt (sulfate) is reduced with potassium
sulfide giving cuprous sulfide as precipitate which is then dissolved by addition of
acetic acid. In the following step, sodium azide is added to the solution,
precipitating CuN3 [78, 107].

Singh published details of the preparation of cuprous azide from cuprous chloride
dissolved in saturated aqueous sodium chloride in presence of a small amount of
potassium bisulfite and acidified by acetic acid. The cuprous azide was precipitated by
addition of aqueous sodium azide [76, 110]. Another way of preparing CuN3 is based
on the reaction of freshly prepared cuprous oxide (from cupric hydroxide and
4.5 Copper Azides 101

hydrazine) with one drop of hydrazine to which solutions of sodium azide and sulfuric
acid are added simultaneously over the period of 30 min [108].

Cupric azide Cu(N3)2 forms by exposing finely ground CuO to hydrazoic acid.
The Cu(N3)2 forms after several days [15, 101, 102, 108].

Cupric Cu(N3)2 azide can be precipitated from a soluble cupric salt and sodium
azide in an aqueous medium [108, 111].

The product of the above reaction is, however, contaminated with a hydrolyzed
surface layer (the product often has a yellow tinge). This layer can be removed by
adding hydrazoic acid and letting the mixture stand for one day. Another possibility
for precipitation of pure cupric azide is using a mixture of hydrazoic acid with sodium
azide (pH 4.5–5.5) on cupric perchlorate. The product forms in the form of clusters of
Cu(N3)2 needles [107]. Hydrolysis may be prevented by carrying out the reaction in a
nonaqueous medium [15]; the dried product must be stored in a desiccator [107].
Cu(N3)2 may be prepared by the reaction of sodium azide with cupric perchlorate in
acetone [112] or by the reaction of cupric nitrate with lithium azide in ethanol [102].

Laboratory preparation of basic cupric azides is based on the reaction of a

soluble copper salt with sodium azide (or hydrazoic acid) in presence of a hydrox-
ide (sodium, barium). The reaction conditions influence the type of basic cupric
azide formed [15, 108].

Lamnevik published details of the preparation of mono, di, and tribasic basic
cupric azides. The monobasic salt was prepared by hydrolysis of cupric azide at
50  C and dibasic cupric azide by hydrolysis of copper diamine azide at 80  C.
Tribasic salts, together with the monobasic form, are prepared by reaction of copper
tetramine perchlorate with sodium azide. The type of resulting product depends on
the reaction conditions [107].
102 4 Azides

100
>32

Partial pressure of azoimide (Pa) >3.87

2.93-32
10

0.44-2.93
1

<0.44

0.1 Cu Cu Cu Cu Cu
N (N (N (N (N
3 3) 3) 3) 3)
2 2 .C 2 .2 2 .3
u( Cu Cu
OH (O (O
)2 H) H)
2 2

Fig. 4.12 Stability ranges of copper azides (from equilibrium measurements at 25  C, the
existence of CuN3 is possible in absence of oxidizing agents) [107]

4.5.4 Undesired Formation of Copper Azides

Lead azide, otherwise a very good primary explosive, has one major drawback,
apart from its toxicity. It reacts with water and forms volatile azoimide (b.p. 35  C)
which may react with copper forming sensitive copper azides. This process is
accelerated by the presence of acidic substances such as carbon dioxide (from the
air) or even lead styphnate, which is often used together with LA [3, 5, 8, 40].
The liberated azoimide attacks copper or its alloys (brass) and copper azides
form on the metal surface. The concurrent use of LA and copper (or brass) in fuses
or blasting caps therefore represents an inherent safety hazard. Although the
LA–copper (copper alloys) reaction has been known since 1913, it has been a
cause of many incidents decades later [49]. These incidents have been sometimes
erroneously reported as spontaneous explosions. The reality, however, is that, in all
known cases, they have been linked to some type of movement and therefore should
not be considered spontaneous [70].
The chemical processes involved in the formation of copper azides may be
summarized by the following set of equations:

The azoimide is the first substance formed from LA in presence of moisture.

It reacts with copper giving cuprous azide—CuN3—which appears as a white
film on the copper surface. The cuprous azide is then oxidized to yellow-brown
4.5 Copper Azides 103

Fig. 4.13 Decomposition of various types of LA over time at 40  C and 95 % RH [113]

Cu(N3)2·Cu(OH)2 (some older reports incorrectly mention oxidation to Cu(N3)2).

Depending on the conditions in the particular system, corrosion may proceed further to
di-, tri-, and octa-basic cupric azides, yellow-green to blue-green in color. The partial
pressure of azoimide is the key factor influencing which azide is formed. The pressure
ranges and corresponding forms of copper azides are graphically summarized
on Fig. 4.12. The presence of light and lack of ventilation accelerate the transformation
of the first formed very sensitive form to the less sensitive ones [49].

While corrosion of the copper surface is usually concentrated in the vicinity of

the source of the LA, diffusion of the azoimide vapor can occur and result in the
formation of the sensitive products at some distance from the LA (for example in
moving parts of fuses).
The corrosion rate of copper and other metals is affected by the following
general conditions [31]:
• Increasing concentration of moisture
• A high degree of metal surface roughness
• A heavy contamination of the metal surface with hygroscopic materials (e.g.,
fingerprints)
• A large number of cold-worked areas
The corrosion of copper by azoimide cannot take place without decomposition
of the LA. Depletion of LA can therefore be used for indirect studies of copper
corrosion. Experiments where copper tubes were held above LA at constant humid-
ity and temperature have shown that different types of LA decompose with different
rates as shown in Fig. 4.13 [113].
Materials not corroded by azoimide, or corroded without formation of explosive
products, include plastics, glass, stainless steel, aluminum, tin, titanium, silver, gold,
zinc, and magnesium. Among these options only aluminum and stainless steel are used
104 4 Azides

in significant amounts in ammunition (for economic and other reasons). Tin, zinc, and
silver are used as a thin (ca. 50 mm) protective layer on brass and copper. Tin and silver
do not react with azoimide and zinc forms zinc oxide. Both tin and silver must be
carefully deposited on the surface in a form with minimal porosity [70].
Nonmetallic protective coatings such as varnishes and lacquers are penetrated by
azoimide in a relatively short time if applied in usual thickness. The only reported
acceptable protective finish is a high molecular weight silicon resin [70]. A coating
by PVA with 1 % 1,2,3-benzotriazole proved to successfully prevent corrosion even
with a very thin layer (5 mm) for a duration of some 2 months at 35  C and 100 %
RH [70]. Another option is the addition of a small amount of o-aminophenol to an
ASA mixture (mixture of LA/LS/Al used in detonators). This prevents copper azide
corrosion for 4–5 years [31].
The copper azides resulting from corrosion of surface copper by lead azide has
been found to propagate detonation in layers with concentration exceeding
0.40 mg cm
2; in the discussion following Lamnevik’s presentation, Dr. Ball stated
that layers of 0.0254 mm thickness detonate with a velocity of 1,400 m s
1 [70].
The corrosion of copper and formation of copper azides has been said to be the
result of the presence of azoimide. Various methods exist that reduce partial
pressure of azoimide in ammunition. The first method involves the use of moisture
and carbon dioxide absorbents in air-tight elements (e.g., American artillery fuses).
The carbon dioxide absorbents unfortunately accelerate decomposition of LA. The
second method involves a ventilated design so that the azoimide can easily escape.
This method yields, in a worst case scenario, the less dangerous basic copper azides.
The drawback of this method is the fact that such a system is open to environmental
effects and that the lead azide gradually decays. A third method uses azoimide
destroying agents such as zinc or magnesium disks placed just above the LA.
Azoimide preferentially reacts with these metals forming nonexplosive products
(oxides, nitrogen, ammonia, hydrazine, and hydroxylamine). The passivation of the
metal surface may, however, present a significant problem. Use of palladium and
platinum has not been successful due to catalyst poisoning and formation of highly
explosive products on the surface of these metals. Another way to prevent copper
azide formation is to avoid use of lead azide and replace it with an alternative
primary explosive such as silver azide or avoid copper by using stainless steel [70].
The incompatibility of LA and copper is the reason why it could not be used
directly in detonators with the otherwise very popular copper tubing [70]. This,
however, does not mean that LA could not be present inside a copper tube detona-
tor. Many designs have been developed in which LA is encapsulated inside a
protective tube made of compatible material and inserted into the copper tube of
a standard detonator. The tin, zinc, or silver coating may also be used in some
special applications.

4.5.5 Uses

The copper azides—both normal and basic—have a very limited field of application
with the exception of cupric Cu(N3)2 which has been reported as a primary
4.6 Other Metallic Azides 105

explosive for detonators. The shape and size of crystals of Cu(N3)2 was modified by
addition of polyvinylalcohol or gelatin [114].

4.6 Other Metallic Azides

Other azides do not have significant importance for practical applications. Most of
them are moisture sensitive hygroscopic solids and some of them hydrolytically
decompose. They also easily form complex compounds. Azides other than those of
lead, copper, mercury, silver, palladium, and thallium are soluble in water and their
isolation from aqueous solutions by crystallization is problematic on an industrial scale.

4.6.1 Physical and Chemical Properties

Some basic physical and chemical properties of selected azides are summarized in
Table 4.12.
Mercurous azide Hg2(N3)2 is probably composed of the linear molecules,
N–N–N–Hg–Hg–N–N–N [76]. Melting point is about 205–210  C [76]. Hitch
reported that mercurous azide does not melt; it turns yellow, sublimes, and starts to
decompose by heating to temperature 215–220  C [80]. It is very sensitive to light and
it easily photodecomposes, liberating nitrogen and turning into a solid brown product
(probably nitride) on the surface without loss of brisance. There is no evidence of
photoconduction [7, 50] and unlike LA it does not react with carbon dioxide [50].
Mercuric azide Hg(N3)2 comes in two forms, a and b (Fig. 4.14). The stable a-
form has orthorhombic crystals, whereas the b-form consists of long extremely
sensitive thin needles [15, 16]. The a-form may be obtained by recrystallization of
Hg(N3)2 from hot water [7]. Miles, however, reported that recrystallization from
water results in a mixture of both crystal forms. In every case when the b-form is
present the material is extremely sensitive to touch and it may spontaneously
explode [12]. The presence of dextrin does not have a significant influence on the
form produced [16].
Azides of mercury darken in color and start to decompose when heated above
212  C. The decomposition process is accompanied by evolution of nitrogen prior
to its explosion [80].
Thallous azide TlN3 is one of the few metallic azides that melt (m.p. 330  C in
vacuum [80] or 334  C [28, 76]) followed by sublimation (at 340  C) prior to its
explosive decomposition with a green flash (at 430  C) [76, 80]. Heat of formation
published by Gray and Waddington is 234 kJ mol
1 [27], heat of decomposition to
elements published by Yoffe is
238 kJ mol
1 [28]. TlN3 should be stored in a
completely dry, dark place as the damp substance has a tendency to discolor [15].
Pure crystals of TlN3 show marked photoconduction when irradiated with light
[7, 76]. Figure 4.15 shows crystals of thallous azide prepared by diffusion process.
This preparation method is based on placing one drop of TlNO3 on glass surface of
a watch glass and one drop of NaN3 next to it but not in contact. The two drops are
106 4 Azides

Table 4.12 Physical and chemical properties of selected azides [5, 15, 83, 115, 116]
Density DHf
(g cm
3) (kJ mol
1) Color Properties
Co(N3)2 – – Reddish- Forms hydrates, hygroscopic, soluble in
brown water in which it slowly hydrolyzes
Ni(N3)2 – – Grainy green Hygroscopic, soluble in water in which it
slowly hydrolyzes
Cd(N3)2 3.24 [3, 5] 445 [103] White Soluble in water, hygroscopic, tends to
5.15 [117] hydrolyze
Hg2(N3)2 – 592 [103] White Slightly soluble in water, photosensitive
593 [27] (turns yellow and gray under light—
colloidal mercury forms), very toxic
Hg(N3)2 – – Clear to lemon Slightly soluble in water, photosensitive
yellow (turns yellow under light due to
formation of colloidal mercury) but
less than Hg2(N3)2
Zn(N3)2 – – White Hygroscopic, soluble in water, has a strong
tendency to decompose hydrolytically,
forms basic salt with water
TlN3 5.74 [117] 234 [103] Pale yellow Slightly soluble in water, highly toxic

Fig. 4.14 Crystals of mercuric azide: a-form (left), b-form (right)

then connected, the solutions diffuse into each other, and crystals begin to appear.
However, different crystals form on the side of TlNO3 and different on the side of
the azide. The left picture on Fig. 4.15 shows what forms on the side of TlNO3 and
the right one what forms on the side of sodium azide.
Cadmium azide is not physically stable; it easily hydrolyzes. The melting point
of cadmium azide is 291  C accompanied by decomposition [3].

4.6.2 Explosive Properties

Cadmium azide is a powerful primary explosive being superior to LA [3]. It is,

however, extremely sensitive to mechanical stimuli (explodes when rubbed with a
4.6 Other Metallic Azides 107

Fig. 4.15 Crystals of thallous azide prepared by diffusion process (left—what forms on the TlNO3
side, right—what forms on the NaN3 side)

Table 4.13 Impact sensitivity, explosion temperature, and initiating efficiency to tetryl and TNT
of azides of mercury, cadmium, and thallium and comparison with lead azide
Initiating efficiency (g)
Impact sensitivity Ignition temperature ( C) Tetryl TNT
Hg2(N3)2 6 cm/0.5 kg [82] 281a [119]; 270 [80] 0.045 [5] 0.145 [5]
a-Hg(N3)2 6.5 cm/0.6 kg [21] 300 [80] 0.005 [21] 0.03 [21]
Cd(N3)2 Extremely high [15, 118] 291a [119]; 360a [3] 0.01 [5] 0.04 [5]
TlN3 – 430b [80]; 500c, 530d [28] 0.07 [5] 0.335 [5]
Pb(N3)2 43 cm/0.5 kg [82] 327a [119] 0.025 [5] 0.09 [5]
a
Temperature at which explosion occurred within 5 s.
b
Ignition temperature depends on ambient pressure.
c
Instantaneous explosion.
d
Explosion within 1 s.

spatula) [118] or even spontaneously [15]. Danilov reported cadmium azide as

highly thermostable with an ignition temperature of 360  C (within 5 s) [3] while
W€ohler and Martin reported only 291  C [119]. The detonation velocity is
3,760 m s
1 at 2 g cm
3. Values for other densities can be calculated using the
following equation [3]:

Detonation pressure may be calculated in a similar way from the following

equation:

The ignition efficiency of cadmium azide is higher than that of LA (see

Table 4.13) [3, 5].

The sensitivity of mercurous azide Hg2(N3)2 to impact and friction is signifi-

cantly higher than that of mercury fulminate [82, 120]. When Hg2(N3)2 is heated
108 4 Azides

over a flame the solid melts, volatilizes, and explodes if the diameter of the molten
layer is sufficiently large. A thin layer of Hg2(N3)2 only burns with a blue flame. It
explodes if the diameter of the fused azide is greater than a few tenths of a
millimeter [76]. The ignition temperature is 298  C with explosion taking place
instantaneously or within 1 s [82].
The sensitivity of mercuric azide Hg(N3)2 depends on its crystal modification and
the shape and size of the crystals. a-Hg(N3)2 is not abnormally sensitive, its
sensitivity to impact being lower than for cupric azide Cu(N3)2 but higher than for
mercury fulminate. However, as mentioned earlier, b-Hg(N3)2 explodes at the
slightest touch or even spontaneously [12]. Generally, Hg(N3)2 is considered to be
highly sensitive to impact and friction, more than mercury fulminate [5, 80]. Hg(N3)2
explodes with a beautiful white-blue flash resembling an electrical discharge when
initiated by flame (Pachman and Matyáš Unpublished). The summary of sensitivities
of mercury, cadmium, and thallium azides to impact, their explosion temperature,
and initiating efficiency is listed in Table 4.13. The heats of explosion of many
metallic azides have been measured by W€ ohler and Martin [115].
Another disadvantage of mercuric azide Hg(N3)2 is its tendency to agglomerate
into bigger blocks that cause problems during loading. The grinding of such
agglomerates is an operation with high risk of explosion [21].
Although impact and friction sensitivity of thallous azide TlN3 are generally
considered to be lower than for LA it has one unusual property that should be
brought to general attention. Its sensitivity to friction depends on the thickness of
the sample layer and is highest in very thin layers. This phenomenon has been
reported to be a cause of several explosions in laboratories [15]. Its initiation
efficiency is lower than that of LA [3].
Some other metallic azides, like cadmium azide, are extremely sensitive to
mechanical stimuli. Nickel azide is extremely sensitive to friction; it explodes by
slight pressure or rubbing between metal and glass. Cobalt azide is even more
sensitive than nickel azide. On the other hand, zinc azide detonates only under
strong impact [115].

4.6.3 Preparation

Insoluble azides such as AgN3, Pb(N3)2, Hg2(N3)2, Hg(N3)2, CuN3, Cu(N3)2, TlN3
are prepared by precipitation from a solution of a soluble metallic salt by addition of
sodium azide [1, 15, 121].

For example, mercurous azide is prepared by this method; it is precipitated by

combining aqueous solutions of a mercurous salt (nitrate) and sodium azide. The
use of tetramethoxysilane is recommended for producing better crystal structure
[116].
4.6 Other Metallic Azides 109

Mercuric azide (a-form) is prepared by mixing a saturated aqueous solution of

mercuric chloride with the equivalent amount of sodium azide solution in presence
of hydrazoic acid [12].

Some of the water-soluble metallic azides may be prepared by reaction of the

metal oxide, hydroxide, or carbonate with excess of hydrazoic acid. This method is
reported for preparation of cadmium azide [3, 5].

The azide is obtained from the aqueous solution by evaporation. The product
(depending on the process of evaporation) often forms long needles that are
extremely sensitive and often explode by touch [50]. It is also possible to obtain
water soluble azides by reaction of barium azide with the relevant soluble metallic
sulfate. The precipitate of barium sulfate is filtered off and the relevant azide can be
crystallized from the aqueous solution.

Soluble azides can be purified by recrystallization from hot water. TlN3 is

considered insoluble at normal temperature and therefore can be prepared by
above-mentioned precipitation and may be purified just like the soluble azides
because it does dissolve in hot water [7].

In many cases (Mg, Mn, Zn, Cr, Co, etc.) metallic azides are not obtainable from
aqueous solution as they give insoluble basic salts or mixtures of varying composi-
tion on standing or evaporation. In the case of Al, Zr, Th the corresponding
hydroxides form [11]. The azides that easily undergo hydrolysis are therefore
prepared by using ether or chloroform solutions of azoimide. A typical example
is shown below. First the basic zinc azide forms by reaction of metallic zinc with an
aqueous solution of azoimide. Then the basic salt is converted to normal zinc azide
by additional reaction with an ether solution of azoimide. The end of the conversion
can be recognized by the complete dissolution of the suspension in water when
insoluble starting metallic salt is used [5, 52, 111, 115].

Azides soluble in methanol can be prepared by shaking the dry metal salt
in absolute methanol with sodium azide (e.g., ferric azide from ferric
sulfate) [115].
110 4 Azides

Arsenic triazide forms by treatment of arsenic trichloride on sodium azide in

trichlorofluoromethane [122]; antimony triazide by reaction of antimony triiodide
with silver azide in acetonitrile [123].

The preparation of arsenic, antimony, and bismuth triazides in pure crystalline

form (suitable for X-ray crystallography) was published by Haiges et al. These
azides form by reaction of arsenic or antimony trifluoride in sulfur dioxide with
trimethylsilyl azide [124, 125].

The same method can be used for preparation of neat pentaazides of arsenic and
antimony whose preparation was not successful for a long time [126].

4.6.4 Uses

Due to low physical and chemical stability (e.g., Zn(N3)2) or high sensitivity (e.g.,
Hg(N3)2) most metallic azides covered in this chapter have never been practically
used despite the high initiating efficiency that most of them have. Cadmium azide
(despite its tendency to hydrolyze [35]) is the only one that is reported to have some
limited application thanks to its high thermostability. It has been used in hermeti-
cally sealed detonators for high temperatures in oil wells as they are able to
withstand 2 h at 250  C or 6 days at 160  C [3].
Mercuric azide was one of the first metallic azides studied because of its similarity
with mercury fulminate. Unexpected and unfortunately fatal accidental explosions
occurred during testing of this substance because of the contamination of mercuric
azide with mercurous azide (highly sensitive substance). Because of these accidents,
further examinations of salts of azoimide were stopped for several years [3].

4.7 Organic Azides

A variety of organic azides exists and has been described in scientific literature.
However, only some of them have the characteristics of primary explosives. The
sensitivity of these substances to the mechanical stimuli necessary for primary
explosives generally increases with content of azido group in the molecule.
4.8 Cyanuric Triazide 111

For example, 1-azido-2,4,6-trinitrobenzene with one azido group in the molecule has
the character of a secondary explosive (its sensitivity is too low for primary explosive)
whereas 1,3,5-triazido-2,4,6-trinitrobenzene is a typical primary explosive.
Most organic azides do not possess the properties required for primary
explosives and generally can be characterized by low physical and chemical
stability (lower alkyl azides, sulfuryl azide explode even spontaneously [8, 11]),
high sensitivity to mechanical stimuli (lower alkyl azides, acyl azides e.g., carbonyl
diazide explode on contact with a glass rod [30]), low thermal stability (e.g.,
cyanogen azide, 1,3,5-triazido-2,4,6-trinitrobenzene, dicyanamid azide, esters of
azidoacetic acid [8]), or sensitivity to light [127].
The thermal stability of organic azides generally decreases in the following
order [3]:

alkyl azides > aryl azides > azidoformates > sulfonyl azides > acyl azides

Organometallic azides do not have the characteristics of explosives (e.g., triethyl

lead azide) [3].
There are two basic methods for preparing organic azides [3]:
1. By nucleophilic substitution of the halogens, nitroxy group, etc. by the azido
group:

2. Via the diazonium salt by action of nitrous acid with hydrazino-compounds or

by reaction of basic azides with the diazonium salt.

NH NH2 N3

+ HNO2 + 2 H 2O

R R

+ -
N N Cl N3

+ NaN3 + N2 + NaCl

R R

4.8 Cyanuric Triazide

Cyanuric triazide (2,4,6-triazido-1,3,5-triazine; TAT; sometimes called simply

“triazide”) was probably first prepared by H. Finger in 1907 by the reaction of 2,4,6-
trihydrazino-1,3,5-triazine with sodium nitrite in an acidic environment [6, 46, 128].
112 4 Azides

He, however, did not examine this new compound too closely and did not discover its
possible usefulness in priming [46, 128]. It is therefore Erwin Ott who is sometimes
cited as the discoverer of cyanuric triazide as he was the first to perform a detailed
examination of this compound and he patented it as a primary explosive [129, 130].
N3 N N3

N N

N3

4.8.1 Physical and Chemical Properties

Cyanuric triazide forms white crystals with density 1.54 g cm
3 [5, 45, 131]
(1.5 g cm
3 reported in older literature [132, 133]) or 1.71–1.72 g cm
3 [3, 46,
134, 135] with melting point 94  C. This compound is easily soluble in acetone, hot
alcohol, chloroform, benzene, pyridine; slightly soluble in cold alcohol; and insol-
uble in water [46, 129, 131, 132, 136, 137]. Yoffe studied the behavior of cyanuric
triazide during heating under various pressures. He reported that cyanuric triazide
can be melted without decomposition (even at 112  C no decomp. over several
hours) or even at 198  C in a vacuum without any observable decomposition. The
azide simply condensed on a cold part of the vessel [28]. Other authors, however,
reported that decomposition begins when this material is heated above 100  C and
explosion occurs in the range from 150 to 180  C depending on the heating rate. It
may entirely decompose without explosion when heated slowly [129, 131, 132].
Gillan described its thermal decomposition as follows: clear liquid forms during
melting (94–95  C), gas liberating starts at 155  C, orange to brown solution
coloration appears around 170  C, solidification to an orange-brown solid by
200  C, and rapid decomposition at 240  C (capillary examination) [138].
Cyanuric triazide is slightly hygroscopic and slightly volatile [6, 17, 30, 47,
136], but significantly more hygroscopic than MF and LA [47]. Danilov et al.,
however, reported noticeable volatility even at 30  C [3]. Muraour published heat of
formation 917 kJ mol
1 [46, 139], but according to Meyer it is 931 kJ mol
1 [40]
and according to recent work of Gillan DHf ¼ 1,053 kJ mol
1 [138]. It does not
react with metals, water, and carbon dioxide [132, 136, 137].
Cyanuric triazide is reduced by action of hydrogen sulfide to melamine—nitrogen
is evolved and sulfur is precipitated [130]. It also decomposes in aqueous sodium
hydroxide (0.1 M) at 50  C within several minutes yielding the sodium salt of cyanuric
acid and sodium azide [46, 52]. The substance is not irritating to the skin [17].

4.8.2 Explosive Properties

Small crystals of cyanuric triazide are more sensitive to mechanical stimuli than
small crystals of MF [47]. It explodes when pressed into a detonator capsule. Large
4.8 Cyanuric Triazide 113

Table 4.14 Impact sensitivity of cyanuric triazide

Cyanuric triazide Comparison with LA
Converted to As reported Converted As reported Value
energy (J) in literature to energy (J) in literature reported Apparatus Reference
0.34 7 cm/0.5 kga 2.1 43 cm/0.5 kg hmin Small impact [82]
machine
0.69 7 cm/1 kg 2.0 10 cm/2 kgb h50 BM apparatus [45]
0.18 0.9 cm/2 kg 1.6 32 cm/0.5 kg – BM apparatus [5]
– 25.4 cm – 17.8–28 cm – Ball Drop [140]
Impact
a
Needles of cyanuric triazide from 0.04 to 0.2 mm in diameter and averaging 0.1 mm in length.
b
Pure LA.

Fig. 4.16 Crystals of raw cyanuric triazide (left) and recrystallized sample (right) [140].
Reprinted by permission from Neha Mehta

crystals (obtained by recrystallization) can explode when broken by pressure of a

rubber [17]. Long needles of cyanuric triazide (obtained by evaporation of organic
solutions) can explode even spontaneously [136]. Some of the values of impact
sensitivity of cyanuric triazide are summarized in Table 4.14.
The sensitivity of cyanuric triazide to friction and electrostatic discharge has
recently been measured by Mehta et al. [140]. They observed that sensitivity to
friction of a recrystallized sample is lower than that of a nonrecrystallized one
contrary to sensitivity to electrical discharge. The photographs of both samples are
presented in Fig. 4.16. The values observed for these two types of cyanuric triazide
are compared with lead azide in Tables 4.15 and 4.16 [140].
Taylor and Rinkenbach [82] determined the ignition temperature of cyanuric
triazide to be 252  C (the sample dropped on the surface of the molten alloy with a
constant temperature, explosion took place immediately or within 1 s) [82].
The substance explodes when heated to 205–208  C (heating rate 20  C min
1)
[47] and at 170  C (heating rate 5  C min
1) [5]. The experimentally determined
values of the detonation velocity for cyanuric triazide are summarized in Table 4.17.
Cyanuric triazide decomposes explosively into molecular nitrogen and cyano-
gen (C2N2) when initiated under vacuum. Ignition in a confined space leads to
formation of a black sooty residue (with high yield >91 wt.%) consisting of
114 4 Azides

Table 4.15 Sensitivity to Cyanuric triazide (g)

friction of cyanuric triazide
and LA measured as a piston Nonrecrystallized Recrystallized LA (g)
loading (in g) on small BAM No go at – 10 (0/10) 10–20
friction test [140] Go at 10a 20 30
a
The lowest level of the apparatus.

Table 4.16 Sensitivity to Cyanuric triazide (mJ)

electric discharge of cyanuric LA
triazide compared with Nonrecrystallized Recrystallized (mJ)
LA (in mJ) [140] No go at 31 (0/20) 1.2 (0/20) 1.2
Go at – – 1.6

Table 4.17 Detonation velocity of cyanuric triazide

Density (g cm
3) Detonation velocity (m s
1) Note Reference
1.02 5,500 Unconfined [40]
1.15 5,440–5,650 [47]
5,550 [139]
5,600 [141]

Table 4.18 Initiation efficiency of cyanuric triazide

Initiating efficiency (g)
TNT Tetryl PETN Comment Reference
0.1 (with RC) 0.04 – – [5, 17]
0.12 (without RC)a – – 1.4 g cm
3 [139]
a
0.08 (with RC)
0.20 (with RC)a – – 1.5 g cm
3 [139]
– – 0.005 49 MPa [6]
0.13 0.06 – – [21]
0.07 0.02 – – [46]
(0.1 for LA) (0.02–0.03 for LA)
a
TNT compressed to a density 1.35 g cm
3 in copper detonator tube.

nanostructured carbon materials [142, 143]. Interesting material—carbon nitrides

(e.g., C3N4, C3N5) form by thermal decomposition (185  C) of cyanuric triazide in a
high-pressure reactor [138].
Cyanuric triazide belongs to the group of explosives having brisance superior to
mercury fulminate:
• Brisance by sand test: 32.2 g (67 % TNT and 264 % MF) [5, 45]
• Lead block test: 415 cm
3/10 g (138 % TNT [40]; 140 % TNT [5])
The values of initiating efficiencies for TNT, tetryl, and PETN are summarized
in Table 4.18.
After ignition, small crystals of cyanuric triazide burn (unlike silver azide) even
though Ficheroulle and Kovache reported them exploding violently by the action of
flame [136]. The outcome of initiation by hot wire depends on temperature. At
20–50  C it only cracks while at 75  C it explodes [136].
4.8 Cyanuric Triazide 115

Burning speed of a 3-mm-long crystal with diameter 0.35 mm is about 0.3 m s
1 and
increases with increasing diameter. Crystals with length 1.8–3 mm and cross-section
0.6–0.7  0.6–1.0 mm burn with velocity from 1 to 1.5 m s
1. The burning has an
accelerating character and with larger crystals explosions may occur (e.g., burning of
crystal 2  2  1 mm transitions to explosion) [85]. Fogelzang et al. found a linear
dependence of combustion rate on pressure in range 0.1–40 MPa [144].
Cyanurazide can be dead-pressed by pressure above about 20 MPa [3, 46, 52].

4.8.3 Preparation

Cyanuric triazide can easily be obtained by the action of cyanuric chloride on

sodium azide in an aqueous solution at room temperature. The product forms as a
crystalline precipitate [6, 129, 132].
Cl N Cl N3 N N3

N N + 3 NaN3 N N + 3 NaCl

Cl N3

The substance is highly dangerous. Explosion during the manufacturing process,

more specifically during drying, has been encountered [30]. The suitable solvent for
recrystallization of cyanuric triazide is ethanol [6, 132]. Recrystallization of cyanuric
triazide is a dangerous operation due to potential formation of large, extremely
sensitive, crystals [45]. Long needles that form by evaporation of an organic solution
can even explode spontaneously. Small crystals, formed by dilution of cyanuric
triazide acetone solution, can explode when being dried at around 50  C [136].
Cyanuric triazide also forms by reaction of 2,4,6-trihydrazino-1,3,5-triazine with
sodium nitrite in an acidic environment [33, 137]. However, Bagal reported that this
way of preparation is not suitable for making pure cyanuric triazide [46].

4.8.4 Uses

Cyanuric triazide was patented as an initiating explosive by Erwin Ott in 1919 [133]
but it has not been used practically due to high sensitivity, volatility, and hygro-
scopicity [5, 8, 40, 45]. This substance has recently again been considered as an
LA/LS replacement in initiator mixtures, an alternative to NOL-130, and an LA
replacement in stab detonators [140]. Other authors again excluded it for practical
use due to its low thermal stability [145, 146]. Some investigations of possible
ways of preparation of carbon nanotubes via explosive decomposition of cyanuric
triazide in confining cavity have been investigated [142, 143].
116 4 Azides

4.9 4,40 ,6,60 -Tetra(azido)hydrazo-1,3,5-triazine and 4,40 ,6,60 -

Tetra(azido)azo-1,3,5-triazine

These two new high-nitrogen compounds were probably first reported by Huynh
et al. in 2004 [147].
N3 N3 N3 N3
N N N N
N NH NH N N N N N
N N N N
N3 N3 N3 N3

4,4',6,6'-Tetra(azido)hydrazo-1,3,5-triazine 4,4',6,6'-Tetra(azido)azo-1,3,5-triazine
TAHT TAAT

4.9.1 Physical and Chemical Properties

4,40 ,6,60 -Tetra(azido)hydrazo-1,3,5-triazine (TAHT) has only one polymorph in

which two 1,3,5-triazine rings are not co-planar but have a torsion angle of 105 .
The density of this polymorph is 1.649 g cm
3. On the other hand, 4,40 ,6,60 -tetra
(azido)azo-1,3,5-triazine (TAAT) crystallizes as an a or b polymorph with density
1.724 g cm
3 and 1.674 g cm
3, respectively. The b polymorph has two
conformers whose azido groups are oriented in different directions. The presence
of hydrazo and azo linkages significantly decreases the volatility and dramatically
increases the melting point relative to cyanuric triazide (m.p. is not observable up to
decomposition at 200 and 202  C, respectively). Both molecules have very high
positive heat of formation 1,753 kJ mol
1 for TAHT and 2,171 kJ mol
1 for TAAT
(it is believed that the DHf for TAAT is the highest ever experimentally measured
for an energetic high-nitrogen compound) [147, 148].
Pyrolysis of TAAT yields carbon nitrides such as C2N3 and C3N5 when
decomposed under mild conditions (e.g., low temperature and without applied
pressure) [149, 150].

4.9.2 Explosive Properties

It was to be expected that the hydrazo and azo linkages in TAHT and TAAT
molecules would desensitize these compounds relative to cyanuric triazide.
Reported values are summarized in Table 4.19 [147].
The impact sensitivity of TAHT is inferior to cyanuric triazide and even PETN,
and sensitivity to friction is between the values for cyanuric triazide and PETN.
TAAT is generally more sensitive than its hydrazo analogue and is comparable to
cyanuric triazide itself (impact sensitivity is about the same, friction sensitivity is
significantly lower) [147].
4.9 4,40 ,6,60 -Tetra(azido)hydrazo-1,3,5-triazine and 4,40 ,6,. . . 117

Table 4.19 Sensitivity of TAHT and TAAT to mechanical stimuli and their thermal stability
compared with PETN and cyanuric triazide [147, 148]
Impact sensitivity Friction sensitivity Spark sensitivity DSC fast
Compound (h50, type 12) (cm) (BAM) (kg) (J) decomp. ( C)
Cyanuric triazide 6.2 <0.5 <0.36 187
Hydrazo comp. 18.3 2.9 <0.36 202
Azo comp. 6.2. 2.4 <0.36 200
PETN 14.5 5.4 >0.36 178

4.9.3 Preparation

4,40 ,6,60 -Tetra(chloro)hydrazo-1,3,5-triazine (prepared from cyanuric triazide

[151]) is the starting material for both compounds. Its reaction with excess of
hydrazine hydrate in acetonitrile forms 4,40 ,6,60 -tetra(hydrazino)hydrazo-1,3,5-tri-
azine which undergoes diazotization to TAHT. TAAT forms by oxidation of TAHT
by chlorine in a water/chloroform suspension [147, 148, 150]. Simplified method of
preparation of the key intermediate TAHT was published by Li et al. [152]. Instead
of hydrazinolysis and diazotation they used nucleophilic substitution of 4,40 ,6,60 -
tetra(chloro)hydrazo-1,3,5-triazine with sodium azide for preparation of TAHT
which they in the last step oxidized with N-bromosuccinimide.
Cl Cl Cl
N N N
N Cl + NH2NH2 N NH NH N
N N N
Cl Cl Cl
NH2NH2
DT
NaN 3
DT acetone
CH 3 CN

H2NHN NHNH2 N3 N3
N N N N
N NH NH N N NH NH N
N N N N
H2NHN NHNH2 N3 N3

NaNO 2/HCl N-Bromosuccinimide CH3CN

N3 N3 N3 N3
N N N N
N NH NH N N N N N
N N N N
N3 N3 N3 N3
Cl 2 CHCl3/H2O

N3 N3
N N
N N N N
N N
N3 N3
118 4 Azides

4.9.4 Uses

Huynh and Hiskey patented the use of TAAT for preparation of carbon nitrides,
more specifically C2N3 and C3N5 [150].

4.10 1,3,5-Triazido-2,4,6-trinitrobenzene

1,3,5-Triazido-2,4,6-trinitrobenzene (TATNB, TNTAB) was first prepared by

Oldřich Turek in 1924 by the action of sodium azide on 1,3,5-trichloro-2,4,6-
trinitrobenzene [153, 154].
N3

O2N NO2

N3 N3
NO2

4.10.1 Physical and Chemical Properties

1,3,5-Triazido-2,4,6-trinitrobenzene is a substance which crystallizes in the form of

bright yellow crystals. The melting point of TATNB is 131  C and density
1.805 g cm
3 (pycnometric) [153, 154] or 1.84 g cm
3 (X-ray) [155]. The heat
of formation is 765.8 kJ mol
1 or 2.28 MJ kg
1 (a value significantly higher than
for TNT or HMX), TATNB is strongly endothermic compound. The experimentally
determined heat of combustion is 3,200 kJ mol
1 [155]. TATNB is soluble in
acetone and benzene, slightly soluble in alcohols, and insoluble in water. It
decomposes in pyridine or monoethanolamine [153, 154, 156]. TATNB is stable
in water (no change within 3.5 years of storage under water) [153, 154]. Turek
reported the nonhygroscopic nature of TATNB [153, 154]; Ficheroulle and
Kovache reported slight hygroscopicity (it absorbs 1.35 wt.% of water within
40 days of exposure to moist air) [156]. On exposure to light, the yellow color
deepens and by very long exposure to sunlight, surface layers of TATNB crystals
decompose to benzotrifuroxane [153, 154]. TATNB is compatible with most
common metals and reactions do not take place in a moist atmosphere [153, 154].
Reaction was not observed for iron, steel, copper, and brass even when wet [33, 45].
Ficheroulle and Kovache, however, reported reaction with steel and lead on one
hand and good resistance of aluminum, brass, and copper on the other, both in moist
atmospheres [153, 154, 156]. TATNB can be chemically decomposed by action of
aqueous sodium hydroxide when trinitrofluoroglucinol forms [156].
TATNB has low thermal stability. It decomposes by heating to benzotrifuroxane
and gaseous nitrogen. This decomposition is quantitative and occurs even at low
temperatures [153, 154].
4.10 1,3,5-Triazido-2,4,6-trinitrobenzene 119

14

12 50°C

10
Weight loss (%)

4 35°C

2
20°C

0
0 200 400 600 800 1000 1200 1400

Time (days)

Fig. 4.17 Dependence of weight loss of TATNB on temperature and time [153, 154]

- O
N3 O N
+ +
O2N NO2 N N -
DT O
O + 3 N2

N3 N N
N3
+
NO2 - N
O O

The dependence of the rate of decomposition (in weight loss) on temperature has
been determined by Turek and is presented in Fig. 4.17. TATNB rapidly
decomposes at 100  C; full transformation is achieved within 14 h. The decompo-
sition is not self-catalyzed [153, 154].

4.10.2 Explosive Properties

Sensitivity to impact is mostly mentioned significantly lower than for MF [5, 30, 40,
153, 154] (expect [33, 157]). The published values of sensitivity to impact are
summarized below:
• 50 % probability of ignition at 2.5 J (1/2 kg hammer from 50 cm) [156].
• 0 % probability of ignition at 2 J and 100 % probability of ignition at 3.9 J vs.
0 % probability of ignition at 3.9 J and 50 % probability of ignition at 5.9 J for
LA (2 kg hammer from relevant height) [33].
• Ignition at 5 J vs. 1–2 J for MF [40].
• Higher than 1.5 J (0.25 kg hammer from 60 cm) [155].
• Significantly lower than MF [3, 153, 154].
120 4 Azides

Table 4.20 Detonation Density (g cm
3) Detonation velocity (m s
1) References

velocity of TATNB
1.50 7,200 [33]
1.54 7,500 [30]
1.70 8,100 [33]

Sensitivity to friction is reported generally relatively low, but depends on crystal

size [5]. Under water, TATNB is not sensitive to friction [153, 154].
TATNB is sensitive to flame and when lit, loose TATNB burns with a blinding
blue flame without fumes [153, 154]. The burning behavior of the material pressed
at 98, 196, and 294 MPa has been studied by Ficheroulle [156]. A thin layer of
TATNB (0.5 mm thick) burns slowly with rate about 0.03 mm s
1 and a single
crystal with burning speed about 0.05 m s
1. These rates are slower than those of
most other primary explosives (SA, LS, MF, or cyanuric triazide) [85]. However, if
confined, for example pressed in a blasting cap, TATNB explodes violently
[153, 154]. TATNB explodes when heated to 150  C within 10 s [5].
TATNB is a powerful primary explosive. The dependence of detonation velocity
on density is given in Table 4.20.
Brisance of TATNB is high; it is superior to that of TNT and tetryl in plate dent
test. Power of TATNB determined by a Trauzl lead block test is 150 % TNT
(vs. 27 % for LA and 38 % for MF) [153, 154] or 179 % TNT [5]. Ignition efficiency
of TATNB is superior to that of both MF and LA:
• 0.02 g TATNB for TNT and 0.01 g for tetryl (TNT and tetryl were pressed at
49 MPa, TATNB at 29 MPa) [153, 154].
• 0.08 g TATNB for TNT and 0.05 g for tetryl (with reinforcing cap, TNT and
tetryl was pressed at 49 MPa, TATNB at 29 MPa) vs. 0.12 g for LA and
0.25–0.30 g for MF (both for TNT) [33].
TATNB can be dead-pressed. It can be loaded into blasting caps by pressure up
to 29 MPa; at higher pressures its brisance rapidly decreases. In combination with
LA it can be pressed at significantly higher pressures (29–196 MPa) [153, 154,
158]. Fedoroff, Shefield any Kaye’s encyclopedia mentions that pure TATNB
becomes dead-pressed at pressures of about 290 MPa [5].

4.10.3 Preparation

1,3,5-Triazido-2,4,6-trinitrobenzene can be easy synthesized by the action of alkaline

azide on 1,3,5-trichloro-2,4,6-trinitrobenzene. The product is slightly soluble in the
reaction mixture from which it precipitates. The sodium azide can be used in the form
of an aqueous ethanol solution while 1,3,5-trichloro-2,4,6-trinitrobenzene in the form
of an acetone solution or alone [153, 154, 159, 160]. Purification of TATNB may be
done by crystallization from solvents such as chloroform [153, 154, 159, 160], acetic
acid, or mixture of acetic acid and acetone 1/1 (the last mixture is recommended for
preparation of single crystals for structural studies) [155].
4.11 2,3,5,6-Tetraazido-1,4-benzoquinone 121

Cl Cl N3
O2N NO2 O2N NO2
DT NaN3
+ 3 NaCl
oleum/HNO3

Cl Cl Cl Cl N3 N3
NO2 NO2

The starting substance, 1,3,5-trichloro-2,4,6-trinitrobenzene, can be prepared

from 1,3,5-trichlorobenzene by nitration in a strong nitration mixture such as
oleum/nitric acid at high temperatures [153, 154, 159, 160]. TATNB can also be
prepared by nitration of 1,3,5-triazido-2,4-dinitrobenzene [155].

4.10.4 Uses

Turek suggested 1,3,5-triazido-2,4,6-trinitrobenzene as a replacement of mercury

fulminate for detonators and blasting cartridges in 1927–1930 [158, 161, 162] and
several years later again for filling in percussion caps [157, 163]. TATNB has high
initiation efficiency; ideal sensitivity to mechanical stimuli; good chemical stability and
it does not contain heavy metals. It would be an ideal candidate for a “green” primary
explosive if it was not for its low thermal stability which disqualifies it from practical
use. Some large-scale experiments have been carried out in the past to examine the
possibilities of a practical application for TATNB, but without success being reported
[30].

4.11 2,3,5,6-Tetraazido-1,4-benzoquinone

2,3,5,6-Tetraazido-1,4-benzoquinone (TeAzQ) was first prepared by Fries and

Ochwat in 1923 by the action of sodium azide on 2,5-diazido-3,6-dichloro-1,4-
benzoquinone [164].
O

N3 N3

N3 N3
O

4.11.1 Physical Properties

2,3,5,6-Tetraazido-1,4-benzoquinone forms dark blue crystals with metallic luster

[165] or nice brownish yellow prismatic crystals with a blue-black gloss [164]. It is
soluble in acetone, slightly soluble in ethanol, and insoluble in water. The main
122 4 Azides

45

40

35

30
Weight loss (%)

25

20

15

10

0
0 20 40 60 80 100

Time (days)

Fig. 4.18 Dependence of weight loss of TeAzQ on storage time [165]

drawback of this substance is its low thermal stability. It rapidly decomposes at

laboratory temperature generating nitrogen. Nice blue crystals lose their gloss, break
apart, and the substance quickly loses its initiating ability. The dependence of weight
loss of TeAzQ on time (at room temperature) is shown in Fig. 4.18. To exclude the
possibility that the substance is just volatile and that the weight loss is due to
evaporation, Šorm encapsulated a sample in a closed vessel connected to a manometer
and, from the pressure rise, calculated the amount of evolved nitrogen. He found that
the substance is not volatile and that the weight loss is due to decomposition [165].
TeAzQ yields white 2,3,5,6-tetraazido-1,4-hydroquinone on reduction, but this
is unstable and reoxidizes back to blue quinone while standing in air [165]. It
decomposes under the action of sulfuric acid or sodium hydroxide liberating
nitrogen [164].

4.11.2 Explosive Properties

The impact sensitivity of 2,3,5,6-tetraazido-1,4-benzoquinone is high; significantly

higher than for LA. Values published in scientific papers are summarized in
Table 4.21.
Sensitivity to friction is high as well; it explodes during gentle adjustment on
sandpaper [166]. Ignition temperature is low, and it explodes at 91  C (heating rate
5  C min
1). By action of flame it violently explodes, whereas 2,3,5,6-tetraazido-
1,4-hydroquinone only ignites. TeAzQ has high ignition efficiency and excellent
resistance to dead-pressing. Using pressures of 49 MPa or 98 MPa resulted in the
same minimal amount of 0.02 g needed for initiating TNT [165].
References 123

Table 4.21 Impact sensitivity of 2,3,5,6-tetraazido-1,4-benzoquinone

Converted to energy (J) As reported in literature Value reported Reference
TeAzQ ~1 20 cm/0.5 kg Not specified [165]
<0.4 <1.5 cm/2.5 kg h50 [166]
LA 1.13 4.6 cm/2.5 kg h50 [166]
LS 2.16 8.8 cm/2.5 kg h50 [166]

4.11.3 Preparation

2,3,5,6-Tetraazido-1,4-benzoquinone can be easily prepared by the action over

several hours of sodium azide on 2,3,5,6-tetrachloro-1,4-benzoquinone (p-
chloranil) in an ethanol suspension [165] or by the action of aqueous sodium
azide on a methylene chloride solution of p-chloranil [166].
O O
Cl Cl N3 N3
+ 4 NaN3 + 4 NaCl

Cl Cl N3 N3
O O

4.11.4 Uses

2,3,5,6-Tetraazido-1,4-benzoquinone has never been used due to its low thermal

stability.

References

1. Curtius, T.: Ueber Stickstoffwasserstoff€aure. Berichte der deutschen chemischen Gesell-

schaft 23, 3023–3033 (1890)
2. Curtius, T., Radenhauser, R.: Zur Kenntniss der Stickstoffwasserstoffs€aure. Journal f€ ur
praktische Chemie 43, 207–208 (1891)
3. Danilov, J.N., Ilyusin, M.A., Tselinskii I.V.: Promyshlennye vzryvchatye veshchestva; chast
I. Iniciiruyushchie vzryvshchatye veshchestva. Sankt-Peterburgskii gosudarstvennyi
tekhnologicheskii institut, Sankt-Peterburg (2001)
4. Bubnov, P.F.: Initsiruyushchie vzryvchatye veshchestva i sredstva initsirovaniya.
Gosudarstvennoe izdatelstvo oboronnoi promyshlennosti, Moskva (1940)
5. Fedoroff, B.T., Sheffield, O.E., Kaye, S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, New Jersey (1960–1983)
6. Krauz, C.: Technologie výbušin. Vědecko-technické nakladatelstvı́, Praha (1950)
7. Evans, B.L., Yoffe, A.D., Gray, P.: Physics and chemistry of the inorganic azides. Chem.
Rev. 59, 515–568 (1959)
8. Urbański, T.: Chemistry and Technology of Explosives. Pergamon, Oxford (1984)
9. Hyronimus, F.: Improvements in and relating to the charge of ammunition primers. GB Patent
1,819, 1908
124 4 Azides

10. Rintoul, W.: Explosives. Rep. Prog. Appl. Chem. 5, 523–565 (1920)
11. Audrieth, L.F.: Hydrazoic acid and its inorganic derivates. Chem. Rev. 15, 169–224 (1934)
12. Miles, F.D.: The formation and characteristic of crystals of lead azide and of some other
initiating explosives. J. Chem. Soc. 2532–2542 (1931)
13. Hattori, K., McCrone, W.: Lead azide, Pb(N3)2. Anal. Chem. 28, 1791–1792 (1956)
14. Stettbacher, A.: Die Ermittlung des absoluten spezifischen Gewichts von Z€ undund
Sprengstoffen. Chemisches Zentralblatt 113, 366–367 (1942)
15. Fair, H.D., Walker, R.F.E.: Energetic Materials. Physics and Chemistry of Inorganic Azides.
Plenum, New York (1977)
16. Miles, F.D.: The formation and constitution of crystals of lead salts containing water-soluble
colloid. Philos. Trans. R. Soc. Lond. A Math. Phys. Sci. 235, 125–164 (1935)
17. Davis, T.L.: The Chemistry of Powder and Explosives. Wiley, New York (1943)
18. Taylor, A.C., Thomas, A.T.: Spontaneous explosions during crystal growth of lead azide.
J. Cryst. Growth 3, 391–394 (1968)
19. Taylor, G.W.C.: The preparation of gamma lead azide. In: Proceedings of Symposium on
Lead and Copper Azide, pp. A-3, 20-23, Waltham Abbey, 1966
20. Lamnevik, S., Soderquist, R.: On lead azides. 1 Refinement of the unit cell dimensions of
alpha- and beta- lead azide. On a transformation of beta- to alpha- lead azide in the solid state.
Report A 1105-F 110. FOA (1963)
21. Špičák, S., Šimeček, J.: Chemie a technologie třaskavin. Vojenská technická akademie
Antonı́na Zápotockého, Brno (1957)
22. Jung, P.C.: Initiation and Detonation in Lead Azide and Silver Azide at Sub-millimeter
Geometrics. Texas Technical University, Lubbock (2006)
23. Roth, J.: Initiation of lead azide by high-intensity light. J. Chem. Phys. 41, 1929–1936 (1964)
24. W€ohler, L., Krupko, W.: Uber € die Lichtempfindlichkeit der Azide des Silbers, Quecksil-
beroxyduls, Bleis und Kupferoxyduls, sowie € uber basisches Blei- und Cupriazid. Berichte der
deutschen chemischen Gesellschaft 46, 2045–2057 (1913)
25. Todd, G., Eather, R., Heron, T.: The decomposition of lead azide under storage conditions.
In: Proceedings of Symposium on Lead and Copper Azide, pp. B-2, 34–44, Waltham Abbey,
1966
26. McLaren, A.C.: The influence of preheating on the detonation velocity of lead azide.
Research 10, 409–410 (1957)
27. Gray, P., Waddington, T.C.: Thermochemistry and reactivity of azides. I. Thermochemistry
of the inorganic azides. Proc. R. Soc. Lond. A Math. Phys. Sci. A235, 106–119 (1956)
28. Yoffe, A.D.: Thermal decomposition and explosion of azides. Proc. R. Soc. Lond. A Math.
Phys. Sci. A208, 188–199 (1951)
29. Graybush, R.J., May, F.G., Forsyth, A.C.: Differential thermal analysis of primary
explosives. Thermochim. Acta 2, 153–162 (1971)
30. Urbański, T.: Chemistry and Technology of Explosives. PWN—Polish Scientific Publisher,
Warszawa (1967)
31. Lamnevik, S.: Lead azide, the ideal detonant? In: Jenkins, J.M., White, J.R. (eds.)
Proceedings of the International Conference on Research in Primary Explosives, vol. 2,
pp. 9/1–9/17, Waltham Abbey (1975)
32. Brown, M.E., Swallowe, G.M.: The thermal decomposition of the silver(I) and mercury(II)
salts of 5-nitrotetrazole and of mercury(II) fulminate. Thermochim. Acta 49, 333–349 (1981)
33. Khmelnitskii, L.I.: Spravochnik po vzryvchatym veshchestvam. Voennaya ordena Lenina i
ordena Suvorova Artilleriiskaya inzhenernaya akademiya imeni F. E. Dzerzhinskogo,
Moskva (1962)
34. Urbański, T.: Chemie a technologie výbušin. SNTL, Praha (1959)
35. Taylor, G.W.C.: Technical requirements and prospects for new primary explosives. In:
Jenkins, J.M., White, J.R. (eds.) Proceedings of the International Conference on Research
in Primary Explosives, vol. 3, pp. 18/1–18/21, Waltham Abbey (1975)
36. Blay, N.J., Rapley, R.J.: In: Jenkins, J.M., White, J.R. (eds.) Proceedings of the International
Conference on Research in Primary Explosives, vol. 3, pp. 20/1–20/19, Waltham Abbey
(1975)
References 125

37. Wyatt, R.H.: Copper azide corrosion. In: Proceedings of Symposium on Lead and Copper
Azide, pp. A-2, 15–19, Waltham Abbey, 1966
38. Wythes, P.E.: Accidents in manufacture of lead azide. In: Proceedings of Symposium on
Lead and Copper Azide, pp. D-2, 99–102, Waltham Abbey, 1966
39. Military Explosives, Report TM-9-1300-214, Headquarters, Department of the Army (1984)
40. Meyer, R., K€ohler, J., Homburg, A.: Explosives. Wiley-VCH, Weinheim (2002)
41. Šelešovský, J., Matyáš, R., Musil, T.: In: Using probit analysis for sensitivity tests - sensitiv-
ity curve and reliability. 14th Seminar on New Trends in Research of Energetic Materials,
pp. 964–968, Pardubice, 2011
42. Matyáš, R., Šelešovský, J., Musil, T.: Sensitivity to friction for primary explosives. J. Hazard.
Mater. 213–214, 236–41 (2012)
43. Clark, A.K., Davies, N., Hubbard, P.J., Lee, P.R.: Cross sensitisation to impact between lead
azide and tetryl. In: Jenkins, J.M., White, J.R. (eds.) Proceedings of International Conference
on Research in Primary Explosives, vol. 3, pp. 22/1-22/15, Waltham Abbey (1975)
44. Medlock, L.E., Leslie, J.P.: Some aspects of the preparation and characteristics of lead azide
precipitated in the presence of gelatin. In: Jenkins, J.M., White, J.R. (eds.) Proceedings of the
International Conference on Research in Primary Explosives, vol. 2, pp. 10/1–10/16,
Waltham Abbey (1975)
45. Tomlinson, W.R., Sheffield, O.E.: Engineering Design Handbook, Explosive Series of
Properties Explosives of Military Interest. Report AMCP 706-177 (1971)
46. Bagal, L.I.: Khimiya i tekhnologiya iniciiruyushchikh vzryvchatykh veshchestv.
Masinostroenie, Moskva (1975)
47. Kast, H., Haid, A.: Uber € die sprengtechnischen Eigenschaften der wichtigsten
Initialsprengstoffe. Zeitschrift f€ ur das angewandte Chemie 38, 43–52 (1925)
48. Wallbaum, R.: Sprengtechnische Eigenschaften und Lagerbest€andigke der wichtigsten
Initialsprengstoffe. Zeitschrift f€ ur das gesamte Schiess- und Sprengstoffwesen 34, 197–201
(1939)
49. Kabik, I., Urman, S.: Hazards of copper azide fuzes. In: Proceedings of Minutes of the 14th
Explosive Safety Seminar, pp. 533–552 (1972)
50. Blechta, F.: Dnešnı́ stav otázky náhražek třaskavé rtuti. Chemický obzor 3, 330–336 (1928)
51. Curtius, T.: Neues vom Stickstoffwasserstoff. Berichte der deutschen chemischen Gesell-
schaft 24, 3341–3349 (1891)
52. Hanus, M.: Méně známé třaskaviny. Synthesia a.s., VÚPCH, Pardubice (1996)
53. Holloway, K.J., Taylor, G.W.C., Thomas, A.T.: Manufacture of dextrinated lead azide. US
Patent 3,173,818, 1965
54. Thomas, A.T.: Spontaneous explosion during crystal growth of lead azide. In: Proceedings of
Symposium on Lead and Copper Azide, pp. D-3, 103–111, Waltham Abbey, 1966
55. Garrett, W.L., Downs, D.S., Gora, T., Fair, H.D., Wiegand, D.A.: Preparation, characteriza-
tion and electric field initiation of lead azide single crystal. In: Jenkins, J.M.,White, J.R.
(eds.) Proceedings of the International Conference on Research in Primary Explosives, vol. 1,
pp. 4/1–4/9, Waltham Abbey (1975)
56. Garrett, W.L.: The growth of large lead azide crystals. Mater. Res. Bull. 7, 949–954 (1972)
57. Herz, E.V.: A process for manufacture of detonating compositions for detonators and
primers. GB Patent 187,012, 1922
58. Herz, E.V.: A process for manufacture of detonating compositions for detonators or primers.
US Patent 1,498,001, 1924
59. Spear, R.J., Elischer, P.P.: Studies of stab initiation. Sensitization of lead azide by energetic
sensitizers. Aust. J. Chem. 35, 1–13 (1982)
60. Friederich, W.: Manufacture of primig compositions. GB Patent 180,605, 1922
61. Todd, G., Tasker, M.P.: The identity of the gamma modification of basic lead azide type I.
Helv. Chim. Acta 54(7), 2210–2212 (1971)
126 4 Azides

62. Sinha, S.K.: Study of basic azides of lead by thermometric titration. In: Hansson, J. (ed.)
Proceedings of 3rd Symposium on Chemical Problems Connected with the Stability of
Explosives, pp. 16–32. Sektionen for detonik och Forbranning, Ystad (1973)
63. Sinha, S.K., Srivastava, R.C., Surve, R.N.: Basic azides of lead as safer primary explosives.
In: Jenkins, J.M., White, J.R. (eds.) Proceedings of the International Conference on Research
in Primary Explosives, vol. 2, pp. 11/1–11/18, Waltham Abbey (1975)
64. Agrawal, J.P.: High Energy Materials—Propellants, Explosives, Pyrotechnics. Wiley-VCH,
Weinheim (2010)
65. Taylor, C.A., Rinkenbach, W.H.: Silber azide: An initiator of detonation. Army Ordnance 5,
824–825 (1925)
66. Piechowicz, T.: Solubilité de l’azoture d’argent dans l’ammoniaque et dans la pyridine.
Bulletin de la Societe Chimique de France 5, 1566–1567 (1971)
67. Taylor, A.C., Nims, L.F.: The standard potential of the silver-silver azide electrode. J. Am.
Chem. Soc. 60, 262–264 (1938)
68. Dennis, L.M., Isham, H.: Hydronitric acid V. J. Am. Chem. Soc. 29, 18–31 (1907)
69. Merwe, L.: The preparation and chemical and physical characterization of silver azide. In:
Proceedings of 12th Symposium on Explosives and Pyrotechnics, vol. 12, 1984
70. Lamnevik, S.: Prevention of copper azide formation in ammunition. In: Proceedings of
Symposium on Lead and Copper Azide, pp. C-6, 92–96, Waltham Abbey, 1966
71. Taylor, G.W.C.: The Manufacture of Silver Azide RD 1336. Report 2/R/50 (Accession No.
ADA 474242), Explosives Research and Development Establishment, Waltham Abbey
(1950)
72. Field, J.E.: The mechanisms of initiation and propagation in primary explosives: a review. In:
Jenkins, J.M., White, J.R. (eds.) Proceedings of the International Conference on Research in
Primary Explosives, vol. 1, pp. 1/1–1/24, Waltham Abbey, Essex (1975)
73. Taylor, G.W.C., Jenkins, J.M.: Progress toward primary explosives on improved stability. In:
Proceedings of 3rd Symposium on Chemical Problems Connected with the Stability of
Explosives, pp. 43–46, Ystad, Sweden (1973)
74. Bates, L.R., Jenkins, J.M.: Search for new detonator. In: Jenkins, J.M., White, J.R. (eds.)
Proceedings of the International Conference on Research in Primary Explosives, vol. 2,
Waltham Abbey (1975)
75. Bekk, J.: The photographic behaviour of silver azoimide. J. Chem. Soc. 108, II200–II201
(1915)
76. Evans, B.L., Yoffe, A.D.: Structure and stability of inorganic azides. II. Some physical and
optical properties, and the fast decomposition of solid monovalent inorganic azides. Proc. R.
Soc. Lond. A Math. Phys. Sci. A250, 346–366 (1959)
77. Courtney-Pratt, J.S., Rogers, G.T.: Initiation of explosion by light and by flying fragments.
Nature 175, 632–633 (1955)
78. W€ohler, L., Krupko, W.: Action of light on silver, mercurous, lead and cuprous azoimides;
basic azoimides of lead and copper. J. Chem. Soc. 104II, 703 (1913)
79. Gray, P.: Chemistry of the inorganic azides. Quart. Rev. 17, 441–473 (1963)
80. Hitch, A.R.: Thermal decomposition of certain inorganic trinitrides. J. Am. Chem. Soc. 40,
1195–1204 (1918)
81. Millar, R.W.: Lead free initiator materials for small electro explosive devices for medium
caliber munitions. Final Report 04 June 2003. Report QinetiQ/FST/CR032702/1.1, QuinetiQ,
Farnborough (2003)
82. Taylor, A.C., Rinkenbach, W.H.: Sensitivities of detonating compounds to frictional impact,
impact, and heat. J. Franklin Inst. 204, 369–376 (1927)
83. W€ohler, L., Martin, F.: Azides; Sensitiveness of. J. Soc. Chem. Ind. 36, 570–571 (1917)
84. Roux, J.J.P.A.: The dependence of friction sensitivity of primary explosives upon rubbing
surface roughness. Propellants Explosives Pyrotechnics 15, 243–247 (1990)
85. Evans, B.L., Yoffe, A.D.: The burning and explosion of single crystals. Proc. R. Soc. Lond.
A238, 325–333 (1956)
86. Bowden, F.P., Williams, R.J.E.: Initiation and propagation of explosion in azides and
fulminates. Proc. R. Soc. Lond. A Math. Phys. Sci. 1951, A176–A188 (1951)
References 127

87. Yoffe, A.D., Evans, B.L., Deb, S.K.: Foreign cations in silver azide. Nature 180, 294–295
(1957)
88. W€ohler, L., Martin, F.: Die Initialwirkung von Aziden und Fulminaten. Zeitschrift f€ ur das
gesamte Schiess- und Sprengstoffwesen, (1917); 12, 18–21
89. Darier, G.E., Goudet, C.: Preventing explosions in handling azides and other explosives. US
Patent 1,349,411, 1920
90. Gray, P., Waddington, T.C.: Detonation and decomposition of silver azide sensitized by the
cyanamide ion. Chem. Ind. 1255–1257 (1955)
91. Blechta, F.: Verfahren zur Herstellung von Initialz€unds€atzen, welche kolloidale Silber- und
Quesksilberazide in lockerer, nicht zusammenbackender Form enthalten. AT Patent 126,150,
1932
92. Blechta, F.: Une nouvelle amorce a l’azothydrure. Chimie et industrie 921–925 (1933)
93. Taylor, G.W.C.: Improvements in the manufacture of silver azide. GB Patent 781,440, 1957
94. Williams, E., Peyton, S.V., Harris, R.C.: Improvements in or relating to the manufacture of
silver azide. GB Patent 887,141, 1962
95. McGuchan, R.: Improvements in primary explosive compositions and their manufacture. In:
Proceedings of 10th Symposium on Explosives and Pyrotechnics, San Francisco, 1979
96. Costain, T.S.: Process for producing silver azide. US Patent 3,943,235, 1976
97. Hirlinger, J.M., Bichay, M.: New Primary Explosives Development for Medium Caliber Stab
Detonators. Report SERDP PP-1364, US Army ARDEC, Washington DC (2004)
98. Hirlnger, J., Fronabarger, J., Williams, M., Armstrong, K., Cramer, R.J.: Lead azide replace-
ment program. In: Proceedings of NDIA, Fuze Conference, 2005
99. Hodgkinson, W.R.: Improvements in and relating to the production of azides. GB Patent
128,014, 1919
100. Turrentine, J.W.: Contributions of electrochemistry of hydronitric acid and its salts. I.
The corrosion of some metals in sodium trinitride solution. J. Am. Chem. Soc.
33, 803–828 (1911)
101. Cirulis, A.: Die explosiven Eigenschaften des Kupferazids Cu(N3)2, Zeitschrift fur das
gesamte Schiess- und Sprengstoffwesen (1943); 38, 42–45
102. Straumanis, M., Cirulis, A.: Das Kupfer(II)-azid. Darstellungsmethoden, Bildung und
Eigenschaften. Zeitschrift f€ur anorganische und allgemeine Chemie 251, 315–331 (1943)
103. Colton, R.J., Rabalais, J.W.: Electronic structure of some inorganic azides from X-ray
electron spectroscopy. J. Chem. Phys. 64, 3481–3486 (1976)
104. Wilsdorf, H.: Die Kristallstruktur des einwertigen Kupferazids, CuN3. Acta Crystallogr. 1,
115–118 (1948)
105. Duke, J.R.C.: The crystallography of copper azides. In: Proceedings of the Symposium on
Lead and Copper Azides, pp. C-5, 87–91, Waltham Abbey, 1966
106. Harris, R.C.: The formation and detection of copper azides corrosions. In: Proceedings of
Symposium on Lead and Copper Azide, pp. C-1, 70–71, Waltham Abbey, 1966
107. Lamnevik, S.: Copper azide corrosion. In: Proceedings of Symposium on Lead and Copper
Azide, pp. C-2, 72–77, Waltham Abbey, 1966
108. Holloway, K.J.: The preparation, identification and sensitiveness of copper azide. In:
Proceedings of Symposium on Lead and Copper Azide, pp. C-3, 78–83, Waltham Abbey,
1966
109. Turrentine, J.W., Moore, R.L.: The action of hydronitric acid on cuprous chloride and
metallic copper. J. Am. Chem. Soc. 34, 382–384 (1912)
110. Singh, K.: Sensitivity of cuprous azide towards heat and impact. Trans. Faraday Soc. 55,
124–129 (1959)
111. Curtius, T., Rissom, J.: Azoimide. J. Chem. Soc. 76, B92 (1899)
112. Senise, P., Neves, E.F.A.: Solubility study of copper(II) azide in aqueous sodium azide
solutions of low ionic strength. J. Inorg. Nucl. Chem. 33, 351–358 (1971)
113. Medlock, L.E.: Corrosion of copper detonator tubes in the presence of lead azide. In:
Proceedings of Symposium on Lead and Copper Azide, pp. C-4, 84–86, Waltham Abbey,
1966
128 4 Azides

114. Okubo, S., Shindo, K., Oinuma, S.: Copper azide detonators. I. Preparation of copper azide
and its impact sensitivity test. CAN 52, 8559 (1958)
€
115. W€ohler, L., Martin, F.: Uber neue Fulminate und Azide. Berichte der deutschen chemischen
Gesellschaft 50, 586–596 (1917)
116. Nockemann, P., Cremer, U., Ruschewitz, U., Meyer, G.: Mercurous azide, Hg2(N3)2.
Zeitschrift f€ur anorganische und allgemeine Chemie 629, 2079–2082 (2003)
117. Belomestnykh, V.N.: Uprugie cvoistva neorganicheskikh azidov pri ctandartnykh
usloviyakh. Neorganicheskie materialy 29, 210–215 (1993)
118. Birckenbach, L.: Cadmium azide (at the same time a warning). Zeitschrift f€ ur anorganische
und allgemeine Chemie 214, 94–96 (1933)
119. W€ohler, L., Martin, F.: Sensitiveness of azides. Angew. Chem. 30(I), 33–39 (1917)
120. Rathsburg, H.: Uber € die Bestimmung der Reibungsempfindlichkeit von Z€ unstoffen.
Zeitschrift f€ur das angewandte Chemie 41, 1284–1286 (1928)
121. Curtius, T., Rissom, J.: Neue Untersuchungen € uber den Stickstoffwasserstoff N3H. J. f€ ur
praktische Chemie 58, 261–309 (1898)
122. Klap€otke, T.M., Geissler, P.: Preparation and characterization of the first binary arsenic azide
species: As(N3)3 and [As(N3)4][AsF6]. J. Chem. Soc. Dalton Trans. 3365–3366 (1995)
123. Klap€otke, T.M., Schulz, A., McNamara, J.: Preparation, characterization and ab initio
computation of the first binary antimony azide, Sb(N3)3. J. Chem. Soc. Dalton Trans.
2985–2987 (1996)
124. Haiges, R., Vij, A., Boatz, J.A., Schneider, S., Schroer, T., Gerken, M., Christe, K.O.: First
structural characterization of binary AsIII and SbIII azides. Chemistry 10, 508–517 (2004)
125. Villinger, A., Schulz, A.: Binary bismuth(III) azides: Bi(N3)3, [Bi(N3)4]-, and [Bi(N3)6]3-.
Angew. Chem. Int. Ed. 49, 8017–8020 (2010)
126. Haiges, R., Boatz, J.A., Vij, A., Vij, V., Gerken, M., Schneider, S., Schroer, T.,
Yousufuddin, M., Christe, K.O.: Polyazide chemistry: Preparation and characterization of
As(N3)5, Sb(N3)5, and [P(C6H5)4][Sb(N3)6]. Angew. Chem. 116, 6844–6848 (2004)
127. Boyer, J.H., Canter, F.C.: Alkyl and aryl azides. Chem. Rev. 54, 1–57 (1954)
€
128. Finger, H.: Uber Abk€ommlinge des Cyanurs. J. f€ ur praktische Chemie 75, 103–104 (1907)
129. Taylor, C.A., Rinkenbach, W.H.: Preparation and detonating properties of cyanuric triazide.
J. Franklin Inst. 196, 551 (1923)
130. Hart, C.V.: Carbonic acid azides. J. Am. Chem. Soc. 50, 1922–1930 (1928)
131. Ott, E., Ohse, E.: Zur Kenntnis einfacher Cyan- und Cyanurverbindungen. II. Uber € das
Cyanurtriazid, (C3N12). Berichte der deutschen chemischen Gesellschaft 54, 179–186 (1921)
132. Ott, E.: Explosive and process of making same. US Patent 1,390,378, 1921
133. Ott, E.: Verfahren zur Herstellung von Initialz€ undmitteln und von Treib- und Sprengmitteln.
DE Patent 350,564, 1922
134. Hughes, E.W.: The crystal structure of cyanuric triazide. J. Chem. Phys. 3, 1–5 (1935)
135. Sutton, T.C.: Structure of cyanuric triazide (C3N3)(N3)3. Philos. Mag. 15, 1001–1018 (1933)
136. Ficheroulle, H., Kovache, A.: Contribution à l‘étude des explosifs d’amorçage. Memorial des
poudres 41, 1–22 (1959)
137. Imray, O.: Manufacture of a new explosive. GB Patent 170,359, 1921
138. Gillan, E.G.: Synthesis of nitrogen-rich carbon nitride networks from an energetic molecular
azide precursor. Chem. Mater. 12, 3906–3912 (2000)
139. Muraour, H.: Sur la théorie des réactions explosives. Cas particulier des explosifs
d’amorçage. Mémories présentés a la Société chimique 51, 1152–1166 (1932)
140. Mehta, N., Cheng, G., Cordaro, E., Naik, N., Lateer, B., Hu, C., Stec, D., Yang, K.:
Performance testing of lead-free stab detonator. In: Proceedings of NDIA Fuze Conference,
2006
141. Pepekin, V.I.: Limiting detonation velocities and limiting propelling powers of organic
explosives. Dokl. Phys. Chem. 414(2), 159–161 (2007)
142. Kroke, E., Schwarz, M., Buschmann, V., Miehe, G., Fuess, H., Riedel, R.: Nanotubes formed
by detonation of C/N precursors. Adv. Mater. 11, 158–161 (1999)
References 129

143. Utschig, T., Schwarz, M., Miehe, G., Kroke, E.: Synthesis of carbon nanotubes by detonation
of 2,4,6-triazido-1,3,5-triazine in the presence of transition metals. Carbon 42, 823–828
(2004)
144. Fogelzang, A.E., Egorshev, V.Y., Pimenov, A.Y., Sinditskii, V.P., Saklantii, A.R.,
Svetlov, B.S.: Issledovanie statsionarnogo goreniya initsiiruyushchikh vzryvchatykh
veshchestv pri vysokykh davleniyakh. Dokl. Akad. Nauk SSSR 282, 1449–1452 (1985)
145. Huynh, M.V., Coburn, M.D., Meyer, T.J., Wetzer, M.: Green primaries: Environmentally
friendly energetic complexes. Proc. Natl. Acad. Sci. 103, 5409–5412 (2006)
146. Huynh, M.V., Coburn, M.D., Meyer, T.J., Wetzer, M.: Green primary explosives:
5-nitrotetrazolato-N2-ferrate hierarchies. Proc. Natl. Acad. Sci. 103, 10322–10327 (2006)
147. Huynh, M.H.V., Hiskey, M.A., Hartline, E.L., Montoya, D.P., Gilardi, R.: Polyazido high-
nitrogen compounds: hydrazo- and azo-1,3,5-triazine. Angew. Chem. Int. Ed. 43, 4924–4928
(2004)
148. Huynh, M.H.V., Hiskey, M.A., Pollarod, C.J., Montoya, D.P., Hartline, E.L., Gilardi, R.:
4,40 ,6,60 -Tetrasubstituted hydrazo- and azo-1,3,5-triazines. J. Energetic Mater. 22, 217–229
(2004)
149. Huynh, M.H.V., Hiskey, M.A., Archuleta, J.G., Roemer, E.L.: Preparation of nitrogen-rich
nanolayered, nanoclustered, and nanodendritic carbon nitrides. Angew. Chem. Int. Ed. 44,
737–739 (2005)
150. Huynh, M.H.V., Hiskey, M.A.: Preparation of high nitrogen compound and materials there-
from. US Patent 2006/0211565, 2006
151. Loew, P., Weis, C.D.: Azo-1,3,5-triazines. J. Heterocyc. Chem. 13, 829–833 (1976)
152. Li, X.T., Li, S.H., Pang, S.P., Yu, Y.Z., Luo, Y.J.: A new efficient route for the synthesis of
4,40 ,6,60 -tetra(azido)azo-1,3,5-triazine. Chin. Chem. Lett. 18, 1037–1039 (2007)
153. Turek, O.: Le 2,4,6-trinitro-1,3,5-triazido-benzene, nouvel explosif d’amorçage. Chimie et
industrie 26, 781–794 (1931)
154. Turek, O.: 1,3,5-Triazido-2,4,6-trinitrobenzen, nová iniciálná výbušina. Chemický obzor 7,
76–79; 97–104 (1932)
155. Adam, D., Karaghiosoff, K., Klapotke, T.M., Hioll, G., Kaiser, M.: Triazidotrinitro benzene:
1,3,5-(N3)3-2,4,6-(NO2)3C6. Propellants Explosives Pyrotechnics 27, 7–11 (2002)
156. Ficheroulle, H., Kovache, A.: Contribution à l‘étude des explosifs d’amorçage. Mémorial des
poudres 31, 1–27 (1949)
157. Zielinski, B.: Ignition mixture for percussion caps of all kind, small munitions, and primers.
US Patent 2,111,719, 1938
158. Turek, O.: Blasting cartridge, percussion cap, detonator, detonating fuse, and the like. US
Patent 1,743,739, 1930
159. Turek, O.: A method of producing 2,4,6-trinitro-1,3,5-triazidobenzene. GB Patent 298,981,
1928
160. Turek, O.: Verfahren zur Herstellung von 1,3,5-Trinitro-2,4,6-triazidobenzol. DE Patent
498,050, 1930
161. Turek, O.: Improvements in and connected with explosive charges for detonators, percussion
caps, boosters, detonating fuses, projectiles and the like. GB Patent 298,629, 1927
162. Turek, O.: Verfahren zur Herstellung von Sprengladungen f€ ur Sprengkapseln, Z€undkapseln,
Detonationsz€undschn€ ure u. dgl. DE Patent 494,289, 1928
163. Improvements in ignition mixtures for percussion caps of all kind, small munitions and
primers. GB Patent 465,768, 1936
164. Fries, K., Ochwat, P.: Neues € uber Dichlor-2.3-naphthochinon-1.4. Berichte der deutschen
chemischen Gesellschaft 56, 1291–1304 (1923)
165. Šorm, F.: O tetrazidobenzchinonu (1,4). Chemický obzor 14, 37–39 (1939)
166. Gilligan, W.H., Kamlet, M.J.: On the explosive properties of tetraazido-p-benzoquinones.
Tetrahedron Lett. 19, 1675–1676 (1978)
Chapter 5
Salts of Polynitrophenols

Many heavy metal salts of polynitrophenols (e.g., phenol, resorcinol, or

phloroglucinol) have the character of primary explosives while alkaline salts are
secondary explosives. Primarily lead and barium salts are used or recommended for
practical applications. In general, lead and barium salts of nitrophenols have high
sensitivity to flame but low initiation efficiency. These properties make them
unsuitable in pure form and they are therefore mainly used in mixtures with other
substances. The increasing number of nitrogroups in the molecule increases the
overall energetic content, which is reflected in its higher sensitivity. The number of
nitro groups may be varied depending on the requirements for particular
applications. For example, lead mononitroresorcinol is used in fuse heads while
lead trinitroresorcinol is used in mixtures with other primary explosives, such as
LA, in detonators. Salts of polynitrophenols containing an azido group in the
molecule (primarily lead salts of mono and dinitroazidophenol) have also been
proposed as primary explosives but have not yet found a practical application [1].

5.1 Salts of Picric Acid

Picric acid forms normal and basic metallic salts. Out of all the salts of picric acid so
far investigated, only the normal lead salt is worth mentioning as it was for some
time used as a primary explosive in various initiating compositions. Investigations
and some limited use were also reported for the potassium salt; however, its low
sensitivity (F of I only 64–67) prevented it from fulfilling the role of a full-fledged
primary explosive and served rather as a energetic component of priming
compositions, igniferous compositions, or as a component of mixtures for
fuseheads [2, 3].

R. Matyáš and J. Pachman, Primary Explosives, 131

DOI 10.1007/978-3-642-28436-6_5, # Springer-Verlag Berlin Heidelberg 2013
132 5 Salts of Polynitrophenols

5.1.1 Normal Lead Picrate

NO2 O2N

O2N O Pb O NO2

NO2 O2N

Normal lead picrate forms several hydrates containing from 1 to 5 molecules of

crystal water. The tetrahydrate of lead picrate is obtained when an aqueous solution
of picric acid is treated with lead carbonate. The monohydrate results when the
tetrahydrate is retained at 80
C and also when the anhydride is exposed to air. The
anhydrous salt is obtained when the tetrahydrate or monohydrate is heated to
150
C [4].
The tetrahydrate forms silky yellow needles while the anhydride forms a yellow
powder [4]. Lead picrate is insoluble in water, ether, chloroform, benzene, and
toluene; sparingly soluble in acetone and alcohol [5].
Lead picrate is considered highly sensitive to mechanical impact and thermal
stimuli [6]. The anhydride is more sensitive to mechanical stimuli than the hydrates.
Impact sensitivity of anhydride is significantly higher than the sensitivity of mercury
fulminate (4 cm/0.5 kg vs. 24 cm for MF) [7, 8]. Handling of lead picrate anhydride
represents the same level of risk as handling of lead styphnate. The ignition
temperature is 281
C (explosion takes place instantaneously or within 1 s) [7].
The formation of lead picrate by reaction of tetryl (which decomposes to picric acid)
with lead azide is reported as a possible reason for the higher sensitivity of this
mixture compared to pure LA [6].

5.1.1.1 Preparation

Neutral lead picrate is prepared by reaction of aqueous solutions of picric acid [5, 9,
10] or mixture of picric acid and its sodium salt [5] with lead nitrate or acetate. Lead
picrate is isolated as a yellow precipitate.
OH
NO2
O2N NO2 O2N

2 + Pb(NO3)2 O2N O Pb O NO2 + 2 NaNO3

NO2 NO2
O2N

5.1.1.2 Use

Lead picrate was used in applications similar to those for lead styphnate, for
example, as part of ignition mixtures in fuses during World War II [8, 9]. Lead
5.2 Salts of Dinitroresorcinol 133

picrate can be used as an active component in initiating mixtures, e.g., for electrical
squibs in bridge-wire detonators. It has been also used in mixtures for electric
fuseheads [11].

5.1.2 Basic Lead Picrate

Lead picrate forms several basic salts with varying lead content. They form citric
yellow crystals practically insoluble in water or alcohol. Its explosive properties are
similar to those of lead styphnate but its flammability is lower [10]. Sensitivity to
electrostatic discharge is high (at the level of LS) and is the reason for the many
accidents which occurred during its manufacture [12]. Sensitivity to impact is 2.5 J
(it explodes by 5 kg hammer from 5 cm) [13].
Basic lead picrate is prepared by reaction of picric acid with yellow lead oxide in
water. The mixture is stirred and boiled during the reaction. Product forms as a
precipitate [11]. Basic lead picrate has similar explosive properties to those of LS
and was therefore used in similar applications (e.g., as a component of percussion
mixtures) [10–12]. Due to its lower flammability, it was, however, replaced in
practical use by LS [12].

5.2 Salts of Dinitroresorcinol

Dinitroresorcine (DNR) forms two isomers: 2,4 and 4,6. Unlike in the nitration of
some other aromatic molecules (toluene, phenol), it is possible to prepare practi-
cally pure dinitro isomers. The position of nitro groups in the ring depends on the
reaction conditions. The 2,4-isomer of DNR can be easily prepared by dinitrosation
of resorcinol followed by alkaline oxidation of 2,4-dinitrosoresorcinol [8, 14]. 2,4-
DNR cannot be prepared by sulfonation of resorcinol followed by reaction with
nitric acid (method used for phenol) because this method yields the trinitro com-
pound. The 4,6-DNR isomer can be prepared in two ways (a) by nitration of 4,6-
diacetylresorcinol and (b) directly by nitration of resorcinol using 98 % nitric acid
at low temperatures (between 20 and 15
C) [8].
Among the various possible lead salts of DNR only two have found industrial
application as primary explosives: normal lead salt of 2,4-dinitroresorcine (2,4-
LDNR) and basic lead salt of 4,6-dinitroresorcine (basic 4,6-LDNR).

5.2.1 Lead salts of 2,4-Dinitroresorcinol

2,4-Dinitroresorcinol (2,4-DNR) forms a variety of lead salts (2,4-LDNRs) includ-

ing acid, normal, and a large number of basic ones. The most commonly used and
best characterized is the normal 2,4-LDNR.
134 5 Salts of Polynitrophenols

Table 5.1 Comparison of impact sensitivity and brisance for LS and LDNR isomers [8]
LS Normal 2,4-LDNR Basic 4,6-LDNR
N content (%) 9.0 6.9 4.3
Pb content (%) 44.2 51.1 64.1
Impact sensitivity (cm for 1 kg hammer) 17 30 60
Brisance (sand test in % TNT) 50 41.7 31.3

0
O O O Pb OH
NO2 Pb NO2 Pb.PbO NO2 . 2PbO

O O O Pb OH
NO2 NO2 NO2

normal 2,4-LDNR monobasic 2,4-LDNR tribasic 2,4-LDNR

Normal 2,4-LDNR exists in two forms: yellow and orange described in one
source [8] or orange and red described in another source [15]. The crystal density is
3.2 g cm3 [8, 15]. These forms have differing physical but similar explosive
properties. Lead 2,4-dinitroresorcinol is insoluble in water, acetone, benzene, and
other common organic solvents [8].

5.2.1.1 Explosive Properties

Normal 2,4-LDNR is a less powerful explosive with even lower initiation efficiency
than lead styphnate. According to Payne, 0.4 g is not sufficient for initiation of tetryl
[8, 14]. 2,4-LDNR is less sensitive to impact and friction than lead styphnate.
Sensitivity and brisance of practically useful lead salts of polynitroresorcines
generally decrease both with increasing amount of lead and decreasing amount of
nitrogen (Table 5.1) [8]. The main reason for the practical application of normal
2,4-LDNR, despite its poorer explosive properties compared to LS, is increased
handling safety (particularly less susceptible to static electricity) [8, 9, 16].

5.2.1.2 Preparation

2,4-LDNR is generally prepared from 2,4-dinitroresorcinol and soluble lead salt

(nitrate or acetate) via the sodium salt (introduced as sodium carbonate). The
reaction is carried out in hot or boiling water [8–10, 14, 15].
+
- Na
OH O O
NO2 NO2 NO2 Pb
Na2CO3 Pb(NO3)2
-
OH O + O
Na
NO2 NO2 NO2
2,4-DNR 2,4-LDNR

The sodium salt can be replaced by other salts (e.g., magnesium) as well [17, 18].
The reaction conditions (pH, temperature regime, rate, and order of addition of
5.2 Salts of Dinitroresorcinol 135

reactants) influence not only the type of the prepared salt but also the shape of the
crystals and free-flowing properties of the final product [14, 17].
Basic 2,4-LDNR (mono-, tri-, and tetra-) are prepared from the corresponding
equimolar amounts of the sodium salt of DNR and lead nitrate in a basic environ-
ment [14]:

5.2.1.3 Use

Normal 2,4-LDNR was discovered at the end of nineteenth century and has been
employed since 1940 [19]. Its application is similar to that of LS due to their similar
explosive properties, particularly as an ingredient of priming mixtures. It has also
been used in compositions for electric detonators [8, 9, 16, 19].

5.2.2 Lead Salts of 4,6-Dinitroresorcinol

NO2 O2N O
O2N Pb
O2N O Pb O NO2
O
HO OH NO2

acid 4,6-LDNR normal 4,6-LDNR

4,6-Dinitroresorcinol (4,6-DNR) forms, just like the 2,4-isomer, a variety of lead

salts (4,6-LDNR) including acid, normal (the structures above), and a large number
of basic ones. The only salt with some recorded practical use in the past and
possibly some potential for future seems to be monobasic 4,6-LDNR.
O O O Pb OH
O2N Pb.Pb(OH)2 O2N Pb.PbO O2N

O O O Pb OH
NO2 NO2 NO2

monobasic 4,6-LDNR monobasic 4,6-LDNR monobasic 4,6-LDNR

formula I formula II formula III

Three structures of monobasic 4,6-LDNR are reported in the literature (a)

formula I—is used by [20, 21], (b) formula II—is used by [22], and (c) formula
136 5 Salts of Polynitrophenols

Table 5.2 Lead salts of 4,6-DNR

Composition Pb/DNR Comments References
Acid salt 1/2 Reported [24, 25]
Normal salt 1/1 Not yet isolated [24]
2/3 Basic salt 5/3 Reported [21, 24]
Monobasic salt (referred as basic salt) 2/1 Not yet isolated in pure form [24]
Reported [8, 14, 20, 23]
Dibasic salt 3/1 Reported [14, 20, 24]
Tribasic salt 4/1 Doubtful existence reported [14, 20, 24]

Table 5.3 Lead salts of 4,6-DNR

Composition Color Comments References
2/3 Basic salt – Density: crystal 3.65 g cm3, bulk 1.3–1.4 g cm3 [21, 24]
Monobasic salt Yellow Less dense “micro-crystalline” [8, 15]
Brick-red Denser red form [8, 14, 15]
Dibasic salt Dark red – [14]
Tribasic salt Deep orange – [14]

III—is used by [8, 14, 15, 23]. For di- and tri-basic 4,6-LDNR, Payne proposed the
following structures [14]:
O Pb OH O Pb OH
O2N . PbO O2 N . 2PbO

O Pb OH O Pb OH
NO2 NO2

dibasic 4,6-LDNR tribasic 4,6-LDNR

The problems related to the correctness of each of the structures are similar to
those encountered with basic lead styphnate and are therefore addressed there.

5.2.2.1 Physical and Chemical Properties

The overview of reported 4,6-LDNR salts is outlined in Table 5.2 and their crystal
form and color in Table 5.3 [20, 22, 24].
The form prepared by Taylor et al. [21] and mentioned in [24] is made of basic
salt containing 3 molecules of lead 4,6-dinitroresorcinol and 2 molecules of lead
hydroxide – 3[PbDNR]·2Pb(OH)2 further reported as 2/3 salt. The ratio of lead to
DNR in this substance is 5:3. The 2/3 basic lead salt has a density 3.65 g cm3 and
it is practically insoluble in water (0.01 g/100 ml). The salt is compatible with
common metals and oxidizers and stable under water for a long time (no change
was observed over a period of 1 year) [24].
5.2 Salts of Dinitroresorcinol 137

The most frequently described, and probably the only lead salt that has been
practically used, is monobasic lead 4,6-dinitroresorcinol, mostly called just basic
lead 4,6-dinitroresorcinol. It can be prepared in two forms—yellow and red (see
Table 5.3) both having the same chemical and explosive properties [15].

5.2.2.2 Explosive Properties

All of the lead salts of DNR have worse explosive properties than LS. The initiation
efficiency of monobasic 4,6-LDNR is poor (0.4 g does not initiate tetryl pressed to
20.7 MPa) [8]. The comparison of 4,6-LDNR with LS and normal 2,4-LDNR was
mentioned previously (see Table 5.1).
The sensitivity data of 2/3 basic lead salt of 4,6-DNR were published by Jenkins.
The figure of insensitiveness (F of I) is 20 (compared to RDX ¼ 80) and ignition
temperature is 248
C at heating rate 5
C min1 [24].

5.2.2.3 Preparation

Preparation of various basic salts is based on the reaction of either (a) lead nitrate in
a basic environment (NaOH) or (b) freshly prepared lead hydroxide (precipitated
from aqueous solutions of lead acetate and sodium hydroxide) with 4,6-
dinitroresorcinol or its salts.

The form of the product (Table 5.4) depends on the reaction conditions (amount
of lead compound, temperature, reaction period, pH, rate and order of addition of
reactants) [24]. The following forms are reported based on the temperature of the
reaction mixture: acid 50–60
C preferably 55
C, normal 40–50
C preferably
45
C, and 2/3 basic at 18–28
C preferably 23
C [25]. The particular basic salts are
formed from exact molar proportions of lead salts in a basic environment (NaOH)
[14, 15, 22]. The manufacturing process of 2/3 basic salt (RD 1353) has been
described by Jenkins [24]. The normal salt is prepared from 4,6-dinitroresorcinol
in an aqueous suspension of freshly prepared lead hydroxide [25]. Crystal modifiers
(e.g., carboxymethyl cellulose) are recommended for preparation of the product in a
more suitable form for processing [26, 27].
138 5 Salts of Polynitrophenols

Table 5.4 Content of Pb in Composition Pb content (%) References

various salts of 4,6-DNR
Acid salt 34.1 [25]
Normal salt 51.1 [25]
2/3 Basic salt 61.0 [21, 24, 25]
Monobasic salt 64.1 [8, 14, 15, 22]
Dibasic salt 71.5 [14, 22]
Tribasic salt 75.9 [14, 22]

5.2.2.4 Uses

Large-scale manufacturing of basic lead 4,6-dinitroresorcinol was developed in

Great Britain during World War II [8, 23].

5.3 Salts of Trinitroresorcine

5.3.1 Lead Styphnate

O
O2N NO2 Pb.H2O

O
NO2

Lead styphnate (lead salt of 2,4,6-trinitrobenzene-1,3-diol, LS, LTNR, tricinate)

was, according to the well-established reference [8], first prepared by Edmund von
Herz in 1914 by reaction of magnesium styphnate with lead acetate in presence of
nitric acid. However, in reality, preparation of LS was published more than 40 years
earlier by Stenhouse [28]. This discrepancy in historical data is probably caused by
the fact that Herz patented the substance as a component of a detonator primary
charge and was therefore the first one who found some real application [29, 30]. The
preparation route used by Stenhouse is based on the reaction of lead acetate with an
aqueous solution of styphnic acid [28].

5.3.1.1 Physical and Chemical Properties

Normal lead styphnate forms a monohydrate with crystal density from 3.06 to
3.1 g cm3 [31, 32]; heat of formation of LS is 835 kJ mol1 [1]. LS exists as
two polymorphs, a and b [24]. Many authors, however, do not distinguish between
these two forms [5, 8, 9, 12].
LS crystallizes as monohydrate in the form of gold, orange, or reddish-brown
monoclinic crystals (Fig. 5.1). The reason for the various colors of LS crystals has
5.3 Salts of Trinitroresorcine 139

Fig. 5.1 Crystals of lead

styphnate

not been successfully explained [33]. Crystals of LS turn red on heating with
concurrent fracture of the crystals into irregular particles of greatly decreased
dimensions. The loss of water leads to formation of a sensitive anhydride with
density 2.9 g cm3. Upon rehydration, the red color of the anhydrous salt reverts
back to the characteristic orange. The crystals containing crystal water are slightly
hydroscopic. Hydroscopicity is mostly reported significantly higher than MF and
LA [34, 35] even though some authors (e.g., Kast and Haid) reported lower
hydroscopicity than LA and MF [36]. LS does not lose crystal water easily at
ambient temperatures and its loss is not significant even up to about 100
C [10, 37].
According to Wallbaum, LS does not change during 2 months of storage at
65–70
C [33, 38]. Above 100
C LS loses crystal water [1]; it takes 16 h at
115
C, 7 h at 135
C, and under 4 h at 145
C as can be seen from Fig. 5.2 [39].
During this process, crystals of LS break apart releasing water from the crystals.
Hailes [37], however, reports that crystal rupture occurs only at rapid heating above
200
C which is in disagreement with our experience and today’s technological
processes. The phenomenon of reversible dehydratation/rehydratation coupled with
crystal rupture is industrially used (at 140
C) for modification of crystal size
leading to elimination of graining, which is a risky operation. The industrial product
before and after the heat treatment is shown at the same magnification in Fig. 5.3.
Efforts aimed at removing the crystal water by storing LS in a desiccator above
calcium chloride at normal temperature failed [33].
LS is slightly soluble in water (0.04 g per 100 g of water at 15
C [10] or 0.09 g
per 100 g of water at 17
C [34]), methanol, pyridine, and amyl acetate; it is
practically insoluble in ether, acetone, and common chlorinated solvents [34].
Lead styphnate is soluble in aqueous ammonium acetate, formamide [1, 20, 33],
acetic acid [28], and ethanolamine (30 g per 100 g of ethanolamine at 17
C.) It can
be precipitated from acetic acid solution by addition of alcohol [28].
LS can be kept under water or a mixture of water and isopropyl alcohol until
used, without decomposition [40]. LS, unlike LA, does not react with carbon
dioxide. Dry LS does not react with common metals; wet LS reacts only with
140 5 Salts of Polynitrophenols

145°C
1
135°C 115°C

0.8
Lost of crystal water (mol)

0.6

0.4

0.2

rehydration at 30°
0
0 2 4 6 8 10 12 14 16

Time (hours)

Fig. 5.2 Rate of loss of water from normal LS mono hydrate at various temperatures [39]

Fig. 5.3 Effect of heat treatment on the crystal structure of LS; left—as synthesized, right—the
same product after heat treatment (by kind permission of Pavel Valenta, Austin Detonator, Vsetı́n,
Czech Republic)

lead forming basic salt [34]. LS is decomposed by action of acids (e.g., sulfuric,
nitric) giving styphnic acid and the relevant lead salt. With bases, LS also
decomposes forming its basic salts and lead hydroxide [1, 10]. The laboratory
destruction of LS may be done using bases. The procedure is based on dissolving
LS in 40 its weight of an aqueous solution of 20 % sodium hydroxide and adding a
solution of sodium dichromate in an amount equal to half the weight of LS [8].
Ficheroulle and Kovache [34] recommended nitric acid (10 %) as a decomposition
agent in which case lead nitrate and styphnic acid are formed. LS is compatible with
most common explosives when dry (e.g., RDX, tetryl, TNT) [20].
The influence of g irradiation (cobalt-60, at 25
C) upon the decomposition of LS
has been published by Flanagan [41]. He observed that LS is many times more
5.3 Salts of Trinitroresorcine 141

resistant to ionizing radiation than LA. The rate of thermal decomposition of LS

increases with the dose of previously applied irradiation. Irradiations in air and in
vacuum gave the same results [41].

5.3.1.2 Explosive Properties

LS is extremely sensitive to flame and electric spark; moreover, various handling

operations, or container characteristics, can easily create an electrostatic charge on
the surface of the crystals. Its sensitivity is higher than MF, LA, DDNP and most
other primary explosives. This extreme sensitivity presents a significant problem
which resulted in the past in many accidents during LS production or handling. The
critical operations include those where movement of the material can result in
electrostatic charge formation, especially mechanical grain size and shape
modifications and sieving [33]. Many accidents occur during production and
handling. Significant safety precautions are therefore necessary to eliminate sources
of static electric.
The extreme sensitivity of LS to electrostatic discharge was the reason behind
the work on desensitized LS development and manufacture. One of the methods of
desensitization is based on washing the final product with a solution of a
desensitizing agent (e.g., benzene solution bee wax) [33]. The LS acquires the
form of uniform granules, less sensitive to mechanical stimuli and electrostatic
discharge, however, still keeping the same desired sensitivity to flame as the non-
desensitized variety [10].
During World War II, Germany developed a method of coating LS with graphite
producing so-called “black LS.” The idea was to make the compound more
conductive and hence less sensitive but the practical experience showed no
improvement as to the number of explosions in production [12].
LS is often used in bridge-wire compositions where it is in direct contact with
wire heated by an electric current. An interesting study of the effect of loading
density on the hot wire initiation of lead and barium styphnates was carried out by
Naval Ordnance Laboratory [42]. It was found that the energy required for the
initiation remained constant and the time to ignition decreased as the loading
density increased.
The sensitivity to mechanical stimuli (impact and friction) is not that critical, as
can be seen from Figs. 2.15 and 2.19. The sensitivity of LS to impact is mostly
reported lower than LA [15, 36, 43–46]; however, some authors report sensitivity
being higher [47, 48]. The same discrepancy in results is published for friction
sensitivity where lower values are reported by [5, 7, 38], while higher sensitivity is
reported by Danilov [1]. Our own results of friction sensitivity testing at room
temperature indicate that LS is less sensitive than LA (see Fig. 2.19). Sensitivity of
LS to mechanical stimuli significantly increases with increasing temperatures (even
at 75
C) [38], while it decreases at low temperatures [20]. Increasing of impact
sensitivity of LS during storage at higher temperatures can be demonstrated by
trials conducted over 60 days at 75
C when it increased from 23 cm to 5 cm using
1 kg hammer [10].
142 5 Salts of Polynitrophenols

Table 5.5 Detonation Density (g cm3) Detonation velocity (m s1) References

velocity of lead styphnate
0.93 2,100 [9]
2.6 4,900 [36]
2.9 5,200 [36]
3.1 5,600 [50]

Table 5.6 The power of LS compared with LA and MF measured in lead block
Trauzl block for Trauzl block for Lead block for Trauzl block for 10 g
10 g (cm3) [1] 10 g (cm3) [38] 2 g (cm3) [36] (%TNT) [15]
LS 130 122 29.0 40
MF 110 133 33.0 51
LA 110 113 25.6 39

According to Danilov et al. [1], the heat of explosion of LS is 725 kJ mol1. The
course of explosive decomposition of LS is difficult to characterize precisely, but
the decomposition is best described by the following equation [33, 36, 49]:
O
O2N NO2 Pb.H2O 80 Pb(g) + 172 CO 2 + 294 CO + 14 HCN +
80
O + 31 H2 + 81 H2O (g) + 113 N2
NO2

The volume of gaseous product is 270 dm3 kg1 [33]. The detonation velocity of
LS at various densities and conditions is summarized in Table 5.5.
The initiating efficiency of LS is very poor and in its pure form it is not able to
initiate any other common high explosives except uncompressed PETN [38].
Bubnov, for example, reported that even 2 g LS are not able to initiate tetryl [51].
This is the reason why it is considered as a poor primary explosive or even not
considered at all as a typical primary explosive [12]; this type of primary explosive
is sometimes described as a pseudo initiating substance [33].
Power of LS is relatively low. The exact values determined by lead block are
listed in Table 5.6 together with MF and LA for comparison [15, 38].
Very interesting results of TNT equivalency for LS were published by Swatosh
et al. [52] from blast wave measurements particularly from max. peak pressure and
positive impulse. Depending on the form of the test and scaled distance, TNT
equivalence was in the range of 30–65 %.
The ignition temperature of LS is 255
C at heating rate 5
C min1 [3] and
275–277
C at heating rate 20
C min1 [36]. The temperature at which explosion
occurred within 5 s was 280
C according to Danilov et al. [1] and instantaneous
explosion occurred at 270
C when measured by Kast and Haid [36]. The depen-
dence of time to detonation of LS on temperature has been published by Hailes [37].
The results are in the original paper presented for varying sample amounts (from 0.5
to 6.7 mg), which makes the data very difficult to compare as the size influences the
5.3 Salts of Trinitroresorcine 143

Fig. 5.4 Time to explosion of LS as a function of temperature [37]

time to explosion. We have therefore summarized only the results from 0.5 to
2.0 mg and the results are presented in Fig. 5.4.

5.3.1.3 Preparation

The earliest published preparation method found by the current authors is based on
addition of a solution of lead acetate to an aqueous solution of styphnic acid [28].
The reaction yielded a yellow gelatinous form of LS when simply mixing the
reactants and deep yellow needles if boiled with slight excess of lead carbonate
instead of lead acetate.
The usual way of LS preparation is based on adding a solution of a soluble
styphnate salt (Na, K, Mg, NH4+), most commonly magnesium styphnate, to a well-
stirred lead nitrate or lead acetate solution. The lead styphnate precipitates from the
reaction mixture.
2+
- Mg
OH O O
O2N NO2 O 2N NO2 Pb(NO3)2 O 2N NO2 Pb.H2O
MgO
H O
- 2
OH O O
NO2 NO2 NO2
TNR LS

The reaction conditions (especially pH and temperature) are the key factors
influencing the type of LS formed. Control of pH is essential to avoid basic
styphnate formation (addition of weak acetic acid).
Magnesium styphnate is prepared by addition of magnesium oxide to trinitror-
esorcine water suspension [8, 10, 12, 53–55]. Precipitation of pure LS requires a
144 5 Salts of Polynitrophenols

higher temperature (mostly 65–80
C) than that required to produce material for
wax coating (around 45–50
C) [10]. Some more complicated temperature profiles
employed in production of LS are summarized in [55]. If the temperature drops
below 40
C during preparation, an amorphous form unsuitable for further techno-
logical processing is formed. The technological details of LS production are
detailed in many books [1, 10, 12, 33, 56]. The addition of crystal modifiers (e.g.,
carboxymethyl cellulose) is recommended for preparation of LS in a more suitable
form for processing [26, 27]; addition of PVA to the reaction mixture very strongly
suppresses formation of b-LS [57]. The purity of styphnic acid has an impact on the
properties of LS as well. If it is prepared from very pure styphnic acid, it has a
markedly increased tendency to hydrolyze in water [3].
The influence of reaction conditions on properties, yield, and purity of LS was
studied in detail by Stettbacher (LS was prepared by reaction of sodium styphnate
and lead nitrate). His observations were summarized by Bagal as follows [33]:
• The yield of LS increases with purity of styphnic acid.
• The order of batching does not have significant influence on quality of LS. It
does not matter which reactant’s pH is adjusted, the quality and quantity of LS
stay the same.
• LS prepared at high temperature forms a precipitate; the gelatinous form of LS
forms when reaction takes place at room temperature. The gelatinous form of LS
only deflagrates by action of flame rather than detonation.
• The amount of acetic acid that is added for modification of pH has to be low, the
yield of LS decreasing with increasing amount of acetic acid.
• The yield of LS is higher with more concentrated solutions.
Free styphnic acid is not a suitable starting material due to its low solubility in
water and formation of nitric acid as a by-product of the reaction (nitric acid
decomposes LS). When the sodium or magnesium salt of styphnic acid is used,
innocuous sodium or magnesium nitrate forms as a by-product [33]. The reagents
for LS production are used in equimolar quantity. However, when excess lead
acetate is used as a starting substance, the double salt of LS and lead acetate is
formed. But the double salt of LS and an initial lead salt only forms when the lead
salt of a weak organic acid is used (e.g., lead acetate) [58].
OH O O
O2N NO2 Pb(CH3COO)2 O2N NO2 Pb O2 N NO2 Pb.Pb(CH3COO)2
Pb(CH3COO)2

OH O O
NO2 NO2 NO2

TNR LS

An unusual dihydrate of LS can be prepared via magnesium styphnate in a

similar way to that for normal LS. However, the solutions used for preparation of
the dihydrate must be diluted, reaction temperature must be low (about 9
C), and
the reaction mixture must not be stirred. The dihydrate forms within several hours
(about 18 h) as red needles [33].
5.3 Salts of Trinitroresorcine 145

Lead styphnate can also be prepared as a jelly [58, 59]. The jelly product forms
by mixing a concentrated solution of lead nitrate or acetate with styphnic acid at
low pH (2.8–5.5) at room temperature. The sequence of addition and the concen-
tration of reagents are critical. At pH >5.5 LS forms in the crystalline form [59].

5.3.1.4 Use

The application of lead styphnate is dictated by its high sensitivity to flame and its
low brisance. Initiating efficiency of lead styphnate is poor but it easily initiates less
flame-sensitive primary explosives. The combination of the high flammability of
lead styphnate and the high initiating efficiency of lead azide has been the reason
for using a mixture of these two substances in blasting caps since 1920 [60, 61].
Mixtures of LS and GNGT were used in percussion and stab-initiated applications
[10]. Another function of lead styphnate in this mixture is coating lead azide and
hence protecting from mechanical stimuli and the chemical influence of moisture
and carbon dioxide from the environment [1, 33, 51]. A drawback, not frequently
considered, is the acid reaction of LS in presence of moisture that accelerates
hydrolysis of LA [3]. The phenomenon of compatibility of LA/LS has already
been discussed in Chap. 4.
LS is also the main component of many pyrotechnic mixtures for primers often
in combination with GNGT (e.g., SINOXIDE composition [62]). It is moreover
used as a component of fusehead composition (Valenta Private Communication).
Despite its excellent properties for primer applications and plenty of experience, the
presence of lead is causing its replacement by non-toxic alternatives.

5.3.2 Basic Lead Styphnate

O O Pb OH
Pb.Pb(OH)2 O2N NO2
O2N NO2

O O Pb OH
NO2 NO2

monobasic LTNR monobasic LTNR

formula I formula II

Lead styphnate forms a variety of basic salts of which only the monobasic salt
(simply called basic) is of practical significance. Monobasic LS was, according to
Fedoroff and Shefield [8], first prepared by Griess in 1874 [63]; however, reference
to preparation of this substance was not found by the current authors in the original
article.
146 5 Salts of Polynitrophenols

Table 5.7 Differing forms of Form Polymorph r (g cm3) References

mono basic lead styphnate
Yellow orthorhombic a 4.05 [67]
Red diamond b 4.12 [65, 67]
4.06 [24]
Yellow amorphous g 4.13 [67]

Two structures of basic lead styphnate are commonly used. The first structure
represents a double salt of lead styphnate and lead hydroxide (formula I) [20, 33,
39, 64]. In the second structure each lead atom is bonded with one oxygen atom of
the trinitroresorcinol molecule (formula II) [8, 65, 66].

5.3.2.1 Physical and Chemical Properties

Basic lead styphnate exists in three polymorphic forms listed in Table 5.7 [20, 64, 67].
Some literature resources list only two forms, red prisms (4.06 g cm3) and
yellow needles (3.88 g cm3) [8, 33, 40, 65]. The bulk density of the red form is
0.6–0.65 g cm3 while for the yellow version it is only 0.25 g cm3 [33].
Basic lead styphnate is practically insoluble in water (red form slightly more
than practically insoluble yellow form—0.0008 g/100 ml at 25
C) [24, 33]. Both of
them are soluble in aqueous ammonium acetate and practically insoluble in organic
solvents that do not dissolve lead styphnate [40]. The hygroscopicity of both forms
is not high; however, when comparing the two forms, the red is significantly less
hydroscopic than the yellow [33]. In presence of moisture it is almost neutral unlike
the acidic normal salt. Basic LS is thermally stable in moist air (90 %) at higher
temperatures (74
C) for a considerable time [20]. The basic salt has superior
thermal stability compared to the normal salt [64]. It is compatible with aluminum
and copper metals and also with oxidizers [24]. It is stable in water (no changes
under water for 2 months) [24] and can be chemically decomposed in similar way to
that for normal lead styphnate [8]. Normal LS is formed on treating styphnic acid
with basic LS in 50 % ethanol at pH ¼ 4 [59].

5.3.2.2 Explosive Properties

Basic lead styphnate is quite sensitive to electrostatic discharge which makes its
handling and loading particularly hazardous. The sensitivity of each form is differ-
ent and varying degrees have been found by various researchers. The sensitivities to
impact are reported according to the following sequence:
Yellow amorphous  yellow orthorhombic < red prism diamond [67]
Red hexagonal < yellow needles [68]
The sensitivity to impact of b form (red) is reported to be the same as or higher
than that for LS (F of I is 10 while 20 for LS); sensitivity to friction is similar to LS
5.3 Salts of Trinitroresorcine 147

and temperature of ignition is 248–250
C at heating rate 5
C min1 [24]. The

temperature of ignition of basic LS is 240
C (heating rate 5
C min1) [69]. Bagal
reported 280
C for the yellow form and 287
C for the red form (explosion within
5 s) [33].
The sensitivity to electrostatic discharge is reported in the following order [24]:
Yellow amorphous (g) < yellow (a) < red (b)
The sensitivity of basic LS to flame is about the same as for LS [33]. The
brisance of the orthorhombic yellow form is higher than that of other forms based
on the results of a sand test [67]. Sensitivity of basic LS to flame rapidly decreases
in presence of water. It cannot be ignited by flame if the water content is higher than
10 % [20].

5.3.2.3 Preparation

The basic lead styphnate is prepared by reaction of the sodium or magnesium salt of
2,4,6-trinitroresorcine in an alkaline reaction medium with lead nitrate [8].
+
- Na
OH O O
O2N NO2 O2N NO2 O2N NO2 Pb.Pb(OH)2
NaOH Pb(NO3)2
-
- OH
OH O + O
Na
NO2 NO2 NO2
TNR basic LTNR

An alternative preparation method involves the ammonia salt of 2,4,6-

trinitroresorcine [24, 64, 66]. The formation of the desired form and crystal shape
depends on reaction conditions. The addition of 2-mononitroresorcinol in an
amount between 0.1 and 5 % is sometimes employed in the preparation of the red
form to improve its bulk density and flowability [24, 64]. The presence of foreign
substances in the starting 2,4,6-trinitroresorcine (added in the sulfonation operation
in the preparation of styphnic acid) has also a significant influence on the shape of
basic LS crystals [70]. Various procedures are patented for preparation of red [24,
64, 65, 71] and yellow [39, 64–67] basic lead styphnate. Just like LS, the basic LS
can also be prepared as a jelly (see lead styphnate).

5.3.2.4 Use

Basic lead styphnate has been used as a component of priming compositions [24]
for percussion primers and stab detonators (e.g., component of NOL 130 primer
mixture that contains 40 % basic LS, 20 % LA, 2 % GNGT, 15 % Sb2S3, and 20 %
BaNO3) [8]. It is also used as a component of fusehead compositions [24].
148 5 Salts of Polynitrophenols

5.3.3 Double Salts of Lead Styphnate

Lead styphnate also forms double salts. Mainly salts with tetrazole compounds
were examined as brisant primary explosives. The main attention was aimed at
double salts of styphnic acid with 1,3-di(5-tetrazoyl)triazene (LDDS) and styphnic
acid with 5-nitraminotetrazole (PbNATNR). The study of these salts was done in
the 1960s and 1970s.
N H N N N
N N
C N N N C C N NO2
N N N
N N N

Pb Pb Pb Pb
NO2 NO2
O O O O

NO2 NO2
O2N O2N

LDDS PbNATNR

5.3.3.1 Physical and Chemical Properties

The double salt of styphnic acid and 5-nitraminotetrazole (PbNATNR) forms

lemon yellow crystals with crystal density 3.6 g cm3 (density of LS is
3.03 g cm3). It is practically insoluble in cold water, slightly soluble in hot
water (0.032 g/100 ml at 25
C and 0.175 g/100 ml at 70
C). PbNATNR is stable
under hot water for a long time, no decomposition being observed after several
months stored at 65
C. Thermal stability is superior to that of LS, and weight loss
after 24 h at 210
C is 0.5 % (compared with 24.3 % for LS) [72].
According to Sinha, LDDS shows higher thermal stability than GNGT, LS and
even higher than LA. The thermal stability is better even at high humidity. The
compound does not lose weight up to 280
C. It is interesting that the double salt
LDDS has higher thermal stability than either of the two components, lead 1,3-di
(5-tetrazoyl)triazene and lead styphnate [72, 73].

5.3.3.2 Explosive Properties

The impact sensitivity of LDDS is higher than LS, sensitivity to friction is reported
to be of the same order as that of service LA or higher (see Table 5.8) [74].
The impact sensitivity of the double salt of styphnic acid and 5-nitramino-
tetrazole (PbNATNR) is higher than LS, and it explodes with far greater force and
vigor. Brisance of PbNATNR is high, it is superior to that of LS, LA, and MF. The
ignition temperature is 340
C (compared with 320
C for LS) [72].
5.3 Salts of Trinitroresorcine 149

Table 5.8 Explosive properties of LDDS and PbNATNR

LDDS PbNATNR LS LA MF References
Impact sensitivity (cm)a – 14 16 – – [72]
Impact sensitivity (kg m cm2) 0.107 – 0.210 0.202 0.112 [73, 74]
Explosion temperature (heating 290, 312 – 255, 270 – – [73]
rate 5
C min1, TGA)
Sand test (g) – 24.0 16.1 14.2 18.9 [72]
a
100 g weight.

5.3.3.3 Preparation

Double salts are prepared by action of aqueous soluble lead salt on an equimolar
mixture of styphnic acid (in the form of the magnesium salt) and soluble salt of the
tetrazole compound [72, 73].

5.3.3.4 Use

Double salts were suggested as a lead azide replacement. Both salts are reported as
powerful as lead azide and show neither low sensitivity to flame nor a tendency to
hydrolyze [72, 73]. Information about their practical application is not available.

5.3.4 Barium Styphnate

O
O2N NO2 Ba.H2O

O
NO2

The scientific literature is a bit puzzling regarding the history of this substance.
Griess is sometimes mentioned as the first chemist who prepared barium styphnate
[63] in 1874. It is, however, not true as the article clearly references work of
Stenhouse [28] who prepared the barium, lead, and silver salts of styphnic acid
for comparison with orcin (5-methylbenzene-1,3-diol) salts of the same metals four
years earlier. In addition, the article of Griess is surprisingly often erroneously
referred to as the first work publishing preparation of lead styphnate.
150 5 Salts of Polynitrophenols

Table 5.9 Differing forms of Aspect Form r (g cm3)

barium styphnate
monohydrate [33] Yellow labile Enol form of TNR –
Red labile Acid form of TNR 2.581
Yellow stable Diketo form of TNR 2.625

Table 5.10 Temperature of ignition (explosion within 5 s) and sensitivity to flame [33]
Temperature of ignition (
C) Sensitivity to flame (cm)a
Monohydrate—yellow 356 1
Monohydrate—red 361 1.5
Anhydride 346 5
a
Height at which 100 % initiation occurs (without pressing) measured on pendulum for investiga-
tion of sensitivity to flame.

5.3.4.1 Physical and Chemical Properties

Barium styphnate (barium salt of 2,4,6-trinitrobenzene-1,3-diol; BaS) forms an

anhydride and two hydrates, monohydrate and trihydrate; only the anhydride and
the monohydrate are used in practical applications [20, 75, 76]. According to Bagal
the monohydrate of barium styphnate exists in three polymorphic forms listed in
Table 5.9 [33].
The red form is not stable and easily changes to the yellow labile form in (a)
acidic environments, (b) large amount of residues of solvent or inorganic
compounds from precipitation in crystals, or (c) in presence of DNR in TNR. In
solution, the red form also changes into the yellow labile form. The red form is
slightly soluble in cold water, better in boiling water, and insoluble in ethanol,
ether, and other organic solvents. The yellow stable form is less soluble in water
than red BaS (about 2.5 times less) [33].
Barium styphnate trihydrate forms yellow-orange needles. It is more soluble in
water than the monohydrate. Trihydrate loses two crystal waters at 105
C and red
needles of monohydrate are formed [33]. The original work of Griess reports the
trihydrate formed as rhombohedric prisms with low solubility in water [63].
The monohydrate is more difficult to dehydrate than LS and it only loses its
molecule of water after heating to 170
C [2] or 160
C at pressure 91 kPa [33].
The anhydride is, however, not stable in air and quickly absorbs moisture reverting
back to its monohydrate form. The monohydrate is slightly hydroscopic, less than LA
[33], and it is thermally stable as it loses only 0.1 % wt. within 2 h at 160
C [2].

5.3.4.2 Explosive Properties

Barium styphnate is not very sensitive to impact; less than LA and LS. The F of I of
this compound is only 40 (while 20 for LS and 15 for LA) [2]. Thermal sensitivity
and sensitivity to flame depends on the form. The values for the anhydride and the
5.3 Salts of Trinitroresorcine 151

two monohydrate forms are summarized in Table 5.10. Brisance of BaS

monohydrate is lower than for LS [33]. It is reported to lose water of crystallization
accompanied by a change of color to orange-red followed by explosion “with
extreme violence” when gently heated on platinum foil [28].

5.3.4.3 Preparation

The earliest method for BaS is described by Stenhouse who dissolved trinitror-
esorcine in 100 parts of boiling water and added excess of barium carbonate [28].
On cooling he obtained pale yellow rhomboidal plates. Analysis showed presence
of three waters of crystallization.
Direct precipitation of BaS anhydride is not possible as one of three polymorphic
forms of the monohydrate is produced depending on reaction conditions. The red
form is created when freshly prepared styphnic acid is used for precipitation of
barium styphnate. It is formed by direct reaction of equivalent amounts of TNR and
barium carbonate. The yellow stable salt is formed when “old TNR” is used for BaS
preparation, in an acidic environment or in excess precipitating agent. It is com-
monly prepared via the sodium salt of styphnic acid. The trihydrate of BaS forms in
reaction mixture with low concentration of reagents and without stirring. The
trihydrate also sometimes contaminates the monohydrate [33].
Preparation of barium styphnate monohydrate for practical applications is simi-
lar to preparation of LS. Magnesium styphnate is used as a starting material which
reacts with barium nitrate, chloride, or acetate resulting in precipitation of barium
styphnate. A reaction temperature of 60–85
C is recommended. Product
precipitates in form of the trihydrate, which dehydrates to the monohydrate by
the slow addition of sufficiently dilute nitric acid [75]. It is difficult to re-crystallize
in a suitable form and it is therefore recommended to use a crystal-modifying agent
(e.g., carboxymethyl cellulose) [2, 26, 27].
Preparation of BaS with physical properties suitable for volumetric loading
using crystal growth modifiers has been described by Orbovic and Codoceo [76].
From the published results it seems that the best product is obtained when using a
mixture of water-soluble cationic copolymer Pel (polyectrolyte AS-3605) and CMC
(carboxymethyl cellulose).

5.3.4.4 Use

Barium styphnate has been used for firearms in Britain since World War II [2]. The
type of production process and shape of prepared crystals determines the applica-
tion of this primary explosive. It is used in delay composition, as an ingredient of
primary compositions, as a component of compositions for electric primers or
igniters, delay compositions, and so on [2, 3, 75, 76].
152 5 Salts of Polynitrophenols

5.3.5 Other Salts of Styphnic Acid

The current authors have not been able to find if styphnate salts other than lead,
basic lead, and barium have ever been practically used. Information about silver
and cupric salts is sparse.
The silver salt of styphnic acid has been proposed as a primary explosive in
several patents [77, 78]. Silver styphnate forms an anhydrous salt or a monohydrate.
The monohydrate loses water of crystallization at 65
C [33]. It is sensitive to flame;
sensitivity to impact is about the same as for LS [33] or higher, approaching MF [7].
The temperature of ignition is 286
C (heating rate 5
C min1) [33]. Silver
styphnate can be prepared in a similar way to that used for LS by the action of
the soluble silver salt on the soluble styphnate (e.g., magnesium, sodium) or by the
action of silver carbonate on styphnic acid [33, 77, 78]. Probably the earliest
recorded method of preparation is based on short time boiling of an aqueous
solution of pure styphnic acid with slight excess of silver oxide followed by
filtration of the precipitate deposited on cooling [28]. The silver salt is precipitated
in the form of long yellowish-brown needles easily re-crystallizable from water.
The cupric salt of styphnic acid forms a tetrahydrate that changes to the
monohydrate by heating at 100
C. According to Bagal, the cuprous salt of styphnic
acid has never been prepared [33]. Styphnic acid also forms many double salts [33].

References

1. Danilov, J.N., Ilyusin, M.A., Tselinskii, I.V.: Promyshlennye vzryvchatye veshchestva; chast
I. Iniciiruyushchie vzryvshchatye veshchestva. Sankt-Peterburgskii gosudarstvennyi tekhnolo-
gicheskii institut, Sankt-Peterburg (2001)
2. Collins, P.H., Holloway, K.J., Williams, R.J.: The development of less-sensitive primary
explosives. In: Jenkins, J.M., White, J.R. (eds.) Proceedings of International Conference on
Research in Primary Explosives, vol. 2, pp. 12/1–12/20. Waltham Abbey, England (1975)
3. Taylor, G.W.C.: Technical requirements and prospects for new primary explosives. In:
Jenkins, J.M., White, J.R. (eds.) Proceedings of the International Conference on Research in
Primary Explosives, vol. 3, pp. 18/1–18/21. Waltham Abbey, England (1975)
4. Sillberrad, O., Phillips, H.A.: The metallic picrates. J. Chem. Soc. 93, 485 (1908)
5. Meyer, R., K€ohler, J., Homburg, A.: Explosives. Wiley-VCH Verlag GmbH, Weinheim (2002)
6. Clark, A.K., Davies, N., Hubbard, P.J., Lee, P.R.: Cross sensitization to impact between lead
azide and tetryl. In: Jenkins, J.M., White, J.R. (eds.) Proceedings of the International Confer-
ence on Research in Primary Explosives, vol. 3, pp. 22/1–22/15. Waltham Abbey, England
(1975)
7. Taylor, A.C., Rinkenbach, W.H.: Sensitivities of detonating compounds to frictional impact,
impact, and heat. J. Franklin Inst. 204, 369–376 (1927)
8. Fedoroff, B.T., Sheffield, O.E., Kaye, S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, New Jersey (1960–1983)
9. Urbański, T.: Chemie a technologie výbušin. SNTL, Praha (1959)
10. Špičák, S., Šimeček, J.: Chemie a technologie třaskavin. Vojenská technická akademie
Antonı́na Zápotockého, Brno, Czechoslovakia (1957)
11. Straka, A.: Specialnı́ technika. FMVS Praha a GRt ZVS Brno, Praha (1976)
References 153

12. Krauz, C.: Technologie výbušin. Vědecko-technické nakladatelstvı́, Praha (1950)

13. Urban, L., Šenkýř, V. (eds.): Speciálnı́ technika, Federálnı́ ministerstvo všeobecného
strojı́renstvı́ Praha, závody všeobecného strojı́renstvı́, generálnı́ ředitelstvı́ Brno, Praha,
p. 536 (1976)
14. Payne, J.R.: Thermochemistry of lead 2,4- and 4,6-dinitroresorcinol. Thermochim. Acta 265,
73–87 (1995)
15. Tomlinson, W.R., Sheffield, O.E.: Engineering Design Handbook, Explosive Series of
Properties Explosives of Military Interest. Report AMCP 706-177 (1971)
16. Peyton, S.V., Williams, E.: Improvements in or relating to ignitory compositions. GB Patent
892,741, 1962
17. Rubenstein, L.: Improvements in or relating to the production of normal lead dinitrore-
sorcinate. US Patent 616,456, 1949
18. Rubenstein, L.: Production of normal lead dinitroresorcinate. US Patent 2,493,551, 1950
19. Tang, T.B.: Decomposition of lead(II) 2,4-dinitroresorcinate. Thermogravimetry, calorimetry,
microscopy and time-resolved mass spectroscopy. Thermochim. Acta 61, 341–356 (1983)
20. Khmelnitskii, L.I.: Spravochnik po vzryvchatym veshchestvam. Voennaya ordena Lenina i
ordena Suvorova Artilleriiskaya inzhenernaya akademiya imeni F. E. Dzerzhinskogo, Moskva
(1962)
21. Taylor, G.W.C., Thomas, A.T.T., Williams, R.J.E.: Lead compounds of 4:6-dinitroresorcinol.
GB Patent 1,374,235, 1974
22. Jones, D.T., Rubenstein, L.: Improvements in or relating to explosive salts and applications
thereof. GB Patent 582,976, 1946
23. Urbański, T.: Chemistry and Technology of Explosives. Pergamon Press, Oxford (1984)
24. Jenkins, J.M.: New processes for manufacture of lead salts of nitrophenols. In: Jenkins, J.M.,
White, J.R. (eds.) Proceedings of the International Conference on Research in Primary
Explosives, vol. 3, pp. 21/1–21/25. Waltham Abbey, England (1975)
25. Taylor, G.W.C., Napier, S.E.: Improvements in or relating to the manufacture of lead 4:6-
dinitroresorcinate. GB Patent 1,094,921, 1967
26. Taylor, G.W.C., Napier, S.E.: Improvements in and relating to the preparation of explosive
substances. GB Patent 849,101, 1960
27. Taylor, G.W.C., Napier, S.E.: Preparation of explosive substances containing carboxymethyl
cellulose. US Patent 3,291,664, 1966
28. Stenhouse, J.: Contributions to the history of Orcin. No. I. Nitro-substitution compounds of the
Orcins. Proc. R. Soc. Lond. 19, 410–417 (1870–1871)
29. Herz, E.R.: Verfahren zur Herstellung von Z€ unds€atzen. DE Patent 285,902, 1914
30. Herz, E.R.: Method of manufacturing detonators, detonating caps and the like. GB Patent
142,823, 1921
31. McCrone, W.C., Adams, O.W.: Crystallographic data. Lead styphnate (normal). Anal. Chem.
27, 2014–2015 (1955)
32. Miles, F.D.: The formation and characteristic of crystals of lead azide and of some other
initiating explosives. J. Chem. Soc. 2532–2542 (1931)
33. Bagal, L.I.: Khimiya i tekhnologiya iniciiruyushchikh vzryvchatykh veshchestv.
Mashinostroenie, Moskva (1975)
34. Ficheroulle, H., Kovache, A.: Contribution à l‘étude des explosifs d’amorçage. Mémorial des
pouders 31, 7–27 (1949)
35. Stettbacher, A.: Bleitrinitroresorcinat. Nitrocellulose 8, 21–27 (1937)
36. Kast, H., Haid, A.: Uber € die sprengtechnischen Eigenschaften der wichtigsten
Initialsprengstoffe. Zeitschrift f€
ur das angewandte Chemie 38, 43–52 (1925)
37. Hailes, H.R.: The thermal decomposition of lead styphnate. Trans. Faraday Soc. 29, 544–549
(1933)
38. Wallbaum, R.: Sprengtechnische Eigenschaften und Lagerbest€andigke der wichtigsten
Initialsprengstoffe. Zeitschrift f€
ur das gesamte Schiess- und Sprengstoffwesen 34, 197–201
(1939)
154 5 Salts of Polynitrophenols

39. Zingaro, R.A.: Lead salt of 2,4,6-trinitroresorcinol. J. Am. Chem. Soc. 76, 816–819 (1954)
40. Military Explosives. Report TM 9-1300-214, Washington, DC (1984)
41. Flanagan, T.B.: Effect of nuclear irradiation upon the decomposition of lead styphnate
monohydrate. Nature 181, 42–43 (1958)
42. Leopold, H.S.: Effect of loading density on the hot wire initiation of normal lead styphnate and
barium styphnate. Report NOLTR-70-96, AD716024, U.S. Naval Ordnance Laboratory,
White Oak, Silver Spring (1970)
43. Fronabarger, J., Sanborn, W.B., Bichay, M.: An investigation of some alternatives to lead
based primary explosive. In: Proceedings of 37th AIAA 2001–3633 Joint Propulsion Confer-
ence and Exhibit, pp. 1–9. Salt Lake City, Utah (2001)
44. Hiskey, M.A., Huynh, M.V.: Primary explosives. US Patent 2006/0030715A1, 2006
45. Huynh, M.H.V., Coburn, M.D., Meyer, T.J., Wetzer, M.: Green primaries: Environmentally
friendly energetic complexes. Proc. Natl. Acad. Sci. 103, 5409–5412 (2006)
46. Clark, L.V.: Diazodinitrophenol, a detonating explosive. J. Ind. Eng. Chem. 25, 663–669
(1933)
47. Millar, R.W.: Lead-free initiator materials for small electro-explosive devices for medium
caliber munitions. Report QinetiQ/FST/CR032702/1.1, QINETIQ Ltd, Farnborough (2003)
48. Wallbaum, R.: Sprengtechnische Eigenschaften und Lagerbest€andigke der wichtigsten
Initialsprengstoffee. Zeitschrift f€ ur das gesamte Schiess- und Sprengstoffwesen 34, 161–163
(1939)
49. Kast, H.: Weitere Untersuchungen € uber die Eigenschaften der Initialsprengstoffe. Zeitschrift
f€ur das Gesamte Schiess- und Sprengstoffwesen 21, 188–192 (1926)
50. Novotný, M., Mečı́ř, R., Sedláček, S., Tamchyna, V.: Teorie výbušin. VŠCHT v Pardubicı́ch,
Pardubice (1981)
51. Bubnov, P.F.: Initsiruyushchie vzryvchatye veshchestva i sredstva initsirovaniya.
Gosudarstvennoe izdatelstvo oboronnoi promyshlennosti, Moskva (1940)
52. Swatosh, Jr. J.J., Napadensky, H.S., Cook, J.R., Levmore, S.: Blast parameters of lead
styphnate, lead azide, and tetracene. Report AD-A021410, Picatiny Arsenal, dist. NTIS (1975)
53. Davis, T.L.: The Chemistry of Powder and Explosives. Wiley, New York (1943)
54. Hill, S.G.: Comercial detonators; Manufacture of lead styphnate and lead azide. Can. Chem.
Process Ind. 26(18), 43 (1942)
55. Holloway, K.J., Jenkins, J.M., Taylor, G.W.C.: Improvements in or relating to the manufacture
of lead styphnate. GB Patent 1,380,437 (1975)
56. Urbański, T.: Chemistry and Technology of Explosives. PWN—Polish Scientific Publisher,
Warszawa (1967)
57. Taylor, G.W.C.: The preparation of gamma lead azide. In: Symposium on Lead and Copper
Azide, pp. A–3, 20–23, Waltham Abbey (1966)
58. Garfield, F.M.: Manufacture of normal lead trinitroresorcinate and double salts thereof. US
Patent 2,295,104, 1942
59. Rosen, B.: The lead styphnate jelly. J. Am. Chem. Soc. 77, 6517–6518 (1955)
60. Friederich, W.: Process for the manufacture of detonating caps for mining and military
purposes. GB Patent 138,083, 1920
61. Grotta, B.: Development and application of initiating explosives. Ind. Eng. Chem. 17, 134–138
(1925)
62. Hagel, R., Redecker, K.: Sintox – a new, non-toxic primer composition by Dynamit Nobel AG.
Propellants Explosives Pyrotechnics 11, 184–187 (1986)
63. Griess, P.: Ueber Einwirkung von Salpeter-Schwafels€aure auf Orthonitrobenzoës€aure.
Berichte der deutschen chemischen Gesellschaft 7, 1223–1228 (1874)
64. Taylor, G.W.C., Thomas, A.T.: Basic lead styphnate. GB Patent 1,381,257, 1975
65. Br€un, W.: Priming mixture. US Patent 1,942,274, 1934
66. Tauson, H.: Process of making basic lead trinitroresorcinol. US Patent 2,020,665, 1935
67. Hitchens, A.L.J., Garfield, F.M.: Basic lead styphnate and process of making it. US Patent
2,265,230, 1941
References 155

68. Br€un, W.: Manufacture of styphnic acid. US Patent 2,275,169, 1942

69. Maksacheff, M., Whelan, D.J.: Thermochemistry of normal and basic lead styphnates using
differential scanning calorimetry. Report MRL-R-1000, Materials Research Laboratories,
Melbourne (1986)
70. Br€un, W.: Manufacture of styphnic acid salts. US Patent 2,275,170–2,275,173 (1942)
71. Br€un, W.: Basic lead styphnate and process of making it. US Patent 2,137,234 (1938)
72. Staba, E.A.: Crystalline double salt of lead nitroaminotetrazole and lead styphnate. US Patent
3,310,569 (1967)
73. Bahadur, K.: Study of some double salts of lead useful as initiatory explosives by thermo
gravimetry and thermometric titration. In: Hansson, J. (ed.) Proceedings of Symposium on
Chemical Problems Connected with the Stability of Explosives, pp. 1–15. Ystad, Sweden
(1973)
74. Sinha, S.K., Srivastava, R.C., Surve, R.N.: Metallic double salts—a new concept of primary
explosive. In: Jenkins, J.M., White, J.R. (eds.) Proceedings of the International Conference on
Research in Primary Explosives, vol. 2, pp. 13/1–13/10. Waltham Abbey, England (1975)
75. Taylor, G.W.C., Napier, S.E., Stansfield, F.: Improvements in and relating to the production of
barium styphnate monohydrate. GB Patent 1,094,981, 1967
76. Orbovic, N., Codoceo, C.L.: Production of exploding materials for detonators: Control of
crystal growth of lead and barium 2,4,6-trinitroresorcinate. Propellants Explosives Pyrotech-
nics 33, 459–466 (2008)
77. Br€un, W.: Priming mixture. US Patent 2,097,510, 1937
78. Br€un, W.: Silver salt of styphnic acid. CA Patent 373,990, 1938
Chapter 6
Diazodinitrophenol

6.1 Introduction

The 2-diazo-4,6-dinitrophenol (dinol, diazol, DDNP, DDNPh, or DADNPh) is the

first-ever synthesized diazonium compound. Its synthesis is attributed to Griess [1]
who prepared it by introducing nitric oxides into an alcoholic solution of 2-amino-
4,6-dinitrophenol (picramic acid) [1, 2]. Its explosive character was, however, first
reported more than 30 years later in 1892 by Lenze [3].

6.2 Structure

Although DDNP has been known for almost 150 years, its structure is still debated
and general consensus does not exist. The most obsolete suggested structures are
not mentioned here but may be found in [4].
The properties (chemical, physical, and spectral) of general ortho (structure I,
benzo [d][1,2,3]oxadiazole) and para (structure II, 2-oxa-3,4-diazabicyclo[3.2.2]
nona-1(7),3,5,8-tetraene) isomers of diazophenols are very similar indicating that
the structures should also be similar. Even though the cyclization and formation of
two rings does not seem to be unreasonable for the ortho-isomer, it definitely does
not look probable for the para-isomer. It is therefore assumed that the structures
I and II are rather improbable for diazophenols [5]. This assumption was confirmed
when structure I was prepared and shown to be unstable even in a solid argon
matrix. The meta-(3-diazo) isomer has not been reported [5, 6].

R. Matyáš and J. Pachman, Primary Explosives, 157

DOI 10.1007/978-3-642-28436-6_6, # Springer-Verlag Berlin Heidelberg 2013
158 6 Diazodinitrophenol

N O
O
N N

structure I structure II

The possible cyclization of the diazo structure III of DDNP and formation of
cyclic isomer IV is improbable based on the property-related assumption mentioned
above. The theoretical studies employing the AM1 level of theory further support
this conclusion [6].

- N
O N O O -
+
N +
N
O2N O2N N O2N N

NO2 NO2 NO2

structure III structure IV structure V

X-ray diffraction of DDNP was first carried out by Lowe-Ma et al. [5] and later
confirmed by Holl et al. [6]. The bonding of DDNP has been discussed on the basis
of theoretical calculations and compared to the results of X-ray diffraction, IR,
and NMR [5, 6].
According to Lowe-Ma et al. [5], neither the zwitterionic (structure III) nor the
quinonoid (structure V) structure provides a satisfactory model for the ortho-
diazophenols including DDNP. Some possible tautomeric structure intermediate
between these two also does not seem to be probable since DDNP exhibits discrete
features of each of them [5]. In later work, these authors incline to structure VI
based on the comparison of X-ray crystallography, NMR, and MO calculations.
This is closely in agreement with the more recent findings of Holl et al. [6] who
proposed diazo structure VII, which is suggested as the best match with single
crystal X-ray diffraction and computational studies.

O O
N +1/2 N
+
O2N N O2N N
-1/2
-

NO2 NO2

structure VI structure VII

6.3 Physical and Chemical Properties 159

Fig. 6.1 Crystals of DDNP

prepared by re-crystallization
from acetone

6.3 Physical and Chemical Properties

DDNP crystals are yellow (Fig. 6.1). However, shades of the technical product can
range from dark yellow or green to dark brown [4]. The density of DDNP is most
often reported as 1.63 g cm 3 [7–11]; however, according to Lowe-Ma et al. the
density is 1.719 g cm 3 (X-ray) [5, 12]. Bagal reports the density of DDNP to be
1.71 g cm 3 and states that the value 1.63 g cm 3 is for the technical product. The bulk
density of DDNP is 0.5–0.9 g cm 3 and only 0.27 g cm 3 for DDNP in fine powder
form [4]. Heat of formation of DDNP is 321 kJ mol 1 [13]. It melts at 157–158 C with
decomposition; explodes violently at higher temperatures [9, 14, 15].
DDNP is mostly reported as a very slightly hygroscopic compound [11, 16].
Špičák and Šimeček [10] reported 1 % weight gain by storing in 70 % relative
humidity (RH) for 40 days; Ficheroulle and Kovache [14] a weight gain of 2.25 %
in 100 % RH compared to 1.22 % for LS; TM9-1300-214 reports 0.04 % in 90 %
RH at 30  C [15].
DDNP is slightly soluble in water (0.08 g in 100 ml at 25  C) [15] but the explosive
properties are not affected as the material does not show any signs of reaction at
ordinary temperatures. The storage under water does not affect the color or sensitivity
of later isolated DDNP [16] and it shows “unimpaired brisance for 24 months at
ordinary temperatures or 12 months at 50  C” when stored under water [15].
The solubility of DDNP in various solvents is shown in Table 6.1. DDNP is
readily soluble in acetic acid, hot acetone, and nitrobenzene, less soluble in metha-
nol, ethanol, and ethyl acetate, poorly in other usual organic solvents [4, 7, 16].
It is photosensitive and turns dark when irradiated by light. The samples exposed
to sunlight show signs of decomposition after only 40 h of irradiation [13].
However, the photolysed crystal surface becomes a protective layer against further
action of the light on the inner portion of the crystal [17]. DDNP is stable in cold
mineral acids; it is decomposed by hot concentrated sulfuric acid and by cold
diluted hydroxide solution, liberating nitrogen [13, 16]. Reaction with alkalis is
160 6 Diazodinitrophenol

Table 6.1 Solubility Solubility (g per 100 g of solvent)

of DDNP
25 C [15] 50 C [7]
Water 0.08 –
Ethyl acetate – 2.45
Methanol 0.57 1.25
Ethanol 0.84 2.43
Trichloromethane – 0.11
Tetrachloromethane – Trace
Benzene 0.09 0.23
Toluene – 0.15
Petrol ether – Insol. (at 20 C)
Ethyl ether 0.04 0.08 (at 30 C)
Carbon disulfide – Trace (at 30 C)
Acetic acid 1.40 –
Acetone 6.0 –

used for non-explosive disposal of diazidodinitrophenol (0.5 % aqueous solution of

sodium hydroxide) [13]. It also reacts with sodium azide forming the sodium salt
of 2-azido-4,6-dinitrophenol and liberating nitrogen. This reaction may be used for
analysis. The quantity of DDNP in the sample is determined from the volume of
nitrogen produced [4].
DDNP is compatible with most usual explosives but is incompatible with LA
[8, 14]. Compatibility of wet DDNP with common metals was examined by
Ficheroulle and Kovache [14]. They observed that DDNP in a moist atmosphere
does not corrode metals, and only attacks them very slightly. The specifications for
military type of DDNP are summarized in MIL-D-82885.
Thermal stability of DDNP is higher than stability of MF but significantly lower
than that of LA. This is a property which may be limiting its use for some
applications [11]. DDNP does not change when stored at 65  C and it loses
1.25 % of its weight over 96 h at 100  C [4]. Extensive study of thermal stability
of DDNP and kinetics of its decomposition was carried out by Kaiser and Ticmanis.
DDNP is stable at moderate temperatures (~60  C) for a long period; however, it
quickly decomposes at temperatures of more than 100  C [18].

6.4 Explosive Properties

Sensitivity of DDNP to impact is about the same as that for mercury fulminate [4]
or slightly less [7, 19] (see Fig. 2.15). Its sensitivity to impact significantly depends
on the size of DDNP particles—fine crystals of DDNP are twice as sensitive as the
coarse product [3].
Its sensitivity of DDNP to friction is reported lower than that of MF and about
the same as that of LA [20]; however, according to our own experiments its
6.4 Explosive Properties 161

Table 6.2 Detonation velocity of DDNP

Density (g cm 3) Detonation velocity (m s 1) References
0.9 4,400 [8]
1.5 6,600 [9]
1.6 6,900 [8]

sensitivity relatively low – it is between MF and PETN (see Fig. 2.19) [21].
Sensitivity to electric discharge and its comparison with other primary explosives
is illustrated in Fig. 2.21. Upon ignition, unconfined and unpressed DDNP burns
like nitrocellulose even in quantities of several grams. It does not ignite or detonate
under water even when initiated by a blasting cap [4, 16, 22].
Smoleński and Pluciński reported that explosive decomposition of DDNP results
mainly in the formation of carbon monoxide, carbon, hydrogen cyanide, and
nitrogen. The reaction proceeds according to the following equation [13]:

The dependency of detonation velocity of DDNP on density is summarized in

Table 6.2. Its initiating efficiency based on tetryl acceptor charge is better that of
MF and LA [12]. The values in TM9-1300-214 [15] confirm superiority of DDNP
to MF but the efficiency with respect to LA differs based on the type of acceptor as
shown in Table 6.3. It indicates that DDNP is a better initiator for less-sensitive
secondary explosives.

Initiating efficiency of DDNP was recently measured by Vala and Valenta.

According to their results, it is about the same as of LA when measured using
PETN acceptor charge when strong confinement is used (Vala and Valenta private
communication).
DDNP belongs to the group of highly brisant explosives being superior to
mercury fulminate and also, in some areas, to lead azide. The results of a sand
test are summarized in Table 6.3 [7]. Sand-crushing strength of DDNP is not
affected by storing under water for 50 days. The power of DDNP measured by a
small Trauzl block is significantly superior to LA and MF (Table 6.3).
The ignition temperature is 185  C [7, 13] or 177  C [23] (within 5 s); 200  C for
explosion within 1 s [7]. According to our experiments, ignition temperatures of
DDNP prepared by Garfield’s method [24] are in the range 161–163  C (heating
rate 5  C min 1, static air atmosphere, sample weight 5 mg). As mentioned
previously, sunlight affects the quality of DDNP. The ignition temperature of
irradiated DDNP is somewhat lower than for a non-irradiated sample [13].
There has been some disagreement about dead-pressing of DDNP. In older
literature, DDNP is reported as a primary explosive, which cannot be dead-pressed
162 6 Diazodinitrophenol

Table 6.3 Initiating efficiency and brisance of LA, MF, and DDNP
Initiating efficiency [15]
(gram of primary explosive) Brisancea [7] Brisanceb [7] Power by small [7]
Tetryl TNT Ammonium picrate (gram of sand) (gram of sand) Trauzl block (cm3)
DDNP 0.12 0.15 0.28 19.3 90.6 25.0
MF 0.19 0.24 No detonation 6.5 48.4 8.1
LA 0.10 0.26 No detonation 7.2 36.0 7.2
a
Sand test values are for 0.2 g charge measured in detonator shell and pressed under a reinforcing
capsule at 23.4 MPa
b
Sand test values are for 1 g charge measured in detonator shell and pressed under a reinforcing
capsule at 23.4 MPa

even at high pressures. The attempts to dead-press DDNP reported by Clark

indicate that he could not dead-press it when using pressures up to 690 MPa. Two
attempts using greater pressures (800 and 900 MPa) both ended by explosion [3, 8,
9, 11]. However, neither the densities obtained at 690 MPa nor other details have
been reported. It is therefore difficult to explain why the explosions occurred.
Later experimental works clearly show that it is easily possible to dead-press
DDNP. The maximum initiation efficiency is reached at densities from 1.2 to
1.3 g cm 3. At density 1.4 g cm 3 it is completely dead-pressed. The density at
which DDNP becomes dead-pressed does not depend on the specific surface of the
material to be pressed as much as it does in the case of MF [25, 26]. Bagal reported
that DDNP becomes dead-pressed by pressure above 19.6 MPa [4].

6.5 Preparation

DDNP is prepared by diazotation of an aqueous solution of 2-amino-4,6-dinitrophenol

(picramic acid) or its sodium salt with sodium nitrite and hydrochloric acid [11].

OH O
+ N
O2N NH2 O2N N
NaNO2
HCl
-

NO2 NO2
DDNP

Needle- or leaf-shaped crystalline DDNP is obtained when pure reactants are

used at common reaction conditions (Fig. 6.2). The addition of acid to the reaction
mixture is the more common way of DDNP preparation [13, 27–29] although
addition of nitrite into acidic solution of picraminate acid is also published [7, 24].
6.5 Preparation 163

Fig. 6.2 Crystals of DDNP prepared by authors following Alexander’s method [27] (left) and
Garfield and Dreher’s method [24] (right)—pure reactants were used at both methods; dyes and
phenols were not used

The free-flowing product can be obtained by both optimization of the reaction

conditions (rate of addition of hydrochloric acid to the mixture) [28] or by use of
some crystal shape modifying substances during reaction. Rounded grains of
DDNP are reported when pyrogallol, hydroquinone, dinitroresorcinol, and some
other substances are added [27] and tabular crystals when adding triphenylmethane
dyes to the reaction mixture [24]. Slow mixing of reagents is one of the most
important factors for producing free-flowing DDNP according to [28, 29]. Babcock
and Kenvil proposed use of an injector or atomizer for acid batching with addition
of the acid under the surface of the diazoting mixture. This way acid is added in the
form of fine droplets. The process eliminates formation of local high acidity regions
and hence prevents the formation of very fine particles of DDNP [29].
Our own experience makes us a bit uncertain about the above-mentioned
methodologies for obtaining technologically acceptable product. After numerous
unsuccessful trials, we have deviated from the published routes and developed our
own which enables us to produce large-size round particles (Fig. 6.3, left). Similar
spherical DDNP with a little bit different structure was obtained by Nesveda
(Fig. 6.3, right).
Another way of DDNP preparation is oxidation of picramic acid with chromic
acid [30]. It is believed by authors that a part of picramic acid is oxidized to
complete decomposition forming nitrogen dioxide and subsequently nitrous acid
which then diazotizes picramic acid. Strong foaming due to a gas evolution (CO,
CO2, and NO2) and low yield (32.5 % by weight) support proposed mechanism
including partial decomposition of picramic acid.
Re-crystallization may be done from nitrobenzene or from acetone solution by
adding the solution to cold ether. DDNP may be purified by dissolving in hot
acetone and precipitation by addition of iced water. The purification turns the
164 6 Diazodinitrophenol

Fig. 6.3 SEM photographs of spherical DDNP prepared by authors (left) and the same prepared
by Jiřı́ Nesveda, Sellier and Bellot, Vlašim (right)

dark brown raw product a brilliant yellow [7, 19]. Several alternative ways of
DDNP preparation are summarized in the literature [7].

6.6 Use

Although first prepared in 1858, DDNP was first proposed for use as an explosive in
1892 when Lenze highlighted its valuable explosive properties [13]. Probably the
first patent treating DDNP as an explosive was by Dehn in 1922 [16]. DDNP found
its application as an initiating explosive in both military and commercial
detonators, particularly in USA and Japan [8, 26, 31, 32]. It is also used in stab
and percussion primer mixtures and in these applications it has been the subject of
many patents including, for example, [31–33]. Due to the absence of heavy metals
in the molecule it is widely used in non-toxic types of primer in which it serves as
the energizing component (e.g. SINTOX [34]). It is practically the only easily
available replacement of LS in today’s percussion priming mixtures [35]. A mixture
containing DDNP and tetrazene has been proposed as an explosive filler for
explosive riveting [36].
Despite its reported use, DDNP exhibits several disadvantages which make it not
an ideal primary explosive:
• It causes allergic reactions in some workers
• It can be dead-pressed
• It has low density and therefore it requires a relatively large volume
• It is easily electrified resulting in difficulties during handling and filling [4]
• Problems of waste water treatment
• Relatively low thermal stability for some applications (Vala and Valenta private
communication)
The use of DDNP in military applications was further questioned by Fronabarger
and Williams pointing out its inability to fulfill shelf-life and reliability
References 165

requirements [37]. On the other hand, the American technical manual TM 9-1300-
214 [15] considers DDNP satisfactory for both commercial and military use.

References

1. Griess, P.: Vorl€aufige Notiz u €ber die Einwirkung von salpetriger S€aure auf Aminitrophe-
nyls€aure. Annalen der Chemie und Pharmacie 106, 123–125 (1858)
2. Griess, P.: Ueber eine neue Klasse organischer Verbindungen, welche Wasserstoff durch
Stickstoff vertreten enthalten. Annalen der Chemie und Pharmacie 113, 200–217 (1860)
3. Urbański, T.: Chemie a technologie výbušin. SNTL, Praha (1959)
4. Bagal, L.I.: Khimiya i tekhnologiya iniciiruyushchikh vzryvchatykh veshchestv.
Mashinostroenie, Moskva (1975)
5. Lowe-Ma, C.K., Nissar, R.A., Wilson, W.S.: Diazophenols – their structure and explosive
properties, report AD-A197439. Naval Weapons Centrum, China Lake, USA (1987)
6. Holl, G., Klap€otke, T.M., Polborn, K., Rien€acker, C.: Structure and bonding in 2-dizo-4,6-
dinitrophenol (DDNP). Propellants, Explosives, Pyrotechnics 28, 153–156 (2003)
7. Clark, L.V.: Diazodinitrophenol, a detonating explosive. J. Ind. Eng. Chem. 25, 663–669
(1933)
8. Fedoroff, B.T., Sheffield O.E., Kaye S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, New Jersey (1960–1983)
9. Meyer, R., K€ohler, J., Homburg, A.: Explosives. Wiley-VCH Verlag GmbH, Weinheim (2002)
10. Špičák, S., Šimeček, J.: Chemie a technologie třaskavin. Vojenská technická akademie
Antonı́na Zápotockého, Brno, Czechoslovakia (1957)
11. Danilov, J.N., Ilyusin, M.A., Tselinsky, I.V.: Promyshlennye vzryvchatye veshchestva; chast I.
Iniciiruyushchie vzryvshchatye veshchestva. Sankt-Peterburgskii gosudarstvennyi tekhnolo-
gicheskii institut, Sankt-Peterburg (2001)
12. Lowe-Ma, C.K., Nissan, R.A., Wilson, W.S., Houk, K.N., Wang, X.: Structure of
diazophenols: 13C NMR spectroscopy, and molecular orbital studies. J. Chem. Res. (S),
214–215 (1988)
13. Urbański, T.: Chemistry and Technology of Explosives. PWN – Polish Scientific Publisher,
Warszawa (1967)
14. Ficheroulle, H., Kovache, A.: Contribution à l‘étude des explosifs d’amorçage. Mémorial des
pouders 31, 7–27 (1949)
15. Military explosives. Report TM 9-1300-214, Washington DC (1984)
16. Dehn, W.M.: Process of increasing the sensitiveness and power of explosive compositions and
product thereof. US Patent 1,428,011, 1922
17. Yamamoto, K.: Primary explosives. VIII. Photolysis of diazodinitrophenol. Chem. Abstr. 64,
3273d; CAN 3264:26627 (1966)
18. Kaiser, M., Ticmanis, U.: Thermal stability of diazodinitrophenol. Thermochim. Acta 250,
137–149 (1995)
19. Tomlinson, W.R., Sheffield, O.E.: Engineering design handbook, explosive series of properties
explosives of military interest. Report AMCP 706-177 (1971)
20. John, H.J., Yeager, C., Pile, D., Webb, T.: Non-toxic primer mix. US Patent 6,478,903 B1,
2002
21. Matyáš, R., Šelešovský, J., Musil, T.: Sensitivity to friction for primary explosives. J. Hazard.
Mater. 213–214, 236–241 (2012)
22. Davis, T.L.: The Chemistry of Powder and Explosives. Wiley, New York (1943)
23. Henkin, H., McGill, R.: Rates of explosive decomposition of explosives. Ind. Eng. Chem. 44,
1391–1395 (1952)
24. Garfield, F.M., Dreher, H.W.: Manufacture of diazodinitrophenol. US Patent 2,408,059, 1946
166 6 Diazodinitrophenol

25. Strnad, J.: Primary explosives and pyrotechnics – lecture notes. Institute of Energetic
Materials, University of Pardubice, Pardubice (1999)
26. Strnad, J.: Iniciačnı́ vlastnosti nejpoužı́vanějšı́ch třaskavin a vývoj nových metodik jejich
měřenı́. Dissertation thesis, Institute of Chemical Technology, Pardubice (1972)
27. Alexander, H.B.: Method of producing diazodinitrophanol and product thereof. US Patent
2,103,926, 1937
28. Hancock, R.S., Pritchett, L.C.: Method for producing diazodinitrophenol. US Patent
1,952,591, 1934
29. Babcock, L.W., Kenvil, N.J.: Diazodinitrophenol and the method of the preparation of the
same. US Patent 2,155,579, 1939
30. Urbański, T., Szyc-Lewańska, K., Bednarczyk, M., Ejsmund, J.: On formation of 2,4-dinitro-
6-diazoxide by oxidation of picramic acid. Bulletin de l’Académie polonaise des sciences
Séries des sciences chimiques 8, 587–590 (1960)
31. Kaiser, H.E.: Percussion cap. US Patent 1,852,054, 1932
32. Lopata, F.G., Mei, G.C.: Non-toxic, non-corrosive rimfire cartridge. US Patent 4,674,409,
1987
33. Burns, J.E.: Ammunition. US Patent 1,862,295, 1932
34. Hagel, R., Redecker, K.: Sintox – a new, non-toxic primer composition by Dynamit Nobel AG.
Propellants, Explosives, Pyrotechnics 11, 184–187 (1986)
35. Jung, S.M., Lee, H.S., Son, J.W., Pak, C.H.: Non-toxic primer powder compositions for small-
caliber ammunition. US Patent S 2005 224147, 2005
36. Tsukii, T., Kikuchi, S.: Explosive for riveting. Chem Abst 49, 10628 (1955)
37. Fronabarger, J.W., Williams, M.D.: Lead-free primers. US Patent 2009/0223401, 2009
Chapter 7
Salts of Benzofuroxan

7.1 Introduction

N N
O O
+
N N
-
O

furoxan ring furazan ring

The furoxan ring (furazan oxide; 1,2,5-oxadiazole 2-oxide) in a molecule is a

sensitizing structure which produces a similar sensitizing effect as, for example, an
azido group. The presence of the furoxan ring itself, however, is not sufficient to
sensitize any compound to a point where it would be useful as a primary explosive.
Even the sensitivity of benzotrifuroxan (BTF), representing a molecule with the
highest possible number of furoxan groups present on an aromatic ring, is insuffi-
cient and places the substance among secondary explosives—between PETN and
RDX to be exact [1]. Metallic salts are much more sensitive and possess the
necessary properties to be considered as primary explosives. The sensitivity of
furoxan salts can further be increased by incorporation of explosophores (energetic
groups like nitro or azido) onto an aromatic ring. Careful variation of the number of
the furoxan and energizing groups gives the organic chemist the possibility to design
molecules with just the correct sensitivity necessary for a primary explosive [2].
-
+ O
O N NO2
N N H2N N
O O
- + + +
O N N O2N N
- -
O O
O N NH2

benzotrifuroxane (BTF) 5,7-diamino-4,6-dinitrobenzofuroxan (CL-14)

R. Matyáš and J. Pachman, Primary Explosives, 167

DOI 10.1007/978-3-642-28436-6_7, # Springer-Verlag Berlin Heidelberg 2013
168 7 Salts of Benzofuroxan

On the other hand, the presence of an amino group on the aromatic ring
decreases the sensitivity of the molecule. This can be illustrated by the example
of 4,6-dinitrobenzofuroxan (4,6-DNBF). 7-Amino-4,6-dinitrobenzofuroxan with
one amino group is significantly less sensitive than 4,6-DNBF itself and the
sensitivity is further dramatically reduced by introduction of another amino
group. 5,7-Diamino-4,6-dinitrobenzofuroxan (CL-14) is half as sensitive to impact
as TNT [3, 4].
The same trend in sensitivity applies also to furoxan salts. The alkaline salts of
CL-14 (sodium, potassium, rubidium, and cesium) are less sensitive to impact and
friction than relevant salts of 4,6-DNBF due to the presence of amino groups in the
aromatic ring [5]. The incorporation of amino groups also significantly increases
the thermal stability of these salts (ignition in the range 240–280
C) compared with
its 4,6-DNBF analogs (ignition in the range 160–220
C) [5]. In practical terms, the
most promising for future applications are potassium salts (lithium and sodium salts
are hygroscopic; rubidium and cesium are expensive).
An alternative to furoxans are furazans which have a similar molecular structure
and also form metallic salts. Far less attention, however, has been paid to this class
of substance. Nitrobenzofurazanes are among the rare cases where at least some
information has been published. Like the nitrobenzofuroxans, they are not suffi-
ciently sensitive, but they do form salts, which in some cases may fulfill the criteria
for use in some specific applications. The most promising substances appear to be
alkaline salts particularly the potassium salt of 4,6-dinitrobenzofurazan. It is,
however, too insensitive for priming applications [6]. Other nitrobenzofurazanes
and their salts were originally investigated as possible LA replacements, but they
failed to provide sufficient performance and were therefore reconsidered as poten-
tial LS replacements. Based on the information available in open literature today, it
is not possible to predict their usefulness in future applications.

7.2 Salts of 4,6-Dinitrobenzofuroxan

4,6-Dinitrobenzofuroxan (4,6-DNBF) was first prepared in 1892. The structure of

the furoxan ring remained unclear for a long time. The furoxans were until the
1960s assumed to be o-dinitroso compounds. Only later was benzofuroxan’s struc-
ture firmly established and confirmed by X-ray crystallography [7, 8].
4,6-DNBF is acidic and easily forms stable salts [9]. Based on the type of metal,
4,6-DNBF forms s Meisenheimer complex salts [10, 11] with resonance structure
corresponding to either formula I or II as shown below [12].
7.2 Salts of 4,6-Dinitrobenzofuroxan 169

+
Me -
- -
O + O O + OH
N N

N N
O O
+ +
O2N N O 2N N
- -
HO H O O H O
Me
structure I structure II
+ + + 2+ 2+ 2+ 3+ 2+ 3+ 3+ 2+
Me = Li , Na , K , Mg , Ca , Sr , Me = Al , Pb , Fe , Cr , Cu
2+ 2+ 2+ 2+ 2+
Mn , Co , Ni , Zn , Cd

Sinditskii et al. [12] performed IR analysis of several of these metallic salts and
based on the results proposed two types of Meisenheimer complex structure
depending on the nature of the metal cation. Both types have nitro groups in the
aci-form, however the cations of the first group (structure I) have the metal atom
bonded to the oxygen atoms of the nitro-group in the aci-form by an ionic type of
bond. The second group comprises adducts in which the metal atom is covalently
bonded to the oxygen atom of the hydroxyl group (structure II) [12]. The latter type
of bond was confirmed by IR and NMR analysis for the Cr3+, Fe3+, and Cu2+ salts
[13]. The IR spectrum of the barium salt does not enable ascribing it unambiguously
to either one of the groups [12].

7.2.1 Physical and Chemical Properties

4,6-DNBF itself melts at 174
C and decomposes at 273
C. The physical properties
of several metallic salts of 4,6-DNBF are summarized in Table 7.1. The potassium
salt of 4,6-DNBF (KDNBF) forms small golden to orange platelets with density
which have poor pouring and mixing properties. Crystal density is 2.21 g cm3
[14]. KDNBF is slightly soluble in water (0.245 g/100 ml at 30
C) [17] and the
solubility increases with temperature allowing it to be re-crystallized at 70
C [18].
Sodium salt (NaDNBF) is soluble in water [18] and its solution is used for
preparation of other salts. Exact details of its solubility are however not reported.

7.2.2 Explosive Properties

4,6-Dinitrobenzofuroxan itself has the characteristics of a secondary explosive. Its

metallic salts, some of which are summarized in Table 7.1, have on the other hand
primary explosive characteristics.
 170

Table 7.1 Properties of metallic salts of 4,6-dinitrobenzofuroxan

Sodium salt Barium salt Silver salt Rubidium salt Cesium salt
Potassium salt (KDNBF) (NaDNBF) (BaDNBF) (AgDNBF) (RbDNBF) (CsDNBF) References
Physical properties Golden orange platelets Red-brown Lustrous black- Red-brown – – [14]
crystals brown crystals crystals
– – – – Brick-red Buff crystals [15]
crystals
Ignition temperature 199–201 174–175 257–259 159–160 – – [14]
(
C) 220 160 – – 188 166 [15]
208–211 172–175 249–254 – – – [12]
207–210a [16]
Impact sensitivity 35.0 (50 %) 33.5 (50 %) – – 35.0 (50 %) 30.0 (50 %) [5, 15]
2 kgb(cm) 29 (F of I) 28 (F of I) 29 (F of I) 24 (F of I)
Friction sensitivity 3.8 5.4 – – 1.0 0.2 [5, 15]
(kg)c
Sensitivity to electric 26.5 24.0 – – 28.9 24.5 [15]
discharge (mJ) Fires at 4500, 450 and 45 Fires at 4500, Fires at 4500 Fires at 4500 – – [14]
450 and 45 No fires at 450 No fires at 450
a
With rapid decomposition from 190
C
b
Sensitivity to impact: RDX 35 cm; tetryl 85 cm; TNT 110 cm [5]
c
Sensitivity to friction: RDX 12 kg; tetryl and TNT 32.4 kg [5]
7 Salts of Benzofuroxan
7.2 Salts of 4,6-Dinitrobenzofuroxan 171

35

83% 10%
30 0%

40%
25
30%
Height (cm)

20 20%

0%

15
100%
90%
100% 40%
10 50% 0%
30%
0%

0
AgDNBF KDNBF NaDNBF BaDNBF

Fig. 7.1 Sensitivity of 4,6-DNBF salts to impact as a probability of ignition (ball and disc method,
6 or 10 trials at one height, maximum test height 30 cm) [14]

Table 7.2 Impact sensitivity of KDNBF

Sensitivity to impact
Converted to As reported in Value
energy (J) literature reported Apparatus Reference
0.67 15.2 cm/0.45 kg hmin Picatinny arsenal [17]
apparatus
2.17 6.1 cm/3.63 kg h50 Bureau of expl. machine [19]
2.47 12.6 cm/2 kg h50 Drop hammer [20]
6.9 35 cm/2 kg h50 Fall hammer [15]
Between MF and LA – [16, 21, 22]

The impact sensitivity of the potassium salt is slightly lower than that of a silver
salt but significantly higher than that of sodium and barium salts as demonstrated by
Fig. 7.1. A discrepancy exists in the literature concerning the absolute values of
impact sensitivity of KDNBF. Some of the values are summarized in Table 7.2. The
sensitivity to friction is reported about the same as the sensitivity of LS [16].
According to our own results (see Fig. 2.19), KDNBF is less sensitive to friction
than most other commonly used primary explosives (e.g., LA, LS) but more than
DDNP [23]. Initiating efficiency is high and according to Zhang et al. it reaches
0.02 g for RDX (both pressed 52.37 MPa) [20]. Brisance of KDNBF by sand test is
92 % TNT [17].
The ignition temperature of KDNBF is 200
C (heating rate 5
C min1; DSC)
according to Whelan et al. [24]. KDNBF does not melt and when heated it
172 7 Salts of Benzofuroxan

decomposes directly from the solid state. A detailed study of the thermal decompo-
sition of KDNBF was carried out by Jones et al. [19, 25–27] and Li et al. [28].
The rubidium salt is slightly more sensitive to impact than LA (8.7 cm for 0.8 kg
hammer compared to 10.3 cm for LA) and slightly more sensitive to impact than
KDNBF. Sensitivity to flame is similar to KDNBF; sensitivity to electrostatic
discharge is lower than LA and LS but higher than KDNBF. The exothermic
decomposition starts at 189
C (heating rate 10
C min1) [29].
The sensitivity of the cesium salt to impact, friction, and electrostatic discharge
is reported higher than for KDNBF [30]. As in the case of KDNBF, discrepancies
exist in the literature about the absolute values of the impact sensitivity of the
cesium salt. Mehilal et al. [15] reported 35 cm for 2 kg hammer (h50) whilst Zhang
et al. [30] reported 8.9 cm/0.8 kg (h50). The sensitivity to flame is the same as for
KDNBF [30].
Sinditskii [12] studied the burning rate characteristics of metallic salts in the
pressure range 0.1–30 MPa. Based on his observations, it is possible to divide salts
of 4,6-DNBF by their burning behavior into two groups which correspond well with
the two previously mentioned structural groups. The substances in the first group
(identical to structural group I) showed fast burning rates regardless of the metal
type. With these substances, the burning rate did not depend significantly on the
surrounding pressure and all of the salts began to burn at atmospheric pressure. The
thermally stable KDNBF has the highest burning rate of all of the salts in the first
group.
The burning rate of the salts from the second group (structure II) significantly
depended on the surrounding pressure and the behavior of these salts differed only
slightly from 4,6-DNBF itself. Some of the substances in this group did not burn at
atmospheric pressure. The barium salt, which could not be previously placed into
either of the structural groups, falls into the second group according to its burning
behavior [12].

7.2.3 Preparation of 4,6-Dinitrobenzofuroxan

The most common general procedure for preparation of benzofuroxans is based on

thermolysis of the benzene compound containing adjacent nitro and azido groups in
the ortho position [31, 32].
4,6-Dinitrobenzofuroxan can be prepared by thermal decomposition of 1-azido-
2,4,6-trinitrobenzene (prepared from 1-chlor-2,4,6-trinitrobenzene) [13, 15] or
more effectively, without isolation of 1-azido-2,4,6-trinitrobenzene, directly from
1-chlor-2,4,6-trinitrobenzene [31]. The other method of 4,6-dinitrobenzofuroxan
synthesis is based on nitration of benzofuroxan (prepared from o-nitroaniline)
[31–33].
7.2 Salts of 4,6-Dinitrobenzofuroxan 173

O
NH2 N - N3 Cl
+
O
NO2 N O2N NO2 O2N NO2
NaClO NaN3

HNO3 NO2 NO2

reflux
H2SO4 - N2

NaN3
O
N - AcOH
O
+
O2N N

NO2

4,6-DNBF

7.2.4 Preparation of 4,6-Dinitrobenzofuroxan Salts

The first salts of 4,6-dinitrobenzofuroxan (potassium, sodium, ammonium, and

silver) were prepared by Drost in 1899. The product of precipitation of 4,6-
DNBF by potassium bicarbonate was however misidentified as the potassium salt
of m-dinitro-o-dinitrosobenzene. The other salts were also thought to be salts of the
same compound [18].
KDNBF is produced by neutralization of an aqueous solution of 4,6-
dinitrobenzofuroxan or its sodium salt with a soluble potassium salt (bicarbonate,
carbonate, nitrate, chloride) [14, 15, 17, 18, 34]. Various crystal modifiers may be
used such as Tween 80 (polyoxyethylenesorbitan monooleate), PVA, dextrin, etc.,
for preparation of spherical KDNBF [22, 33, 35]. Temperature, stirring speed,
dripping speed of reactants, and cooling time all have significant influence on crystal
shape and size [22]. The product prepared at our department is shown in Fig. 7.2. It is
further possible to prepare KDNBF from an acetone/water environment yielding
golden platelets melting at 209
C with explosion [36]. It is recommended to prepare
KDNBF by precipitation from its aqueous solution [17, 37].
+
K
- -
O + O
NO2 N

N N

O + KHCO3 O
+ +
O2N N O2N N
- -
O HO H O

DNBF KDNBF

When methanol is used instead of an aqueous environment, potassium salts of

methoxy derivates of dinitrobenzofuroxan or dinitrobenzofurazan (depending on
reaction conditions) form instead of KDNBF [7].
174 7 Salts of Benzofuroxan

Fig. 7.2 SEM photography

of KDNBF

The sodium salt of 4,6-DNBF may be prepared in the same way as described
above when a sodium salt (bicarbonate) is used for the reaction. Other salts of
4,6-DNBF may be prepared by precipitation of aqueous solutions of the sodium salt
of 4,6-DNBF by relevant soluble metallic inorganic salts (e.g., nitrate, chloride)
[13–15, 30].
One of the problems related to the preparation of 4,6-DNBF by nitration of
benzofuroxan is its variable yield and the amount of side products. It was found by
HPLC that up to 10 % of the isolated product may be 5,6-DNBF. This negatively
influences the color and the shape of the resulting potassium salt [38]. Spear et al.
however disagree with this and report that the presence of the 5,6-DNBF isomer in
the nitrated product is below 1 % [31].

7.2.5 Uses

Although use of several metallic salts of 4,6-DNBF is protected by patent literature

(e.g., barium salt [39]) only the potassium salt has been practically used in explo-
sion initiating compositions. It has been reported in both military and commercial
applications in the USA since the early 1950s [40]. The potassium salt has been
proposed as a nontoxic replacement of lead styphnate for primers for hunting and
sporting ammunition [16].
Patents usually refer to the application of KDNBF in primer composition for
percussion caps. It is recommended in combination with tetrazene [41–45] or some-
times with DDNP. A mixture with the latter was reported to have good stability at wide
temperature ranges and to withstand even very humid environments [46].
The use of KDNBF as the only primary explosive in priming mixtures is
environmentally quite attractive due to the absence of any toxic heavy metal or
DDNP. The absence of GNGT further makes the primer more stable at higher
temperatures and humidity [47]. Pure KDNBF was also patented as a priming
charge in detonators [37] and for use in gas generators for automobile safety
devices (airbags, seat belt tensioners) [44].
7.3 Potassium Salt of 7-Hydroxylamino-4,6-dinitro-4,7-dihydrobenzofuroxan 175

Table 7.3 Stab sensitivity of potassium salt of 7-hydroxylamino-4,6-dinitro-4,7-dihydrobenzofuroxan/

LA and GNGT/LA mixtures [48]
Energy (50 % prob.
Composition Ratio of initiation, mJ)
Potassium 7-hydroxylamino-4,6-dinitro-4,7- 1/10 6.5–7.6
dihydrobenzofuroxan/LA 1/20 9.2
GNGT/LA 1/10 3.3
GNGT/LA 1/20 3.5

7.3 Potassium Salt of 7-Hydroxylamino-4,6-dinitro-4,7-

dihydrobenzofuroxan

-
NO2

N
+
K O-
+
O2N N
-
H NH O
OH

Another interesting substance containing a furoxan ring is the potassium salt of

7-hydroxylamino-4,6-dinitro-4,7-dihydrobenzofuroxan. It forms dark red crystals
with density 1.92 g cm3 and melting point 165
C. It decomposes during melting
with some gas being released. The ignition temperature is however reported in the
same patent to be 152
C (probably due to a different heating rate). The sensitivity
to impact is 2.7 J (11 cm for 2.5 kg hammer; 50 % probability). This compound was
examined as a potential sensitizer of LA in stab priming mixtures. The common
mixtures of LA/GNGT were tested for comparison. The results are summarized in
Table 7.3. The stab energies of mixtures of potassium salt of 7-hydroxylamino-4,6-
dinitro-4,7-dihydrobenzofurxan and LA are twice of those corresponding 1/10
tetrazene compositions and three times of those of 1/20 [48].
Potassium salt of 7-hydroxylamino-4,6-dinitro-4,7-dihydrobenzofuroxan can be
prepared in the same way as KDNBF. It is formed by the reaction of 4,6-
dinitrobenzofuroxan with hydroxylamine in presence of a methanolic solution of
potassium bicarbonate. The yield is nearly quantitative [48].
NO2 -
NO2
N N
+
O + NH 2OH + KHCO 3 K O-
+ +
O2N N O2N N
- -
O H NH O
DNBF OH
176 7 Salts of Benzofuroxan

7.4 Potassium Salt of 7-Hydroxy-4,6-dinitrobenzofuroxan

-
NO2

N
+
K O
+
O2N N
-
- O
O

The potassium salt of 7-hydroxy-4,6-dinitrobenzofuroxan (KDNP) has a very

similar chemical structure to KDNBF. However, as opposed to KDNBF which
forms Meisenheimer adducts, this compound is aromatic. The aromaticity of KDNP
has been confirmed by X-ray analysis [46].

7.4.1 Physical and Chemical Properties

The potassium salt (KDNP) exists in two forms. The first is a monohydrate which is
prepared in aqueous solution. The second form is an anhydrous salt resulting from
using a nonaqueous reaction medium [46].
The density of the anhydrous salt is 1.94–2.13 g cm3. The monohydrate forms
brown crystals with density depending on crystal morphology. The potassium salt is
only slightly hygroscopic compared with its more hygroscopic sodium analog [46].
KDNP is moderately soluble in water [49].

7.4.2 Explosive Properties

Sensitivity to impact and friction of the various forms of KDNP is summarized in

Table 7.4. The sensitivity of crystalline KDNP to impact is equivalent to milled LS
while the needles and amorphous compound are half as sensitive. The sensitivity of
KDNP to friction is much lower than that of LS of similar crystal size; the needle
crystals are significantly more sensitive than either the crystalline or amorphous
form [46].
KDNP is more thermally stable than KDNBF; it remains stable at 120
C for
90 days. The higher thermal stability compared with KDNBF is probably due to
loss of aromaticity of the KDNBF molecule. The DSC data indicate that KDNP is
roughly equivalent to LS in terms of onset and peak temperatures [46].
The comparison of KDNP’s performance in terms of the ignition time was
carried out in a steel closed bomb. The results were compared to results obtained
for standard LS under the same conditions. Samples were loaded at 103 MPa and
7.4 Potassium Salt of 7-Hydroxy-4,6-dinitrobenzofuroxan 177

Table 7.4 Sensitivity to impact, friction, and DSC of various crystal morphologies of KDNP [46]
Impact Friction sensitivity DSC
sensitivity Small BAM at 20
C min1
Ball drop (g) (
C)
Compound (mJ) No-fire level Low fire level Onset Peak
KDNP—needles 51 175 200 278 283
KDNP—crystalline 25 1,300 1,400 280 284
KDNP—amorphous 51 1,400 1,500 266 275
Milled LS 25 40 50 280 305

fired in a closed bomb. The ignition time of KDNP is comparable to LS. The time
from first indication of pressure increase to its maximum rise is faster for the needle
and crystalline material. The amorphous form of KDNP performed worse than LS.
The reason of this divergence is not known [46].
Some other results of KDNP investigations were summarized by Fronabarger
et al. [49]. The report unfortunately does not specify the crystal form of the
material. Nevertheless, the reported properties are as follows: impact sensitivity
by ball drop method—51  22 mJ, friction sensitivity by BAM 175 g (no-fire
level) 200 g (low fire level), thermal properties by DSC at 20
C min1—small
endo at 145
C, decomposition onset 278
C, solubility in water—moderately
soluble at normal temperature. Reactivity with aluminum, stainless steel, brass,
and cadmium was not observed. Output measured as an impetus is reported better
than LS in a closed bomb test.

7.4.3 Preparation

Two preparation procedures for KDNP are published: one by Norris et al. [50] and
the second by Fronabarger et al. [46].
The starting material in the synthesis of KDNP according to Norris is commer-
cially available 5-chlorobenzofuroxan. Nitration of this material gives 5-chloro-
4,6-dinitrobenzofuroxan which is thermally unstable and spontaneously changes to
7-chloro-4,6-dinitrobenzofuroxan (undergoes a Boulton-Katritzky rearrangement
[51]). The alkaline salt forms by reaction of this compound with the relevant
carbonate (potassium, sodium, cesium [46]) in aqueous environment [50].
178 7 Salts of Benzofuroxan

- -
O O
+ O + O
N N NO2

N N N
HNO3/H2SO4 D
O
+
O2N NO2 O2N N
-
O
Cl Cl Cl
5-chlorobenzofuroxan 5-chloro-4,6-dinitrobenzofuroxan 7-chloro-4,6-dinitrobenzofuroxan

-
NO2 NO2

N N
KHCO3 +
O K O
H2O
+ +
O2N N O2 N N
- -
O - O
Cl O
7-chloro-4,6-dinitrobenzofuroxan KDNP

The product of this reaction is monohydrate KDNP in the shape of brown

needles. This form is not suitable for handling and loading in standard initiators
due to particle morphology. The anhydride can be obtained by re-crystallization
of monohydrate from 2-methoxyethanol by slow addition of isopropanol.
Re-crystallized KDNP gives a fine, amorphous material more suitable for initiator
loading [46].
The above reaction resembles previously mentioned preparation of
Meisenheimer adducts by reaction of benzofuroxan with potassium carbonate in
aqueous solution. It is interesting that using 7-chlorofuroxan instead of furoxan as a
starting material, under otherwise similar conditions, leads to a nucleophilic aro-
matic substitution and formation of fully aromatic phenol salts. The same is true for
furazans (Read, Personal Communication).
An alternative synthetic procedure for preparation of KDNP was recently pro-
posed by Fronabarger et al. [46]. The starting compound is readily available
3-bromoanisole, which is nitrated with nitric acid/oleum in ethylene dichloride
forming 3-bromo-2,4,6-trinitroanisole [52]. The bromine in the molecule is
substituted for the azido group (reaction with sodium or preferably with potassium
azide in methanol solution) giving furoxan ring by following reflux. Exchanging
methanol for the higher boiling point diethyl carbonate allows reduction of the
reaction time. This synthetic route provides KDNP in its anhydrous form [46].
7.5 Salts of Bis(furoxano)-2-nitrophenol 179

OCH3 OCH3 OCH3

O 2N NO2 O2N NO2

HNO3/H2SO4 KN3
CH3OH

Br Br N3
NO2 NO2
3-bromoanisole 3-bromo-2,4,6-trinitroanisole 3-azido-2,4,6-trinitroanisole

+
K
-
OCH3 O -
O
+
O2N NO2 O 2N N
DT
CH3OH or diethyl carbonate O
N3 N

NO1 NO2

KDNP

The sodium salt can be prepared in the same way as the potassium salt. It appears
in an anhydrous form (as opposed to the Norris method [50]), which is, however,
highly hygroscopic and rapidly absorbs water on standing (18 % water uptake on
standing at 25
C for 5 h in humid conditions 92 % RH). The potassium salt did not
demonstrate a tendency to adsorb water even under these conditions [46].

7.4.4 Uses

The potassium salt of 7-hydroxy-4,6-dinitrobenzofuroxan is proposed as a low

toxicity LS replacement with application in hot-wire igniter systems [51, 53].

7.5 Salts of Bis(furoxano)-2-nitrophenol

- - - - -
O + O O + O
N N
-
N N O N
+ +
Me O O Me O
+ + - + +
N N O N N
- - -
O O O
O O N
structure I structure II

The salts of bis(furoxano)-2-nitrophenol (BFNP, hydroxynitrobenzodifuroxan)

have been recently reported by Fronabarger et al. [54] and Sitzmann et al. [55]
180 7 Salts of Benzofuroxan

emerging from a program focused on development of drop in replacements of LS

and LA.
An interesting discovery was made in the molecular structure of the potassium
salt of BFNP (KBFNP). The crystal structure analysis showed that two isomers co-
crystallized together (structure I and II). Relative occupancy for structure I and
structure II was determined to be 51:49. It is interesting that other salts (rubidium
and guanidinium) were found to exist in discrete forms. To make it even more
interesting, the rubidium salt exists in “trans” form (structure I, carbonyl and nitro
group in para position) while the guanidinium salt exists in “cis” form (structure II,
oxy and nitro groups in para to each other). NMR spectra indicate that all of the salts
exist as mixtures of both isomers in solution [2, 54–56].

7.5.1 Physical and Chemical Properties

Alkaline salts of bis(furoxano)-2-nitrophenol are red-brown while the guanidinium

salt is light yellow. Fronabarger et al. assume that the red-brown color is due to
structure I. It is supported by the fact that when yellow crystals of the guanidinium
salt (type II structure) are dissolved in dimethyl sulfoxide the color of the solution is
red-brown, the same as for the other salts. The content of both forms of the
guanidinium salt in solution was proved by NMR analysis. Removing solvent
leads to a light yellow residue [2].
Density of the potassium salt is 2.106 g cm3 [55] and it explodes at about
165
C on heating. The sodium salt forms a monohydrate and is highly water
soluble [2, 55]. The rubidium salt has properties similar to the potassium salt; it
forms red-brown crystals with density 2.399 g cm3 and ignition temperature
200
C by DSC at 20
C min1 [2, 56].

7.5.2 Explosive Properties

The comparison of the explosive properties of KBFNP with LA and LS are

summarized in Table 7.5. KBFNP is relatively highly impact and friction-sensitive,
exceeding LS. The ignition time and time to peak pressure of KBFNP were
examined in a closed bomb and compared with KDNBF. It was observed that
KBFNP has a much shorter ignition time and a much shorter time to peak pressure
and a substantially higher impetus relative to LS (ignited with ZPP—zirconium/
potassium perchlorate mixture). In another study, ignition of ZPP by KBFNP and
KDNBF was investigated. Slightly faster ignition and significantly faster pressure
rise times to peak pressure were observed for KBFNP than for KDNBF (thin film
bridges, capacitor discharge firing mode) [57, 58].
7.5 Salts of Bis(furoxano)-2-nitrophenol 181

Table 7.5 Sensitivity and DSC of KBFNP compared with LA and LS [53, 55]
Friction sensitivity DSC
Impact sensitivity Small BAM (g) at 20
C min1 (
C)
Compound Ball drop (mJ) No-fire level Low fire level Onset Peak
KDNBF 92 20 30 203 209
LA (RD1333) – – 10 332 341
LS 25  1 40 50 290 305

KBFNP performance in a witness plate test is almost imperceptible in compari-

son with LA (0.8 mm dent in aluminum block vs. 37.3 mm for LA; both compounds
pressed at 10 MPa) [53, 55].
KBFNP lacks good long-term thermal stability at higher temperatures (weight
loss at 120
C was about 34.7 % within 90 days), however it seems good at
temperatures below 100
C at which the weight loss was only 0.6 % after 150 h.
The thermal stability of other alkaline, ammonium, and guanidinium salts is lower
than that of the potassium salt (DSC onset was found to be 189
C for Rb, 194
C
for Cs, 149
C for Na salt) [2, 54–56].

7.5.3 Preparation

The preparation of bis(furoxano)-2-nitrophenol salts is a four-step procedure devel-

oped by Fronabarger and his collaborators. It is based on formation of a diazidotri-
nitrobenzene intermediate containing a hydrolysable group. This intermediate gives
bis(furoxano)-2-nitrophenol by hydrolysis [54].
3,5-Dichloroanisole is suggested as a starting material thanks to its commercial
availability and due to a presence of a readily hydrolyzed methoxy group. 3,5-
Dichloroanisole is nitrated in the first step to 3,5-dichloro-2,4,6-trinitroanisole. The
procedure was patented by Ott and Benziger and gives nearly a quantitative yield
[57, 58]. 3,5-Dichloro-2,4,6-trinitroanisole is then converted to 3,5-diazido-2,4,6-
trinitroanisole by reaction with sodium azide in water/dimethylcarbonate under
phase transfer conditions. The intermediate 3,5-diazido-2,4,6-trinitroanisole is
thermally labile and can be easily converted to bis(furoxano)nitroanisole by reflux
in toluene. The methoxy group is readily hydrolyzed under mild conditions to form
the desired bis(furoxano)nitrophenol [2, 54–56].
182 7 Salts of Benzofuroxan

OCH3 OCH3 OCH3

O2N NO2 O 2N NO2

HNO3/H2SO4 NaN 3, (Bu) 4 NBr
DMC/H2O

Cl Cl Cl Cl N3 N3
NO2 NO2
3,5-dichloroanisole 3,5-dichloro-2,4,6-trinitroanisole 3,5-diazido-2,4,6-trinitroanisole

- -
OCH3 O OCH3 O OH
+ +
O 2N NO2 N NO2 N NO2
D D
Toluene
O O
acetone/H 2 O

N3 N3 N N N N
+ +
NO2 N N
O O
- -
O O
bis(furoxano)nitroanisole bis(furoxano)-2-nitrophenol

The salts of bis(furoxano)-2-nitrophenol can be prepared by reaction of bis

(furoxano)nitrophenol with the relevant carbonate, acetate, or hydroxide in aqueous
solution [54–56].
- - -
- O + O + + O + O
O OH N K K N
+ -
N NO2 N N O N
K2CO3
O O O + O
+ + - + +
N N N N O N N
- - -
+ O O O
-
N O O N
O
O
bis(furoxano)-2-nitrophenol KBFNP (structure I) KBFNP (structure II)

The salts can be also prepared by metal exchange from the potassium salt (e.g.,
cesium salt from cesium iodide and KBFNP in water) [2].

7.5.4 Uses

Alkaline salts of bis(furoxano)-2-nitrophenol (primarily KBFNP) were proposed as

heavy metal-free primary explosives. Even the most promising candidate—
KBFNP—exhibits low thermal stability at temperatures over 100
C and even
more importantly it has a very low performance in comparison with LA. As an
unsuitable LA replacement, it may find some use in igniting compositions replacing
LS. KBFNP has been also investigated for use in actuators or micro-propulsion
systems [54].
References 183

References

1. McGuire, R.R.: The Properties of Benzotrifuroxan. Report UCRL-52353. California Univer-

sity and Lawrence Livermore Laboratory, Livermore (1978)
2. Sitzmann, M.E., Bichay, M., Fronabarger, J.W., Williams, M.D., Sanborn, W.B., Gilardi, R.:
Hydroxinitrobenzodifuroxan and its salts. J. Heterocyc. Chem. 42, 1117–1125 (2005)
3. Doherty, R.M., Simpson, R.L.: A comparative evaluation of several insensitive high
explosives. In: Proceedings of 32nd International Annual Conference of ICT, vol. 28, pp.
32-31–32-33, Karlsruhe, Germany (1997)
4. Norris, W.P.: Synthesis of 7-amino-4,6-dinitrobenzofuroxan. US Patent H476, 1988
5. Mehilal, S.N., Chougule, S.K., Sikder, A.K., Gandhe, B.R.: Synthesis, characterization, and
thermal and explosive properties of alkali metal salts of 5,7-diamino-4,6-dinitrobenzofuroxan
(CL-14). J. Energetic Mater. 22, 117–126 (2004)
6. Millar, R.W.: Lead Free Initiator Materials for Small Electro explosive Devices for Medium
Caliber Munitions: Final Report 04 June 2003. Report QinetiQ/FST/CR032702/1.1, QuinetiQ,
Farnborough, 2003
7. Norris, W., Spear, R.J., Read, R.W.: Explosive Meisenheimer complexes formed by addition
of nucleophilic reagents to 4,6-dinitrobenzofurazan 1-oxide. Aust. J. Chem. 36, 297–309
(1983)
8. Prout, C.K., Hodder, O.J.R., Viterbo, D.: The crystal and molecular structure of 4,6-
dinitrobenzfuroxan. Acta Crystallogr. B 28, 1523–1526 (1972)
9. Green, A.G., Rowe, F.M.: Nitro-derivates of isoOxadizole oxides and of isoOxadozoles.
J. Chem. Soc. 113, 67–74 (1918)
10. Boulton, A.J., Clifford, D.P.: Two explosive compounds: the potassium salt of 4,6-
dinitrobenxofuroxan, and 3,4-dimethyl-4-(3,4-dimethyl-5-isoxazolylaxo)isoxazolin-5-one.
J. Chem. Soc. 5414–5416 (1965)
11. Norris, W.P., Osmundsen, J.: 4,6-Dinitrobenzofuroxan. I. Covalent hydration. J. Org. Chem.
30, 2407–2409 (1965)
12. Sinditskii, V.P., Egorshev, V.Y., Serushkin, V.V., Margolin, A.V., Dong, H.W.: Study on
combustion of metal-derivatives of 4,6-dinitrobenzofuroxan. In: Proceedings of 4th Interna-
tional Autumn Seminar on Propellants, Explosives and Pyrotechnics, pp. 69–77, Shaoxing,
2001
13. Shinde, P.D., Mehilal, R.B.S., Agrawal, J.P.: Some transition metal salts of 4,6-
dinitrobenzofuroxan: Synthesis, characterization and evaluation of their properties.
Propellants Explosives Pyrotechnics 28, 77–82 (2003)
14. Spear, R.J., Norris, W.P.: Structure and properties of the potassium hydroxide-
dinitrobenzofuroxan adduct (KDNBF) and related explosive salts. Propellants Explosives
Pyrotechnics 8, 85–88 (1983)
15. Mehilal, S.A.K., Pawar, S., Sikder, N.: Synthesis, characterization, thermal and explosive
properties of 4,6-dinitrobenzofuroxan salts. J. Hazard. Mater. 90, 221–227 (2002)
16. Danilov, J.N., Ilyusin, M.A., Tselinskii, I.V.: Promyshlennye vzryvchatye veshchestva; chast I.
Iniciiruyushchie vzryvshchatye veshchestva. Sankt-Peterburgskii gosudarstvennyi tekhnolo-
gicheskii institut, Sankt-Peterburg (2001)
17. Tomlinson, W.R., Sheffield, O.E.: Engineering Design Handbook, Explosive Series of
Properties Explosives of Military Interest. Report AMCP 706-177, 1971
18. Drost, P.: Ueber Nitroderivates des o-Dinitrosobenzols. Justus Liebigs Annalen der Chemie
307, 49–69 (1899)
19. Jones, D.E.G., Lightfoot, P.D., Fouchard, R.C., Kwok, Q., Turcotte, A.-M., Ridley, W.:
Hazard characterization of KDNBF using a variety of different techniques. Thermochim.
Acta 384, 57–69 (2002)
20. Zhang, Y., Sheng, D., Ma, F., Zhu, Y., Chen, L., Yang, B.: New primary explosive bis-furoxano-
nitrophenol potassium salt. Hanneng Cailiao 15, 600–603 (2007)
184 7 Salts of Benzofuroxan

21. Fedoroff, B.T., Sheffield, O.E., Kaye, S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, New Jersey (1960–1983)
22. Li, Y., Zhang, T., Miao, Y., Zhang, J.: A new way to synthesize spherical KDNBF. Huozhayao
Xuebao 26, 53–56 (2003)
23. Matyáš, R., Šelešovský, J., Musil, T.: Sensitivity to friction for primary explosives. J. Hazard.
Mater. 213–214, 236–241 (2012)
24. Whelan, D.J., Spear, R.J., Read, R.W.: The thermal decomposition of some primary explosives
as studied by differential scanning calorimetry. Thermochim. Acta 80, 149–163 (1984)
25. Jones, D.E.G., Feng, H.T., Fouchard, R.C.: In: 26th International Pyrotechnics Seminar, pp.
195–202, Nanjing, 1999
26. Jones, D.E.G., Feng, H.T., Fouchard, R.C.: Kinetic studies of the thermal decomposition of
KDNBF, a primer for explosives. J. Therm. Anal. Calorim. 60, 917–926 (2000)
27. Jones, D.E.G., Lightfoot, P.D., Fouchard, R.C., Kwok, Q., Turcotte, A.-M.: In: Proceedings of
the 28th NATAS Annual Conference on Thermal Analysis and Applications, pp. 308–313,
Orlando, 2000
28. Li, Y., Zhang, T., Zhang, J.: Thermal decomposition processes and non-isothermal kinetics of
KDNBF. Hanneng Cailiao 12, 203–206 (2004)
29. Wang, S., Zhang, T., Sun, Y., Zhang, J.: Synthesis, structural analysis and sensitivity
properties of RbDNBF. Hanneng Cailiao 13, 371–374 (2005)
30. Wang, S., Zhang, T., Yang, L., Zhang, J., Sun, Y.: Synthesis, thermal decomposition and
sensitivity study of CsDNBF. Propellants Explosives Pyrotechnics 32, 16–19 (2007)
31. Spear, R.J., Norris, W.P., Read, R.W.: 4,6-Dinitrobenzofuroxan: An Important Explosive
Intermediate. Report MRL-TN-470. Department of Defence Material Research Laboratories,
Melbourne (1983)
32. Green, A.G., Rowe, F.M.: The conversion of orthonitroamines into isooxadiazole oxides
(furoxans). J. Chem. Soc. 103, 2023–2029 (1913)
33. Gaughran, R.J., Picard, J.P., Kaufman, J.V.R.: Contribution to the chemistry of benzofuroxan
and benzfurazan derivates. J. Am. Chem. Soc. 76, 2233–2236 (1954)
34. Piechowicz, T.: Procédé de préparation d’un explosif d’amorçage. FR Patent 1,519,799, 1968
35. Brown, N.E., Keyes, R.K.: Structure of salts of 4,6-dinitrobenzofuroxan. J. Org. Chem. 30,
2452–2454 (1965)
36. McGirr, R.: Ignition composition for detonators and squibs. US Patent 3,135,636, 1964
37. McGuchan, R.: Improvements in primary explosive compositions and their manufacture.
In: Proceedings of 10th Symposium on Explosives and Pyrotechnics, San Francisco, 1979
38. Piechowicz, T.: 4,6-Dinitrobenzofurazan 1-oxide barium salt explosive primer. FR Patent
1,522,297, 1969
39. Meyer, R., K€ohler, J., Homburg, A.: Explosives. Wiley-VCH, Weinheim (2002)
40. Bjerke, R.K., Ward, J.P., Ells, D.O., Kees, K.P.: Primer composition. US Patent 4,963,201, 1990
41. Duguet, J.R.: Priming charge with annular percussion and process for its manufacture. US
Patent 5,353,707, 1994
42. Scott, H.A.: Priming composition. WO Patent 9,914,171, 1999
43. Pile, D.A., Jonn Jr. Henry J.: Bismuth oxide primer composition. US Patent 2005 189053, 2005
44. Mei, G.C., Pickett, J.W.: Lead-free nontoxic priming mix. EP Patent 1,440,958, 2004
45. Fronabarger, J.W., Williams, M.D., Sanborn, W.B., Sitzmann, M.E., Bichay, M.: Preparation,
characterization and output testing of salts of 7-hydroxy-4,6-dinitrobenzofuroxan. SAFE J. 35,
14–18 (2007)
46. Carter, G.B.: Composition pour appret primer composition. CA Patent 2,156,974, 1996
47. Norris, W.P.: Primary explosive. US Patent 4,529,801, 1985
48. Fronabarger, J., Sanborn, W.B., Bichay, M.: An investigation of some alternatives to lead
based primary explosive. In: Proceedings of 37th AIAA/ASME/SAE/ASEE (2001-3633);
Joint Propulsion Conference and Exhibit, pp. 1–9, Salt Lake City, Utah, 2001
49. Norris, W.P., Chafin, A., Spear, R.J., Read, R.W.: Synthesis and thermal rearrangement of
5-chloro-4,6-dinitrobenzofuroxan. Heterocycles 22, 271–274 (1984)
References 185

50. Boulton, A.J., Katritzky, A.R.: N-oxide and related compounds. Part XXII. The rearrangement
of 4-nitrobenzofuroxans to 7-nitrobenzofuroxans. Revue de chimie 7, 691–697 (1962)
51. Hein, D.W., Radkowski, S.J.: Process for preparing 3,30 -diamino-2,20 ,4,40 ,6,60 -hexanitrobiphenyl.
US Patent 3,402,202, 1968
52. Bichay, M., Hirlinger, J.: New Primary Explosives Development for Medium Caliber Stab
Detonators. Report SERDP PP-1364, p. 18, US Army ARDEC, 2004
53. Fronabarger, J., Williams, M., Sanborn, W.B.: Characterization and output testing of the novel
primary explosive, bis(furoxano)nitrophenol, potassium salt. In: Proceedings of 41st AIAA/
ASME/SAE/ASEE Joint Propulsion Conference and Exhibit, pp. 1–6, Tucson, AZ, 2005
54. Sitzmann, M., Bichay, M., Fronabarger, J., Williams, M., Sanborn, W., Gilardi, R.: Prepara-
tion, characterization and output testing of the novel primary explosive, bis(furoxano)
nitrophenol, potassium salt. In: Proceedings of 31st International Pyrotechnics Seminar,
pp. 729–734, Fort Collins, CO, 2004
55. Fronabarger, J., Sitzmann, M.: Nitrobenzodifuroxan compounds, including their salts, and
methods thereof. US Patent 7,271,267, 2007
56. Ott, D.G., Benziger, T.M.: Preparation of 1,3,5-triamino-2,4,6-trinitrobenzene from 3,5-
dichloranisole. J. Energetic Mater. 5, 343–354 (1987)
57. Ott, D.G., Benziger, T.M.: Preparation of 1,3,5-triamino-2,4,6-trinitrobenzene from 3,5-
dichloranisole. US Patent 4,952,733, 1990
Chapter 8
Tetrazoles

Tetrazoles are chemical compounds characterized by a doubly unsaturated five-

membered ring containing four nitrogen atoms and one carbon atom. The tetrazole
ring usually exists in two tautomeric forms, 1H and 2H:
R R
C H C
N N N N
N N N N
H
5-R-1H-Tetrazole 5-R-2H-Tetrazole

where R represents any substituent. The nitrogen atoms of its structure make
tetrazole a strong acid. Many tetrazole derivatives are also acids and often yield
explosive salts.
Unsubstituted tetrazole (1H- or 2H-tetrazole sometimes referred as “free
tetrazole”) forms colorless crystals with density 1.632 g cm
3 (X-ray) which melt
at 155.5  C without decomposition according to Fedoroff, Shefield, and Kaye’s
encyclopedia [1] or at 157–158  C according to Bagal [2]. Tetrazole is easily
soluble in water, ethanol, acetone, and acetic acid [2]. Heat of formation is
236 kJ mol
1 [3]. Free tetrazole does not have the characteristics of a primary
explosive. Tetrazole easily forms metallic salts owing to the acidic nature of its
hydrogen atom [2]. A large number of its derivatives or derivative’s salts do have
explosive properties and many fall into the category of primary explosives.
Explosive properties of tetrazoles and their salts vary considerably, ranging from
nonexplosive behavior to being extremely sensitive and powerful explosives. In
general terms, the 5-substituted tetrazoles and their salts may be ranked in terms of
their explosive behavior in the following order [4]:

R. Matyáš and J. Pachman, Primary Explosives, 187

DOI 10.1007/978-3-642-28436-6_8, # Springer-Verlag Berlin Heidelberg 2013
188 8 Tetrazoles

H H
N N
N N
CH3 = Ph < NH 2 < H < NHNO 2 < R < R N N C
N N
N N
mild ignitions compounds explode do not detonate RDX some very sensitive

+
< Cl < NO 2 < N3 < N2
powerful explosives very sensitive unstable explosives
detonate RDX

This behavior is probably related to the electron-withdrawing power of the

substituent in position 5 of the ring. Tetrazoles with substituents having higher
electron-withdrawing power exhibit more explosive behavior [4] and also seem to
be more sensitive [5]. In the case of metal salts, the nature of the metal ion also
influences the explosive behavior. Heavy metals, including silver, lead and mercury,
give more sensitive substances with greater initiating efficiency than alkali metal
salts [4]. 5-Substituted tetrazoles are more stable than 1- and 2-substituted ones [5].
Haskins [6] also compared the empirical ranking of explosive behavior proposed
by Bates and Jenkins [4] with one devised according to the total charge in the
substituent group. Extended H€ uckel molecular orbital (EHMO) calculations
provided a quantitative measure of electron-withdrawing power of the substituents
in the following order:

CH3 < H < NH2 < NHNO2 < N3 < NO2

Haskins [6] suggested that the EHMO calculations, although not in agreement
with the qualitative ordering, were in good enough agreement to indicate a rela-
tionship between explosive behavior and electron withdrawal power from the ring.
Chen et al. [5] performed theoretical calculations (PM3 MO) on the thermolysis
of 5-substituted tetrazole derivatives and their metal salts. They compared the
observed sensitivity and the activation energies of the thermolysis and found that
the two follow a similar order. The order of values of activation energies is as
follows:
H
N
N +
Ph > CH3 > H > NH2 > NHNO 2 > R > Cl > NO 2 > N3 > N2
N
N

The sensitivities of these derivatives are in the reverse order [5].

A number of metal salts of 5-(N-nitramino)tetrazoles have a short predetonation
zone (fast DDT). Silver salts of 1-(N-nitramino)- (I), 2-(N-nitramino)- (II), 5-(N-
nitramino)- (III), and 1-methyl-5-(N-nitramino)-tetrazoles (IV) were prepared to
study the effect of the position of the substituting group on the initiating efficiency.
8.1 Tetrazene 189

N N N N
N N N N NHNO2 N N N N
N N N N
H NHNO2 H O2NHN H O2NHN CH3

I II III IV

The silver salts of (I) to (IV) are white crystalline substances, sparingly soluble
in water and organic solvents, but soluble in aqueous ammonia. The initiating
efficiency was determined as the smallest amount of the salt needed for initiation
of RDX in tubing of a number 8 detonator. The details of the procedure are reported
by Avanesov [7]. The experimental values of the minimal amount increases in the
following order:

AgðIIÞ:AgðIÞ:AgðIIIÞ:AgðIVÞ ¼ 1:5:60:120

The salts of 1- and 2-(N-nitramino)tetrazole have much better initiating

efficiency than their 5-(N-nitramino)tetrazole analogs. The silver salt of 2-(N-
nitramino)tetrazole (II) is a powerful initiating explosive with efficiency higher
than LA [8].
Tetrazoles, their salts, and their complexes have been studied as replacements
for lead-containing substances such as lead azide or lead styphnate in detonators
and priming mixtures. Despite the existence of a vast variety of such compounds,
only a few have found practical application in primer mixes or as a primary
explosive (tetrazene, the mercury salt of 5-nitrotetrazole, CP, BNCP). Many
tetrazole derivatives often suggested for use in gas generators with application in
automobile safety devices (airbags and seat belt tensioners) are subject to patent
protection. Due to the large number of possible tetrazole compounds, we have
decided to cover only a small group of selected candidates. Our intention has been
to cover those that have already been applied as primary explosives or, to a lesser
extent, those most often discussed.

8.1 Tetrazene

N H H
N
- C- N N
N
N N N H
C N
+
H H N H
O
H
H

1-Amino-1-(tetrazol-5-yldiazenyl)guanidin monohydrate known as tetrazene

(GNGT, in earlier literature referred to as tetracene) is without question the most
190 8 Tetrazoles

Fig. 8.1 Crystals of GNGT—left optical microscopy (by kind permission of Dr. Šelešovský),
right SEM

common tetrazole substance used as a primary explosive. In fact it was the first
tetrazole compound which found a use as an explosive. GNGT was first prepared by
Hoffman and Roth in 1910 by reaction of aminoguanidine with nitrous acid [9].
Hoffman and his co-workers assigned tetrazene a linear structure on the basis of its
chemical reactions (historical formula I). Their suggested structure was later
disproved and substituted by a structure with the tetrazole ring (historical formula II)
[10]. On the basis of X-ray analysis, it was, however, determined that the molecular
structure of tetrazene is represented as the zwitterion with the hydrogen-bonded water
molecule as shown above [11].

HN NH N NH
N
C N N NH NH C . C N N NH NH C .H O
2
ON NH NH NH2 N NH2
N
H
GNGT GNGT
historical formula I historical formula II

8.1.1 Physical and Chemical Properties

Tetrazene crystallizes as a monohydrate in the form of a fluffy solid made up of

colorless or pale yellow crystals [12–15] (see Fig. 8.1) with crystal density
1.64–1.65 g cm
3 [15, 16] or 1.7 g cm
3 [13, 16]. The bulk density of GNGT is
very low, only 0.45 g cm
3 according to Rinkenbach and Burton [15], Meyer’s
encyclopedia reports only 0.3 g cm
3 [16].
Tetrazene is practically insoluble in water and most common organic solvents
(alcohol, acetone, ether, benzene, ethylene dichloride). It is slightly hygroscopic as
it absorbs 0.77% water (at 30  C; 90% relative humidity). In boiling water, GNGT
decomposes [14, 16, 17]. GNGT does not react with concentrated ammonia, metals
(steel, copper, aluminum) or high explosives (TNT, tetryl, PETN, RDX) at room
8.1 Tetrazene 191

temperature [2, 14]; sodium and potassium hydroxide provoke chemical decompo-
sition producing ammonia [18], whilst carbon dioxide decomposes GNGT only in
the presence of water [14].
GNGT does not react with diluted acids (10%) but in concentrated acids it dissolves,
forming explosive salts (nitrates, perchlorates, sulfates, etc.) [2, 12, 13, 15]. Tetrazene
may be precipitated from these salts by dilution [13] or by neutralization with ammonia
or sodium acetate [11, 16]. One disadvantage of these salts is their tendency to undergo
hydrolysis in a humid environment [14]. All of these salts also react with salts of heavy
metals forming double salts. For example, C2H7N10OAg·AgNO3·3H2O (which does
not undergo hydrolysis in humid air) may be precipitated from a slightly acidified
solution of GNGT by addition of excess aqueous AgNO3 [13, 14]. Tetrazene
decomposes by the action of bases producing the relevant salt of 5-azidotetrazole [17].
It is stable at normal temperatures but its thermal stability decreases as the
temperature increases. In presence of moisture, degradation occurs even at
temperatures as low as 60  C. The decomposition of GNGT in boiling water is
practically quantitative leading to a variety of products including 5-azidotetrazole
which is a very sensitive primary explosive. It is therefore not recommended to
decompose larger amounts of GNGT in boiling water. Some explosions of decom-
position solutions have been reported after cooling down the water with what was
believed to be innocent decomposition products [14].
The poor thermal stability (it explodes at 135–140  C [15]) along with its
tendency to become easily dead-pressed are some of its drawbacks.

8.1.2 Explosive Properties

Impact sensitivity of GNGT is reported to be (a) about the same as MF [19];

(b) slightly more sensitive than MF [14, 15, 17, 18]; or (c) slightly less sensitive
than MF [1, 20]. Values of impact sensitivity reported by various authors are
summarized in Fig. 2.15. Sensitivity to friction is about the same as that of MF
according to our own measurement (see Fig. 2.19) [21]. The sensitivity to electro-
static discharge was found to be 2.7 mJ and, as can be seen from Fig. 2.21, is
comparable to that of DDNP. GNGT is often mixed with hard inert particles to
increase its sensitivity especially when used in percussion and stab priming
mixtures.
GNGT detonates more easily when uncompressed and undergoes “gradual dead-
pressing” when subjected to higher compacting pressures. This is clearly
demonstrated by the gradual decrease of apparent brisance (measured by the
amount of crushed sand) with increasing compacting pressure (see Table 8.1).
Pressing GNGT with 20.7 MPa results in material with a density of 1.05 g cm
3.
Increasing the compacting pressure above 30 MPa results in dead-pressed material
[15, 17].
In addition, tetrazene shows a variation in the “order of detonation” depending
on the method of initiation. This is reflected in a lower brisance when initiated by
192 8 Tetrazoles

Table 8.1 Brisance of Amount of GNGT (g) Loading pressure (MPa) Crushed sand (g)
GNGT as a function of
compacting pressure [15] 0.4 0 13.1
0.4 250 9.2
0.4 500 7.5
0.4 3,000 2.0

flame or small amounts of other primary explosives, and a higher brisance when
initiated by the severe shock of a large priming charge. A wide range of detonation
parameters is therefore obtainable for GNGT by varying the compacting pressure
and the type of initiation [15].
GNGT is easily ignited by flame and when small enough amount is used it
deflagrates without observable flame.
The initiating efficiency of GNGT is rather poor even when the conditions are
combined in such way that gives maximum brisance. It is capable of initiating tetryl
but not TNT [15].

8.1.3 Preparation

Tetrazene is produced by the reaction of an aminoguanidine salt (aminoguanidine is

not soluble in water; the most frequently used are sulfate, carbonate, or nitrate) with
sodium nitrite [2, 13, 14, 17, 22]. The reaction of aminoguanidine with sodium
nitrite can produce three different compounds depending on the environment [23]:
• Azidoformamidine (formerly guanyl azide) in a solution of a strong mineral acid
• Tetrazene in a slightly acidic environment
• 1,3-Di-1H-(tetrazol-5-yl)triazene in a solution of acetic acid

N3
C NH azidoformamidine
NH2
strong acid
N H H
N
- C- N N
N
H2N N N N H
slightly acidic
C NH NH2 + HNO2 C N GNGT
HN +
H H N H
O
H
H
acetic acid H
N N
N N
C N N N C 1,3-di-1H-(5-tetrazoyl)triazene
N N
N H N
H

The preparation of GNGT is carried out in a slightly acidic environment; the

solution of aminoguanidine is acidified before the reaction (pH ~4–5; nitric acid or
8.1 Tetrazene 193

acetic acid are often used). The solutions of aminoguanidine salt and sodium nitrite
are preheated to 50–60  C and the reaction temperature is kept at 50–55  C.
Tetrazene gradually precipitates from the solution. The dosage rate affects the
crystal size of the product. Preparation of GNGT can be done using the same
technology as that used for LA or LS production [2, 13, 14, 17, 22]. Dextrin is
sometimes used for obtaining more uniform crystals [22]. A pure white product
may be obtained by recrystallization from nitric acid [14].
H2N H2N
+ -
C NH NH2 + HNO2 C N N N
HN HN
aminoguanidine

H H H2N
N N C NH NH2
N HNO2 N HN
C NH2 C N N OH
N N
N N

N H H
N
- C- N N
N
N N N H
C N
+
H H N H
O
H
H
GNGT

If the reaction temperature is high (about 65  C or more) and the pH of the reaction
mixture too low, azidoformamidine forms instead of GNGT. By neutralization of the
reaction mixture, azidoformamidine undergoes transformation to 5-aminotetrazole
[17].
GNGT residues or any product of inappropriate crystal size can be chemically
decomposed by boiling in water [17]. The risk associated with such operation was
described earlier in this chapter (physical and chemical properties of GNGT).

8.1.4 Uses

Tetrazene is classified as an initiating explosive but its own initiating efficiency is

low. It is capable of initiating only unpressed PETN and tetryl [12, 15]. It can be
used in detonators when initiated by another primary explosive or in a mixture with
another primary explosive. Addition of even small amounts (ca. 0.5–5%) of GNGT
to other explosives dramatically increases the sensitivity to mechanical stimuli and
flame of the resulting mixture. GNGT therefore more often acts as an energetic
sensitizer in many compositions—particularly in primers [24] and various fuse
mixtures. It is used in applications where high sensitivity to friction, impact, stab,
194 8 Tetrazoles

flame, and spark is demanded. Mixtures of tetrazene with lead styphnate have
replaced earlier mixtures based on MF in primers. These mixtures are less toxic
(do not contain mercury), generally noncorrosive and, in particular, do not corrode
firearm barrels [1, 18]. Tetrazene is also used in nontoxic lead-free primer
compositions (alone or in combination with DDNP and other substances)
[24–26]. The content of GNGT in explosive mixtures generally does not exceed
10% [17].
Tetrazene is a heavy metal-free primary explosive that could be used in many
applications. Its main drawbacks are its poor thermal stability, low initiating
efficiency, and the tendency toward dead-pressing [27]. The use of GNGT is further
limited by its low flame temperature which is a problem if it is used in priming
mixtures. One possible solution to this problem (employed in NONTOX priming
mixture) is the addition of pyrotechnic components that increase the flame temper-
ature sufficiently to reliably ignite the gun powder [26].

8.2 5-Aminotetrazole Salts

NH2

C H
N N

N N
5-ATZ

5-Amino-1H-tetrazole (subsequently just 5-ATZ) was first synthesized by Johannes

Thiele in 1892. He obtained this compound by cyclization of azidoformamidine in a
boiling aqueous solution [28, 29].

8.2.1 Physical and Chemical Properties

Free 5-ATZ contains the acidic tetrazole ring and the basic amino group. Its chemical
behavior is similar to that of amino acids. Free 5-ATZ forms a monohydrate that loses
water of crystallization above 100  C. The melting temperature of 5-ATZ is 203  C [2].
This compound is very hygroscopic, soluble in hot water, acetone, and ethanol [1, 2].
Most metallic salts of 5-ATZ are soluble in water as well (except the silver,
cupric, and mercurous salts). Many metallic salts form various hydrates [1]. The
sodium salt forms yellow crystals, crystallizes with three molecules of water of
crystallization and is soluble in water [2]. Some physical properties of heavy
metallic salts are summarized in Table 8.2 [30].
8.2 5-Aminotetrazole Salts 195

Table 8.2 Physical properties of some metallic salts of 5-aminotetrazole [30]

Color Comment
AgATZ Colorless Microcrystalline precipitate
Cu(ATZ)2·H2O Green Precipitated from acetone
Pb(ATZ)2 Colorless Precipitated with acetone from water
Co(ATZ)2·xH2O Pink Precipitated from acetone
Ni(ATZ)2·H2O Blue Precipitated from acetone

Table 8.3 Sensitivity and ignition properties of some metallic salts of 5-aminotetrazole
Impact sensitivity; Ignition temperature; Ignition temperature; heating
2.5 kg [31] (cm) hot bar [31] ( C) rate 5  C min
1 [30]( C)
AgATZ 22 366 352 (smoke)
HgATZ 38 256 (expl) –
Cu(ATZ)2 68 256 164 (flame)
Pb(ATZ)2 – – 303 (flame)
Co(ATZ)2·xH2O – – 228 (expl.)
Ni(ATZ)2·H2O – – 290 (expl.)

8.2.2 Explosive Properties

Most metallic salts of 5-ATZ are not typical primary explosives. Similarly to free
5-ATZ, the sodium salt is not sensitive to impact [2] and even the sensitivity to
impact of heavy metal salts is relatively low in comparison with common primary
explosives (see Table 8.3).
Bates and Jenkins reported that all salts of 5-ATZ mentioned in Table 8.3 show
irregular burning behavior with occasional explosions. They are considered as
“substances with little promise of being technically useful” [30].

8.2.3 Preparation

5-ATZ was first successfully prepared by Thiele by diazotization of aminoguanidine

nitrate. Aminoguanidine salts (nitrate, carbonate, sulfate) are used for synthesis
because free aminoguanidine has low stability. The intermediate azidoformamidine
is sufficiently stable to be isolated. The cyclization of azidoformamidine by heating
with sodium acetate, sodium carbonate, diluted acid, or an aqueous solution of
ammonia yields 5-ATZ [28, 29, 32–34].
NH2

HN HN C H
HNO2 CH3COONa
C NH NH2 C N3 N N
H 2N H2N N N
aminoguanidine azidoformamidine 5-ATZ
196 8 Tetrazoles

Another method was published by Stollé [35, 36]. 5-ATZ is prepared by treating
cyanamide, or the more readily available dicyandiamide, with hydrazoic acid [32, 36].
Alternatively, hydrazoic acid can be substituted by its sodium salt in presence of
hydrochloric acid (hydrazoic acid forms in situ) [28].

H2N C N NH2
HN3
C H
N N
HN3 N N
H2N C NH C N 5-ATZ
NH

Metallic salts of 5-ATZ can be prepared by treating an aqueous solution of

5-ATZ (or its sodium salt) with the relevant soluble salt [29, 37]. In case of salts of
first row transition elements, it is recommended to carry out the precipitation in
acetone [30].
The type of anion of the metallic salt influences the purity of the resulting 5-ATZ
salt. Using nitrate, sulfate, or carbonate results in a product contaminated by
relevant anion. These ions cannot be removed from the product by washing with
water [29, 37]. Daugherty, however, reported that contaminated product forms
when using sulfate and chloride, but that nitrate and perchlorate yield a pure
product. In the case of the latter two, the product precipitates only after standing
for a week or more (in case of Cu(ATZ)2) [37]. Bates and Jenkins reported that salts
of 5-ATZ free from this unwanted anion can be prepared by repeated precipitation
(precipitation of aqueous solution of salt of 5-ATZ with acetone) and centrifuging
out the precipitate [30].
NH2 NH2
C H C Ag
H2O
N N + AgNO3 N N
N N N N
5-ATZ AgATZ

The reaction of 5-ATZ with silver salts may, in certain conditions, lead to
complex rather than normal salts. The only metallic complex salt of 5-amino-
1H-tetrazole that has been reported as suitable as a primary explosive is the
complex disilver 5-amino-1H-tetrazolium perchlorate Ag2(ATZ)ClO4. It was first
reported by Charles Rittenhouse in 1972 [38]. The analogous nitrate complex has
been published recently [39]. Both complexes are insoluble in water and other
common solvents. They are only soluble in concentrated acid solutions (e.g.,
hydrochloric, nitric, perchloric acid) forming the corresponding salts [39].
The disilver 5-amino-1H-tetrazolium perchlorate has comparable explosive
properties to those of lead azide—it is highly thermally stable and easily initiated
by standard bridge-wire initiators [38]. The impact sensitivity is 2 J and 15 J for its
nitrate analogue. The friction sensitivity is reported below 5 N for the perchlorate
and 18 N for the nitrate. Relatively high thermal stability has been observed for both
8.3 5-Nitrotetrazole Salts 197

substances. The perchlorate decomposed at 319  C and the nitrate at 298  C when
heated in DSC with heating rate 5  C min
1 [39].
The complex disilver 5-amino-1H-tetrazolium perchlorate and nitrate are
formed by the reaction of an aqueous solution of silver perchlorate with 5-ATZ in
presence of perchloric acid [38].

HClO4
5-ATZ þ AgClO4







! Ag2 ð5-ATZÞClO4

Preparation of a nitrate derivative may be carried out in a similar way [39].

8.2.4 Uses

Free 5-ATZ, its simple or complex salts and its other derivatives are not used as
standalone primary explosives. They are however often mentioned in patent literature
as suitable replacements for azide-containing pyrotechnic mixtures (due to the high
nitrogen content in the molecule). These mixtures are suggested in gas-generating
compositions for inflation of vehicle airbags, seat belt pretensioners, and for other
similar devices. Free 5-ATZ is also used as a starting material for the preparation of
other tetrazole derivatives.

8.3 5-Nitrotetrazole Salts

NO2

C H
N N

N N
HNT

Free 5-nitro-1H-tetrazole (subsequently just 5-nitrotetrazole; HNT) is an

extremely sensitive substance that explodes with the slightest stimulus or even
spontaneously [40–42]. However, its metallic salts are stable and heavy metallic
salts have the characteristics of primary explosives.

8.3.1 Physical and Chemical Properties

Free 5-nitrotetrazole forms colorless, extremely hygroscopic, crystals which, if

exposed to humid air, dissolve into a simple solution (the material shows strong
deliquescence). Melting point of HNT is 101  C; enthalpy of formation is
198 8 Tetrazoles

Table 8.4 The properties of metallic salts of 5-nitrotetrazole

Compound Physical appearance Solubility
Cu(NT)2·HNT·4H2O Light blue needles [1] Slightly soluble in water [44]
Cu(en)2(NT)2a Violet crystals [4] Slightly soluble in cold water, readily
soluble in hot water [4]
Hg(NT)2 Heavy granular crystals [45] Poor solubility in water (0.09 g in
100 ml at 30  C [46]), soluble in
ammonium acetate solution [1]
AgNT White fluffy needles [45] Practically insoluble in water [1]
Cu(NT)2 Blue crystals [47] Slightly soluble in water [48]
CuNT Brown crystals, density –
2.81 g cm
3 [49, 50]
Co(NT)2, Ni(NT)2 Reddish-white, Practically insoluble in water [45],
microcrystalline [45] Ni(NT)2 forms intractable
gelatinous precipitate [4]
Pb(NT)2·Pb(OH)2 Pale yellow crystals [45] Soluble in hot water, slightly in cold
water [1]
a
en - Ethylenediamine.

Fig. 8.2 Crystals of the cupric salt of 5-nitrotetrazole [47]. Reprinted by permission of the
Department of the Navy employees, M. Bichay, K. Armstrong, R. J. Cramer and the Pacific
Scientific employess, J. Fronabarger and M. D. Williams

261 kJ mol
1. It is strongly acidic (pKa ¼
0.8) [43]. Some properties of heavy
metallic salts of 5-nitrotetrazole are summarized in Table 8.4.
Metallic salts are mostly soluble in water (e.g., alkaline, salts of alkaline earths,
cadmium, and thallium). The silver, mercury, cobalt, and nickel salts are insoluble
in cold water; cobalt and cupric salts give a dihydrate [4]. Nitrotetrazole salts have
good chemical stability and are not sensitive to carbon dioxide nor influenced by
moisture. They may be stored without deterioration in hot and humid climates [1].
The cupric salt of 5-nitrotetrazole is not hygroscopic [48]. The crystals of this salt
are shown in Fig. 8.2.
8.3 5-Nitrotetrazole Salts 199

Table 8.5 Properties of alkali salts of 5-nitrotetrazole [51]

Li Na K Rb Cs
Water molecules in crystal 5 2 0 0 0
Crystal system Monoclinic Triclinic Monoclinic Monoclinic Monoclinic
Density (g cm
3) 1.609 1.731 2.027 2.489 2.986

Recently reported properties of alkali salts of 5-nitrotetrazole are summarized in

Table 8.5 [51]. The sodium salt is not stable; it forms various hydrates with one to
four molecules of water of crystallization [52] in the form of colorless crystals
highly soluble in water. Ferrous 5-nitrotetrazole forms a dihydrate (even after
drying in vacuo over P2O5) [53].
Silver salt of 5-nitrotetrazole is known to exist in six polymorphic forms which is
the major disadvantage of this compound [4], whereas the mercuric salt does not
exhibit polymorphism [54]. The very wide range of crystal structures of Hg(NT)2 has
been reported [4]. The big drawback of mercury 5-nitrotetrazole is its incompatibility
with aluminum [42].
Compatibility of the silver salt of 5-nitrotetrazole has been investigated by Blay
and Rapley [55]. They exposed a thin layer of AgNT on a metal surface at 50–60  C
to humid conditions for up to 8 weeks. They observed that it is incompatible with
aluminum, the metal being corroded at humidity levels as low as 75% (significantly
more than for SA). Copper and brass were less affected, and only at 100% relative
humidity, and no corrosion of stainless steel was observed under the conditions of
the test. The silver salt of 5-nitrotetrazole is compatible with HMX, RDX, and the
lead salt of dinitroresorcine. However, when a mixture of AgNT with tetrazene was
stored at high humidity, both tetrazene and AgNT rapidly decomposed, but a
similar mixture stored at low humidity showed no decomposition. The silver salt
of 5-nitrotetrazole is more resistant to rubbers and plastics than SA. Spectrophoto-
metric determination of the silver salt of 5-nitrotetrazole has also been published by
Blay and Rapley [55].

8.3.2 Explosive Properties

Free 5-nitrotetrazole is mostly reported as an extremely sensitive substance. Despite

this fact, Koldobskii et al. experimentally determined its detonation velocity as
8,900 m s
1 at density 1.73 g cm
3 [43].
Sensitivity of the alkaline salts basically depends on the amount of water of
crystallization in the molecule. Lithium and sodium salts form hydrates and the
sensitivity of both to impact and friction is therefore low. However, the potassium,
rubidium and cesium salts form anhydrous compounds with sensitivity significantly
higher, approaching that for standard primary explosives [51].
The sensitivity to impact of the heavy metallic salts of 5-nitrotetrazole, and their
initiating efficiency to tetryl are summarized in Table 8.6. The ammonium salt has
200 8 Tetrazoles

Table 8.6 Impact sensitivity, ignition temperature and initiating efficiency against tetryl for
certain tetrazole salts
Initiating
efficiency Ignition
Impact sensitivity (against tetryl) temperature
Converted to
Compound As reported energy (J) (g) ( C) References
NaNT·2–4H2O insens. (compl. dry sensitive) – – [1]
Cu(NT)2·HNT·4H2O 5 cm/5 kga 2.5 – – [1]
– – 237 [52]
[Cu(en)2](NT)2 20 cm/5 kg 9.8 – – [1]
50 cm/2.5 kg 12 – – [46]
(burns)
– – 204 [52]
Hg(NT)2 7 cm/2.5 kg 1.7 – – [46]
Same as MF 0.006 ~ 215 [45]
Significantly more than LA – 202–235b [56]
7 cm/2.5 kg 1.7 – 210, 215 [1]
5 cm/5 kgc 2.5
– – – 268 [2]
AgNT Little more than MF 0.005 230 [45]
22.7 cmf – – 259, 262 [52]
~LA 0.004d – [2]
More than LA – 273e [57]
Co(NT)2, Ni(NT)2 ~MF – 220 [45]
Pb(NT)2.Pb(OH) Little more than MF 0.02 220 [45]
LA (for comparison) – 0.02 – [45]
19 cm (F of I 29)f – 319 [52]
a
>60 cm/5 kg for wet product.
b
Range for various batches.
c
Same value for wet substance.
d
Pressed at 15.7 MPa.
e
Decomposition temperature (DSC, heating rate 5  C min
1).
f
(h50, Ball & Disc test).

the characteristics of a secondary explosive; it is less sensitive to impact than RDX

[58]. The dihydrate of the sodium salt is reported to have relatively low sensitivity
(Table 8.6). On dehydration, however, it forms the very sensitive anhydrous sodium
salt. An initiation attributed to dehydration of this substance has been reported
during manipulating NaNT·2H2O with a wooden spatula [56].
Comparison of the sensitivity of AgNT and Cu(NT)2 with their complexes with
ethylenediamine (EDA) and the ammonium ligand has been published recently.
According to this study, both AgNT and Cu(NT)2 are more impact sensitive than lead
azide; ethylenediamine complex compounds are significantly less sensitive [57].
Nitrotetrazole salts have good flammability that is not affected by moisture [45].
Most of them (even the alkaline salts) are powerful primary explosives, e.g., the
cesium salt has a performance similar to that of lead azide [42].
Cupric Salt of 5-Nitrotetrazole 201

Mercuric Salt of 5-Nitrotetrazole

The mercuric salt is sensitive to stab initiation. Larger particles are more sensitive
than smaller ones. Just as in the case of LA, a small content of tetrazene signifi-
cantly increases stab sensitivity of the resulting mixture. Initiation by hot wire is
slightly more difficult than in the case of milled dextrinated LA and LS [59]. The
variability of the explosive properties (impact and stab sensitivity, ESD, initiation
temperature, plate dent test) of Hg(NT)2 for different methods of preparation and
batches have been examined by Redman and Spear [56]. Dead-pressing of the
mercury salt depends on the way it is prepared. The pure mercury salt cannot be
dead-pressed by pressure up to 276 MPa according to Bates and Jenkins [4]; or even
up to 700 MPa according to Scott [59]. Mercuric salt of 5-nitrotetrazole is more
powerful than LA (RD 1333—co-precipitated with carboxymethylcellulose) in a
plate dent test when loaded into an electric detonator (modified MK71) [59].

Silver Salt of 5-Nitrotetrazole

The sensitivity to impact of AgNT, initiating efficiency, and ignition temperature are
summarized in Table 8.6. Sensitivities of this substance have also been examined by
Millar [52]. Sensitivity to friction was determined by the emery paper friction test as
the pendulum velocity required to produce a 50% probability of ignition. The value
for AgNT is 1.7 m s
1 (for LA 1.2 m s
1 and 1.8 m s
1 for LS). Electric discharge
sensitivity of AgNT is presented in Table 8.7. The author tested sensitivity using two
tests, the standard test and the test for sensitive explosives No. 7 (this test is used for
highly sensitive explosives).
Thermal stability of AgNT has been studied by Blay and Rapley [55]. Temperature
of ignition is 262  C at a heating rate of 5  C min
1. The silver salt of 5-nitrotetrazole
is thermally less stable than SA. Typically, a 20% mass loss occurs within 3 h at 240  C
(compared with 3% for SA) [55].
The silver salt is a powerful primary explosive with a performance similar to that
of lead azide [42]. Unlike Hg(NT)2, the silver salt can be dead-pressed even at
relatively low pressures (~20 MPa) [2, 4].

Cupric Salt of 5-Nitrotetrazole

The cupric salt of 5-nitrotetrazole has been studied as a potential green primary
explosive by Fronabarger, Sanborn and Bichay et al. [48]. The values of sensitivity
and performance reported by these authors are summarized in Tables 8.8 and 8.9.
Bagal reported an ignition temperature of 224  C (heating rate 5  C min
1) [2].
202 8 Tetrazoles

Table 8.7 Electric discharge sensitivity of AgNT [52]

Compound Standard test (mJ) Test for sensitive explosives (No. 7) (mJ)
AgNT 45 ignition 2.6 ignition; not 1.9
LAa – 2.5
LSa – 7
a
Service material RD 1343—LA (precipitated from sodium carboxymethylcellulose/sodium
hydroxide) and RD 1303—LS.

Table 8.8 Sensitivity and DSC data of the cupric salt of 5-nitrotetrazole [48]
Impact sensitivity Friction sensitivity DSC onset
Ball drop Small BAM (g) (20  C min
1, argon atm.)
Compound (mJ) No-fire level Low fire level ( C)
Cu(NT)2a 57 55 65 245
Cu(NT)2b 79 1,000 1,030 206
LA (RD 1333) 50 Not determined 10c 332
a
Prepared from NaNT and the cupric salt.
b
Prepared by hydrolysis of acidic cupric salt.
c
Minimum weight setting; samples discharged at this level.

Table 8.9 Results of plate dent test of the cupric salt of 5-nitrotetrazole compared with LA
(aluminum plate)
Loading Cu(NT)2a [48, 49, 60, 61] LAb [47, 48] LAb [60, 62]
pressure Density Average dent in Density Average dent in Density Average dent in
(MPa) (g cm
3) Al block (mm) (g cm
3) Al block (mm) (g cm
3) Al block (mm)
34.5 1.26 9.0 2.62 27.7 2.87 30.5
69 1.38 22.6 2.99 33.7 3.17 34.0
138 1.53 31.7 3.18 39.0 3.60 36.9
276 1.77 29.0 3.55 46.3 3.98 39.4
a
Prepared from NaNT and the cupric salt.
b
Different values for LA (RD 1333) in the literature.

Brisance of the cupric salt of 5-nitrotetrazole at various densities has been

measured by the plate dent test (see results in Table 8.9). Cu(NT)2 detonates even
at low density but it did not match the performance achieved by LA [47, 48]. This
may be because of its longer DDT compared to LA. It is interesting that the method
used for synthesizing has a significant impact on the detonation parameters of
Cu(NT)2. The cupric salt of 5-nitrotetrazole prepared from NaNT and a cupric
salt detonates in witness plate test while the same compound prepared directly by
hydrolysis of an acidic cupric salt of 5-nitrotetrazole does not detonate [48].
The dibasic salt Cu(NT)2·2Cu(OH)2 does not have the characteristics of a
primary explosive, and the ethylenediamino and propanediamino complex salts
behave more like pyrotechnic compositions [4].
Cuprous Salt of 5-Nitrotetrazole 203

Table 8.10 Sensitivity and brisance of CuNT compared to LA [49, 50]

Sensitivity to impact Sensitivity to friction Dent block testing
Compound (mJ) Low fire level/no fire level (g)a Average dent (mm)b
CuNT 40 10/0 0.94
LA (RD 1333) 50 10/0 0.84
a
Small-scale Julius Peters BAM tester.
b
Aluminum block; materials pressed at 69 MPa.

Cuprous Salt of 5-Nitrotetrazole

The cuprous salt of 5-nitrotetrazole (CuNT) has been patented as a potential green
primary explosive by Fronabarger et al. Sensitivity to impact is higher than that of
LA and sensitivity to friction is about the same. The brisance of CuNT measured by
PDT is superior to that of LA. Sensitivity and performance data are summarized in
Table 8.10 [49, 50].
Thermal stability is superior to that of LA (by TGA); onset of thermal decom-
position is at 322–331  C (DSC, heating rate not reported) [50].

8.3.3 Preparation

Free 5-nitrotetrazole can be prepared by treating a warm aqueous suspension of its

acid copper salt with hydrogen sulfide [1, 45, 46]. If hydrochloric acid is used
instead of hydrogen sulfide, the 5-nitrotetrazole becomes unstable and explodes
without any external stimulus after a period of 2–3 weeks in storage [1, 4].
NO2 NO2 NO2 NO2

C Cu C C H C H
H2S
N N N N N N 3 N N
4 H2O
N N N N N N N N

Cu(NT)2·HNT HNT

Free 5-nitrotetrazole can be also synthesized by acidification of its sodium salt

followed by its extraction by diethyl ether [43]. The ion-exchange column can be
used as a safe and convenient method for preparing a dilute solution of free
5-nitrotetrazole from its sodium salt. This solution can be used for preparation of
other metallic salts (e.g., Tl+, Rb+, Cs+, K+, Ba2+, Pb2+). The product is obtained
after crystallization from the reaction solution. Spontaneous explosions occur
during isolation of the thallium and lead salts [42].
The monobasic lead salt of 5-nitrotetrazole can be easily prepared by dripping
the 5-nitrotetrazole solution from the ion-exchange column directly into a warm
suspension of lead oxide or hydroxide [42].
The preparation of 5-nitrotetrazole by direct nitration of tetrazole is not possible
due to the acidic nature of hydrogen bound on the tetrazole ring. 5-Nitrotetrazole is
204 8 Tetrazoles

therefore synthesized by the Sandmeyer reaction of 5-ATZ (treating an acidic

solution of 5-ATZ with an excess of sodium nitrite in the presence of finely divided
copper or copper compounds) when the acidic copper salt forms [1, 42, 45, 46, 52,
61, 63].
+
NH2 N N NO2 NO2 NO2

C + C 2+ C Cu C C H
H /NaNO2 Cu N N N N N
N NH N NH N
NaNO2 4 H2O
N N N N N N N N N N

5-ATZ Cu(NT)2·HNT

The other metallic salts of 5-nitrotetrazole can be prepared via the sodium salt
according to the original von Herz procedure [45]. The sodium salt is prepared by
the reaction of sodium hydroxide with acid copper 5-nitrotetrazole Cu(NT)2·HNT
in an aqueous solution. The sodium 5-nitrotetrazole is isolated by crystallization
[1, 46, 57, 63, 64]. The product can by purified by recrystallization from acetone
[42] followed by filtration and precipitation by addition of hexane [64] or
crystallized by evaporation of most of the acetone [56].

NO2 NO2 NO2 NO2

Cu +
C C C H C Na
N N N N N N NaOH N - N
4 H2O 3 + CuO
N N N N N N N N

Cu(NT)2·HNT NaNT

Spontaneous explosion of NaNT·2H2O during drying has been reported. The

explosion was attributed to acid spray from the nearby hydrochloric solution when
it is probable that the extremely unstable free 5-nitrotetrazole formed [56].
The sodium salt can also be prepared in one step from 5-ATZ without isolation
of the acid copper salt [58, 65].
The original von Herz procedure (via sodium salt) was found to have several
drawbacks, which are described below [46, 66]:
• Minor explosions occur during the diazotization stage (increasing frequency
with increasing temperature).
• Acid copper salt is gelatinous, long periods to separate by filtration, problematic
purification.
• Sodium salt forms variable hydrates; sensitive if allowed to dehydrate.
• Yield and quality of Hg(NT)2 is very dependent on purity of sodium salt.
• Sodium salt must be purified by recrystallization.
• Overall yield on 5-ATZ is below 50%.
The Hg(NT)2 obtained by the von Herz procedure further exhibits a tendency to
be dead-pressed unlike the product obtained from recrystallization. The dead-
pressing of Hg(NT)2 is closely related to the quality of the sodium salt used as a
starting material in the synthesis. The pure salt gives material which is more
Cuprous Salt of 5-Nitrotetrazole 205

Table 8.11 The effect of recrystallization of NaNT on properties of the Hg salt [4]
Ignition temperature Bulk density Dead-pressing level
Treatment of sodium salt intermediate (at 5  C min
1) (g cm
3) (MPa)
Crude—no purification 190 0.75 103–138
Partially purified 234 0.61 241–276
Once recrystallized from acetone 242 0.88 >276
Twice recrystallized from acetone 246 0.86 >276

resistant to dead-pressing than the unpurified material as can be seen from

Table 8.11 [46, 66]. Technologically it is not suitable, as the recrystallization of
sodium salt is quite a time-consuming process.
Careful optimization of the process leads to elimination of the minor explosions
and improved yield. The method itself has however been superseded by the diamine
complex route. These complexes are synthesized by the reaction of acidic copper
salt of 5-nitrotetrazole with the relevant diamine (mostly 1,2-ethylenediamine or
less frequently 1,3-diaminopropane) in the presence of copper sulfate [4, 40, 41, 46,
56, 66]. These coordination compounds could be readily purified by recrystallization
from water and they are safer and easier to handle in the dry state than the sodium salt
(1,2-ethylenediamine complex only burns when impacted by 2.5 kg hammer from
50 cm) [42, 46].
N N

C N
O2N
N
NO2 NO2 NO2 H
H
N N
C Cu C C H
H2C CH2
N N N N N
2 N 4 H2O + CuSO 4 + 6 H 2N(CH2)2NH2 3 Cu 4-
H2C CH2
N N N N N N
N N
Cu(NT)2·HNT H H
N NO2
N C

N N

[Cu(en)2](NT)2

Other metallic salts of 5-nitrotetrazole (e.g., silver) are prepared by treating

aqueous solutions of NaNT, [Cu(en)2](NT)2, or [Cu(pn)2](NT)2 with the soluble
version of the relevant metallic salt [4, 41, 42, 46, 47, 53, 54, 59, 65, 67]. In the case
of [Cu(en)2](NT)2 or [Cu(pn)2](NT)2 diamine must first be broken down and
destroyed or made inactive to prevent complex formation with the metal. This is
easily achieved by reaction with nitric acid (to tie up the diamine) followed by
addition of the mercuric nitrate solution (mercuric salt forms) [4, 42, 46, 56, 66].
The several methods of Hg(NT)2 analysis are summarized in [67].
206 8 Tetrazoles

NO2
+
C Na
N - N
2
N N
Hg(NO3)2
NaNT HNO3
NO2 NO2

C Hg C
N N N N N N
C N N N N N
O 2N
N Hg(NO3)2
Hg(NT)2
HNO3
H H
N N
H2C CH2
Cu 4-
H2C CH2
N N
H H
N NO2
N C

N N
[Cu(en)2](NT)2

The cuprous salt of 5-nitrotetrazole is prepared by the reaction of the sodium

salt of 5-nitrotetrazole with cuprous chloride suspended in boiling water (reflux)
[49, 50]. The addition of acid to the reaction during preparation improves its
thermal stability [49]. Recently, Fronabarger et al. improved the preparation proce-
dure by using the more accessible cupric salt as a starting reactant which is reduced
to the cuprous salt directly in the reaction mixture. Sodium ascorbate or ascorbic
acid is recommended as the reducing agent [68].
The preparation of various alkaline salts via the ammonium salt of
5-nitrotetrazole has been reported recently. They are prepared by the action of the
relevant hydroxide or carbonate on the ammonium salt in a methanol or ethanol
solution upon reflux [51].
The preparation and analytical characterization of a number of organic salts of
5-nitrotetrazole have recently been published by Klap€otke et al. However, these
salts have the characteristics of secondary rather than primary explosives and are
therefore not discussed in this book [57].

8.3.4 Uses

The salts of 5-nitrotetrazole have been studied as possible lead azide replacements.
They were however for various reasons rejected for practical purposes [4].
The mercury salt of 5-nitrotetrazole has been developed as a less hazardous
replacement for lead azide [61, 70] and mercury fulminate [18]. This substance is
superior to dextrinated lead azide with lower sensitivity to impact and electrostatic
discharge, and higher initiating efficiency and, in addition, it does not react with
8.4 5-Chlorotetrazole Salts 207

carbon dioxide and metals [62, 63, 71, 72]. The mercury salt has also been suggested
as a primary explosive applied in electric detonators [69], in stab-initiated detonators
with a small amount of tetrazene (5–10%) [71] or in a composition applied to the
head of percussion fuses [72]. In today’s environment, it has been however rejected
on toxicological grounds.
The silver salt has also been suggested for practical use in percussion-initiated
devices such as heads of percussion fuses [72]. This salt has recently been proposed
as a potential green primary explosive that could replace LA. A potential drawback,
however, of AgNT is its high sensitivity to electrostatic discharge [52].
The cupric salt of 5-nitrotetrazole has also been recently studied as a promising
alternative “green” LA replacement [47, 48, 60, 62].
The cesium salt of 5-nitrotetrazole has been reported by Hagel and Bley [73] for
use in electrical igniters in the automotive industry. Most other salts (e.g., barium
and thallium) have been found unstable due to excessive hygroscopicity or high
solubility in water [40, 41].

8.4 5-Chlorotetrazole Salts

Cl
C H
N N
N N

8.4.1 Physical and Chemical Properties

5-Halogentetrazoles form a variety of metallic salts including the most common,

the cupric salt of 5-chlorotetrazole, which forms light blue crystals with density
2.04 g cm
3 [1, 2]. Its bromo counterpart exists as a green compound. Both of them
are soluble in hot diluted mineral acids. Melting point of 5-chlorotetrazole is 305  C
(with decomposition); it is slightly hydroscopic as it absorbs 3.11% water (at 30  C;
90% relative humidity) [1].

8.4.2 Explosive Properties

The cupric salt of 5-chlorotetrazole is as sensitive as its 5-bromo derivate (2.54 cm for
2 kg hammer). Brisance of the chloro-derivative is about the same as bromo-derivative.
They both also have about the same initiating efficiency (0.3 g for RDX) [1]. Bagal [2]
208 8 Tetrazoles

reported ignition efficiency of the chloro-derivative to be 0.1 g for tetryl and an ignition
temperature of 305  C (heating rate 5  C min
1). The substance is also sensitive to
stabbing [2]. Silver 5-chlorotetrazole was found to be an effective initiating substance
at low pressing loads but it gets readily dead-pressed at higher loads [42].

8.4.3 Preparation

Both 5-chloro and 5-bromotetrazoles are prepared from 5-ATZ by the Sandmeyer
reaction [32]. The reaction is carried out in sufficiently diluted solutions in presence
of the cupric halide and produces the cupric salt of 5-halogentetrazole. The reaction
must be cooled to low temperatures, as is usual for most diazotizations. Preparation
of the cupric salt of 5-chlorotetrazole has been described by several authors, e.g.,
Stollé [35]. If the solutions of the reacting substances are diluted too much, blue
crystals of CuCl2·4(5-ATZ) are formed [74].
Optimizing the reaction conditions by inverting the order of chemical addition
tends to eliminate otherwise frequent explosions. The idea of the optimization is
based on the addition of nitrite to the 5-ATZ hydrochloride solution already
containing CuCl2. The product is formed immediately after addition of the nitrite.
A carefully controlled rate of addition of the nitrite can therefore lower the amount
of the diazonium salt in the mixture [74].
+ -
NH2 N2 Cl Cl Cl

C H C H C Cu
HCl CuCl2
N N + NaNO2 N N N N N N
-N2
N N N N N N N N

The other metallic salts of 5-halotetrazoles can be prepared via the sodium salt,
which is obtained by reaction of the cupric salt of 5-halotetrazole with sodium
hydroxide to give the sodium salts [42, 53]. The sodium salt can be also obtained
directly from 5-ATZ [75].
Cl Cl Cl
+
C Cu C C Na
N N N N + 2 NaOH 2 N - N + CuO + H2O
N N N N N N

In earlier work, the cupric salt of 5-chlorotetrazole was rejected for practical
applications due to its corrosive nature toward metals. However, it was later found
that the corrosive behavior is not caused by the cupric salt itself but by chloride ions
absorbed in the product from the hydrochloric acid medium in which it was
prepared. This impurity is very difficult to remove by washing. It is therefore not
recommended to prepare the cupric salt of 5-chlorotetrazole directly by the
Sandmeyer reaction from 5-ATZ, but rather by precipitation from the sodium salt
of 5-chlorotetrazole [42].
8.5 5-Azidotetrazole Salts 209

8.4.4 Uses

Out of the whole range of 5-halotetrazole salts, only the cupric salt of
5-chlorotetrazole has found a use—e.g., in primers for space applications [1].
Many other metallic salts of 5-chlorotetrazole (e.g., silver salt) have been
disqualified from application mainly due to their high mechanical sensitivity [76].

8.5 5-Azidotetrazole Salts

N3
C H
N N

N N

8.5.1 Physical and Chemical Properties

5-Azido-1H-tetrazole (subsequently just 5-azidotetrazole) forms monoclinic colorless

needles with a theoretical maximum density 1.72 g cm
3. Melting point is 75  C [77].
It is, just like its alkali metal salts, soluble in water, acetone, ether, and ethanol. Lead,
mercury, and silver salts are insoluble in these solvents [1, 78]. The potassium salt of
5-azidotetrazole is stable in aqueous and alcoholic solutions, but it explodes sponta-
neously if traces of acetic acid are present, even in acetone solution [78]. The
5-azidotetrazoles are fairly stable in storage when in the pure state [1].

8.5.2 Explosive Properties

Free 5-azidotetrazole is reported in Fedoroff, Sheffield, and Kaye’s encyclopedia

as less sensitive to impact than its alkaline salts [1]. Other authors reported
5-azidotetrazole as a highly sensitive compound [2, 77]. Stierstorfer et al. [77]
reported sensitivity to impact below 1 J, sensitivity to friction below 5 N, and
sensitivity to electrostatic discharge 2.2 mJ. 5-Azidotetrazole melts and decomposes
at 165  C when heated with heating rate 5  C min
1 [77]. Pure 5-azidotetrazole is
fairly stable in storage. However, it may spontaneously explode in presence of some
impurities especially in presence of traces of acetic acid (it can explode even in
acetone solution; explosions do not occur in aqueous or ethanol solutions) [1].
210 8 Tetrazoles

Sensitivities of the silver and potassium salts are extremely high. The potassium
salt can even be detonated by touching it with a spatula [1]. The cesium salt is
another very sensitive compound which is, together with the potassium salt,
reported to be a substance which “cannot be handled without violent explosion”
[77]. On the other hand, the published value for impact sensitivity of the barium salt
is 35 cm/0.5 kg (h50) [1]. Friedrich published an impact sensitivity for 1 kg hammer
of 3 cm for the copper salt and 3–5 cm for the cadmium salt [79]. The lead salt
detonates when touched with a flame [1].
Metallic salts of 5-azidotetrazole are brisant primary explosives (even amounts
as small as 10 mg of the potassium salt can cause damage) [1]. Initiating efficiency
of these substances is high; an amount of only 1–2 mg is sufficient to initiate
PETN [80].

8.5.3 Preparation

5-Azidotetrazole can be prepared by several methods. The simplest method is the

direct cycloaddition reaction between alkaline azides and cyanogen halogen. An
alkaline salt of 5-azidotetrazole forms according to the following reaction [81, 82]:
N3

C
+ N N + KBr
2 KN3 + BrCN K -
N N

The reaction is carried out in an aqueous solution and at low temperatures;

sodium azide may be used as well [77]. The resulting salt can be converted to free
5-azidotetrazole by hydrochloric acid [83].
Pure 5-azidotetrazole can be prepared by the same reaction in presence of
azoimide [81].
N3
C H
KN3 + BrCN + HN3 N N + KBr
N N

Another way of preparing 5-azidotetrazole is based on the diazotization reaction.

5-ATZ is mostly used as the starting material. Tetrazole diazonium salt forms as an
intermediate which is converted into the desired tetrazole azide by treatment with
sodium azide [84].
+ -
NH2 N2 Cl N3
C H C H C H
HCl NaN3
N N + HNO2 N N N N + N2 + NaCl
N N N N N N
8.5 5-Azidotetrazole Salts 211

The 5-azidotetrazole can be purified by recrystallization from anhydrous

diethylether [84].
5-Hydrazino-1H-tetrazole can also be used as a starting material for
5-azidotetrazole preparation. Preparation may be done by treating sodium nitrite
and hydrochloric acid with 5-hydrazino-1H-tetrazole in an aqueous environment
[77, 85, 86]:
NHNH2 N3

HCl
N NH + NaNO2 N NH
N N N N

Diaminoguanidine is another possible starting material which can be used for

preparation of 5-azidotetrazole and its salts. It forms when diaminoguanidine
nitrate is treated with two moles of nitrous acid in an acetic acid solution [78].
N3

H2N NH CH3COOH
C
+ - + N N
C NH2 NO 3 + KNO2 K -
H2N NH N N

Another, rather unusual, way to 5-azidotetrazole referred to in [77] is partial

degradation of tetrazene with barium hydroxide [10]:

H N3
N NH2
N Ba(OH)2
N N N · H2O N NH
N NH
N
N N
H2N

GNGT

Various salts of 5-azidotetrazole can be prepared by treating it with relevant salts

[78]. Preparation, crystallographic studies, and characterization of hydrazinium,
ammonium, aminobiguanidinium, guanidinium, lithium, sodium, potassium, cesium
and calcium salts of 5-azidotetrazole were described by Klap€otke and Stierstorfer [83].
Some experimental data from this paper are summarized in Table 8.12. The
guanidinium salt forms as a semihydrate, whereas the lithium and sodium salts of
5-azidotetrazole form hydrates. The structure of the calcium salt is more complicated as
it forms a complex with the following formula: [Ca(CN7)2(H2O)10][Ca(H2O)6](CN7)2.

8.5.4 Uses

Despite the high initiating efficiency of many metallic salts of 5-azidotetrazole,

most of them are too sensitive for practical use.
212 8 Tetrazoles

Table 8.12 Selected experimental properties of 5-azidotetrazole salts [83]

TMD Crystal Impact Friction ESD Tdec
(g cm
3) system Color (J) (N) (mJ) ( C)
Hydrazinium 1.57 Monoclinic Colorless <1 5 5 136
needles
Ammonium 1.61 Monoclinic Colorless <1 5 10 157
needles
Aminoguanidinium 1.52 Triclinic Colorless 1 7 40 159
blocks
Guanidinium 1.55 Monoclinic Colorless rods 70
semihydrate
Lithium hydrate 1.68 Monoclinic Colorless 70
needles
Sodium hydrate 1.74 Monoclinic Colorless <1 <5 20
needles
Potassium 1.92 Monoclinic Colorless rods 148
Cesium 2.81 Orthorhombic Colorless
plates
Calcium complex 1.66 Monoclinic Colorless 2 25 160
needles
RDX 1.82 7 120 >150 213

8.6 5,50 -Azotetrazole Salts

H
N N
N N
C N N C
N N
N N
H
azotetrazole

Free 5,50 -azo-1H-tetrazole (subsequently just 5-azidotetrazole; AzTZ) is an

unstable compound that immediately decomposes at room temperature. However
it forms stable metallic salts, many of which have the characteristics of primary
explosives. The first salts of AzTZ were prepared by Johannes Thiele in 1893. He
described their properties and determined that they form hydrates [2, 29, 87, 88].
Salts of 5,50 -azotetrazole with protonated nitrogen bases (e.g., ammonium,
guanidinium, triaminoguanidinium) are suggested as nitrogen-rich gas-generating
agents for gas generators.
8.6 5,50 -Azotetrazole Salts 213

Table 8.13 Density and water of crystallization contents in one molecule of relevant alkaline and
alkaline earth metal salts of AzTZ [89, 91, 92]
Salt of AzTZ Li Na K Rb Cs Mg Ca Sr Ba
Moles of water of crystallization 6 5 5 1 2 8 8 6 5
Density (g cm
3) 1.528 1.684 – 2.396 – – 1.677 – 2.298

8.6.1 Physical and Chemical Properties

Free 5,50 -azotetrazole forms a yellow solid that is unstable and decomposes within
seconds at room temperature. However, it can be handled at
30  C and stored for
several months at
80  C [89].
Most metal salts are yellow (K, Ca, Zn, Pb), while others range from orange
(basic lead salt) to brown-colored solids (mercuric, iron) [2, 90, 91]. The cupric salt
forms dark green crystals [2].
Most metallic salts of 5,50 -azotetrazole form hydrates. The water of crystallization
content in these salts is summarized in Table 8.13. During storage of alkaline, alkaline
earth metal salts and some trivalent metal salts (Al, La, Y, Ce, Nd, and Gd) all
compounds lose water; this takes place over a period of hours for lithium, potassium,
and the trivalent salts studied, and for other salts it takes between days and weeks.
Upon loss of water of crystallization, magnesium and the trivalent salts of AzTZ
decompose to colorless substances [89, 91, 92]. The cupric and mercuric salts form
anhydrous salts, and the monobasic lead salt (PbAzTZ·PbO·5H2O) forms a
pentahydrate [2].
According to Bagal [2], the sodium salt forms a pentahydrate at room tempera-
ture that loses two molecules of crystalline water above 30  C and forms an
anhydride salt above 75  C. Contrary to other authors, Reddy and Chatterjee [90]
have reported the formation of a monohydrate for the sodium and barium salts (on
the basis of TGA results). Lead and mercury salts form as anhydrides [90].
Density and crystal structure of alkali metal, alkaline earth metal, and several
trivalent cations have been described by Hammerl et al. using X-ray diffraction [89];
the basic lead salt (density 4.62 g cm
3) has been described by Pierce-Butler [93].
The silver and mercuric salts are highly hygroscopic [2] unlike the basic lead salt
of 5,50 -azotetrazole, which is not, and further does not react with common metals
(including copper) [80].
Alkali metal and alkaline earth metal salts of AzTZ are mostly soluble in water
with the exception of the barium and strontium salts that are almost insoluble [89].
The potassium salt is hardly soluble in cold water, but more soluble in hot water [2].
The mercury and lead salts are also almost insoluble [90]. The lead salt is insoluble
in inorganic solvents but soluble in weak acids and bases. The monobasic salt is
insoluble in water and slightly soluble in most organic solvents. The best solvent for
this salt is diluted nitric acid or a solution of ammonium acetate [2].
The sodium salt is not stable in acids. It decomposes to the unstable intermediate
free AzTZ which decomposes to diazomethyl(tetrazol-5-yl)diazene and nitrogen.
Diazomethyl(tetrazol-5-yl)diazene is the final product of decomposition in less acidic
214 8 Tetrazoles

environments (e.g., in 2% HCl). In the more acidic environment, decomposition of

diazomethyl(tetrazol-5-yl)diazene continues to salts of 5-hydrazino-1H-tetrazole,
nitrogen, and formic acid [94].
N N
+ -
N N N CH N N
N N 2% HCl
- C N N C - N NH .H O + N2
2
N N N
N N
+ +
Na Na

N N NH NH2 . HCl
+ -
N CH N N N
conc. HCl + N 2 + HCOOH
N NH N NH
N N

8.6.2 Explosive Properties

Sensitivity of metallic salts of 5,50 -azotetrazole noticeably depends on the presence

of water of crystallization. Upon loss of water, the sensitivity of the compounds to
impact and friction increases dramatically [89, 92, 95]. For example, the anhydrous
sodium salt is highly sensitive to friction and impact while its hydrates are signifi-
cantly less sensitive. Pentahydrate and trihydrate of sodium salt only crackle after
ignition by a Bickford fuse while the anhydrous salt explodes. It is possible to grind
the pentahydrate in a mortar while the anhydrous salt explodes with such treatment
[2]. Many explosions of 5,50 -azotetrazole salts have occurred during drying under
vacuum [89, 92].
According to Reddy and Chatterjee, sodium and barium monohydrates are not
sensitive to friction and impact under the conditions generally used for primary
explosives, whereas lead and mercury salts are highly sensitive to both [90]. In the
Fedoroff, Sheffield, and Kaye’s encyclopedia, it is however mentioned that sensi-
tivity of the sodium, potassium, and barium salts is only about twice as high as for
lead azide (not specified if the values concern anhydride or hydrates) [1].
Heavy metal salts of 5,50 -azotetrazole are highly sensitive to impact and friction
[2, 14]. The lead salt of 5,50 -azotetrazole coated with dextrine showed reduced
sensitivity [90]. The values of impact and friction sensitivity, ignition temperature,
and sensitivity to electric discharge given by various authors are summarized in
Tables 8.14 and 8.15.
As can be seen in Table 8.14, the mercury salt of 5,50 -azotetrazole is more
sensitive to electric discharge than lead styphnate [90].
Sensitivity of several salts to impact is also reported by Bagal [2]; sensitivity of
AgAzTZ to impact is about the same as for MF; mercuric and cupric salts are
reported as very sensitive. The monobasic lead salt exceeds MF in sensitivity to
impact and friction. On the contrary, the iron salt is reported as not sensitive to
8.6 5,50 -Azotetrazole Salts 215

Table 8.14 Initiation temperature, sensitivity to friction (weight used 4 kg), and sensitivity to
electric discharge (gap between the needle and vial 2 mm) of metallic salts of 5,50 -azotetrazole
Ignition temperature Friction sensitivity (cm s
1) Electrostatic charge

( C) [90] sensitivity E (mJ)
min
Compound [90] [14] [2] 0 % Prob. 50 % Prob. [90]
Na2AzTZ·H2O 265 – – Not sensitive Not sensitive
BaAzTZ·H2O 180 – – Not sensitive Not sensitive
PbAzTZ 180 173 – 5.1 7.6 30.3
PbAzTZ—dextr. – – – 6.4 8.3 58
HgAzTZ 144 152 155 3.8 6.4 2.2  10
3
PbAzTZ·PbO·5H2O – – 194–196 – – –
Ag2AzTZ – 185 186 – – –
CuAzTZ – – 162 – – –
ZnAzTZ – – 161–176 – – –
LA—dextr. – – – 10 11 157.5
LS – – – 18 20 9  10
3

Table 8.15 Impact sensitivity of metallic salts of 5,50 -azotetrazole [90]

Impact sensitivity
Not specified method, Not specified method, ATS apparatus,
ball weight ¼ 28 g (cm) [90] 0.5 kg hammer (cm) [14] 2 kg (cm) [1]
Compound 0 % Prob. 50 % Prob.
Na2AzTZ·H2O Not sensitive – 40
K2AzTZ – – – 40
BaAzTZ·H2O Not sensitive – 40
PbAzTZ 5.0 7.0 12 12
PbAzTZ—dextr. 8.0 9.5 – –
CdAzTZ – – – 13
HgAzTZ 4.0 6.5 5 –
Ag2AzTZ – – 8 –
LA—dextr. 12.0 13.5 – 22
LS 5.0 6.0 – –

impact and friction [2]. Thermal stability of the basic lead salt of azotetrazole has
been reported by Blay and Rapley [55]. This salt loses about 1% mass in 5 h at
172  C under vacuum [55].
The initiating efficiency of the lead salt of 5,50 -azotetrazole exceeds that of other
tested metallic salts, but it does not exceed that of standard composition lead azide/
lead styphnate/aluminum (ASA compound). The mercury salt was not tested
because of the “press fire problem” [90]. The values of initiating efficiency are
summarized in Table 8.16.
Initiating efficiency of the silver and mercuric salts has been reported by Bagal
[2]. Initiating efficiency of AgAzTZ is high, 0.03 g for PETN (AgAzTZ pressed
under 15.7 MPa) and 0.13 g when AgAzTZ is pressed under 49 MPa. This implies
that the silver salt is susceptible to dead-pressing. Initiating efficiency of the
216 8 Tetrazoles

Table 8.16 Initiating Compound Initiating efficiency (g)

efficiency of metallic salts of
5,50 -azotetrazole compared Na2AzTZ·H2O 0.35
with ASA composition in BaAzTZ·H2O 0.30
no. 6 detonator [90] PbAzTZ 0.20
HgAzTZ –
ASA comp. 0.060
PETN was used as secondary charge.

mercuric salt is 0.11 g for PETN (pressure is not reported). The monobasic lead salt
lacks initiating ability [2].
The lead salt of 5,50 -azotetrazol is a powerful primary explosive that can be used
as an initiator either alone or in a mixture. Its flame sensitivity is higher than that of
lead azide and therefore PbAzTZ can be used in a mixture with lead azide to
improve its flammability [90].

8.6.3 Preparation

The sodium salt of 5,50 -azotetrazole is prepared by oxidation of 5-ATZ. Potassium

permanganate (or persulfate [85]) is used as an oxidizing agent in the presence of
excess sodium hydroxide [18, 90, 91, 95]. The sodium salt of 5,50 -azotetrazole
crystallizes from aqueous solution as a pentahydrate [95]. The alkalinity of the
permanganate solution is an important parameter. Reaction of weakly alkaline
permanganate and 5-ATZ results in the formation of hydrogen cyanide and
carbon dioxide, while strongly alkaline permanganate leads to salts of 5-azotetrazole
[29, 32].
H
N N N
N NaOH
N N
C NH2 + KMnO4 - C N N C -
N N N
N N N
+ +
Na Na

The heavy metallic salts of 5,50 -azotetrazole can be prepared by precipitation

from a solution of the sodium salt by addition of a soluble metallic salt [14, 90–92].
N N N N
N N N N
- C N N C - + Pb(NO3)2 C N N C + 2 NaNO3
N N N N
N N N N
+ +
Na Na Pb

Reaction of the barium salt of 5,50 -azotetrazole (prepared by treating barium

chloride with the sodium salt of 5,50 -azotetrazole) with the relevant sulfate can be
also used for preparation of soluble salts of 5,50 -azotetrazole (e.g., alkali salts).
Synthesis of many salts (alkaline and alkaline earth), including analytical data, is
described by Hammerl et al. [89].
8.7 Tetrazoles with Organic Substituent 217

The basic lead salt of 5,50 -azotetrazole is prepared by the same reaction in
presence of sodium hydroxide, ammonia, etc. [2, 18, 96]. This salt is probably the
only one which has been practically manufactured. The same technology equip-
ment can be used for this as is used for production of LA. The production details are
described in Bagal [2].
Free 5,50 -azotetrazole can be synthesized from the sodium salt and HBF4·Et2O at

30  C in methanol. A crystal structure analysis showed the presence of two
methanol molecules [89].
H
N N N N
N N CH3OH N N
- C N N C - + 2 HBF 4.Et2O C N N C . 2 CH 3OH + 2 NaBF
4
N N N N
N N N N
+ +
Na Na H

8.6.4 Uses

Taylor and Jenkins have reported that the cadmium, cupric, and silver salts of
5,50 -azotetrazole are too sensitive for any technical use [76]. The lead salt of
5,50 -azotetrazole has been suggested for primers and detonators [80, 97] but it is
hygroscopic at high relative humidity and has worse properties than its monobasic
salt [76]. These disadvantages have not been observed in case of the lead monobasic
salt which is a base compound for many patents for fuse heads [2]. This salt was
also used with nitrocellulose varnish on the resistance bridge for electric igniters in
Germany during World War II [18] and later in the British armed forces [42]. The
ammonium, guanidinium, and triaminoguanidinium salts of 5,50 -azotetrazole have
been investigated for application in gas generators.

8.7 Tetrazoles with Organic Substituent

Many tetrazoles with an organic substituent have been published in open literature.
Some of them have the characteristics of primary explosives especially those
containing azido, picryl, or other nitrogen-rich functional groups. Unfortunately,
many of these substances are too sensitive for practical application. We have
therefore decided to limit our selection to only those substances that are referred
to as potentially useful primary explosives.
218 8 Tetrazoles

Table 8.17 Comparison of sensitivity of 5-PiATZ with LA and LS [52]

Friction Sensitivity to electric discharge
Impact sensitivity—h50; sensitivity Test for sensitive
Compound Ball & Disc test (cm) (m s
1)a Standard test (J) expl. (No.7) (mJ)
5-PiATZ >50 >3.7 0.45 –
but not at 0.045
LAb 19 1.2 – 2.5
LSb 11 1.8 – 7
a
Emery paper friction test; values are pendulum velocities required to produce a 50 % probability
of ignition
b
Service material RD 1343 for LA (precipitated from sodium carboxymethylcellulose/sodium
hydroxide) and RD 1303 for LS

8.7.1 5-Picrylaminotetrazole

H O2N
N
N
C NH NO2
N
N
O2N

8.7.1.1 Physical and Chemical Properties

5-(2,4,6-Trinitrofenylamino)-1H-tetrazole (subsequently just picrylaminotetrazole;

5-PiATZ) exists as a yellow powder with density 1.91 g cm
3 and melting point
224  C [98] or 232  C [52]. It is soluble in acetone, and slightly soluble in ether and
water [98].
5-PiATZ forms metallic salts. The silver salt forms yellow crystals that are
insoluble in nitric acid and only slightly soluble in ammonia. The cupric salt exists
as a green powder and the lead salt forms golden-colored crystals [98].

8.7.1.2 Explosive Properties

Sensitivity values of 5-picrylaminotetrazole compared with LA and LS are

summarized in Table 8.17 [52]. It follows from the table that the sensitivity of
5-picrylaminotetrazole is relatively low, almost at a level of secondary explosives.
The silver, cupric, and lead salts are sensitive to impact. These salts explode by
heating (ignition temperature is not specified) [98].
8.7 Tetrazoles with Organic Substituent 219

8.7.1.3 Preparation

5-Picrylaminotetrazole can be prepared by the reaction of 5-ATZ with 1-chloro-

2,4,6-trinitrobenzene (picrylchloride) in acetic acid. The raw product can be
purified by recrystallization from glacial acetic acid [52, 98].
Cl H
NH2 O 2N
O2N NO2 N
C H CH3COOH N
N N + C NH NO2
N
N N N
O 2N
NO2
5-ATZ PiC 5-PiATZ

Metallic salts can be prepared by reaction of 5-picrylaminotetrazole with soluble

metallic salts (nitrates, acetates) [98].

8.7.1.4 Uses

5-Picrylaminotetrazole has been studied as a potential green primary explosive

replacement for LS, but its low sensitivity excluded it from this application [52].

8.7.2 1-(1H-Tetrazol-5-yl)guanidinium Nitrate

H
N
N
C NH
NH . HNO3
N
N C
NH2

8.7.2.1 Physical and Chemical Properties

1-(1H-Tetrazol-5-yl)guanidinium nitrate (formerly 5-(guanylamino)-tetrazolium

nitrate) forms white plate crystals [35]. The compound is referred to as an anhydride
by Stollé [35] or as a monohydrate by Millar [52]. Crystal density is 1.58 g cm
3
[52] and melting point 183 or 185  C (decomp. with crack) [35, 52]. It is soluble in
water, hardly soluble in ethanol, and insoluble in ether. It forms a free base by
repeated crystallization from water [35].
220 8 Tetrazoles

Table 8.18 Sensitivity of 1-(1H-tetrazol-5-yl)guanidinium nitrate compared with LA and LS [52]

Impact sensitivity Friction Sensitivity to electric discharge
h50; Ball & Disc test sensitivity Standard Test for sensitive
Compound (cm) (m s
1)a test (J) expl. (No.7) (mJ)
1-(1H-tetrazol-5-yl) >50 >3.7 Not at 4.5 –
guanidinium
nitrate
LAb 19 1.2 – 2.5
LSb 11 1.8 – 7
a
Emery paper friction test; values are the pendulum velocity required to produce a 50 % probabil-
ity of ignition.
b
Service material RD 1343 for LA (precipitated from sodium carboxymethylcellulose/sodium
hydroxide) and RD 1303 for LS.

8.7.2.2 Explosive Properties

Sensitivities of 1-(1H-tetrazol-5-yl)guanidinium nitrate are compared with LA and

LS in Table 8.18 [52].
It follows from Table 8.18 that the sensitivity of 1-(1H-tetrazol-5-yl)
guanidinium nitrate is relatively low, similar to secondary explosives. Ignition of
1-(1H-tetrazol-5-yl)guanidinium nitrate takes place at 186  C and the DSC onset is
at 163  C (10  C min
1) [52].

8.7.2.3 Preparation

1-(1H-Tetrazol-5-yl)guanidinium nitrate is easily formed by the reaction of 1-(1H-

tetrazol-5-yl)guanidine with nitric acid, the nitrate crystallizing from the solution
by cooling. 1-(1H-Tetrazol-5-yl)guanidine is prepared by the reaction of 5-ATZ
with cyanamide in an aqueous environment [52]. The product can be recrystallized
from diluted nitric acid [35].
NH2 H
C H N
N N
N NH
+ N C NH2 C NH
N N N
N C
NH2

H H
N N
N N
C NH C NH
NH + HNO3 NH . HNO3
N N
N C N C
NH2 NH2
8.8 Organic Derivatives of 5-Nitrotetrazole 221

8.7.2.4 Uses

1-(1H-Tetrazol-5-yl)guanidinium nitrate has been studied as a green primary

explosive potentially replacing LS, but the low sensitivity of the compound
excluded it from this application [52].

8.8 Organic Derivatives of 5-Nitrotetrazole

NO2 NO2 NO2

C C C
N N CH3 N N N N
NO2
N N N N N N
CH3

O2N
NO2

The organic derivatives of 5-nitrotetrazole form two isomers substituted either in

position 1 or 2 of the ring. Some attention has been given to methyl-5-
nitrotetrazoles and to 2-picryl-5-nitrotetrazole. The melting point of 1-methyl-5-
nitrotetrazole is 56  C and of 2-methyl-5-nitrotetrazole is 86  C. However 2-methyl-
5-nitrotetrazole was found not to initiate RDX in a commercial detonator setup. 5-
Nitro-2-(2,4,6-trinitrofenyl)tetrazole (subsequently just 5-nitro-2-picryltetrazole) has
the characteristics of primary explosives but unfortunately is very sensitive to
friction. The p-nitrobenzyl derivate of 5-nitrotetrazole is not a primary explosive
and behaves more like a secondary explosive [4].
Alkyl derivatives of 5-nitrotetrazole form by alkylation of the metallic salts of
5-nitrotetrazole (e.g., sodium, silver) by alkylhalogenide [4].
NO2 NO2 NO2
+
C Na C CH3 C
N N N N N N
- + CH3I + + NaI
N N N N N N
NaNT CH3

The alkylation leads to a mixture of isomers with the methyl group in positions
1 and 2. Electronegative substituent on carbon makes substitution in position
2 predominant. The methyl derivate is formed according to the reaction shown,
but the ethyl, propyl, and isopropyl derivatives could not be isolated (silver salt of
5-nitro-1H-nitrotetrazole was used for synthesis) by Bates and Jenkins [4].
222 8 Tetrazoles

Table 8.19 Impact sensitivities of organic derivatives of 5-azidotetrazole in comparison with the
cupric and cadmium salts of 5-azidotetrazole [79]
Compound Impact sensitivity for 1 kg hammer (cm)
5-Azido-1-methyltetrazole 5–8
5-Azido-1-picryltetrazole 25–30
Cupric salt of 5-azidotetrazole 3
Cadmium salt of 5-azidotetrazole 3–5

5-Nitro-2-picryltetrazole can be prepared by the reaction of picrylchloride with

sodium salt of nitrotetrazole in acetone. When water is present, picric acid is
formed, casting doubts on the hydrolytic stability of the picryl derivative [4].

8.9 Organic Derivatives of 5-Azidotetrazole

O2N
N3 N3 N3
NO2
C CH3 C CH2CH3 C
N N N N N N
N N N N N N
O2N

8.9.1 Explosive Properties

Organic derivatives of 5-azidotetrazole have been reported by Friedrich [99]. They

are more stable and less sensitive than the metallic salts. The methyl and ethyl
derivatives are very strong igniting explosives. Ethylene tetrazylazide, that forms
an oily liquid, possesses extraordinary brisance and is easily ignited by spark and
flames. It easily gelatinizes nitrocellulose [1, 99]. Impact sensitivities of 5-azido-1-
methyltetrazole and 5-azido-1-picryltetrazole in comparison with the copper salt
are summarized in Table 8.19 [79].

8.9.2 Preparation

Organic derivatives of 5-azidotetrazole can be prepared from the alkali salts of

5-azidotetrazole and organic chlorides of sulfates [99].
References 223

N3 N3

C C CH2CH3
+ N N N N
Na - + CH3CH2Cl + NaCl
N N N N

References

1. Fedoroff, B.T., Sheffield, O.E., Kaye, S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, New Jersey (1960–1983)
2. Bagal, L.I.: Khimiya i tekhnologiya iniciiruyushchikh vzryvchatykh veshchestv. Mashinostrojenije,
Moskva (1975)
3. Matushin, Y.N., Lebedev, V.P.: Thermochemical properties of mononitroderivates of azoles and
oxadiazoles. In: Proceedings of 28th International Annual Conference of ICT, pp. 98/1–98/10,
Karlsruhe, 1997
4. Bates, L.R., Jenkins, J.M.: Search for new detonators. In: Proceedings of International Conference
on Research in Primary Explosives, pp. 14/1–14/18, Waltham Abbey, England, 1975
5. Chen, Z.X., Xiao, H., Yang, S.: Theoretical investigation on the impact sensitivity of tetrazole
derivates and their metal salts. Chem. Phys. 250, 243–248 (1999)
6. Haskins, P.J.: Electronic structure of some explosives and its relationship to sensitivity In:
Jenkins, J.M., White, J.R. (eds.) International Conference on Research of Primary Explosives,
vol. 1, pp. 6/1–6/28, Waltham Abbey (1975)
7. Avanesov, D.C.: Praktikum po fiziko-khimicheskim icpytaniyam vzryvchatykh veshchectv.
Gosudarstbennoe izdatelstvo oboronnoi promyshlennosti, Moskva (1959)
8. Ilyushin, M.A., Tselinskii, I.V., Sudarikov, A.M.: Razrabotka komponentov vysokoenergi-
cheskikh kompozitsii. SPB:LGU im. A. S. Pushkina – SPBGTI(TU), Sankt-Peterburg (2006)
9. Hoffman, K.A., Roth, R.: Aliphatische Diazosalze. Berichte der deutschen chemischen Gesell-
schaft 43, 682–688 (1910)
10. Patinkin, S.H., Horwitz, J.P., Lieber, E.: The structure of tetracene. J. Am. Chem. Soc. 77,
562–567 (1955)
11. Duke, J.R.C.: X-ray crystal and molecular structure of “tetrazene”, (“tetracene”), C2H8N10O.
Chem. Commun. 1, 2–3 (1971)
12. Davis, T.L.: The Chemistry of Powder and Explosives. Wiley, New York (1943)
13. Krauz, C.: Technologie výbušin. Vědecko-technické nakladatelstvı́, Praha (1950)
14. Špičák, S., Šimeček, J.: Chemie a technologie třaskavin. Vojenská technická akademie
Antonı́na Zápotockého, Brno (1957)
15. Rinkenbach, W.H., Burton, O.E.: Explosive characteristics of tetracene. Army Ordonance 12,
120–123 (1931)
16. Meyer, R., K€ohler, J., Homburg, A.: Explosives. Wiley-VCH, Weinheim (2002)
17. Danilov, J.N., Ilyushin, M.A., Tselinskii, I.V.: Promyshlennye vzryvchatye veshchestva; chast
I. Iniciiruyushchie vzryvshchatye veshchestva. Sankt-Peterburgskii gosudarstvennyi tekhnolo-
gicheskii institut, Sankt-Peterburg (2001)
18. Urbański, T.: Chemistry and Technology of Explosives. Pergamon, Oxford (1984)
19. Wallbaum, R.: Sprengtechnische Eigenschaften und Lagerbest€andigkei der wichtigsten
Initialsprengstoffe. Zeitschrift f€ ur das gesamte Schiess- und Sprengstoffwesen 34, 161–163
(1939)
20. Tomlinson, W.R., Sheffield, O.E.: Engineering Design Handbook, Explosive Series of
Properties Explosives of Military Interest. Report AMCP 706-177, 1971
21. Matyáš, R., Šelešovský, J., Musil, T.: Sensitivity to friction for primary explosives. J. Hazard.
Mater. 213–214, 236–241 (2012)
224 8 Tetrazoles

22. Urbański, T.: Chemistry and Technology of Explosives. PWN—Polish Scientific Publisher,
Warszawa (1967)
23. Lieber, E., Smith, G.B.L.: The chemistry of aminoguanidine and related substances. Chem.
Rev. 25, 213–271 (1939)
24. Hagel, R., Redecker, K.: Sintox—a new, non-toxic primer composition by Dynamit Nobel AG.
Propellants Explosives Pyrotechnics 11, 184–187 (1986)
25. Brede, U., Hagel, R., Redecker, K.H., Weuter, W.: Primer compositions in the course of time:
From black powder and SINOXID to SINTOX compositions and SINCO booster. Propellants
Explosives Pyrotechnics 21, 113–117 (1996)
26. Nesveda, J., Brandejs, S., Jirásek K.: Non toxic and non-corrosive ignition mixtures. WO
Patent 01/21558, 2001
27. Whelan, D.J., Spear, R.J., Read, R.W.: The thermal decomposition of some primary explosives
as studied by differential scanning calorimetry. Thermochim. Acta 80, 149–163 (1984)
28. Mihina, J.S., Herbst, R.M.: The reaction of nitriles with hydrazonic acid: Synthesis of
monosubstituted tetrazoles. J. Org. Chem. 15, 1082–1092 (1950)
29. Thiele, J.: Ueber Nitro- und Aminoguanidin. Justus Liebigs Annalen der Chemie 270, 1–63
(1892)
30. Bates, L.R., Jenkins, J.M.: Salts of 5-Substituted Tetrazole: Part 2: Metallic Salts and Complexes
of Tetrazole 5-Aminotetrazole, 5-Phenyltetrazole, and 5-Methyltetrazole. Report AD 727350.
Explosives Research and Development Establishment, Waltham Abbey (1970).
31. Taylor, F.: Primary Explosive Research. Report NAVORD 2800, Naval Ordinance, 1953
32. Benson, F.R.: The chemistry of the tetrazoles. Chem. Rev. 41, 1–61 (1947)
33. Hantzsch, A., Vagt, A.: Ueber das sogenannte Diazoguanidin. Justus Liebigs Annalen der
Chemie 314, 339–369 (1901)
34. Arient, J., Vobořil, I.: Způsob přı́pravy 5-aminotetrazolu. CS Patent 190,055, 1979
35. Stollé, R.: Zur Kenntnis des Amino-5-tetrazols. Berichte der deutschen chemischen Gesellschaft
62, 1118–1126 (1929)
36. Stollé, R., Schick, E.: Verfahren zur Darstellung von Aminotetrazol. DE Patent 426,343, 1926
37. Daugherty, N.A., Brubaker, C.H.J.: Complexes of copper(II) and some 5-substituted
tetrazoles. J. Am. Chem. Soc. 83, 3779–3782 (1961)
38. Rittenhouse, C.T.: Di-silver aminotetrazole perchlorate. US Patent 3,663,553, 1972
39. Karaghiosoff, K., Klap€ otke, T.M., Sabaté, C.M.: Energetic silver salt with 5-aminotetrazole
ligands. Chemistry 15, 1164–1176 (2009)
40. Bates, L.R., Jenkins, J.M.: Production of 5-nitrotetrazole salts. US Patent 4,094,879, 1978
41. Bates, L.R., Jenkins, J.M.: Improvements in or relating to production of 5-nitrotetrazole salts.
GB Patent 1,519,796, 1978
42. Bates, L.R.: The potential of tetrazoles in initiating explosives systems. In: Proceedings of 13th
Symposium on Explosives and Pyrotechnics, pp. III1–III10, 1986
43. Koldobskii, G.I., Soldatenko, D.S., Gerasimova, E.S., Khokhryakova, N.R., Shcherbinin,
M.B., Lebedev, V.P., Ostrovskii, V.A.: Tetrazoles: XXXVI. Synthesis, structure, and
properties of 5-nitrotetrazole. Russ. J. Org. Chem. 33, 1771–1783 (1997)
44. Khmelnitskii, L.I.: Spravochnik po vzryvchatym veshchestvam. Voennaya ordena Lenina
i ordena Suvorova Artilleriiskaya inzhenernaya akademiya imeni F. E, Dzerzhinskogo,
Moskva (1962)
45. Herz, E.: C-nitrotetrazole compounds. US Patent 2,066,954, 1937
46. Gilligan, W.H., Kamlet, M.J.: Synthesis of Mercuric 5-nitrotetrazole. Report NSWC/WOL TR
76-146. Navel Surface Weapons Center, Silver Spring, MD (1976)
47. Hirlinger, J., Fronabarger, J., Williams, M., Armstrong, K., Cramer, R.J.: Lead azide replacement
program. In: Proceedings of NDIA, Fuze Conference, Seattle, Washington, April 5-7, 2005
48. Fronabarger, J., Sanborn, W.B., Bichay, M.: An investigation of some alternatives to lead based
primary explosive. In: Proceedings of 37th AIAA 2001-3633; Joint Propulsion Conference and
Exhibit, pp. 1–9, Salt Lake City, Utah, 2001
References 225

49. Fronabarger, J.W., Williams, M.D., Sanborn, W.B.: Lead-free primary explosive composition
and method of preparation. US Patent 2009/0069566 A1, 2009
50. Fronabarger, J.W., Williams, M.D., Sanborn, W.B.: Lead-free primary explosive composition
and method of preparation. WO Patent 2008/048351 A2, 2008
51. Klap€otke, M., Sabaté, C.M., Welch, J.M.: Alkali metal 5-nitrotetrazolate salts: prospective
replacements for service lead(II) azide in explosive initiators. Dalton Trans. 6372–6380 (2008)
52. Millar, R.W.: Lead-free Initiator Materials for Small Electro-explosive Devices for Medium
Caliber Munitions. Report QinetiQ/FST/CR032702/1.1, QINETIQ Ltd, Farnborough, 2003
53. Harris, A.D., Herber, R.H., Jonassen, H.B., Wertheim, G.K.: Complexes of iron(II) and some
5-substituted tetrazoles. J. Am. Chem. Soc. 85, 2927–2930 (1963)
54. Brown, M.E., Swallowe, G.M.: The thermal decomposition of the silver(I) and mercury(II)
salts of 5-nitrotetrazole and of mercury(II) fulminate. Thermochim. Acta 49, 333–349 (1981)
55. Blay, N.J., Rapley, R.J.: The testing of primary explosives for stability and compatibility In:
Jenkins, J.M., White, J.R. (eds.) Proceedings of the International Conference on Research in
Primary Explosives, vol. 3, pp. 20/1–20/19, Waltham Abbey (1975)
56. Redman, L.D., Spear, R.J.: Mercuric 5-Nitrotetrazole, a Possible Replacement for Lead Azide
in Australian Ordnance. Part 1. An Assessment of Preparation Methods. Report MRL-R-901,
Department of Defense, Material Research Laboratories, Ascot Vale, 1983
57. Klap€otke, M., Sabaté, C.M.: Less sensitive transition metal salts of the 5-nitrotetrazolate anion.
Cent. Eur. J. Energetic Mater. 7, 161–173 (2010)
58. Lee, K., Coburn, M.D.: Binary eutectics formed between ammonium nitrate and amine salts of
5-nitrotetrazole I. Preparation and initial characterization. J. Energetic Mater. 1, 109–122
(1983)
59. Scott, C.L.: Mercuric 5-nitrotetrazole as a lead azide replacement. In: Proceedings of the
International Conference on Research in Primary Explosives, vol. 2, pp 15/1-15/23 Waltham
Abbey, (1975)
60. Hirlinger, J.M.: Investigating alternative “green” primary explosives. In: Proceedings of NDIA
39th Annual Gun & Ammunition Missiles & Rockets Conference & Exhibition, Baltimore,
MD, 2004
61. Gilligan, W.H., Kamlet, M.J.: Method of preparing the acid copper salt of 5-nitrotetrazole. US
Patent 4,093,623, 1978
62. Hirlinger, J.M., Bichay, M.: New Primary Explosives Development for Medium Caliber Stab
Detonators. Report SERDP PP-1364, US Army ARDEC, 2004
63. Talawar, M.B., Agrawal, A.P., Asthana, S.N.: Energetic co-ordination compounds: Synthesis,
characterization and thermolysis studies on bis-(5-nitro-2H-tetrazolato-N2)tetraammine cobalt
(III) perchlorate (BNCP) and its new transition metal (Ni/Cu/Zn) perchlorate analogues.
J. Hazard. Mater. 120, 25–35 (2005)
64. Spear, R.J., Elischer, P.P.: Studies of stab initiation. Sensitization of lead azide by energetic
sensitizers. Aust. J. Chem. 35, 1–13 (1982)
65. Lee, K., Coburn, M.D.: Ethylenediamine salt of 5-nitrotetrazole and preparation. US Patent
4,552,598, 1985
66. McGuchan, R.: Improvements in primary explosive compositions and their manufacture. In:
Proceedings of 10th Symposium on Explosives and Pyrotechnics, San Francisco, 1979
67. Glover, D.J.: Analysis of Mercuric 5-nitrotetrazole. Report NSWC/WOL/TR 77-71. Naval
Surface Weapon Center, Silver Spring, MD (1977)
68. Fronabarger, J.W., Williams, M.D.: Preparation of lead-free primary explosive. US Patent
2010/0280254 A1, 2010
69. Scott, C., Leopold, H.S.: Single chemical electric detonator. US Patent 3,965,951, 1976
70. Tompa, A.S.: Thermal stability of an explosive detonator. Thermochim. Acta 80, 367–377
(1984)
71. Scott, C.L., Leopold, H.S.: Stab-initiated explosive device containing a single explosive
charge. US Patent 4,024,818, 1977
226 8 Tetrazoles

72. Duguet, J.: Priming composition which is sensitive to percussion and a method for preparing it.
US Patent 4,566,921, 1986
73. Hagel, R., Bley, U.: Anz€ undmittel. DE Patent 10,221,044, 2002
74. Piechowicz, T.: Les explosifs d‘amorcage nouveaux et leurs applications spatiales. In:
Proceedings of Utilisation des éléments pyrotechniques et explosifs dans les systèmes
spatiaux; Colloque International, pp. 99–104, Tarbes, 1968
75. Henry, R.A., Finnegan, W.G.: An improved procedure for the deamination of 5-aminotetrazole.
J. Am. Chem. Soc. 76, 290–291 (1954)
76. Taylor, G.W.C., Jenkins, J.M.: Progress toward primary explosives on improved stability. In:
Proceedings of 3rd Symposium on Chemical Problems Connected with the Stability of
Explosives, pp. 43–46, Ystad, 1973
77. Stierstorfer, J., Klap€ otke, T.M., Hammerl, A., Chapman, R.D.: 5-Azido-1H-tetrazole—
Improved synthesis, crystal structure and sensitivity data. Zeitschrift f€ ur anorganische und
allgemeine Chemie 634, 1051–1057 (2008)
78. Lieber, E., Levering, D.R.: The reaction of nitrous acid with diaminoguanidine in acetic acid
media. Isolation and structure proof of reaction products. J. Am. Chem. Soc. 73, 1313–1317
(1951)
79. Friedrich, W.: Spreng- und Z€ undstoffe. DE Patent 695,254, 1940
80. Rathsburg, H.: Explosive compound for primers and detonators. US Patent 1,511,771, 1924
81. Friedrich, W., Flick, K.: Verfahren zur Herstellung von Tetrazylazid bzw. seinen Salzen. DE
Patent 719,135, 1942
82. Marsh, F.D.: Cyanogen azide. J. Org. Chem. 37, 2966–2969 (1972)
83. Klap€otke, T.M., Stierstorfer, J.: The CN7- anion. J. Am. Chem. Soc. 131, 1122–1134 (2009)
84. Hammerl, A., Klap€ otke, T.M., Noth, H., Warchhold, M.: Synthesis, structure, molecular
orbital and valence bond calculations for tetrazole azide, CHN7. Propellants Explosives
Pyrotechnics 28, 165–173 (2003)
85. Rathsburg, H.: Initial primers and a process for their manufacture. GB Patent 185,555, 1921
86. Thiele, J., Ingle, H.: Ueber einige Derivate des Tetrazols. Justus Liebigs Annalen der Chemie
287, 233–265 (1895)
87. Thiele, J.: Ueber Isocyantetrabromid. Berichte der deutschen chemischen Gesellschaft
26, 2645–2647 (1893)
88. Thiele, J., Marais, J.T.: Tetrazolderivate aus Diazotetrazots€aure. Justus Liebigs Annalen der
Chemie 273, 144–160 (1893)
89. Hammerl, A., Holl, G., Klap€ otke, T.M., Mayer, P., Noth, H., Piotrowski, H., Warchhold, M.:
Salts of 5,50 -azotetrazolate. Eur. J. Inorg. Chem. 834–845 (2002)
90. Reddy, G.O., Chatterjee, A.K.: A thermal study of the salts of azotetrazole. Thermochim. Acta
66, 231–244 (1983)
91. Thiele, J.: Ueber Azo- und Hydrazoverbindungen des Tetrazols. Justus Liebigs Annalen der
Chemie 303, 57–75 (1898)
92. Singh, R.P., Verma, R.D., Meshri, D.T., Shreeve, J.N.M.: Energetic nitrogen-rich salts and
ionic liquids. Angew. Chem. 45, 3584–3601 (2006)
93. Pierce-Butler, M.A.: Structure of bis[hydroxolead(III)] 5,50 -azotetrazolediide. Acta
Crystallogr. B 38, 2681–2683 (1982)
94. Mayants, A.G., Vladimirov, V.N., Razumov, N.M., Shlyanochnikov, V.A.: Razlozhenie solei
azotetrazola v kislykh sredakh. Zhurnal organicheskoi khimii 27, 2450–2455 (1991)
95. Hiskey, M.A., Goldman, N., Stine, J.R.: High-nitrogen energetic materials derived from
azotetrazolate. J. Energetic Mater. 16, 119–127 (1998)
96. Taylor, G.W.C., Thomas, A.T.: Improvements in the manufacture of lead azotetrazole. GB
Patent 986,631, 1965
97. Rathsburg, H.: Manufacture of detonating compositions. US Patent 1,580,572, 1926
98. Stollé, R., Roser, O.: Abk€ ommlinge des Amino-5-tetrazols. Journal f€ ur praktische Chemie
139, 63–64 (1934)
99. Friederich, W.: Disruptive or brisant explosive composition. US Patent 2,170,943, 1939
Chapter 9
Tetrazole Ring-Containing Complexes

Heterocycles with high nitrogen content (triazoles and tetrazoles) have been studied
by researchers of energetic materials for a very long time. The triazole derivatives
were found to be useful in the area of secondary explosives and propellants, while
tetrazole compounds were found to have some potential in priming. Heavy metal
salts of a variety of tetrazole derivatives were examined in early studies and some
even found practical applications.
One of the reasons stimulating the search for new primary explosives today is the
need to replace toxic lead azide with some environmentally benign alternative
(other reasons are described in Chap. 1). A suitable replacement needs to have
many of lead azide’s properties within relatively narrow ranges. It would therefore
be desirable to have the ability to influence the properties of the resulting substance
by slightly modifying its structure. This goal is not achievable with metal salts
alone but seems to be realistic with metal complexes or coordination compounds or,
as recommended by IUPAC, coordination entities [1].
The structure of these complexes consists of a central metal atom bonded to a
surrounding array of molecules or anions (ligands or complexing agents). The
general formula may be described as [Mx(L)y](An)z or (Cat)z[Mx (L)y] where M is
a metal cation, L is a ligand, Cat is a cation and An is an anion of an acid, often with
the function of oxidizer. The structure of such compounds enables changes of the
physical, chemical, and explosive properties in a relatively wide range by altering
the number and type of the ligands, the type of cation, the anion, or the coordinating
metal. Research activities on these substances have been reported from Europe,
USA, Russia, India, and China.
Transition metals are known to influence the burning behavior of energetic
materials. The metal atom in the coordination compound therefore plays two
roles (1) it serves as a bonding element for ligands and ions, (2) it influences
(catalyzes) burning rate. Burning rate affects the ability of a substance to undergo
deflagration to detonation transition (DDT) and therefore directly influences
initiating efficiency. Hence a variation in the central metal atom of a complex
structure affects its ability to serve as an initiating substance. Both of the above-
mentioned properties also depend on the nature of the oxidizing group. Changing

R. Matyáš and J. Pachman, Primary Explosives, 227

DOI 10.1007/978-3-642-28436-6_9, # Springer-Verlag Berlin Heidelberg 2013
228 9 Tetrazole Ring-Containing Complexes

the nitrate anion for a perchlorate one usually leads to an increase in burning rate.
The type of ligand often determines the sensitivity parameters of the resulting
complex. Some methods of selection of particular building blocks of the resulting
complex are nicely summarized by Sinditskii and Fogelzang [2]. Careful variation
of central atom, ligand, and ions enables design of a structure with properties
tailored to specific applications.

9.1 Cobalt Perchlorate Complexes

An interesting insight into primary explosives and their perspectives including

some complex salts with substituted tetrazoles in the molecule have been published
by Ilyushin [3]. It was stated there that, for tetrazole-containing complexes,
initiating efficiency depends on composition and that the length of the prede-
tonation zone is affected by metal (cation), ligand, and anion (oxidizer). Further,
the DDT process depends on the enthalpy of formation and it is also faster for
complexes with those substituents which exhibit exothermal reactions in the first
stages of decomposition.
Almost endless possibilities exist for combining metal atoms, ligands, and ions.
For the purpose of this chapter, we have selected only some of the more common
complexes with at least some potential in initiating devices.

9.1.1 Pentaamine(5-cyano-2H-tetrazolato-N2)cobalt(III)
perchlorate (CP)

CN 2+
N C
N N
-
N (ClO 4)2
H3N NH3
Co
H3N NH3
NH3

Pentaamine(5-cyano-2H-tetrazolato-N2)cobalt(III) perchlorate (CP) was devel-

oped in the late 1960s as an alternative primary explosive material that has a rapid
DDT while maintaining a high level of manipulation safety [4–6].
The structure of pentaamine (5-cyano-2H-tetrazolato-N2)cobalt(III) perchlorate
is shown above. Bonding via the N2 ring nitrogen in the final product has
been confirmed by single-crystal X-ray structure determination [7] and 15N NMR
analysis [8].
9.1 Cobalt Perchlorate Complexes 229

The strength of the coordinate bond between cobalt and the various nitrogen
atoms differs. The bond between cobalt and nitrogen in the tetrazole ring is the
strongest due to the negative electronic charge of the 5-cyanotetrazole ligand. The
four equatorial bonds have equal strength which is weaker than the tetrazole cobalt
bond but stronger than the reverse side Co
N bond: bond connecting tetrazole
ring > bonds in equatorial position > bond in axial position [9, 10].

9.1.1.1 Physical and Chemical Properties

CP forms yellow monoclinic crystals with crystal density 1.97 g cm
3 [11]. It is
compatible with most metallic and ceramic materials used in typical detonator
design and also epoxies cured by amines or anhydrides. This is interesting since
many organic explosives and amine cured epoxy materials have compatibility
problems. It is also compatible with PETN [12].
However, it has been found to be incompatible with copper and should not be
considered for designs containing this metal [5, 11, 13]. The good compatibility of
this material may be jeopardized by impurities from the CP synthesis process
(nitrate and perchlorate ions) [11].
The solid decomposition products and impurities from CP preparation
(CP co-product 5-carboxamidotetrazolatopentaamminecobalt(III) perchlorate, see
Sect. 9.1.1.3) in amounts from 1 to 10 % have no apparent autocatalytic or
inhibitive effect on CP decomposition. But impurities from the CP synthesis
process (nitrate, perchlorate ions) can lead to compatibility problems. Gaseous
decomposition products such as ammonia inhibit the decomposition by pushing
the reactions to higher temperatures [11].

9.1.1.2 Explosive Properties

The sensitivity of CP to shock, electrostatic discharge, and hot wire noticeably

depends on its form. It is relatively insensitive to these stimuli in bulk form
(practically comparable to secondary explosives). However, in the pressed state,
CP is as sensitive as primary explosives. This behavior is the main advantage of this
compound [4].
The sensitivity of CP to electrostatic discharge (ESD) is highly dependent on
density. The sensitivity to ESD further depends on its particle size, with smaller
particles showing higher sensitivity (Fig. 9.1).
The overall behavior is therefore controlled by a combination of particle size and
density that both contribute to the resulting U-shaped curve dependency of ESD
sensitivity (Fig. 9.2). At lower densities, crushing of crystals during pressing and
therefore decrease of particle size may contribute to the higher sensitivity (lower
initiation energy) overtaken at higher densities by increase of dielectric strength.
230 9 Tetrazole Ring-Containing Complexes

Fig. 9.1 Sensitivity of CP to electrostatic discharge as a function of particle size (increasing

particle size from lot A to lot E) [13]. Reprinted by permission of IPSUSA Seminars, Inc.

Loose CP powder and unconfined pellets are not ignitable by the human body
equivalent electrostatic discharge (20 kV, 600 pF, 500 O) [11].
The comparison of sensitivity to the mechanical stimuli between CP and sec-
ondary explosives (PETN, RDX) is shown in Table 9.1 [6]. CP unlike LA or LS
does not show sensitivity typical for primary explosives. In bulk form it exhibits
sensitivity on the level of secondary explosives. After the thermal initiation it
undergoes DDT only when confined [4].
The detonation velocity of CP in a confined state can be obtained from the
following formula:

D ¼ 0:868 þ 3:608r

where D is detonation velocity (in km s
1) and r is the initial density of CP

(in g cm
3). The relation is valid for a sample with a 6.35 mm diameter [13].
CP is thermally stable up to 80  C (Co(II) concentration from CP decomposition
was below 800 ppm following 3 years of aging). At 120  C average 2.2 % of CP
decomposes after 1,078 days of aging [11].
9.1 Cobalt Perchlorate Complexes 231

Fig. 9.2 Sensitivity of CP to electrostatic discharge as a function of density [13]. Reprinted by

permission of IPSUSA Seminars, Inc.

Table 9.1 Impact (drop-hammer machine, 2.5 kg hammer, 50 % probability) and friction
sensitivity (BAM apparatus, 1 event in 10 trials) of powdered CP [6]
Impact sensitivity h50 (cm) Friction sensitivity (kg)
CP PETN RDX CP RDX
60.6 15.5 34.5 1 1

9.1.1.3 Preparation

Preparation of 5-Cyanotetrazole

5-Cyanotetrazole is a main intermediate for preparation of CP. The most

convenient route for its preparation (and also other substituted tetrazoles) is
232 9 Tetrazole Ring-Containing Complexes

the 1,3-dipolar cycloaddition reaction of azides with nitriles [14]. Pure

5-cyanotetrazole is prepared by treating a hydrazonic acid with cyanogen via the
following reaction [15, 16]:
CN

C H
N C C N N N
+ HN3
N N

The reaction conditions influence the composition of the final product. The forma-
tion of side products 5,50 -bitetrazole or 5-carboxyamidetetrazole is possible with this
reaction [17]. The metallic salts of 5-cyanotetrazole can be prepared when metallic
azides are used instead of hydrazonic acid in presence of sulfur dioxide [14].
The other method of preparing 5-cyanotetrazole is based on treatment
of 1-cyanoformimidic acid hydrazide with nitrous acid. The intermediate
1-cyanoformimidic acid hydrazide could be prepared by the reaction of cyanogen
and hydrazine [18, 19].
CN
NH C
HNO2 H
N C C N + NH2 NH2 H2N NH C N N
CN
N N
1-cyanoformimidic acid hydrazide

Preparation of CP

CP is prepared via a batch process described by Fleming et al. (cited by Lieberman

[4]). The four steps are summarized below:
H 2O
2 Co(NO3)2 + 8 NH 3(aq) + 2 (NH 4)2CO 3 + 1/2 O 2 2 [Co(NH3)5CO 3]NO 3 + 2 NH 4NO 3 + H 2O
CPCN

H 2O
[Co(NH3)5CO 3]NO 3 + 3 HClO 4 [Co(NH3)5H2O](ClO 4)3 + CO 2
APCP

CN
C H
H 2O
C2N2 + NaN 3 + HCl N N + NaCl
N N
CN 2+
N C
CN
N N
C H -
H 2O N (ClO 4)2
N N + [Co(NH3)5H2O](ClO 4)3
H3N NH3
N N Co
H3N NH3
NH3

CP
9.1 Cobalt Perchlorate Complexes 233

The intermediate APCP is purified by recrystallization from an excess of an

aqueous perchloric acid. CP is purified by recrystallization from a slightly acidified
(by perchloric acid) aqueous solution containing ammonium perchlorate [13].
Two main side products form during the preparation of CP. The first one is
5-carboxamidotetrazolatopentaaminecobalt(III) perchlorate referred to as “amide
complex” and the second one referred to as “amidine chelate” of CP (see scheme
below). The formation of the amide is assumed to be a simple hydrolysis reaction.
The following reaction sequence has been proposed for the formation of these two
side products [4, 13]:

CN 2+ 2+
N C N N

N N N C
CN
N N
H3N NH3 H3N NH3
Co Co
H3N NH3 H3N NH3
NH3 NH3

-
OH

O 2+ 2+
C NH2 N N
N C
N C C NH2
N N N
N H3N NH
H3N NH3 Co
Co H3N NH3
H 3N NH3 NH3
NH3

"amide complex" "amidine chelate"

The “amide complex” is about as soluble as CP [11]. It is however possible to

purify CP by recrystallization from an aqueous solution of ammonium perchlorate
slightly acidified by perchloric acid. The amount of amide complex decreases from
the original content of around 10 % to 2–3 %. In order to obtain a particle size
suitable for application in detonators it is necessary to reprecipitate the purified CP
from a slightly acidified aqueous solution by controlled addition to chilled stirred
isopropyl alcohol [13].

9.1.1.4 Uses

The production of CP began in 1977 and by 1979 the first production of a CP

detonator for Department of Energy (USA) had been successfully accomplished
[6]. It has been used alone as a primary explosive in “Spark-Safe Low-Voltage
Detonators.” A generalized CP detonator is shown in Fig. 9.3.
234 9 Tetrazole Ring-Containing Complexes

Fig. 9.3 Generalized CP detonator design [4, 20]. Reprinted by permission of IPSUSA Seminars,
Inc.

Fig. 9.4 Hot wire ignition sensitivity of CP as a function of density [13]. Reprinted by permission
of IPSUSA Seminars, Inc.

CP is pressed in several layers by various loading pressures. The resulting

density determines the function of each of the layers as demonstrated in Fig. 9.4
for the all-mean fire energy [20] and in Fig. 9.5 for the run to detonation length [21].
First layer—igniter charge—is initiated by the hot resistive bridgewire. CP in
this region is pressed by a higher compacting pressure (at 172–276 MPa) for two
reasons: First, to ensure powder-to-bridgewire contact, and secondly to lower the
energy necessary for reliable ignition. It can be seen from Fig. 9.4 that the all-fire
energy is reduced by increasing CP powder density and decreasing its particle size.
9.1 Cobalt Perchlorate Complexes 235

Fig. 9.5 Run to detonation length of CP as a function of theoretical maximum density [21].
Reprinted with permission from Luebcke P. E., Dickson P. M., and Field J. E.: “An experimental
study of the deflagration-to-detonation transition in granular secondary explosives”, Proceedings
of the Royal Society of London, Series A: Mathematical, Physical and Engineering Sciences,
1995, 448, 439–448. Copyright (1995) The Royal Society

For these reasons, a fine CP material (nominally 15 mm average crystal size)

is utilized and the ignition regions are loaded to a density of about 1.7 g cm
3
[12, 13, 20, 22].
The second layer—transfer column—is loaded by lower pressure (69 MPa). The
lower loading pressure of CP permits desired gas flow through the column and
thereby promotes the desired deflagration-to-detonation transition (DDT). Reduced
density of the powder in this region is required to yield reliable DDT (see Fig. 9.5).
Consequently, the DDT region utilizes powder density 1.5 g cm
3 (whereas values
approaching 1.7 g cm
3 fail to yield transition) [12, 13, 20, 22].
The third—an output charge of the detonator—may be the end, or an extension,
of the transfer column. If an enhanced output is desired, it can be loaded to higher
density (about 1.7 g cm
3) [12, 13, 20, 22].
A high-voltage detonator (HDV) based on CP was also developed for the Titan
IV launch vehicle [23]. The production of CP had been discontinued due to its
toxicity [21].

9.1.2 CP Analogs

A large number of CP analogs have been synthesized. They varied in either having
the cyano group replaced by other groups or the central metal cation replaced with
another metal.
236 9 Tetrazole Ring-Containing Complexes

The complexes with other 5-substituted

 (–X is substituent) tetrazole have the
general formula CoðNH3 Þ5 N4 CX ðCIO4 Þ2 with the same structure as CP. They can
be synthesized by the reaction of 5-substituted tetrazole with APCP in an aqueous
medium in the same way as CP [24].

X 2+
N C
X
N N
C H H2O N
-
(ClO 4)2
N N + [Co(NH 3)5H2O](ClO 4)3
H3N NH3
N N APCP Co
H3N NH3
NH3

Fleming et al. prepared cobalt complexes with 5-substituted tetrazole with the
following substituents –X: –CN, –Cl, –H, –NO2, –CH3, and –CF3. The analyses
showed the formation of only one isomer of each compound. The substituted
tetrazoles are generally N-2 bonded to the cobalt atom. Density values of such
substances are in the range from 1.84 to 2.03 g cm
3. All compounds exhibited
exothermic decomposition above 250  C. The increasing electrostatic sensitivity
and the increasing ease of transition to detonation correlate with increasing
electron-withdrawing ability of the moiety [24].
Johnson et al. studied analogs of CP in which the cobalt atom was replaced
by chromium, iridium, rhodium, and ruthenium. The rhodium  and chromium
complexes can be prepared by reaction of the APCP analog MeðNH3 Þ5 ðH2 OÞ
ðClO4 Þ3 with 5-cyanotetrazole in an aqueous solution, whereas the others have been
shown to consist of product mixtures. The rhodium complex is the most thermally
stable (comparable to CP) while the iridium, chromium, and ruthenium complexes
are significantly less stable (determined by DSC) [4, 25].
Very broad studies into cobalt pentaaminate analogs of CP have been reported
from the Saint Petersburg State Technological Institute group of Ilyushin and
Tselinskii. Numerous articles have been summarized into two monographs [26, 27].
All synthesized complexes were found to have an octahedral structure with the
tetrazole molecule coordinated via the N2 atom. Some of these monosubstituted
tetrazoles are summarized in Table 9.2.
Studies of thermal stability of pentaamine cobalt(III) perchlorate complexes
during slow heating revealed that only two analogs of CP(–X ¼ –NO2 and
–CH¼NON¼CH–N3) decompose in one macroscopic step. The decomposition of
the rest of the complexes is a more complicated multistep process. Due to this it is
quite difficult to determine exact decomposition mechanisms. It was, however,
found that the process is diffusion controlled. The complexes listed in Table 9.2
undergo pyrolysis if heated in vacuum. Gaseous products evolved in this process do
not depend on the type of the substituent in position 5 of the cycle and contain
ammonia, nitrogen, water, hydrogen chloride, carbon dioxide, carbon monoxide,
oxides of nitrogen, and a small amount of hydrogen cyanide. The perchlorate anion
takes part in the oxidation of the ligands only at the end of the decomposition
process [27].
9.1 Cobalt Perchlorate Complexes 237

Table 9.2 Densities, detonation velocities, and temperatures of decomposition of analogs of CP,
reprinted from [27]
rcalculated rexperimental Dcalculated Dexperimental Tdecomposition
Substituent (–X) (g cm
3) (g cm
3) (km s
1) at r (km s
1) at r ( C)
–H 1.97 1.97 7.14 (1.97) – 280
–NO2 2.01 2.03 6.30 (1.61) 6.65 (1.61) 265
–CH3 1.90 1.88 6.94 (1.90) – 282
–N¼NO2
NH4+ 1.87 1.87 – 6.33 (1.52) 250
–NH2 1.96 1.95 6.14 (1.62) 6.50 (1.62) 270
–C(NO2)2
NH4+ 1.88 1.88 – 6.32 (1.48) 201
–CH2N3 1.92 1.94 7.44 (1.94) – 302 (explosion)
–C(NO2)3 2.01 2.05 8.03 (2.05) – 132
O 1.99 1.97 7.76 (1.97) – 280
N N

NO2

O 1.94 1.95 7.71 (1.95) – 198

N N

N3

O – 1.93 7.34 (1.93) – 280

N N

NH2

O 1.87 1.83 7.42 (1.83) – 255

N N

-
N NO2
NH4+

Sensitivity to impact of 5-substituted CP analogs has been determined by

Ilyushin et al. [26] and is reprinted in Table 9.3.
The sensitivity of various analogs of CP to laser monoimpulse was summarized
by Ilyushin et al. [28] and more generally in [29].
Best properties from all analogs of CP are reported for pentaamine (5-nitro-2H-
tetrazolato-N2)cobalt(III) perchlorate (abbreviated by authors to NKT). It has low
sensitivity to electrostatic discharge; predetonation distance is 4.5 mm with charge
diameter 6.5 mm and density 1.60–1.63 g cm
3. NKT is thermally stable—heating
it at 200  C in a hermetically sealed container for 6 h does not change its properties.
It is not hygroscopic and, unlike CP, it is not too toxic. Careful optimization of
reaction conditions gives up to 90 % yields [26].
238 9 Tetrazole Ring-Containing Complexes

Table 9.3 Sensitivity to Impact height for 10 %

impact, hammer weight 2 kg, Substituent (–X) probability of initiation (cm)
sample weight 15 mg [26]
–CN 65
–H 95
–NO2 65
–CH3 60
–Cl 55
–CF3 55
RDX 75
PETN 30

9.1.2.1 Uses

NKT has been tested in oil well perforators. It was found that NKT works safely in
PVP-1 at temperatures up to 150  C under 80 MPa in a borehole environment even
after being there for 6 h [26].

9.1.3 1,5-Cyclopentamethylenetetrazole Complexes

Experimental work on the preparation of low toxicity primary explosives from the
group of cobalt perchlorate complexes has been reported from Russia [26, 30]. The
ligand chosen for the complex was “corazol”—1,5-cyclopentamethylenetetrazole:
N
N
N
N
corazol

The first coordination compound published was pentaamine(1,5-cyclopenta-

methylene-tetrazolato-N3) cobalt(III) perchlorate (PAC):

NH3 3+

H3N NH3
III
Co -
+ N (ClO 4 )3
H3N N
NH3 N
N

PAC

X-ray crystallography of the complex is not available and the bonding atom of
corazol has therefore not been determined. It is however expected to have the
above-mentioned general formula. In a recent paper, Ilyushin et al. [31] reported
9.1 Cobalt Perchlorate Complexes 239

compatibility of organic polynitro compounds with CP analogs having

1,5-cyclopentamethylenetetrazole (PMT) in its molecule. The substances studied
included the above-mentioned PAC and its analog with the (1-methyl-
5-aminotetrazole-N2) ligand, and complexes with copper and nickel as central
atoms and PMT as ligand:
3+
NH3 NH3 3+

H3N NH3 H3N NH3

III III
Co - Co -
+ N (ClO 4 )3 + N (ClO 4 )3
H3N N H3N N
NH3 N NH3 N NH2
N N
CH3

PAC Co1M5AT

2+
N N
Cu N (H2O)2 (ClO4)2 Cu N (ClO4)2
N N
N N
2 4

CuL2 CuL4

N N
N (ClO4)2 Ni N (ClO4)2
Ni N
N N
N 4
6

NiL6 NiL4

9.1.3.1 Physical and Chemical Properties

The thermal decomposition of the PAC complex determined by nonisothermal

heating at 5  C min
1 rate showed relatively good thermal stability. The first
mild endothermal process in the form of a broad peak from 95 to 245  C is
accompanied by 14.7 % weight loss. The inner molecules of ammonia break
away in this process. At 245  C melting begins followed by significant exothermal
decomposition (250–350  C) with 71 % mass loss. At even higher temperatures
cobalt is oxidized to Co2O3 [26]. Thermal stability of CuL4 is similar—onset of fast
decomposition is at 230  C under nonisothermal conditions at a heating rate
5  C min
1. Some slow exothermal decomposition accompanied by 30 % weight
loss is observed in the temperature range from 185 to 235  C [32].
240 9 Tetrazole Ring-Containing Complexes

The thermal stability studies of PAC showed that the decomposition of the
complex is a multistep process where the first step is related to a breaking away
of internal molecules of ammonia leading to the destruction of the complex.
The second step is the decomposition of the corazol ligand supported in later stages
by oxidative action of the perchlorate anion [26]. The kinetics of decomposition of
the PAC complex as determined by TG, DTG, and DTA provided the following
parameters: beginning of the fast decomposition 245  C; logarithm of preexpo-
nential factor in Arrhenius equation 8.6; activation energy 116 kJ mol
1 and first
reaction order (without diffusion processes) [31]. From these values, it seems that
the half-life at 80  C is around 8 years.
The compatibility (STANAG 4147) of the above-mentioned complexes with
tested explosives varies. HMX is compatible with NiL6 and CuL4, has some
interaction with NiL4, CuL2 and PAC and is incompatible with Co1M5AT.
CL-20 is compatible with NiL6, CuL4, Co1M5AT, PAC, some interaction exists
for NiL4 and minor incompatibility occurs with CuL2. FOX-7 is compatible with
NiL6, NiL4, CuL2, partially compatible with CuL4 and incompatible with PAC and
Co1M5AT. Details of thermal analysis and burning rate studies of mixtures of these
complexes with HMX, CL-20, and FOX-7 are reported in the same reference
[31–33]. The toxicity of PAC is lower than that of TNT [34].
Oral toxicity was tested on mice. This showed LD50 ¼ 70 mg kg
1 for corazol
and LD50 ¼ 300 mg kg
1 for the complex (PAC) placing it in toxicity class 3 (low
risk substances). The toxicity of Co(III) ammoniacal complexes is comparable to
the toxicity of the Co(III) nitrate (calculated on the metal content). For comparison,
it is less toxic than TNT which belongs to class 2 [26].

9.1.3.2 Explosive Properties

Co1M5AT and PAC are known to have short DDT distances. The impact sensitivity
of PAC determined by GOST-4545-88 (2 kg hammer, impact height 25 cm) is
16 %. The initiation efficiency for RDX is 0.4 g; the calculated detonation velocity
is 6.98 km s
1 for density 1.82 g cm
3. This clearly indicates that the complex is a
primary explosive (with relatively low initiation efficiency) but with sensitivity to
mechanical stimuli comparable to secondary explosives [26].

9.1.3.3 Preparation

Pentaamine(1,5-cyclopentamethylene-tetrazolato-)cobalt(III) perchlorate (PAC) is

prepared by the substitution of water by corazol in a slightly acidic aqueous solution
according to the following scheme:

The reaction is carried out at 90–100  C for 2–3 h [26].

9.1 Cobalt Perchlorate Complexes 241

Previous preparation of copper(II) tetrakis-[1,5-cyclopentamethylenetetrazol]

perchlorate (CuL4) in a solution of 2,2-dimethoxypropane (yield 96 %) [35] was
replaced by a less efficient (yield 80 %) but economically more suitable route using
an aqueous solution or isopropyl alcohol. Schematic representation of the preparation
of CuL4 from cupric perchlorate hexahydrate and 1,5-cyclopentamethylenetetrazol
(PMT) is shown according to the following scheme:

N
Cu(ClO 4)2.6H2O + 4 (CH2)5CN4 Cu N (ClO4)2
N
N
PMT 4

CuL4

9.1.3.4 Uses

The complexes are in an experimental stage of development. PAC and Co1M5AT

have been tested in model detonators while complexes of nickel and copper have
been used as burn rate modifiers in model propellants.

9.1.4 Tetraammine-cis-bis(5-Nitro-2H-tetrazolato-N2)cobalt(III)
perchlorate (BNCP)

In 1986, Bates reported three new similar coordination structures all very much like
CP. Most attention was given to tetraammine-cis-bis(5-nitro-2H-tetrazolato-N2)
cobalt(III) perchlorate (BNCP) [36].
NO2 +
C
N
NH3
N
H3N N -
N ClO 4
Co
N
H3N N
C NO2
NH3 N
N

The structure of BNCP is an octahedrally coordinated cobalt atom with

four Co
NH3 bonds and two slightly shorter Co
N bonds for the cis-tetrazolato
ligands [37].
BNCP forms a yellow-gold crystalline solid which is typical for octahedral
cobalt(III) complexes having six coordinating nitrogens (as in the case with CP).
BNCP crystallizes in a monoclinic system [38]. The density of the BNCP mono-
crystal is 2.05 g cm
3 [27].
242 9 Tetrazole Ring-Containing Complexes

9.1.4.1 Explosive Properties

BNCP is slightly more sensitive to impact and friction than CP and exhibits similar
sensitivity to electrostatic discharge. Different values of sensitivity of BNCP are
published in the literature some of which are summarized in Table 9.4. Ilyushin
et al. reported BNCP to be less sensitive to impact than PETN (see Table 9.5).
Decreasing particle size decreases sensitivity [27].
BNCP undergoes the DDT process more rapidly than CP under steel confine-
ment and also performs moderately well under aluminum and to a lesser extent also
under plastic (Lexan) confinement (Lexan DDT confinement provides velocities of
about 70 % of the steel value). CP does not undergo DDT when using either of these
two materials for confinement (Al, Lexan) [38, 42].
BNCP and its analogs are sensitive to light and may be detonated by laser pulses.
Initial studies [43] report use of a variety of laser sources at 800 and 1,060 nm, with
later activities, studying the sensitivity of pressed powders to a single pulse, using
solid state neodymium laser (1,060 nm, 1.5 J, 2 ms, beam diameter 1 mm) [44].
BNCP analogs are evaluated as alternatives to substances such as hydrazino
tetrazole mercury(II) perchlorate which is probably the most sensitive substance
with respect to laser pulses (initiation time around 30 ns at 1.10
4 J) [39].
BNCP is also a more powerful explosive than CP (0.66 mm at 80 % TMD versus
0.46 mm at 76 % TMD for CP using depth of dent in a steel witness plate) and
further has a very good initiation efficiency—13 mg to initiate PBXN-301 (PETN
based PBX). Detonation velocity of CP is 3.2 km s
1 at 80 % TMD (1.58 g cm
3)
and of BNCP 2.7 km s
1 at 76 % TMD (1.54 g cm
3) [38, 45].
Calculated detonation velocity of BNCP is reported to be 8.1 km s
1 at density
1.97 g cm
3, beginning of the intensive decomposition is at 269  C, initiating
efficiency is 50 mg for RDX in a number 8 detonator tube, time of the DDT is
around 10 ms, and heat of decomposition is 3.32 kJ g
1 [27].

9.1.4.2 Preparation

BNCP is prepared by a two-step reaction. Tetraaminecarbonatocobalt(III) nitrate

(CTCN) is prepared in the first step followed by its reaction with the sodium salt of
5-nitrotetrazole.
4 Co(NO3)2 + 12 NH 3(aq) + 4 (NH 4)2CO3 + O 2 4 [Co(NH3)4CO3]NO3 + 4 NH 4NO3 + 2 H 2O
CTCN
NO2 +

NO2 C
N
NH3
N
C HClO4 / H 2O
H3N N
+ N N + [Co(NH 3)4CO3]NO3 N -
2 Na - Co ClO 4
pH < 2 N
H3N N
N N C NO2
NH3 N
N
BNCP
9.1 Cobalt Perchlorate Complexes 243

Table 9.4 Comparison of sensitivity of BNCP and CP, h10 (10 %) and h50 (50 %) fire level,
confined
BNCP CP Reference
Density (g cm
3) 2.03 1.98 [38]
2.05 – [39]
Impact sensitivity (cm), 2 kg hammer 50 (h10) 55–70a (h10) [38]
32 (h50) – [40]
Same as PETN – [41]
Friction sensitivityb (g) 600 >1,000 [38]
Electrostatic discharge sensitivityc (kV) >25 (loose powder) >25 (loose powder) [38]
4.8d (79 % TMD) 5.2d (82 % TMD)
d
8.5 (89 % TMD) 8.0d (86 % TMD)
a
Lot-dependent
b
Julius Peters BAM tester, threshold
c
600 pF, 500 O
d
Conf

Table 9.5 Comparison of sensitivity of BNCP and some other energetic materials (50 % proba-
bility of fire) [27]
BNCP CP LA PETN RDX
h50 (cm) 17.0 20.9 4.0 12.0 24.0
2,5 kg Hammer, 35 mg sample size

The preparation of the intermediate CTCN is described in inorganic synthesis

[46]. The second step in the synthesis of BNCP is carried out using the dihydrate of
the sodium salt of 5-nitrotetrazole. The raw BNCP is recrystallized to remove
impurities that could compromise its performance and stability [38, 42, 47].
The yield of the reaction is reported to be in the range 50–70 %. Careful analysis
of the influence of the reaction conditions revealed that the most important factor is
the reaction temperature and the best yield (70 %) is achieved at 90  C. Alterna-
tively, microwave heating may be employed, which reduces reaction time to one
half and increases the yield to 78 % of theoretical [27].
The main drawback of the standard preparation route as described above is the
necessity of isolating the highly sensitive intermediate copper 5-nitrotetrazole
salt in preparation of sodium 5-nitrotetrazole salt (see salts of 5-nitrotetrazole in
Chap. 8.3). A safer way of preparing sodium 5-nitrotetrazole is by a noncatalyzed
Sandmayer reaction. It is extremely important to carefully purify the resulting
sodium 5-nitrotetrazole from sodium nitrite which otherwise competes with the
nitrotetrazole anion in the formation of BNCP leading to complexes with a coordi-
nated nitro group at lower temperatures or to sensitive Co(II) 5-nitrotetrazole
monohydrate at higher temperatures. The presence of the latter in BNCP is not
acceptable. Details of the reaction conditions and its optimization with respect
to suppression of formation of sensitive side products are described by Ilyushin
et al. [27].
244 9 Tetrazole Ring-Containing Complexes

9.1.4.3 Uses

BNCP was originally proposed as a possible replacement of lead azide and other
primary explosives in semiconducting bridge and hot wire detonators [36, 38].
BNCP has also been investigated for application in optical ordinance particularly
with regard to laser diode-initiated detonators. Carbon-doped BNCP (1%) is some-
what more sensitive to the diode laser output (800 nm) than comparably doped CP
[38, 43].

9.1.5 BNCP Analogs

A number of molecules that could be described as BNCP analogs were studied.

Preparation of energetic complexes with
NO2 group bonded to the tetrazole ring
replaced by
NH2,
H, and
CH3 is possible according to the general equation
[44]:
R

R N
NH3 NH3 N
H3N OH2 H3N N
N NH
HClO4 N ClO4
Co (ClO4)3 + Co
N
H3N OH2 H3N N
N N N
NH3 NH3 N

R
NO2

N
where R: NH2 , H, CH3 ,
O
N

The resulting substances (except for the one resulting from 5(30 -nitro-10 ,20 ,50 -
oxadiazolyl-40 -)tetrazole) however showed a metal to ligand ratio of 2:3. This
would indicate that the general formula of the cation is [Co2(NH3)8(NT
R)3]3+.
According to Ilyushin et al., it is believed that one of the three tetrazole rings acts as
a bridge between two cobalt atoms giving a structure with the following general
formula [27]:

R 3+

N N
NH3 N N+ H3N
H3N NH3

H3N Co Co NH3
H3N N N NH3
N N N N
N N
R R
9.1 Cobalt Perchlorate Complexes 245

Fig. 9.6 Crystals of

1,5-diaminotetrazole ferrous
perchlorate complex [50].
Reprinted by permission of
the Department of the Navy
employees, M. Bichay,
K. Armstrong, R. J. Cramer
and the Pacific Scientific
employess, J. Fronabarger
and M. D. Williams

9.1.6 Perchlorate Complexes of 1,5-Diaminotetrazole

1,5-Diaminotetrazole forms complex compounds with metals. The ferrous (DFeP)

and cupric complexes as perchlorate salts have been reported as the most promising
candidates for “green” primary explosives [48–50]. The probable chemical
formulas of both compounds are shown below.
ClO4 ClO4

N NH NH N N C NH NH C N
C C N
N Cu N N Fe
N N NH NH N
N NH NH N N N N

ClO4 ClO4

9.1.6.1 Physical and Chemical Properties

Very little is published about the physical and chemical properties of these
1,5-diaminotetrazole complexes. Crystals of the 1,5-diaminotetrazole ferrous
perchlorate complex are shown in Fig. 9.6.

9.1.6.2 Explosive Properties

Sensitivity values of cupric and ferrous perchlorate complexes of 1,5-

diaminotetrazole are compared to LS in Table 9.6 and the performance data
measured by plate dent test and compared to LA are summarized in Table 9.7.
The effect of the density of the primary explosive on the efficiency of detonators
is shown in Table 9.8. Performance of both complexes decreases with increasing
loading pressure and density contrary to LA. This phenomenon is greater for the
cupric complex. Performance of the ferrous complex is significantly higher at all
246 9 Tetrazole Ring-Containing Complexes

Table 9.6 Sensitivity and thermal stability of cupric and ferrous perchlorate complex of 1,5-
diaminotetrazole [48, 51]
Impact Friction sensitivity small BAM (g) DSC (20  C min
1) ( C)
sensitivity
Compound ball drop (mJ) No-fire level Low fire level Onset Peak
Cu(II) complex 11 100 110 235 240
Fe(II) complex 13 40 50 216 223
LS 25 40 50 290 305

Table 9.7 Plate dent test results of Cu(II) and Fe(II) perchlorate complex of 1,5-diaminotetrazole
[48, 50, 51]
Compound Loading pressure (MPa) Density (g cm
3) Average dent in Al block (mm)
Cu(II) complex 69 1.412 16.8
Fe(II) complex 69 1.465 27.0
LA (RD 1333) 69 3.119 37.3

Table 9.8 Results of the plate dent test of Cu(II) and Fe(II) perchlorate complex of 1,5-
diaminotetrazole compared with LA (aluminum plate) [48, 51]
Loading Density (g cm
3) Average dent in Al block (mm)
pressure Cu(II) Fe(II) LA Cu(II) Fe(II) LA
(MPa) complex complex (RD 1333) complex complex (RD 1333)
34.5 1.18 1.28 2.62 25.0 35.3 27.7
69 1.33 1.40 2.99 23.7 40.3 33.7
138 1.52 1.52 3.18 14.7 37.7 39.0
276 1.62 1.63 3.55 7.7 23.3 46.3

tested densities than the cupric complex. It surpasses LA at lower densities but
brisance of LA is superior to that for the Fe(II) complex at higher densities.

9.1.6.3 Preparation

The metallic complexes are prepared in two steps (a) preparation of the heterocyclic
ligand 1,5-diaminotetrazole and (b) preparation of the final complex.
1,5-Diaminotetrazole is prepared by the reaction of thiosemicarbazide, sodium
azide, and lead monoxide in a dimethylformamide solvent [48].
NH2

C NH2
PbO N N
H2N C NH NH2 + NaN3 DMF
S N N
9.2 Perchlorate-Free Complexes 247

The 1,5-diaminotetrazole then reacts with the appropriate perchlorate to yield

the final product [48].
NH2 ClO4
C NH2 N NH NH N
C C
N N + Fe(ClO4)2 N Fe N
N NH NH N N
N
N N
ClO4

9.1.6.4 Uses

Bichay and Hirlinger have recently reported the ferrous and cupric perchlorate
complexes as the most promising candidates for LA replacement [48, 50].
The ferrous complex has been tested as a primary explosive in stab detonators
(M59) [50].

9.1.7 Other Perchlorate-Based Complexes

An interesting study on the burning rate of various coordination complexes has

been published by Fogelzang et al. [52]. They studied the effect of oxygen-
containing oxidant anion (X), organic fuel (L–ligand), and the type of central
metal atom (M) of substances of general formula [M(L)n]X2 on burning behavior
of the same. The highest burning rate was observed for complexes with BrO3
,
ClO3
, and ClO4
as anion oxidizers. Faster burning rates were also observed for
coordination compounds with an easily oxidizable carbohydrazide ligand compared
to the ethylenediamine ligand. Variation of the type of oxidant was found to change
the burning rate by two orders of magnitude whereas a change in the type of ligand
resulted only in a 5- to 10-fold increase. The catalyzing effect was studied for
complexes with the following metals: Ni, Co, Cu, Cd, Pb, Zn, Mg, Ca, Ba, and Sr as
central atoms. The oxidizer anion was either perchlorate or nitrate and the
carbohydrazide was used as the ligand [52].

9.2 Perchlorate-Free Complexes

9.2.1 Iron- and Copper-Based 5-Nitrotetrazolato-N2 Complexes

A relatively new group of initiating explosives has recently been described by

Americans. It is reported as a group of: “previously undescribed green primary
explosives based on complex metal dianions and environmentally benign cations,
248 9 Tetrazole Ring-Containing Complexes

NO2
- N
2-
OH2 -
O2N O 2N N N
N N
N
- N OH2 - N OH 2
N II N II
N Fe N Fe
N N OH2 N N OH 2
- N - N
N N
O2N N N O 2N N N
N - N -
N N
NO2 NO2
II II 2-
Fe [NT3]- Fe [NT4 ]

NO2
NO2 3- 4-
N
N NO2 NO2
-
O 2N O 2N
N N
-
NN N N N
N N
- N N - N - N - N
N II N N II N
N Fe N N Fe N
N N
N N OH 2 N N
-
- N -
N N N NO2
N O 2N
O 2N N N N N - N N
N -
N N
NO2 NO2

II 3- II 4-
Fe [NT 5] Fe [NT 6]

Fig. 9.7 Anions of 5-nitrotetrazolato-N2-ferrate coordination complexes [53]

NH2 NO
H H
H 2N H 2N N
+ + + + N +
Na O N N C NH2 H N H H N NH2 N H N
+
H H N N N
NCAm H2N H
Hyzm TATm ANTm

Fig. 9.8 Cations of 5-nitrotetrazolato-N2-ferrate coordination complexes [53]

 
ðcatÞ2 MII ðNTÞ4 ðH2 OÞ2 (where cat is NH4+ or Na+, M is Fe2+ or Cu2+, and NT
is
5-nitrotetrazolato-N2)” [53, 54].
The explosive performance is controlled by changing the number of the
nitrotetzrazole ligands and the sensitivity by selection of the cation. Four anions
with iron as the central atom denominated FeII ½NT3  , FeII ½NT4 2
, FeII ½NT5 3
,
FeII ½NT6 4
(Fig. 9.7) and six cations—sodium (Na+), nitrosocyanaminium (NCAm),
ammonium (NH4+), hydrazonium (Hyzm), 1,2,5-triamino-1,2,3-triazolium (TATm)
and 5-amino-1-nitroso-1,2,3,4-tetrazolium (ANTm) were reported (Fig. 9.8) [53].
9.2 Perchlorate-Free Complexes 249

Table 9.9 Selected properties and sensitivities of ammonium 5-nitrotetrazolato-N2-ferrate

hierarchies (reprinted from [53, 54])
NH4[FeII(NT3)] (NH4)2[FeII(NT4)] (NH4)3[FeII(NT5)] (NH4)4[FeII(NT6)]

3
Density (g cm ) 2.10  0.02 2.20  0.03 2.34  0.02 2.45  0.02
Exo. DSC ( C)a 261 255 253 252
ESD (J) >0.36 >0.36 >0.36 >0.36
Friction (kg) 4.2 2.8 1.3 0.8
Impact (cm) 15 12 10 8
a
Heating rate 5  C min
1

9.2.1.1 Physical and Chemical Properties

The primary explosives prepared from the above-mentioned cations and anions are
sparingly soluble in most common organic solvents and water, are moisture and
light resistant, and thermally stable up to 250  C. The densities of some of the
candidates are summarized in Table 9.9.

9.2.1.2 Explosive Properties

All of the above-mentioned primary explosives are insensitive to electrostatic spark

regardless of cation type even when dry. When wet they are insensitive to friction,
impact, and open flame. The complexes with the greater number of nitrotetrazole
ligands are more sensitive and have better performance. Regardless of the number
of the ligands, the complexes with a sodium cation detonate while those with an
ammonium cation undergo DDT when exposed to open flame. The complexes
containing the sodium cation are more sensitive to friction and impact than their
ammonium analogs (e.g., friction sensitivity of ðNH4 Þ2 ½FeII ðNT4 Þ increased from
2,800 g to 20 g for ðNaÞ2 ½FeII ðNT4 Þ). The sensitivity of the ammonium complexes
is summarized in Table 9.9 [53, 54].

9.2.1.3 Preparation

The salts are prepared from stoichiometric amounts of NT salt and FeII salt (e.g.,
[Fe(H2O)6]Cl2) in refluxing water (or ethanol) for 2 h [55]. Stoichiometric
equivalents of the reactants lead to high yields of pure compounds thereby avoiding
dangerous purification steps. Further, the preparation leads only to relatively
innocuous waste (chlorides and nitrates) [53].

9.2.1.4 Uses
 
The sodium complex Na2 MII ðNTÞ4 ðH2 OÞ2 with M being either Fe2+ or Cu2+ has
been tested in MK1 electric and M55 stab detonators. The tests with MK1 detonator
proved that both LA and LS may be fully replaced by the complex (the text does not
specify if Fe2+ or Cu2+ was used). The complex further successfully replaced LA in
the transfer charge of an M55 detonator [53].
250 9 Tetrazole Ring-Containing Complexes

9.2.2 Perchlorate-Free CP Analogs

Replacing the perchlorate anion in pentaamine cobalt (III) perchlorate complexes

seems to be a logical way of eliminating the potentially ecologically problematic
anion. The effect of such replacement was studied by Ilyushin et al. using
dinitroguanidine which was considered suitable due to its ability to form
complexes, its enthalpy of formation, and its oxidizing ability [27].
N NO 2
H2N C
N NO 2
H

For comparison, Ilyushin et al. [27] selected complex cobalt(III) pentaaminate

perchlorates having temperature of decomposition in the range 265–280  C and
initiating efficiency around 0.2 g for RDX.
The preparation of the complex substance was achieved by dosing of an aqueous
solution of the relevant perchlorate complex to a stirred alcoholic solution of
dinitroguanidine at room temperature. Excess of dinitroguanidine was about
100 % compared with the theoretical. Over 30–40 min, the dinitroguanidine
complex precipitated from the reaction mixture with an almost quantitative yield
according to the following reaction scheme [27]:
N
N N NO2
Co(NH3)5 - C NO2 (ClO4)2 + 2 H2N C
N
N N NO2
H

N NH2
N
Co(NH3)5 - C NO2 C NNO2 + 2 HClO4
N
N NNO2
2

The following two complexes were prepared from other perchlorate analogs to
complement the one mentioned above:
O
N N NH2
N C NNO2
N
Co(NH3)5 - C NH2 NNO2
N 2
N

II

O
N N
N (N3)2
N
Co(NH3)5 - C NH2
N
N

III
9.3 Other Transition Metal-Based 5-Nitrotetrazolato-N2 Complexes 251

Table 9.10 Properties of pentaamine cobalt(III) complex dinitroguanidines [27]

Temperature at Initiating Experimental detonation
Calculated start of fast efficiency velocity (km s
1) at

3
Complex 
TMD (g cm ) decomposition ( C) (mg) density (g cm
3)
I 1.83 185 >500 6.42/1.736
II 1.98 200 480 6.50/1.38
III 1.95 165 >500 –

The temperature of the start of fast decomposition (DTA, 5  C min
1) decreases

by 80–100  C when the perchlorate anion is exchanged for dinitroguanidine or
azide. Unlike pentaamine (5-nitro-2H-tetrazolato-N2)cobalt(III) perchlorate
(NKT), which decomposes in one step, complex I decomposes in four steps when
heated by 5  C min
1. It also loses crystal water around 110  C.
All three complexes (I–III) listed in Table 9.10 are less sensitive to impact than
PETN. Theoretical detonation velocities of all three complexes at their TMD are
over 8 km s
1. From the experimental results, it seems that these complexes can be
dead pressed. The results in Table 9.10 clearly indicate that replacement of per-
chlorate by dinitroguanidine or azide leads to a product with insufficient thermal
stability and insufficient performance [27].

9.3 Other Transition Metal-Based 5-Nitrotetrazolato-N2

Complexes

Analogs of the previously mentioned 5-nitrotetrazolato-N2-ferrate type complexes

can be prepared using other transition metals including cobalt (Co2+), copper
(Cu2+), manganese (Mn2+), nickel (Ni2+), and zinc (Zn2+). Other types of cations
including alkaline metals, alkaline earth metals, aliphatic and catenated high-
nitrogen cations, and heterocyclic nitrogen cations have also been patented by
Huynh [54]. The same author also patented a number of complexes based on the
1,5-diamino tetrazole ligand [56].
Interesting complexes have been reported to form by reaction of Cu2+ ions
with bis(tetrazolyl)amine—(H2bta). Depending on the reaction conditions
three substances may form: CuðbtaÞðNH3 Þ2 , CuðbtaÞðNH3 Þ2  H2 O or ðNH4 Þ2 Cu
ðbtaÞ2  2:5 H2 O . These are all high nitrogen compounds but are surprisingly
reported as being insensitive to impact and friction [57].
252 9 Tetrazole Ring-Containing Complexes

References

1. Connelly, N.G., Damhus, T., Hartshorn, R.M., Hutton, A.T. (eds.): Red Book: Nomenclature of
Inorganic Chemistry: IUPAC Recommendations 2005. Royal Society of Chemistry Publishing,
Cambridge (2005)
2. Sinditskii, V.P., Fogelzang, A.E.: Energeticheskie materialy na osnove koordinacionnykh
soedinenii. Rossiiskii khimicheskii zhurnal XLI, 74–80 (1997)
3. Ilyushin, M.A., Tselinskii, I.V.: Iniciiruyushchie vzryvshchatye veshchestva Sostoyanie
i perspektivy. Rossiiskii khimicheskii zhurnal XLI, 3–13 (1997)
4. Lieberman, M.L.: Chemistry of (5-cyanotetrazolato-N2)pentaamminecobalt(III) perchlorate
and similar explosive coordination compounds. Ind. Eng. Chem. Prod. Res. Dev. 24,
436–440 (1985)
5. Massis, T.M., Morenus, P.K., Huskisson, D.H., Merrill, R.M.: Stability and compatibility
studies with the inorganic explosive 2-(5-cyanotetrazolato)pentaamminecobalt(III) perchlorate
(CP). J. Hazard. Mater. 5, 309–323 (1982)
6. Weese, R.K., Burnham, A.K., Fontes, A.T.: A study of the properties of CP: Coefficient of
thermal expansion, decomposition kinetics and reaction to spark, friction and impact.
Int. Annu. Conf. ICT 36, 37/1–37/12 (2005)
7. Graeber, E.J., Morosin, B.: Structures of pentaammine(5-cyanotetrazolato-N2)cobalt(llI) perchlo-
rate (CP), [Co(C2N5)(NH3)5](ClO4)2, and (5-amidinotetrazolato-N1, N5)tetraamminecobalt(III)
bromide (ATCB), [Co(C2H3N6)(NH3)4]Br2. Acta Crystallogr. C39, 567–570 (1983)
8. Balahura, R.J., Purcell, W.L., Victoriano, M.E., Lieberman, M.L., Loyola, V.M., Fleming, W.,
Fronabarger, J.W.: Preparation, characterization, and chromium(II) reduction kinetics of
tetrazole complexes of pentaamminecobalt (III). Inorg. Chem. 22, 3602–3608 (1983)
9. Geng, J., Lao, Y.: Electronic structure and thermal decomposition of high energy coordination
compound CP. In: Proceedings of 17th International Pyrotechnics Seminar, pp. 410–415,
Beijing, China, Oct 28-31, 1991
10. Geng, J., Lao, Y.: The electronic energy-state structure of new explosive 2-(5-cyanotetrazolato)
pentaamminecobalt(III) perchlorate. In: Proceedings of 16th International Pyrotechnics Seminar,
pp. 304–313, J€onk€oping, Sweden, June 24-28, 1991
11. Massis, T.M., Morenus, P.K., Huskisson, D.H., Merrill, R.M.: In: Barton, L.R. (ed.) Compatibility
of Plastics/Materials with Explosives Processing Explosives, pp. 105–119. Materials Process
Division, American Defense Preparedness Association, Washington, DC (1980)
12. Lieberman, M.L.: Bonfire-safe low-voltage detonator. US Patent 4,907,509, 1990
13. Lieberman, M.L., Fronabarger, J.W.: Status of the development of 2-(5-cyano-
2 H-tetrazolato) penta ammine cobalt (III) perchlorate for DDT devices. In: Proceedings of
7th International Pyrotechnic Seminar, pp. 322–355, Vail, Colorado, 1980
14. Arp, H.P.H., Decken, A., Passmore, J., Wood, D.J.: Preparation, characterization, X-ray
crystal structure, and energetics of cesium 5-cyano-1,2,3,4-tetrazolate: Cs[NCCNNNN].
Inorg. Chem. 39, 1840–1848 (2000)
15. Oliveri-Mandala, E., Passalacqua, T.: Azione dell’acido azotidrico sul cianogeno. Formazione
del ciano-tetrazolo. Gazzetta Chimica Italiana 41, II, 430–435 (1911)
16. Lifschitz, J.: Synthese der Pentazol-Verbindungen I. Berichte der deutschen chemischen
Gesellschaft 48, 410–420 (1915)
17. Benson, F.R.: The chemistry of the tetrazoles. Chem. Rev. 41, 1–61 (1947)
18. Matsuda, K., Morin, L.T.: Preparation and reactions of 1-cyanoformimidic acid hydrazide.
J. Org. Chem. 26, 3783–3787 (1961)
19. Morin, L.T., Matsuda, K.: Preparation of 5-cyanotetrazoles. US Patent 3,021,337, 1962
20. Lieberman, M.L., Villa, F.J., Marchi, D.L., Lause, A.L., Yates, D., Fronabarger, J.W.: Review
of low voltage detonators. In: Proceedings of 11th Symposium on Explosives and Pyrotechnics,
Philadelphia, 1981
References 253

21. Luebcke, P.E., Dickson, P.M., Field, J.E.: An experimental study of the deflagration-to-
detonation transition in granular secondary explosives. Proc. R. Soc. Lond. A Math. Phys.
Eng. Sci. 448, 439–448 (1995)
22. Lieberman, M.L.: Spark-safe low-voltage detonator. US Patent 4,858,529, 1989
23. Munger, A.C., Tibbitts, E.E., Neyer, B.T., Thomes, J.A., Knick, D.R., Demana, T.A.: Devel-
opment of a full qualified detonator for the Titan IV launch vehicle. In: Proceedings of 22nd
International Pyrotechnics Seminar, pp. 591–615, Fort Collins, CO, 1996
24. Fleming, W., Fronabarger, J.W., Lieberman, M.L., Loyola, V.M.: Synthesis and characteriza-
tion of 5-substituted tetrazolatopentaamminecobalt(III) perchlorates. In: Proceedings of 2nd
Chemical Congress of the North American Continent, Las Vegas, NV, 1980
25. Johnson, R., Fronabarger, J., Fleming, W., Lieberman, M., Loyola, V.: Synthesis and charac-
terization of 5-substituted tetrazolatopentaamminecobalt(III) perchlorates. In: Proceedings of
International Chemical Congress of Pacific Basin Societies, Honolulu, HI, 1984
26. Ilyushin, M.A., Tselinskii, I.V., Sudarikov, A.M.: Razrabotka komponentov vysokoenerge-
ticheskikh kompozicii. SPB:LGU im. A.S.Pushkina – SPBGTI(TU), Sankt Peterburg (2006)
27. Ilyushin, M.A., Sudarikov, A.M., Tselinskii, I.V.: Metallokompleksy v vysokoenergeti-
cheskikh kompoziciyakh. SPB:LGU im. A.S.Pushkina – SPBGTI(TU), Sankt Peterburg
(2010)
28. Ilyushin, M.A., Tselinskii, I.V., Chernai, A.V.: Svetochustvitelnye vzryvshchatye veshchectva
i sostavy i ich iniciirovanie lazernym monoimpulsom. Rossiiskii khimicheskii zhurnal XLI,
81–88 (1997)
29. Ilyushin, M.A., Tselinskii, I.V.: Ispolzovanie lazernogo iniciirovaniya energoemkikh
coedinenii v nauke i tekhnike (obzor). Zhurnal prikladnoi khimii 73, 1233–1239 (2000)
30. Ilyushin, M.A., Tselinskii, I.V., Bachurina, I.V., Novoselova, L.O., Konyushenko, E.N.,
Kozlov, A.S., Gruzdev, Y.A.: Application of energy saturated complex perchlorates.
In: Avrorin, E.N., Simonenko, V.A. (eds.) Proceedings of Zababakin Scientific Talks—
International Conference on High Energy Density Physics, vol. 849, Snezhinsk, Russia (2005)
31. Ilyushin, M.A., Bachurina, I.V., Smirnov, A.V., Tselinskii, I.V., Shugalei, I.V.: Study of
the interaction of polynitro compounds with transition metal complexes with
1,5-pentamethylenetetrazole as a ligand. Cent. Eur. J. Energetic Mater. 7, 33–46 (2010)
32. Bachurina, I.V., Ilyushin, M.A., Tselinskii, I.V., Gruzdev, Y.A.: High-energy complex copper
(II) perchlorate with 1,5-pentamethylenetetrasole as ligand. Russ. J. Appl. Chem. 80,
1643–1646 (2007)
33. Ilyushin, M.A., Gruzdev, Y.A., Bachurina, I.V., Smirnov, A.V., Tselinskii, I.V., Andreeva, Y.N.:
The compatibility of high explosives with energetic coordination complexes of cobalt(II).
In: Otis, J., Krupka, M. (eds.) Proceedings of New Trends in Research of Energetic Materials,
vol. 2, pp. 640–644. Univerzita Pardubice, Pardubice (2007)
34. Zhilin, A.Y., Ilyushin, M.A., Tselinskii, I.V., Nikitina, Y.A., Kozlov, A.S., Shugalei, I.V.:
Complex energetic perchlorates of cobalt(III) amminates, with cyclopentamethylenetetrazole
as ligand. Russ. J. Appl. Chem. 78, 188–192 (2005)
35. Kuska, H.A., Ditri, F.M., Popov, A.I.: Electron spin resonance of pentamethylenetetrazole
manganese(II) and copper(II) complexes. Inorg. Chem. 5, 1272–1277 (1966)
36. Bates, L.R.: The potential of tetrazoles in initiating explosives systems. In: Proceedings of 13th
Symposium on Explosives and Pyrotechnics, pp. III1–III10, Hyatt, Palmetto Dunes, Hilton
Head Island. South Carolina. December 2-4, 1986
37. Morosin, B., Dunn, G.R., Assink, R., Massis, T.M., Fronabarger, J., Duesler, E.N.: The
secondary explosive tetraamine-cis-bis(5 H-nitro-2 H-tetrazolato-N2)cobalt(III) perchlorate
at 293 and 213 K. Acta Crystallogr. C53, 1609–1611 (1997)
38. Fronabarger, J., Schuman, A., Chapman, R.D., Fleming, W., Sanborn, W.B., Massis, T.:
Chemistry and development of BNCP, a novel DDT explosive. In: Proceedings of 31st
AIAA 95-2858; Joint propulsion conference and exhibit, San Diego, CA, 1995
254 9 Tetrazole Ring-Containing Complexes

39. Ilyushin, M.A., Tselinskii, I.V., Zhilin, A.Y., Ugryumov, I.A., Smirnov, A.V., Kozlov, A.S.:
Coordination complexes as inorganic explosives for initiation systems. Hanneng Cailiao
(Energetic Materials) 12, 15–19 (2004)
40. Talawar, M.B., Agrawal, A.P., Asthana, S.N.: Energetic co-ordination compounds: Synthesis,
characterization and thermolysis studies on bis-(5-nitro-2H-tetrazolato-N2)tetraammine cobalt
(III) perchlorate (BNCP) and its new transition metal (Ni/Cu/Zn) perchlorate analogues.
J. Hazard. Mater. 120, 25–35 (2005)
41. Zeman, S.: Technologie základnı́ch výbušin. Univerzita Pardubice, Pardubice (2005)
42. Fronabarger, J.W., Sanborn, W.B., Massis, T.: Recent activities in the development of the
explosive-BNCP. In: Proceedings of 22nd International Pyrotechnics Seminar, pp. 645–652,
Fort Collins, Colorado USA, July 15-19, 1996
43. Merson, J.A., Salas, F.J., Harlan, J.G.: The development of laser ignited deflagration-to-
detonation transition (DDT) detonators and pyrotechnic actuators. In: Proceedings of 19th
International Pyrotechnics Seminar, pp. 191–206, Christchurch, NEW ZEALAND, Feb 21-25,
1994
44. Zhilin, A.Y., Ilyushin, M.A., Tselinskii, I.V., Kozlov, A.S., Lisker, I.S.: High energy capacity
cobalt (II) tetrazolates. Zhurnal prikladnoi khimii 76, 592–596 (2003)
45. Fyfe, D.W., Fronabarger, J., Brickes, R.W.: BNCP prototype detonator studies using a
semiconductor bridge initiator. In: Tulis, A.J. (ed.) International Pyrotechnics Seminar,
vol. 20, pp. 341–343. IIT Research Institute, Colorado Springs, CO (1994)
46. Schlessinger, G.: Inorganic Synthesis. McGraw-Hill, New York (1960)
47. Fronabarger, J., Schuman, A., Chapman, R.D., Fleming, W., Sanborn, W.B., Massis, T.:
Chemistry and development of BNCP, a novel DDT explosive. In: Proceedings of Interna-
tional Symposium on Energetic Materials Technology, ADPA Meeting #450, pp. 254–258,
Orlando, FL, 1994
48. Hirlinger, J.M., Bichay, M.: New Primary Explosives Development for Medium Caliber Stab
Detonators. Report SERDP PP-1364. US Army ARDEC, Washington, DC (2004)
49. Hirlinger, J.M.: Ivestigating Alternative ‘GREEN’ Primary Explosives In: Proceedings of
NDIA 39th Annual Gun & Ammunition Missiles & Rockets Conference & Exhibition;
Presentation, Baltimore, USA, 2004
50. Hirlinger, J., Fronabarger, J., Williams, M., Armstrong, K., Cramer, R.J.: Lead azide replace-
ment program. In: Proceedings of 49th Annual Fuze Conference. National Defense Industrial
Association (NDIA), Seattle, WA (2005)
51. Hirlinger, J.: Investigating alternative “green” primary explosives. In: Proceedings of 39th
Annual Gun & Ammunition Conference, Baltimore, MD, 2004
52. Fogelzang, A.E., Sinditskii, V.P., Egorshev, V.Y., Serushkin, V.V.: Effect of structure of
energetic materials on burning rate. In: Brill, T.B., Russel, T.P., Tao, W.C., Wardle, R.B. (eds.)
Proceedings of Material Research Society Symposia, vol. 418, pp. 151–161. Materials
Research Society, Boston, MA (1995)
53. Huynh, M.H.V., Coburn, M.D., Meyer, T.J., Wetzer, M.: Green primaries: Environmentally
friendly energetic complexes. Proc. Natl. Acad. Sci. 103, 5409–5412 (2006)
54. Huynh, M.H.V.: Lead-free primary explosives. Patent WO2008054538, 2008
55. Huynh, M.H.V., Coburn, M.D., Meyer, T.J., Wetzer, M.: Green primary explosives:
5-nitrotetrazolato-N2-ferrate hierarchies. Proc. Natl. Acad. Sci. 103, 10322–10327 (2006)
56. Huynh, M.H.V.: Explosive complexes. US Patent 20080200688A1, 2008
57. Friedrich, M., Gavez-Ruiz, J.C., Klap€ otke, T.M., Mayer, P.: BTA copper complexes.
Inorg. Chem. 44, 8044–8052 (2005)
Chapter 10
Organic Peroxides

10.1 Peroxides of Acetone

The reaction of acetone with hydrogen peroxide gives various types of organic
peroxides of acetone. The simple linear hydroperoxides and hydroxyperoxides
form at first and then condense to the linear dimer and trimer analogs. The linear
dihydroperoxide 2,2-dihydroperoxypropane (I) and its dimer bis(2-hydroperox-
ypropane)peroxide (II) form as a main product in an acetone and hydrogen peroxide
mixture, in the absence of an acidic catalyst [1].
CH3 CH3 CH3

HOO C OOH HOO C O O C OOH

CH3 CH3 CH3

I II

Depending on the reaction conditions—primarily pH, concentration of reagents—

the cyclic dimer, trimer form from their linear analogs. Cyclic dimer and trimer
crystallize from the reaction mixture when catalyzed by an acid. The reaction
mechanisms of cyclic peroxide formation have been investigated by several authors
and are schematically summarized below [1–7].

R. Matyáš and J. Pachman, Primary Explosives, 255

DOI 10.1007/978-3-642-28436-6_10, # Springer-Verlag Berlin Heidelberg 2013
256 10 Organic Peroxides

CH3
H3C
C O + H O HO C OOH
2 2
H3C
CH3
H3C H2O2 / -H2O
C O
H3C

CH3 CH3 CH3

HO C OO C OH HOO C OOH
CH3 CH3 CH3

CH3

HO C OOH / - H 2 O
H 2 O 2 / -H 2 O H3 C
C O CH3
H3 C

CH3 CH3 CH3 CH3

H3C O O CH3 H 2 O 2 / -H 2 O
C C HO C OO C OOH HOO C OO C OOH
+
H / -H 2 O
H3C O O CH3 CH3 CH3 CH3 CH3
DADP
H3 C H3 C
C O C O
H3 C H3 C
H3C CH3
CH3 CH3 CH3 CH3 CH3 CH3 C
H2O 2 / - H2O + O O
H / -H 2 O
HO C OO C OO C OH HO C OO C OO C OOH O O
CH3 CH3 CH3 CH3 CH3 CH3 H3C C C CH3
H3C O O CH3
TATP

The reaction conditions for the preparation of dimer and trimer peroxides are
quite similar. This may seem a little confusing, as the same reactants and catalysts
are used for preparation of TATP as well as for DADP. The issue of particular
reaction conditions leading to dimer and trimer remains without a clear explanation.
We found that the key factor governing the composition of the final product (which
is either DADP, TATP, or a mixture of both) is the acidity of the reaction mixture.
The trimer forms in a slightly or moderately acidic solution while the dimer (or
mixture of both) forms in a highly acidic environment [8].
The formation of higher linear peroxides (oligoperoxides) of acetone as
by-products in the preparation of the trimer has recently been published. Sigman
et al. proved the presence of peroxides terminated by n hydroperoxygroups where
n ¼ 1–8. These peroxides have low thermal stability and convert into the trimer
upon heating [9, 10].

CH3 CH3

HOO C O O C OOH
n=1-8
CH3 CH3

Linear peroxides of acetone have never been used as primary explosives and
therefore we have decided to focus exclusively on cyclic organic peroxides in the
following sections.

10.1.1 Diacetone Diperoxide

H3C O O CH3
C C
H3C O O CH3
10.1 Peroxides of Acetone 257

Diacetone diperoxide (3,3,6,6-tetramethyl-1,2,4,5-tetroxane; DADP) was first

synthesized by Baeyer and Villiger in 1899 by the reaction of acetone with “Caro’s”
reagent (H2SO5, prepared by rubbing potassium persulfate with concentrated sul-
furic acid and then adding potassium sulfate) [11]. This substance showed similar
properties (identical elemental analysis, similar solubility and explosiveness) as
already 4 years known “Wollfenstein’s superoxide” (TATP) but melted at a signifi-
cantly higher temperature (132–133  C vs. 90–94  C for TATP). Baeyer and
Villiger have therefore continued their research and, based on the results of
cryoscopic measurements, concluded that this substance is a dimer [12].

10.1.1.1 Physical and Chemical Properties

The molecule of diacetone diperoxide exhibits chain conformation in the solid state
(see Fig. 10.1) [13, 14]. These conformers are bonded by intermolecular hydrogen
bonds which result in the formation of layers of molecules as shown in Fig. 10.2.
This picture further clearly shows that all of the oxygen atoms of DADP are
involved in hydrogen bond bridges [13].
Diacetone diperoxide forms colorless crystals (see Fig. 10.3) with crystal density
1.33 g cm3 (X-ray) [13, 14] and melting point published mostly in the range
130–132  C [11, 15–18].
DADP is a very volatile substance; vapor pressure of DADP is 17.7 Pa at 25  C
(determined by gas chromatography). The Clapeyron equation, which describes
dependence of vapor pressure (P in Pa) on temperature (T in K), is:

ln P ¼ 35:9  9; 845:1=T

DADP is a more volatile substance than TATP [19]. Its vapor pressure is,
according to Oxley, about 2.6 times higher than that of TATP at the same
temperature. The reason is most likely due to a lower molecular weight. The
heat of sublimation of DADP is 81.9 kJ mol1 (calculated from the Clapeyron
equation) [20].
Egorshev et al. [19] described the dependence of the vapor pressure (P in atm) on
temperature (T in K) by the following equations:

ln P ¼ 20:82  8; 569:1=T ðfor temperature range 67  120  CÞ

ln P ¼ 13:5  5; 600=T ðDADP in liquid state  above 120  CÞ

Heat of sublimation, evaporation, and melting for DADP are 71.3 kJ mol1,
46.5 kJ mol1, and 24.7 kJ mol1 respectively. These values were determined from
the above-mentioned equations by Egorshev et al. [19].
DADP is soluble in most organic solvents and practically insoluble in water and
dilute acids and bases. DADP does not react with water even when boiling. It shows
very good compatibility with metals [17, 18] and only slowly decomposes by the
action of a solution of zinc sulfate or cupric chloride in combination with metallic
258 10 Organic Peroxides

Fig. 10.1 3D structure of the

DADP molecule [13].
Reprinted with permission C3´ C2
from Dubnikova et al.,
01
Decomposition of TATP Is an
Entropic Explosion, J. Am.
Chem. Soc. 2005, 127, 02
1146–1159. Copyright (2005) C1
American Chemical Society C1´
02´

01´
C2´ C3

Fig. 10.2 Hydrogen-bonded

network via C(sp3)H···O
bridges in the plane [13].
Reprinted with permission
from Dubnikova et al.,
Decomposition of TATP Is an
Entropic Explosion, J. Am.
Chem. Soc. 2005, 127,
1146–1159. Copyright (2005)
American Chemical Society

zinc or copper at room temperature within several hours [21]. In solutions, DADP
slowly decomposes on heating. Cafferata et al. studied thermal decomposition of
DADP in benzene in the temperature range 135.5–165  C. Acetone, oxygen, and
toluene are major decomposition products; methyl isopropyl ether, methyl acetate,
bibenzyl, methanol, methane, ethane, and carbon dioxide are minor products. The
authors also proposed a chemical mechanism for thermolysis [22].

10.1.1.2 Explosive Parameters

The impact sensitivity of DADP reported in Fedoroff, Shefield, and Kaye’s

encyclopedia is 7 cm for 2 kg hammer [17]; the Zhukov encyclopedia reported
lower sensitivity than lead azide [18]. Egorshev et al. measured the impact
10.1 Peroxides of Acetone 259

Fig. 10.3 DADP crystals

sensitivity of DADP and TATP and compared it with tetrazene (GNGT). Results
are summarized in Table 10.1. DADP is almost two times less sensitive than
TATP, and the sensitivity of GNGT is in-between the sensitivity of TATP and
DADP [19].
The friction sensitivity of DADP is according to own results about the same
as the sensitivity of TATP and slightly lower than LS (see Fig. 2.19) [23].
Sensitivity of DADP to electrostatic discharge was measured and found to be
lower than that for its trimer analog and other common primary explosives (see
Fig. 2.21) [24].
Ignition of small amounts of DADP by flame produces high flames similar
to those produced by combustion of nitrocellulose. In comparison to the
trimer, combustion is slower and less violent without any sound effect and
producing a bit more soot. The dependence of burning rate of DADP and
TATP on pressure has recently been studied by Egorshev et al. (see Fig. 10.4).
The burning rate increases proportionally with pressure for both peroxides to
reach about 1 cm s1 at atmospheric pressure for TATP and 0.2 cm per second
for DADP. Diperoxide burns approximately five times slower than TATP. The
flame temperature of TATP exceeds that of DADP [19].
Brisance of DADP determined by the sand test is 30.1 g (0.4 g of peroxide
initiated by 0.2 g mercury fulminate) which corresponds to 63 % TNT [17]. The
initiation efficiency of DADP reported by Zhukov encyclopedia is between MF
and LA [18]. This however disproved by Egorshev et al. [19] who tested DADP
samples from 0.1 to 0.5 g pressed at 30 MPa with RDX as secondary charge in a
blasting cap tube. Even 0.5 g DADP was not able to induce detonation of RDX,
unlike TATP which caused full detonation of RDX in an amount of 0.1 g in the
same conditions [19].
260 10 Organic Peroxides

Table 10.1 Sensitivity of h50 E50

DADP, TATP and GNGT to (cm) (J)a
impact (measured on Russian
K-44-1 impact machine for DADP 21.2  1.5 0.42
primary explosives; h50; 200 g GNGT 16  2 0.31
weight; 12 mg pressed TATP 11.7  0.8 0.23
a
sample) [19] Drop height converted to drop energy.

500
300
200

100
Burning rate (mm.s-1)

50
30
20

10

5
TATP
3 DADP
2

1
0.01 0.02 0.05 0.1 0.2 0.5 1 2 5 10 20
Pressure (MPa)

Fig. 10.4 Dependence of burning rate of TATP and DADP on various ambient pressures [19]

10.1.1.3 Preparation

DADP may be prepared in several different ways. The most common one is the
reaction of acetone with hydrogen peroxide using acid catalysis. This may be
carried out either in an aqueous or in a nonaqueous environment. A method suitable
for relatively easy preparation of smaller scale laboratory samples is based on the
transformation of TATP to DADP. It is further possible to prepare DADP by
ozonolysis which is, however, not very practical.
The most common way of preparing DADP, by the reaction of acetone with
hydrogen peroxide using acid catalysis, may be summed up by the following
simplified equation:
H3C H3C O O CH3
catalyst
C O + H2O2 C C
H3C H3C O O CH3
DADP

TATP forms by a similar reaction. As mentioned previously, our investigations

have led us believe that the most important factor affecting the composition of the
10.1 Peroxides of Acetone 261

product is the acidity of the reaction mixture. DADP forms in a highly acidic
environment while TATP forms in less acidic conditions. The high concentrations
and amounts of the acid catalyst necessary for the formation of DADP may however
lead to decomposition of the reaction mixture. The reaction mixture was observed
to change color locally to light yellow just before runaway occurs [8].
The preparation of DADP in an aqueous environment in the presence of large
amounts of sulfuric acid as catalyst has been published by Bayer and Villager,
Phillips and Pastureau [17, 25, 26] and in presence of other mineral acids by us [8].
Preparation in a nonaqueous environment has been reported from acetonitrile [2, 22,
27, 28], ether [11], dichloromethane [13], or acetic anhydride [29]. Other catalysts
including Caro’s acid [11] and methanesulfonic acid [13] have also been reported.
It was observed that TATP spontaneously transforms to DADP in an acidic
environment both in solution and solid state, while acid-free TATP (purified by
recrystallization) does not transform. Pure DADP can be prepared by the reaction of
TATP with p-toluenesulfonic acid or trifluoroacetic acid in a dichloromethane
solution for several hours or days. In these conditions, TATP transforms completely
into DADP [13, 30].
H3C CH3
C
O O
O O H
+ H3C O O CH3
C C
H3C C C CH3 H3C O O CH3
O O CH3
H3C
TATP DADP

In our investigations, we have found that raw TATP also spontaneously

transforms to DADP in solid state if certain types of catalyst (such as sulfuric,
perchloric, or methanesulfonic acids) are used. Acid probably remains closed in the
crystal lattice of raw TATP and causes the transformation. The rate of transformation
depends on temperature and on the reaction conditions used during the preparation of
TATP. The rate of transformation increases with increasing temperature and is higher
for TATP samples where the catalyst content during preparation was higher [31, 32].
Cyclic organic peroxides (including DADP) further form by ozonolysis of
alkenes. Ozonide forms at first and cyclic organic peroxide is the final product of
these reactions which typically yields many by-products [15, 16, 33–36].

10.1.1.4 Uses

DADP has been proposed for only a small number of applications: in the explosives
industry as a substitute for mercury fulminate in detonators and igniters [17], in the
petrochemical industry as an additive for Diesel fuels [37] and in the polymer
industry as a polymerization initiator for methyl methacrylate [27]. It has, however,
never been used practically [38] due to its low physical stability.
262 10 Organic Peroxides

10.1.2 Triacetone Triperoxide

H3C CH3
C
O O
O O
H3C C C CH3
H3C O O CH3

Triacetone triperoxide (3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxonane; TATP)

was first synthesized by Richard Wolffenstein in 1895 [39]. He discovered the
compound accidentally while working on his thesis called “Effects of hydrogen
peroxide treatment on alkaloids” [40]. During his investigation of the effects of
hydrogen peroxide treatment on coniine alkaloid, Wolffenstein used acetone as a
solvent (as the author puts it, he used acetone because of its indifference toward
hydrogen peroxide). However, in this particular case, instead of the 1 % solution of
hydrogen peroxide that had been previously used, he used a higher concentration
(10 %). After letting the solution stand for several days, crystals of a new, so far
undiscovered, compound were formed, and Wolffenstein carried out an analysis of
this new compound. He successfully identified the compound on the basis of elemen-
tal analysis and cryoscopic determination of its molecular weight. He described its
physical properties and recognized it as an explosive compound. During his
subsequent experiments, he increased the yields of TATP by adding phosphoric
acid to the hydrogen peroxide and acetone reaction mixture. His method, i.e., reaction
of acetone with hydrogen peroxide in an acidic medium, is still a common method for
obtaining TATP [39].
The nine-membered ring of the TATP molecule forms a “twist boat chair”
conformation (Fig. 10.5). The crystal packing (Fig. 10.6) consists of stacks around
the molecular threefold axis with no apparent CH···O interactions [13]. Theoretical
studies of other possible conformations have been published by Yavari et al. [41].

10.1.2.1 Physical and Chemical Properties

Triacetone triperoxide forms colorless crystals which appear white when finely
ground (Fig. 10.7). Its crystal density is 1.272 g cm3 (X-ray) [13, 42]; melting
point is reported in the range 95–98.8  C and decomposition above 150–160  C
[17, 39, 43–46]. The heat of formation of TATP is 90.8 kJ mol1 [47]. Triacetone
triperoxide is nonhygroscopic and very volatile [17].
It spontaneously recrystallizes at room or even at subambient temperatures
(0  C) into nicely formed cubes as can be seen in Fig. 10.8. The detail of the
surface of the crystal during recrystallization is presented in Fig. 10.9. The storage
temperature and the type of acid used for TATP preparation both have significant
impacts on the rate of TATP recrystallization. The process is much faster for TATP
10.1 Peroxides of Acetone 263

Fig. 10.5 3D structure of

TATP molecule [13].
Reprinted with permission
from Dubnikova et al.,
Decomposition of TATP Is an
Entropic Explosion, J. Am.
Chem. Soc. 2005, 127,
1146–1159. Copyright (2005)
American Chemical Society

Fig. 10.6 Packing of TATP as capped-stick model along the crystallographic screw axis in a
perpendicular view [13]. Reprinted with permission from Dubnikova et al., Decomposition of
TATP Is an Entropic Explosion, J. Am. Chem. Soc. 2005, 127, 1146–1159. Copyright (2005)
American Chemical Society

prepared using sulfuric or perchloric acid than it is if hydrochloric or nitric acid is

used. Increased temperature speeds up the recrystallization in general.
The type of acid used during TATP preparation has a significant impact on its
long-term stability. TATP prepared using sulfuric or perchloric acid decomposes
and lose weight more quickly than pure TATP (by recrystallization). The loss of
weight of TATP prepared using hydrochloric or nitric acid is much slower and
about the same as observed for pure TATP and is related to sublimation rather than
decomposition [48].
Reany et al. recently published that TATP forms at least six different polymorphic
crystals. The type of acid used as a catalyst for TATP preparation and the solvent used
for TATP crystallization have an impact on the crystal morphology of the product.
264 10 Organic Peroxides

Fig. 10.7 Spontaneous recrystallization of powdery TATP at room temperature (after 1 month)

Fig. 10.8 Same sample of TATP crystals left—as prepared, center—2 weeks and right—2 months
at room temperature

Fig. 10.9 Detail of surface of TATP crystals (2 months old sample)

10.1 Peroxides of Acetone 265

Three different crystal forms are present in raw TATP: needles, prisms, and plates. X-
ray crystallography revealed that these three forms represent three different
polymorphs: needles form monoclinic, prisms form orthorhombic, and plates form
triclinic crystal systems. Strong acids (sulfuric, nitric, and hydrochloric) produce a
mixture of polymorphs where the major one is needle crystals while weak acids (acetic,
citric) produce a mixture of needles and plates. Another three polymorphs (all are
monoclinic) form by crystallization from various organic solvents [30].
The vapor pressure of TATP has recently been determined by Oxley et al. by gas
chromatography. The vapor pressure is 6.95 Pa [49] or 7.87 Pa [20] at 25  C which
is about 104 times higher than TNT. The Clapeyron equation which describes
dependence of vapor pressure (P in Pa) on temperature (T in K) is:

ln P ¼ 31:4  8; 719:9=T

The heat of sublimation of TATP is 72.5 kJ mol1 (calculated from the

Clapeyron equation) [20].
Egorshev et al. [19] described dependence of vapor pressure (P in atm) on
temperature by the following equations:

ln P ¼ 22:73  9; 695:5=T ðfor temperature range 12  97  CÞ

ln P ¼ 15:29  6; 978:8=T ðtemperature above
melting point, TATP in liquid stateÞ

Heat of sublimation, evaporation, and melting of TATP are 80.6 kJ mol1,

58.1 kJ mol1, and 22.6 kJ mol1 respectively. These values were determined
from the above-mentioned equations by Egorshev et al. [19].
TATP does not react with water (even when boiling) nor with common
metals (except a slight reaction with lead) [50]. It is practically insoluble in
water and aqueous ammonia but soluble in most organic solvents (see
Table 10.2) [17, 43, 50, 51].
TATP does not decompose by action of diluted bases and its decomposition by
diluted, but strong, inorganic acids proceeds to completion only at higher
temperatures. Concentrated hydroiodic acid causes it to decompose violently with-
out flames [18, 52] however in contact with concentrated sulfuric acid it ignites.
TATP also slowly decomposes by the action of concentrated hydrochloric acid and
35 % sulfuric acid. The chemistry of decomposition by the action of these acids has
been studied by Armitt et al. [53]. TATP decomposes both on exposure to
acid vapors and suspended in liquid acid. Acetone, DADP, chloroacetone, and
1,1-dichloroacetone are the major products of decomposition by hydrochloric
acid in the vapor phase. As the decomposition progresses, DADP decomposes
and other poly-chlorinated acetones form (as far as hexachloroacetone). When
the decomposition took place in liquid hydrochloric acid the main product
was 1,1-dichloroacetone and poly-chlorinated acetones were only minor products.
Sulfuric acid causes TATP to decompose to DADP and acetone, and DADP
266 10 Organic Peroxides

Table 10.2 Solubility of TATP in organic solvents

Solubility (g/100 ml solvent)
At 17  Ca At room temperature
Solvent [50] [43]
Acetone 7.96 16.5
Benzene 19.3 –
Carbon disulfide 11.2 –
Carbon tetrachloride 52.5 –
Chloroform 110 111
Diethylether 4.2 –
Ethanol 0.12 3.5
Hexane – 11.1
Methanol – 3.8
Pyridine 17.9 –
Toluene – 34.7
a
Units unspecified; assumed to be wt.% in reference; converted to g per 100 ml of solvent in this table.

gradually decomposes to acetone in its turn. Degradation of TATP occurs at a faster

rate in liquid acid than by the action of acid vapors [53].
TATP also slowly decomposes by boiling in methanol solutions in presence of
stannous chloride. Combustion of a toluene solution of TATP was proposed by
Bellamy as a suitable method for disposal [43]. Extensive study of TATP decom-
position by the action of chemical agents has recently been published by Oxley
et al. [21]. They observed that TATP best decomposes by application of a solution
of zinc sulfate or cupric chloride. The process takes only several hours at room
temperature if these salts are used in combination with metallic zinc or copper.
The chemical destruction of larger amounts of dry TATP is however hazardous
and not recommended, as it is exothermic. The heat liberated during decomposition
could possibly ignite any remaining TATP [21, 52].
Stability of TATP in solutions in organic solvents is affected by residual acidity
in TATP crystals (comes from synthesis). Pure (recrystallized) TATP without
residual acids is relatively stable similar to TATP prepared from hydrochloric
acid. In contrast TATP from sulfuric and perchloric acid relatively quickly
decomposes. The extensive study focused on problems with stability of TATP
solutions (aimed primarily on forensic labs) has been published recently [54].
The formation of TATP complexes with metal ions has been experimentally
studied in the gas phase. Two groups of structures were proposed based on the
theoretical calculations. The first, cyclic, is similar to crown ethers and the second,
is formed by three fragments of TATP bonded to a cation [55, 56]. In the complexes
of the first group, the cation (Cu+, Li+, Na+, K+, Cd2+, Zn2+, and In3+) is centered in
and slightly above the binding cavity and is equidistant from the oxygen atoms of
TATP (see Fig. 10.10), probably due to steric effects related to the size of cations
and the cavity. The bonding energies decrease with increasing ionic radii and their
values are similar to the values for 18-crown-6 ether complexes with corresponding
cations [56]. This approach of complex formation is often used in the mass
spectrometry of TATP. Addition of alkali metals (or small ions, such as NH4+) to
10.1 Peroxides of Acetone 267

Cring

u
lon
b

Fig. 10.10 The lowest-energy geometry for the ion–TATP complex [56]. Reprinted with permis-
sion from F. Dubnikova et al., Novel Approach to the Detection of Triacetone Triperoxide
(TATP): Its Structure and Its Complexes with Ions, The Journal of Physical, J. Phys. Chem. A
2002, 106, 4951–4956. Copyright (2002) American Chemical Society

the spray solution or mobile phase and subsequent molecular adduct formation in
the gas phase can be used to improve the selectivity and sensitivity of TATP
detection during the mass spectrometric analysis [55].
Structure of the complexes of the second group is quite different. They are
formed by three fragments of TATP (breaking of the three CO bonds in the TATP
molecule) and metal cation with bond OOmetal (complex of TATP with Sb3+,
Sc3+ and Ti4), see Fig. 10.11 [56].

10.1.2.2 Thermal Stability

The thermal decomposition of recrystallized TATP identified as the onset of the

DSC curve begins above 160  C (10  C min1, sealed pan) [43].
Thermal stability of raw TATP (but well washed to neutral pH) depends markedly
on the type (Fig. 10.12) and amount (Fig. 10.13) of acid used as the catalyst used in its
preparation. The decomposition of TATP begins around 145  C when hydrochloric
or nitric acid is used. The amount of catalyst in this case does not have a meas-
urable influence on the thermal stability of prepared TATP (acid to acetone molar ratio
nc/na from 2.5  104 to 5  101). A significant influence was however found
when using sulfuric or perchloric acid. A low concentration of these two acids
(nc/na  1  102) yields product that decomposes above 145  C just as in the
case of pure TATP. Higher concentrations however yield TATP that decomposes
during melting, or even before that, in the solid phase (Fig. 10.13, Table 10.3). It is
presumed that the lower thermal stability is a result of a combination of two
factors—overall residual acidity within the TATP crystals and acid strength [57].

10.1.2.3 Explosive Properties

Impact sensitivity of TATP is reported by various authors with very wide ranges.
Some authors have reported sensitivity of TATP as very high [58] or even as one
of the most sensitive explosives known [59]. This is however a bit exaggerated.
268 10 Organic Peroxides

Fig. 10.11 Top view (left) and side view (right) of the lowest-energy geometry for the Sb3+–TATP
complex [56]. Reprinted with permission from F. Dubnikova et al., Novel Approach to the Detection
of Triacetone Triperoxide (TATP): Its Structure and Its Complexes with Ions, The Journal of
Physical, J. Phys. Chem. A 2002, 106, 4951–4956. Copyright (2002) American Chemical Society

Fig. 10.12 DTA thermograms of TATP prepared using inorganic acids (nc/na ¼ 2.5  101 for
all acids) as catalyst and pure TATP (heating rate 5  C min1, 30 mg samples and static air
atmosphere) [57]

Our own experimental data clearly indicate that TATP is much less sensitive. The
reasons why such a large scatter is reported in the literature is not clear, but may
relate to one or more of the following (a) tendency of TATP to recrystallize forming
large crystals, (b) spontaneous transformation of TATP to other peroxides, (c) the
type of acid used in preparation, (d) crystal size, or (e) experimental setup. Most of
the authors who measured the sensitivity of TATP generally did not fully describe
the measured samples in terms of shape, size, age, storage temperature, and
preparation route. Published values of impact sensitivity are summarized in
Fig. 2.15 irrespective of the previously mentioned incomplete description.
The impact sensitivity of pure TATP and its mixtures with other substances has
been studied by Mavrodi [60]. His results are summarized in Table 10.4.
10.1 Peroxides of Acetone 269

Fig. 10.13 DTA thermograms of TATP demonstrating the influence of the concentration of
sulfuric acid in reaction mixture—nc/na on the thermal stability of resulting product (heating
rate 5  C min1, 30 mg samples and static air atmosphere) [57]

Table 10.3 The dependence of the onset of decomposition of TATP (prepared using various
inorganic acids as catalyst) on acetone to acid molar ratio nc/na (heating rate 5  C min1) [57]
Molar ratio
nc/na Sulfuric acid Perchloric acid Hydrochloric acid Nitric acid
5  101 Decomposition Decomposition Decomposition Decomposition
2.5  101 starts before starts before starts above starts above
melting melting 145  C 145  C

1  101 Decomposition
5  102 during melting Decomposition
2.5  102 during melting

1  102 Decomposition Decomposition

5  103 starts above starts above
2.5  103 145  C 145  C
2.5  104

Extremely high friction sensitivity reported in Meyer’s encyclopedia (TATP 10

more sensitive than LA and 50 more sensitive than MF [58]) seems quite
exaggerated. Our measurements are shown along with Meyer’s data in Fig. 2.19.
Friction sensitivity of TATP is based on our experience comparable to other common
primary explosives; it is between LA and MF (see Fig. 2.19) [23, 48, 61]. Neither type
of acid used for preparation of TATP nor aging have significant influence on its
sensitivity [48].
Comparison of sensitivity to electric discharge with other primary explosives is
presented in Fig. 2.21. Yeager tested pure TATP and found that E50 is 160 mJ
(325 mJ for PETN). When calculating the probability of initiation at lower energies
he found that it is statistically possible to initiate TATP at an energy level that can
be generated by the human body in approximately 1–2 % of cases. Further, he found
that unpurified samples are more sensitive than pure recrystallized ones [62].
270 10 Organic Peroxides

Table 10.4 Sensitivity of TATP, TATP mixtures, and reference explosives [60]
Impact energy Drop height 2 kg weight
(J) (cm)
TATP (fine powder) 3.1 16
TATP (small crystals) 2.4 12
TATP þ 20 % glass rubble 1.0 5
TATP þ 20 % glass rubble and KClO3 0.49 2.5
TATP þ 8–10 % oil 4.3–5.5 22–28
TNT þ 7 % TATP 18–19 90–95
Mercury fulminate 0.6 3
Black powder 13 65
Dynamite (75 %) 1.3 6.5
TNT 35 180

Table 10.5 Detonation Density Detonation velocity

velocity for TATP (g cm3) (m s1) References
0.47 1,430 [64, 65]
0.68 3,065 [66]
0.92 3,750 [47]
0.95 3,950 [47]
1.18 5,300 [47]

Analysis of detonation products has been carried out by Muraour who found the
following gases: carbon dioxide, carbon monoxide, methane, ethane, some higher
alkines, hydrogen, and water vapor [47]. Our own experiments led us to believe that
at least ethylene is also present.
In small quantities TATP burns quickly after being lit by an open flame (in
similar way as dry nitrocellulose); in larger quantities or when sealed it explodes.
The dependence of combustion rate on ambient pressure has been measured by
Fogelzang et al. [63] and recently by Egorshev et al. [19].
Some values of detonation velocities for TATP for different densities are
summarized in Table 10.5.
TATP belongs to the group of highly brisant primary explosives, being superior
to both mercury fulminate and lead azide [51]:
• Brisance by send test: 71 % TNT [17]; 46.2–50.5 % TNT (LA 29 %, MF 33 %) [51]
• Plate dent test: depth 3.65 mm—TATP (r ¼ 1.26 g cm3), 5.9 mm RDX
(r ¼ 1.4 g cm3) and 5.43 mm TNT (r ¼ 1.3 g cm3) [67]
• Lead block test: TATP 250 cm3 (88 % TNT) [17, 58, 66]; TATP 320 cm3 (101 %
TNT), TNT with 5 % TATP 370 cm3 (116 % TNT) [60]
The initiation efficiency of TATP is high (but lower than LA [38]): 0.05 g of
TATP initiates PETN (both pressed under 25 MPa) [66], 0.09 g initiates tetryl [68]
and 0.16 g [47] or 0.18 g [51, 68] initiates TNT. The comparison with other primary
explosives is given in Fig. 2.2. TATP is susceptible to dead pressing. According to
Rohrlich and Sauermilch, TATP can be dead pressed at 49 MPa [66].
10.1 Peroxides of Acetone 271

The explosive properties (detonation velocity, brisance, power) of mixtures of

TATP with ammonium nitrate are at the level of common industrial explosives
[69, 70]. These mixtures are however highly sensitive to mechanical stimuli;
according to our study some of them are more sensitive to impact than pure
dry TATP.

10.1.2.4 Preparation

The most commonly employed way of TATP preparation is based on the reaction
of acetone with hydrogen peroxide in the presence of an acid catalyst [17, 24, 39,
46, 51, 71]:
H3C CH3
C
H3C + O O
H
C O + H2O2 O O
H3C
H3C C C CH3
H3C O O CH3
TATP

The issue of reaction conditions was addressed above in a previous chapter

(DADP) but to summarize it, TATP forms at lower molar ratios of catalyst to
acetone and with lower concentrations of catalyst [8]. The formation of chlorinated
TATP (3-(chloromethyl)-3,6,6,9,9-pentamethyl-1,2,4,5,7,8-hexoxonane and 3,6-
bis(chloromethyl)-3,6,9,9-tetramethyl-1,2,4,5,7,8-hexoxonane) was recently published
by Matyáš et al. when hydrochloric acid is used as a catalyst in very large excess. Other
hydrohalic acids do not provide similar halogenated cyclic peroxides by this method;
TATP forms as a product of the following reaction [72].
O
+ H2O2

HBr
HF HCl

O O O O O O O O
O O O O O O
+
O O
O O O O O O

CH2Cl CH2Cl

O O O O
+ O O + O O

O O ClH2C O O
272 10 Organic Peroxides

TATP always contains small amount of side products which is reported to be either
a tetramer—TeATeP (3,3,6,6,9,9,12,12-octamethyl-1,2,4,5,7,8,10,11-octaoxacyclo-
dodecane) [73, 74] or a structural conformer of TATP [75] showing up as a small
peak accompanying the main TATP peak in chromatographic studies. This substance
may not be eliminated by recrystallization or resublimation (Matyáš and Pachman
Unpublished).
Some other less common catalysts are reported for preparation of TATP such as
oxone (2KHSO5·KHSO4·K2SO4) [76].
The synthesis of TATP in a mixture of acetone and hydrogen peroxide can also
be catalyzed by some metals. For example, titania-incorporated mesoporous mate-
rial leads to TATP formation in acid-free conditions [77].
Just as with DADP, it is possible to obtain TATP by ozonolysis of alkenes. The
final product is however not pure as it contains a variety of side products including
DADP [16, 33, 35, 44].
TATP also forms by spontaneous transformation of bis(2-hydroperoxypropan-
2-yl)ether over several days. Peroxides containing an ether group rearrange sponta-
neously, whereas peroxides containing peroxy groups do so only in the presence of
strong acids [78].
CH3 CH3

HOO C O C OOH H3C CH3

CH3 CH3 C
O O
O O

CH3 CH3 H 3C C C CH3

+
H H3C O O CH3
HOO C O O C OOH

CH3 CH3 TATP

TATP easily sublimates and may therefore be purified by this method. Unlike
the spontaneously recrystallized product (see Figs. 10.7 and 10.8), the resublimated
one forms beautiful snow white structures resembling tree branches (see Fig. 10.14)
(Matyáš and Pachman Unpublished).
Unfortunately, TATP is formed by the action of atmospheric oxygen on
diisopropylether. Many explosions have been known to occur during handling or
processing (especially distillation) of old diisopropylether due to the formation of
TATP [45, 79, 80].
H3C CH3
C
H3C CH3 O O
O2
CH O HC O O
H3C CH3
H3C C C CH3
H3C O O CH3
TATP
10.1 Peroxides of Acetone 273

Fig. 10.14 TATP crystals obtained by sublimation (left—camera photo, right—optical

microscopy)

Several other accidental explosions of TATP, unknowingly formed during

chemical reactions, have been reported [81–84]. The unwanted formation of ace-
tone peroxides is therefore a problem which needs to be addressed in any industrial
scale production. One example of measures for suppressing acetone reaction
mixtures resulting from the synthesis of phenol, diphenols, or phenol derivates
has been published by Costantini who suggests (a) adjusting pH to a value between
4 and 8; (b) adding a copper compound to the reaction mixture; (c) maintaining
reaction temperature between 50 and 150  C [85]. To avoid unwanted formation of
TATP, it is generally recommended never to use acetone as a solvent in reactions of
hydrogen peroxide [86].

10.1.2.5 Uses

TATP has been largely studied in the first half of the twentieth century. Due to its
simple preparation and sufficient explosive performance, it had been considered for
use as a primary charge for detonators [87]. It is astonishing that patent application
was registered for the same application of TATP again in 2009 [88]. The reason why
it has not been implemented industrially is often incorrectly related to its “high
sensitivity.” This is however not true, as can be seen from the comparison of
sensitivity of peroxides with other primary explosives (see Chap. 2). The real
reasons are its high volatility, which is a cause of spontaneous recrystallization
(see Figs. 10.7 and 10.8), and unsuitable thermal behavior (melting at low tempera-
ture) (Matyáš and Pachman Unpublished).
Apart from its application as a primary explosive, TATP has been suggested for
use in mixtures or as a part of secondary explosives. A mixture with ammonium
nitrate has been suggested by Mavrodi for use in coal mines. This explosive is said
to have low detonation temperature and force equivalent to TNT [60].
274 10 Organic Peroxides

A number of publications focusing on demonstrating interesting or otherwise

visually effective chemical experiments [89, 90] have proposed a relatively effec-
tive way of TATP deflagration accompanied with formation of a powerful fireball.
However, it is strongly recommended to avoid using TATP for such purposes due to
the not insignificant risk of detonation.
Although TATP has found neither industrial nor military applications, it has
become very popular among the general public. On top of being very popular
among young “scientists,” this substance has also attracted attention of criminals,
extremists, and terrorists who use it for preparing detonators as well as main
charges [91–94]. The main reason for this popularity is the availability of
precursors (acetone, hydrogen peroxide, and acids in chemists’ stores) [95], wide
knowledge of how to make it (broadcasted via internet), and an undemanding
procedure for synthesis with high yield.
TATP has been used by terrorists in many bomb attacks around the world
(Europe, USA, Middle East, Africa, etc.) [62, 93, 96–99]. Probably the most
well-known abuse of TATP was by Richard Reid which used TATP as a
primary explosive in his shoe bomb in the attempted bombing of a US airliner
on 22 December 2001 [99].
Some organic peroxides, including TATP, have been suggested as additives for
diesel fuels [37].

10.1.3 Tetraacetone Tetraperoxide

H3C CH3
C
O O
O O
H3C CH3
C C
H3C CH3
O O
O O
C
H3C CH3

The formation of tetraacetone tetraperoxide (3,3,6,6,9,9,12,12-octamethyl-

1,2,4,5,7,8,10,11-octaoxacyclododecane; TeATeP) as a co-product of the reaction
creating mainly TATP is reported in several articles [55, 73, 74]. TeATeP is
reported to form under conditions very similar to those for DADP or TATP. Peña
et al. reported that this peroxide forms in the reaction mixture when the temperature
rose above 10  C [74].
10.2 Hexamethylene Triperoxide Diamine 275

H3C CH3 H3C CH3

C C O3 C
O O
H3C CH3 Et2O O O
H3C CH3
C C
H3C CH3
O O
H3C O3 O
C O
C CH2 Et2O
CH3
H3C
H3C
TeATeP

Jiang has reported a method of preparation of TeATeP using the reaction of

acetone with hydrogen peroxide in presence of tin (II and IV) chloride or
hydrochloric acid as the catalyst [100]. This method can however be disputed and
according to our experience, normal TATP is formed [8].
The formation of tetraacetone tetraperoxide by ozonolysis (see reaction above)
of tetramethylethene or isobutene has been described by Obinokov et al. [101].
These authors report a melting point of 61–65  C.

10.2 Hexamethylene Triperoxide Diamine

CH2 O O CH2

N CH2 O O CH2 N

CH2 O O CH2

Hexamethylene triperoxide diamine (1,6-diaza-3,4,8,9,12,13-hexaoxabicyclo

[4,4,4]tetradecane; HMTD) was first prepared by Legler in 1885. He discovered it
while working on the slow combustion of ether. He obtained a solid which, on
treatment with ammonia, gave an explosive compound—HMTD [51, 102, 103].
The early history of this substance is described by Bagal [51].
The two nitrogen atoms in the HMTD molecule form an interesting and rare,
totally planar, hybridization [104–106]. Two major hypotheses exist which try to
explain this planarity; an earlier one based on the steric effect [105] which has
subsequently been superseded by a later one, based on an electronic effect [107].
The 3D model of HMTD molecule is shown in Fig. 10.15.

10.2.1 Physical and Chemical Properties

HMTD forms colorless crystals (Fig. 10.16). Freshly prepared HMTD does not
smell; older samples acquire an unpleasant odor of rotten fish. Density of HMTD is
mostly reported as 1.57 g cm3 [17, 58, 68, 103, 108] but X-ray investigation of
276 10 Organic Peroxides

Fig. 10.15 HMTD geometry

and atom labeling [105].
Reprinted with permission
from A. Wierzbicki and
E. Cioffi, Density Functional
Theory Studies of
Hexamethylene Triperoxide
Diamine, J. Phys. Chem. A
1999, 103, 8890–8894.
Copyright (1999) American
Chemical Society

Fig. 10.16 HMTD crystals (left—optical microscopy; polarized light; right—SEM)

Table 10.6 Solubility of HMTD in water and organic solvents at 22  C

Solvent Solubility (g/100 g solvent at 22  C) References
Absolute ethanol <0.01 [103]
Acetone 0.33 [103]
Carbon disulfide <0.01 [103]
Carbon tetrachloride 0.013 [103]
Chloroform 0.64 [103]
Diethylether 0.017 [103]
Ethane-1,2-diyl diacetate 0.90 [109]
Glacial acetic acid 0.14 [103]
Water 0.01 [103]

HMTD crystal reports 1.597 g cm3 [106]. Heat of formation is 363 kJ mol1
according to Muraour [47] or 335 kJ mol1 according to Danilov et al. [38]. It is
slightly hygroscopic and it does not seem to be toxic. HMTD is practically insoluble
10.2 Hexamethylene Triperoxide Diamine 277

in cold water and most common organic solvents, slightly soluble in acetonitrile,
chloroform, dimethyl sulfoxide, dimethyl formamide and glycol acetate (see
Table 10.6); HMTD is soluble in hot water [103, 109–111].
HMTD is less chemically stable than TATP; it is commonly reported as unstable
in storage and it easily decomposes, particularly at higher temperatures [17, 46].
Low stability of HMTD has been reported for example by S€ulzle and Klaeboe. They
proved by IR spectroscopy that the compound slowly decomposes on storage even
when purified by crystallization from ethanol [112]. Nevertheless, Danilov et al.
reported that it can be stored for long periods without decomposing [38].
HMTD slightly hydrolyzes in cold water if left standing for several months,
slowly decomposes at 40  C and more quickly in boiling water according to the
following equation [38, 108]:
CH2 O O CH2
DT
N CH2 O O CH2 N + 3 H 2O 2 NH3 + 3 CH 2O + 3 HCOOH

CH2 O O CH2

According to Bagal and Ilyushin [51, 108], HMTD is stable when stored under
water for about 4 weeks at 30  C.
HMTD decomposes by the action of diluted acids (H2SO4, HBr, HCl) at room
temperatures; aqueous sodium hydroxide decomposes HMTD at higher temperatures.
It violently reacts with concentrated hydroiodic acid and explodes in contact with
bromine [52, 103, 113]. Examination of HMTD decomposition by the action of
chemical agents has recently been published by Oxley et al. They observed that
HMTD decomposes by application of inorganic salts (e.g., KMnO4, SnCl2, ZnCl2,
ZnSO4, KI, NaBr) in an acidic environment at room temperature within several
hours. The chemical destruction of larger amounts of dry HMTD is however not
recommended due to the exothermic nature of the decomposition.
Dry HMTD reacts with most common metals (e.g., zinc, copper and lead)
according to Ficheroulle and Kovache [50]. However, Danilov et al. have
reported that dry HMTD does not react with metals, but rather rapidly reacts
when wet [38, 108].
By the action of nitric acid, in presence of ammonium nitrate, HMTD could be
nitrated yielding hexogen (RDX). The total yield of RDX is reported to be 26 % of
the theoretical. The reaction can be described by the following equation [114]:
NO2

CH2 O O CH2 N
NH4NO3
N CH2 O O CH2 N + HNO3 + H2C O + H 2 O + O2
N N
CH2 O O CH2 O2N NO2

HMTD RDX
278 10 Organic Peroxides

Fig. 10.17 HMTD—

recrystallized from
chloroform

10.2.2 Explosive Properties

HMTD is sensitive to impact not only in its dry state but also when wet [17]. Its
impact sensitivity is mostly referred to as slightly [24, 103, 115, 116] or signifi-
cantly [51] lower than that of MF. Only Meyer reports it to be significantly more
sensitive than MF [58] while Yeager reported surprisingly low sensitivity; between
PETN and RDX [62]. The values of impact sensitivity are summarized in Fig. 2.15
from which is clear that it is about the same as for MF.
HMTD is furthermore highly sensitive to friction. Yeager reported HMTD as
one of the most friction-sensitive explosives [62]; extremely high sensitivity of
HMTD is reported in Meyer’s encyclopedia (10 more sensitive than LA and 50
more sensitive than MF [58]). According to our own results is friction sensitivity of
HMTD not extreme; it is slightly lower than LA but significantly higher than MF
(see Fig. 2.19).
Sensitivity of HMTD to electric discharge is about the same as that of lead azide,
according to our measurements (see Fig. 2.21).
HMTD crystals obtained by recrystallization from chloroform have been
reported to undergo spontaneous explosions at room temperature without any
other external stimuli [117]. This type of behavior has not been reported for the
raw material. The shape of the crystals obtained by recrystallization from chloro-
form can be seen in Fig. 10.17. The current authors have not encountered any
spontaneous explosions while preparing the material for this picture.
The dependence of detonation velocity of HMTD on density is summarized in
Table 10.7.
HMTD belongs to the group of highly brisant and powerful primary explosives.
The values of brisance, power, and ignition efficiency are summarized below:
• Brisance by send test: 71 % TNT [17]; superior 2.5–3 times MF [103]
• Lead block test: 242 cm3 [109, 118], 330 cm3 (110 % TNT) [58]
• Initiation efficiency: 0.05 g with reinforcing cap and 0.06 without it for tetryl;
0.08 g with reinforcing cap and 0.10 without it for TNT [103]; comparison with
10.2 Hexamethylene Triperoxide Diamine 279

Table 10.7 Detonation Density Detonation velocity

velocity of HMTD (g cm3) (m s1) References
0.38 2,820 [64, 65]
0.88 4,511 [103]
1.05 4,500 [47]
1.15 5,100 [47]

other primary explosives see Fig. 2.2. The initiating efficiency is three to four
times better than that of mercury fulminate.
The equation of HMTD explosion (ignited by impact) is, according to Muraour,
the following [47]:
CH2 O O CH2

N CH2 O O CH2 N 0.35 CO 2 + 3.88 CO + 0.03 C 2H2 + 0.55 CH 4 + 0.58 C

CH2 O O CH2
+ 2.44 H 2 + 1.42 H 2O + 0.48 NH 3 + 0.47 N 2 + 0.58 HCN

Volume of gaseous products is 1,097 dm3 kg1 according to above-mentioned

equation [47]. Ilyushin et al. published different result referring volume of gaseous
products of HMTD explosion to be 813 dm3 kg1 and the heat of explosion
1,058 kJ mol1 [108].
The dependence of burning rate on ambient pressure is linear and is about the
same as for TATP [63]. Ignition of small amounts of HMTD by flame results in
formation of an orange flame with muffled sound (Matyáš and Pachman Unpub-
lished) [115]. Immediate ignition (explosion) occurs at 200  C, 0.05 g sample
ignited at 149  C in three seconds [103]. Metz reported that HMTD ignites in the
temperature range 125–140  C [119]. The ignition temperature of HMTD by
heating is 123–136  C (when inorganic acids are used as a catalyst for HMTD
preparation) and 146–148  C (when citric acid is used as a catalyst) at heating rate
5  C min1 (Matyáš and Pachman Unpublished); Girsewald reported 139  C at
heating rate 20  C min1 [118].
Pressed or confined HMTD detonates after ignition by flame with a strong
acoustic effect. HMTD does not become dead-pressed under 76 MPa [103] or
even at 294 MPa [50, 51]. Explosions however occur when pressing coarse crystal-
line HMTD by a pressure 20 MPa or even more at 49 MPa [51].

10.2.3 Preparation

The easiest way for preparing HMTD is by the reaction of hexamethylenetetramine

with hydrogen peroxide in presence of an acidic catalyst [68, 116, 118, 120]. Citric
acid is often used as the catalyst but other organic and inorganic acids could be used
as well [24, 46, 121].
280 10 Organic Peroxides

N CH2 O O CH2
+
H
+ 3 H2O2 N CH2 O O CH2 N + 2 NH3
N N
N CH2 O O CH2
HMT HMTD

Other starting materials that produce hexamethylene tetramine in situ such as

formaldehyde with aqueous ammonia or formaldehyde with an ammonium salt
(e.g., sulfate) can be used instead of hexamethylenetetramine [68, 122]. The yield
of HMTD is, however, low for the latter mentioned example (Matyáš and Pachman
Unpublished). Ethanol (in large excess; about 1 l per 1 g HMTD) is recommended
for purification of HMTD by crystallization [112].

10.2.4 Uses

HMTD has been patented as a primary explosive for detonators [123] but, due to its
low physical and chemical stability and incompatibility with metals, has never been
used [17, 50]. However, Danilov et al. have reported that it can be used in war
situations when short turnaround time is expected [38]. Recently, investigations of
HMTD as a “green” primary explosive for laser-initiated applications have been
carried out by Ilyushin et al. [108, 124].
HMTD is, just like TATP, a very popular improvised explosive and as such is
often prepared by young “scientists,” criminals, extremists, and terrorists [91, 125,
126]. This compound is for example reported to be used by the terrorists in the
London bombings of 2005 [99, 127]. The main reason for this popularity is the
availability of precursors (hexamethylene tetramine as a firelighter, hydrogen
peroxide as hair bleach or disinfectant and citric acids as a seasoning) [95],
generally good knowledge of its preparation (broadcasted via internet) and an
undemanding procedure for its synthesis with high yield.
HMTD was also investigated as a potential antimalarial drug [128].

10.3 Tetramethylene Diperoxide Dicarbamide

H H
N CH2 O O CH2 N
O C C O
N CH2 O O CH2 N
H H

Tetramethylene diperoxide dicarbamide (1,2,8,9-tetraoxa-4,6,11,13-tetraazacy-

clotetradecane-5,12-dione; TMDD) was first synthesized by Girsewald in 1914 by
the reaction of urea and formaldehyde with hydrogen peroxide in presence of nitric
10.3 Tetramethylene Diperoxide Dicarbamide 281

acid [129]. There is very little information about this peroxide in scientific litera-
ture; only a few papers have been published to date. The structure of TMDD has
been recently studied by Peña-Quevedo [130].

10.3.1 Physical and Chemical Properties

TMDD forms white crystals with a melting point of approximately 180  C [130]. It
is insoluble in water, methanol, ethanol, chloroform, pyridine, and other organic
solvents [129–131]. It is, however, soluble in concentrated sulfuric and nitric acids;
TMDD can be precipitated back from these solutions by addition of water. TMDD
decomposes to hydrogen peroxide, formaldehyde, urea, ammonia, and carbon
dioxide by boiling in diluted acids. Similarly, it decomposes by boiling in diluted
bases forming hydrogen peroxide and formaldehyde (respectively formic acid due
to oxidation by hydrogen peroxide) [129].

10.3.2 Preparation

TMDD is prepared by dissolving urea and formaldehyde in hydrogen peroxide in

presence of concentrated nitric acid [129].
H H
H2N NH2 N CH2 O O CH2 N
HNO3
C O + H2O2 O C C O
+ H2C
O N CH2 O O CH2 N
H H
TMDD

The reaction mixture with dissolved reactants is then placed in a refrigerator for
several days during which time TMDD precipitates [110, 129, 131]. The highest
yield is, according to Peña-Quevedo, obtained after 3 days of the reaction [130].
This type of peroxide cannot be purified by crystallization due to its very low
solubility in all solvents; organic solvents only remove soluble impurities in TMDD
[110, 130, 131].

10.3.3 Use

TMDD was suggested in 1934 as a component of priming mixtures for increasing the
combustibility of the mixture [132] and as a primary explosive for blasting caps [133].
282 10 Organic Peroxides

References

1. Milas, N.A., Golubovič, A.: Studies in organic peroxides. XXVI. Organic peroxides derived
from acetone and hydrogen peroxide. J. Am. Chem. Soc. 81, 6461–6462 (1959)
2. McCullough, K.J., Morgan, A.R., Nonhebel, D.C., Pauson, P.L., White, G.J.: Ketone-
derivated peroxides. Part I. Synthetic methods. J. Chem. Res. (S), 34 (1980)
3. Pacheco-Londoño, L., Peña, Á.J., Primera, O.M., Hernández-Rivera, S.P., Mina, N., Garcı́a, R.,
Chamberlain, R.T., Lareau, R.: An experimental and theoretical study of the synthesis and
vibrational spectroscopy of triacetone triperoxide (TATP). Proc. SPIE 5403, 279–287 (2004)
€
4. Rieche, A.: Uber Peroxyde der Äther, der Carbonyl-Verbindungen und die Ozonide. Angew.
Chem. 70, 251–266 (1958)
5. Sauer, M.C.V., Edwards, J.O.: The reactions of acetone and hydrogen peroxide. II. Higher
adducts. J. Phys. Chem. 76, 1283–1288 (1972)
6. Jensen, L., Mortensen, P.M., Trane, R., Harris, P., Berg, R.W.: Reaction kinetics of acetone
peroxide formation and structure investigations using Raman spectroscopy and X-ray dif-
fraction. Appl. Spectrosc. 63, 92–97 (2009)
7. Schulz, M., Kirschke, K.: Advances in Heterocyclic Chemistry. Cyclic Peroxides. Academic
Press, London (1967)
8. Matyáš, R., Pachman, J.: Study of TATP: Influence of reaction conditions on product
composition. Propellants Explosives Pyrotechnics 35, 31–37 (2010)
9. Sigman, M.E., Clark, C.D., Caiano, T., Mullen, R.: Analysis of triacetone triperoxide (TATP)
and TATP synthetic intermediates by electrospray ionization mass spectrometry. Rapid
Commun. Mass Spectrom. 22, 84–90 (2008)
10. Sigman, M.E., Clark, C.D., Painter, K., Milton, C., Simatos, E., Frisch, J.L., McCormick, M.,
Bitter, J.L.: Analysis of oligomeric peroxides in synthetic triacetone triperoxide samples by
tandem mass spectrometry. Rapid Commun. Mass Spectrom. 23, 349–356 (2009)
11. Baeyer, A., Villiger, V.: Einwirkung des Caro‘schen Reagens auf Ketone. Berichte der
deutschen chemischen Gesellschaft 32, 3625–3633 (1899)
12. Baeyer, A., Villiger, V.: Ueber die Einwirkung des Caro’schen Reagents auf Ketone.
Berichte der deutschen chemischen Gesellschaft 33, 858–864 (1900)
13. Dubnikova, F., Kosloff, R., Almog, J., Zeiri, Y., Boese, R., Itzhaky, H., Alt, A., Keinan, E.:
Decomposition of triacetone triperoxide is an entropic explosion. J. Am. Chem. Soc. 127,
1146–1159 (2005)
14. Gelalcha, F.G., Schulze, B., L€ onnecke, P.: 3,3,6,6-Tetramethyl-1,2,4,5-tetroxane: A twinned
crystal structure. Acta Crystallogr. C Cryst. Struct. Commun. C60, o180–o182 (2004)
15. Milas, N.A., Davis, P., Nolan, J.N.: Organic peroxides. XX. Peroxides from the ozonization
of olefins in the presence of carbonium ions. J. Am. Chem. Soc. 77, 2536–2541 (1955)
16. Murray, R.W., Agarwal, S.K.: Ozonolysis of some tetrasubstitued ethylenes. J. Org. Chem.
50, 4698–4702 (1985)
17. Fedoroff, B.T., Sheffield, O.E., Kaye, S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, New Jersey (1960–1983)
18. Zhukov, B.P.: Energeticheskie kondesirovannye sistemy. Izdat. Yanus-K, Moskva (2000)
19. Egorshev, V., Sinditskii, V., Smirnov, S., Glinkovsky, E., Kuzmin, V.: A comparative study
on cyclic acetone peroxides. In: 12nd Seminar on New Trends in Research of Energetic
Materials, pp. 113–123, Pardubice, Czech Republic, 2009
20. Oxley, J.C., Smith, J.L., Luo, W., Brady, J.: Determining the vapor pressure of diacetone
diperoxide (DADP) and hexamethylene triperoxide diamine (HMTD). Propellants
Explosives Pyrotechnics 34, 539–543 (2009)
21. Oxley, J.C., Smith, J.L., Jiaorong, H., Wei, L.: Destruction of peroxide explosives. J. Forensic
Sci. 54, 1029–1033 (2009)
22. Cafferata, L.F.R., Eyler, G.N., Mirifico, M.V.: Kinetics and mechanism of acetone cyclic
diperoxide (3,3,6,6-tetramethyl-1,2,4,5-tetraoxane) thermal decomposition in benzene solu-
tion. J. Org. Chem. 49, 2107–2111 (1984)
References 283

23. Matyáš, R., Šelešovský, J., Musil, T.: Sensitivity to friction for primary explosives. J. Hazard.
Mater. 213–214, 236–241 (2012)
24. Matyáš, R.: Investigation of properties of selected organic peroxides. University of
Pardubice, Ph.D. Thesis, Pardubice (2005)
25. Baeyer, A., Villiger, V.: Ueber die Einwirkung des Caro’schen Reagens auf Ketone. Berichte
der deutschen chemischen Gesellschaft 33, 124–126 (1900)
26. Pastureau, M., Haller, M.A.: Sur un mode de formation d´acétol et d´acide pyruvique par
oxydation directe de l´acétone. Comptes rendus de l’Académie des sciences 88, 1591–1593
(1905)
27. Lockley, J.E., Ebdon, J.R., Rimmer, S., Tabner, B.J.: Cyclic diperoxides as sources of
radicals for the initiation of the radical polymerization of methyl methacrylate. Macromol.
Rapid Commun. 21, 841–845 (2000)
28. Lockley, J.E., Ebdon, J.R., Rimmer, S., Tabner, B.J.: Polymerization of methyl methacrylate
initiated by ozonates of tetramethylethene. Polymer 42, 1797–1807 (2001)
29. Dilthey, W., Inckel, M., Stephan, H.: Die Oxydation der Ketone mit Perhydrol. Journal f€ ur
praktische Chemie 154, 219–237 (1940)
30. Reany, O., Kapon, M., Botoshansky, M., Keinan, E.: Rich polymorphism in triacetone-
triperoxide. Cryst. Growth Des. 9, 3661–3670 (2009)
31. Matyáš, R., Pachman, J., Ang, H.G.: Study of TATP: Spontaneous transformation of TATP to
DADP. Propellants Explosives Pyrotechnics 34, 484–488 (2009)
32. Matyáš, R., Pachman, J., Ang, H.G.: Study of TATP: Spontaneous transformation of TATP to
DADP. Propellants Explosives Pyrotechnics 33, 89–91 (2008)
33. Griesbaum, K., Volpp, W., Greinert, R., Greunig, H.-J., Schmid, J., Henke, H.: Ozonolysis of
tetrasubstituted ethylenes, cycloolefins, and conjugated dienes on polyethylene. J. Org.
Chem. 54, 383–389 (1989)
34. Murray, R.W., Kong, W., Rajadhyaksha, S.N.: The ozonolysis of tetramethylethylene.
Concentration and temperature effects. J. Org. Chem. 58, 315–321 (1993)
€
35. Criegee, R.: Uber den Verlauf der Ozonspaltung. Justus Liebigs Annalen der Chemie 583,
1–36 (1953)
36. Murray, R.W., Story, P.R., Kaplan, M.L.: Nuclear magnetic resonance study of conforma-
tional isomerization in acetone diperoxide. J. Am. Chem. Soc. 88, 526–529 (1966)
37. Thiemann, A.E.: Uber € Kraftstoffzus€atze in Diesel€ olen. Automobiltechnische Zeitschrift 45,
454–457 (1942)
38. Danilov, J.N., Ilyushin, M.A., Tselinskii, I.V.: Promyshlennye vzryvchatye veshchestva;
chast I. Iniciiruyushchie vzryvshchatye veshchestva. Sankt-Peterburgskii gosudarstvennyi
tekhnologicheskii institut, Sankt-Peterburg (2001)
39. Wolffenstein, R.: Ueber die Einwirkung Wasserstoffsuperoxyd auf Aceton und Mesityloxyd.
Berichte der deutschen chemischen Gesellschaft 28, 2265–2269 (1895)
40. Scheibler, H.: Richard Wolffenstein {. Zeitschrift f€ ur angewandte Chemie 42, 1149–1151
(1929)
41. Yavari, I., Hosseini-Tabatabaei, M.R., Nasiri, F.: Semiempirical SCF MO study of ring
inversion in 1,1,4,4,7,7-tetramethylcyclononane and trimeric acetone peroxide. J. Mol.
Struct. Theochem 538, 239–244 (2001)
42. Duin, A.C.T., Zeiri, Y., Dubnikova, F., Kosloff, R., Goddard, W.A.: Atomistic-scale
simulations of the initial chemical events in the thermal initiation of triacetonetriperoxide.
J. Am. Chem. Soc. 127, 11053–11062 (2005)
43. Bellamy, A.J.: Triacetone triperoxide: Its chemical destruction. J. Forensic Sci. 44, 603–608
(1999)
44. Keul, H., Griesbaum, K.: Ozonolysis of olefins containing monochloro substituted double
bonds. Can. J. Chem. 58, 2049–2054 (1980)
45. Rieche, A., Koch, K.: Die Oxydation des Diisopropyl€athers. Berichte der deutschen
chemischen Gesellschaft 75, 1016–1028 (1942)
46. Khmelnitskii, L.I.: Spravochnik po vzryvchatym veshchestvam. Voennaya ordena Lenina i
ordena Suvorova Artilleriiskaya inzhenernaya akademiya imeni F. E. Dzerzhinskogo,
Moskva (1962)
284 10 Organic Peroxides

47. Muraour, H.: Sur la théorie des réactions explosives. Cas particulier des explosifs
d’amorçage. Mémories présentés a la Société chimique 51, 1152–1166 (1932)
48. Matyáš, R., Šelešovský, J., Musil T.: Study of TATP: Mass loss and friction sensitivity during
ageing. Cent. Eur. J. Energ. Mater. 9, 251–260 (2012)
49. Oxley, J.C., Smith, J.L., Shinde, K., Moran, J.: Determination of the vapor density of
triacetone triperoxide (TATP) using a gas chromatography headspace technique. Propellants
Explosives Pyrotechnics 30, 127–130 (2005)
50. Ficheroulle, H., Kovache, A.: Contribution à l‘étude des explosifs d’amorçage. Mémorial des
poudres 31, 7–27 (1949)
51. Bagal, L.I.: Khimiya i tekhnologiya iniciiruyushchikh vzryvchatykh veshchestv.
Mashinostroenie, Moskva (1975)
52. Matyáš, R.: Chemical destruction of triacetone triperoxide and hexamethylenetriperoxi-
dediamine. In: Proceedings of 6th Seminar on New Trends in Research of Energetic
Materials, pp. 164–173, Pardubice, Czech Republic, 2003
53. Armitt, D., Zimmermann, P., Ellis-Steinborner, S.: Gas chromatography/mass spectrometry
analysis of triacetone triperoxide (TATP) degradation products. Rapid Commun. Mass
Spectrom. 22, 950–958 (2008)
54. Pachman, J., Matyáš, R.: Study of TATP: Stability of TATP solutions. Forensic Sci. Int. 207,
212–214 (2011)
55. Cotte-Rodriguez, I., Chen, H., Cooks, R.G.: Rapid trace detection of triacetone triperoxide
(TATP) by complexation reactions during desorption electrospray ionization. Chem.
Commun. 9, 953–955 (2006)
56. Dubnikova, F., Kosloff, R., Zeiri, Y., Karpas, Z.: Novel approach to the detection of
triacetone triperoxide (TATP): Its structure and its complexes with ions. J. Phys. Chem. A
106, 4951–1159 (2002)
57. Matyáš, R., Pachman, J.: Thermal stability of triacetone triperoxide. Sci. Technol. Energetic
Mater. 68, 111–116 (2007)
58. Meyer, R., K€ohler, J., Homburg, A.: Explosives. Wiley-VCH, Weinheim (2002)
59. Yinon, J.: Forensic and Environmental Detection of Explosives. Wiley, New York (1999)
60. Mavrodi, G.E.G.: Improvements in or relating to explosives of the organic peroxide class. GB
Patent 620,498, 1949
61. Šelešovský, J., Matyáš, R., Musil, T.: Using of the probit analysis for sensitivity tests -
sensitivity curve and reliability. In: Proceedings of 14th Seminar on New Trends in Research
of Energetic Materials, pp. 963–967, Pardubice, Czech Republic, 2011
62. Yeager, K.: Trace Chemical Sensing of Explosives. Wiley, New Jersey (2007)
63. Fogelzang, A.E., Egorshev, V.Y., Pimenov, A.Y., Sinditskii, V.P., Saklantii, A.R., Svetlov,
B.S.: Issledovanie statsionarnogo goreniya initsiiruyushchikh vzryvchatykh veshchestv pri
vysokykh davleniyakh. Dokl. Akad. Nauk SSSR 282, 1449–1452 (1985)
64. Kuzmin, V.V., Kozak, G.D., Solovev, M.Y., Tuzkov, Y.B.: Forensic investigation of some
peroxides explosives. In: Proceedings of 11th Seminar on New Trends in Research of
Energetic Materials, pp. 387–393, Pardubice, Czech Republic, 2008
65. Kuzmin, V.V., Solovev, M.Y., Tuzkov, Y.B., Kozak, G.D.: Forensic investigation of some
peroxides explosives. Cent. Eur. J. Energetic Mater. 5, 77–85 (2008)
66. Rohrlich, M., Sauermilch, W.: Sprengtechnische Eigenschaften von Trizykloazetonperoxyd.
Zeitschrift f€ur das gesamte Schiess- und Sprengstoffwesen 38, 97–99 (1943)
67. Lefebvre, M.H., Falmagne, B., Smedts, B.: Sensitivities and performances of non-regular
explosives. In: Proceedings of 7th Seminar on New Trends in Research of Energetic
Materials, pp. 164–173, Pardubice, Czech Republic, 2004
68. Bubnov, P.F.: Initsiruyushchie vzryvchatye veshchestva i sredstva initsirovaniya.
Gosudarstvennoe izdatelstvo oboronnoi promyshlennosti, Moskva (1940)
69. Matyáš, R., Šelešovský, J.: Power of TATP based explosives. J. Hazard. Mater. 165, 95–99
(2009)
References 285

70. Matyáš, R., Trzciński, W., Cudzilo, S., Zeman, S.: Detonation performance of TATP/AN-
based explosives. Propellants Explosives Pyrotechnics 33, 296–300 (2008)
71. Groth, P.: Crystal structure of 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexa-oxacyclononane (“tri-
meric acetone peroxide”). Acta Chem. Scand. 23, 1311–1329 (1969)
72. Matyáš, R., Jirásko, R., Lyčka, A., Pachman, J.: Study of TATP: Formation of new chloroderivates
of triacetone triperoxide. Propellants Explosives Pyrotechnics 219–224, 36 (2011)
73. Schulte-Ladbeck, R., Kolla, P., Karst, U.: Trace analysis of peroxide-based explosives. Anal.
Chem. 75, 731–735 (2003)
74. Peña, Á.J., Pacheco-Londoño, L., Figueroa, J., Rivera-Montalvo, L.A., Román-Velazquez, F.
R., Hernández-Rivera, S.P.: Characterization and differentiation of high energy cyclic organic
peroxides by GC/FT-IR, GC-MS, FT-IR, and Raman microscopy. Proc. SPIE 5778, 347–358
(2005)
75. Widmer, L., Watson, S., Schlatter, K., Crowson, A.: Development of an LC/MS method for
the trace analysis of triacetone triperoxide (TATP). Analyst 127, 1627–1632 (2002)
76. Murray, R.W., Jeyaraman, R.: Dioxiranes: Synthesis and reactions of methyldioxiranes. J.
Org. Chem. 50, 2847–2853 (1985)
77. Kim, T.J., Heo, N.H., Kim, J.-H., Seo, G.: Formation of acetone cyclic triperoxide over
titania-incorporated mesoporous materials. React. Kinet. Catal. Lett. 79, 287–293 (2003)
78. Belič, I., Suhadolc, T.: Peroxides of diisopropylether. Experientia 25, 473 (1969)
79. Acree, F., Haller, H.L.: Trimolecular acetone peroxide in isopropyl ether. J. Am. Chem. Soc.
65, 1652 (1943)
80. Kharasch, M.S., Gladstone, M.: Ether peroxides. J. Chem. Educ. 16, 498 (1939)
81. Noponen, A.: Violent explosion. Chem. Eng. News 55, 5 (1977)
82. Stirling, C.J.M.: Explosion warning. Chem. Brit. 5, 36 (1969)
83. Brewer, A.D.: Peroxide/acetone mixture hazard. Chem. Brit. 11, 335 (1975)
84. Micetich, R.G.: 6-Aminopenicillanic acid sulphoxide and ampicillin sulphoxide. Chem. Brit.
13, 163 (1977)
85. Costantini, M.: Destruction of acetone peroxides. US Patent 5,003,109, 1991
86. Davies, A.G.: Organic Peroxides. Butterworths & Co., London (1961)
87. Pyl, G.: Verfahren zur Herstellung von Initialz€ undmitteln. DE Patent 423,176, 1925
88. Holtmeier, U., Holtmeier, L.: Sprengz€ under. DE Patent DE 10,2009,007,178 A1, 2009
89. El-Awady, A.A., Prell, L.J.: Exothermic reactions and unstable compounds: a demonstration
of fires, flames, and smoke In: 2nd Annual Symposium of Chemistry Demonstrations,
Western Illinois University, Macomb, USA, May, 1979
90. Shakhashiri, B.Z.: Chemical Demonstrations. A Handbook for Teachers of Chemistry. The
University of Wiskonsin Press, Madison (1983)
91. Šarapatka, J.: Analýza udalostı́ za rok 2002; Bulletin ochranné služby Policie České
republiky, Report. Ministry of the Interior of the Czech Republic, Praha (2003)
92. IntelCenter: London Tube Bus Attack (LTBA) v 1.5, Report: http://www.intelcenter.com/
LTBA-PUB-v1-5.pdf (Online 29 Jan 2007)
93. Michalske, T., Edelstein, N., Sigman, M., Trewhella, J.: Basic Research Needs for Counter-
ing Terrorism, Report: http://www.er.doe.gov/bes/reports/files/NCT_rpt_screen.pdf (Online
29 Jan 2007), 2007
94. Philpott, D.: The London Bombing. Homeland Defence Journal: http://www.homelandde-
fensejournal.com/pdfs/LondonBombing_SpecialReport.pdf (Online 29 Jan 2007), 2006
95. Dudek, K., Matyáš, R., Dorazil, T.: DIEPE – Detection and identification of explosive
precursors and explosives. In: Proceedings of 14th Seminar on New Trends in Research of
Energetic Materials, pp. 595–600, Pardubice, Czech Republic, 2011
96. Ember, L.R.: Biochemist arrested in London bombing. Chem. Eng. News 83, 11 (2005)
97. Stambouli, A., El Bouri, A., Bouayoun, T., Bellimam, M.A.: Headspace-GC/MS detection of
TATP traces in post-explosion debris. Forensic Sci. Int. 146S, S191–S194 (2004)
98. Matyáš, R.: Improvizované výbušiny. In: 2nd Mezinárodnı́ pyrotechnický seminář,
pp. 100–109, Praha, Czech Republic, 2003
286 10 Organic Peroxides

99. Marshall, M., Oxley, J.C.: Aspects of Explosives Detection. Elsevier, Oxford (2009)
100. Jiang, H., Chu, G., Gong, H., Qiao, Q.: Tin chloride catalysed oxidation of acetone with
hydrogen peroxide to tetrameric acetone peroxide. J. Chem. Res. (S), 288–289 (1999)
101. Obinokov, V.N., Botsman, L.P., Ishmupatov, L.J., Tolstikov, G.A.: Ozonoliz alkenov i
izuchenie reakcii polifunkcionalnykh coedinenii. XVIII. Issledovanije novogo ozonoliti-
cheskogo sinteza karbonovykh kislot. Zhurnal organicheskoi khimii 16, 524–537 (1980)
102. Legler, L.: Ueber Producte der langsamen Verbrennung des Aethyl€athers. Berichte der
deutschen chemischen Gesellschaft 18, 3344–3351 (1885)
103. Taylor, C.A., Rinkenbach, W.H.: H. M. T. D. A new detonating explosive. Army Ordnance 5,
463–466 (1924)
104. Schaefer, W.P., Fourkas, J.T., Tiemann, B.G.: Structure of hexamethylene triperoxide
diamine. J. Am. Chem. Soc. 107, 2461–2463 (1985)
105. Wierzbicki, A., Cioffi, E.: Density functional theory studies of hexamethylene triperoxide
diamine. J. Phys. Chem. A 103, 8890–8894 (1999)
106. Wierzbicki, A., Salter, E.A., Cioffi, E.A., Stevens, E.D.: Density functional theory and X-ray
investigations of P- and M-hexamethylene triperoxide diamine and its dialdehyde derivative.
J. Phys. Chem. A 105, 8763–8768 (2001)
107. Guo, C., Persons, J., Harbison, G.S.: Helical chirality in hexamethylene triperoxide diamine.
Magn. Reson. Chem. 44, 832–837 (2006)
108. Ilyushin, M.A., Tselinsky, I.V., Sudarikov, A.M.: Razrabotka komponentov vysokoenergi-
cheskikh kompozitsii. SPB:LGU im. A. S. Pushkina – SPBGTI(TU), Sankt-Peterburg (2006)
109. Konrad: Die Verwendung von Hexamethylentetramin in der Sprengstoffindustrie. Nitrocel-
lulose 5, 123–124 (1934)
110. Peña-Quevedo, A.J., Mina-Calmide, N., Rodrı́guez, N., Nieves, D., Cody, R.B., Hernández-
Rivera, S.P.: Synthesis, characterization and differentiation of high energy amine peroxides
by MS and vibrational microscopy. Proc. SPIE 6201, 62012E/62011–62012E/62010 (2006)
111. Peña-Quevedo, A.J., Hernández-Rivera, S.P.: Mass spectrometry analysis of hexamethylene
triperoxide diamine by its decomposition products. Proc. SPIE 7303, 730303/
730301–730303/730311 (2009)
112. S€ulzle, D., Klaeboe, P.: The infrared, Raman and NMR spectra of hexamethylene triperoxide
diamine. Acta Chem. Scand. A 42, 165–170 (1988)
113. Marotta, D., Alessandrini, M.E.: Ricerche sull’esametilen-tetrammina. - I. Esametilen-
tetrammina e perossido di idrogeno. Gazzetta Chimica Italiana 59, 942–946 (1929)
114. Szyc-Lewańska, K., Urbański, T.: Chemistry of cyclonite. Nitration of hexamethylene
triperoxide diamine. Bulletin de l’Académie polonaise des sciences; Serie des sciences
chimiques, geologiques et geographiques 6, 165–167 (1958)
115. Stettbacher, A.: Porokha i vzryvshchatye veshchestva. ONTI Glavnaya redakciya
khimicheskoi literatury, Moskva (1936)
116. Urbański, T.: Chemistry and Technology of Explosives. PWN—Polish Scientific Publisher,
Warszawa (1967)
117. Fogelzang, A.E., Serushkin, V.V., Sinditskii, V.P.: O spontannom vzryvje geksametilentri-
peroksiddiamina. Fizika goreniya i vzryva 25, 129–131 (1989)
118. Girsewald, C.: Beitr€age zur Kenntnis des Wasserstoffperoxyds. Uber € die Einwirkung des
Wasserstoffperoxyds auf Hexamethylentetramin. Berichte der deutschen chemischen Gesell-
schaft 45, 2571–2576 (1912)
119. Metz, L.: Die Pr€ ufung von Z€ undh€utchen (Initialsprengstoffen) auf Schlangempfindlichkeit
und Flammenwirkung. Zeitschrift f€ ur das gesamte Schiess- und Sprengstoffwesen 23,
305–308 (1928)
120. Girsewald, C.: Verfahren zur Darstellung von Hexamethylentriperoxyddiamin. DE Patent
263,459, 1912
121. Pease, J., Newell, F.: Process of producing a new organic compound and the compound when
produced thereby. GB Patent 339,024, 1929
References 287

122. Baeyer, A., Villiger, V.: Ueber die Nomenclatur der Superoxyde und die Superoxyde der
Aldehyde. Berichte der deutschen chemischen Gesellschaft 33, 2479–2487 (1900)
123. Girsewald, C.: Verwendung von Hexamethylentriperoxidyddiamin zur Herstellung von
Initialz€undern. DE Patent 274,522, 1912
124. Ilyushin, M.A., Tselinsky, I.V., Shugalei, I.V., Chernay, A.V., Toftunova, V.V.: “Green”
polymer-bound explosive (PBX) for laser initiation. In: Proceedings of 9th Seminar on New
Trends in Research of Energetic Materials, pp. 602–607, Pardubice, Czech Republic, 2006
125. Byall, E.T.: Explosives Report 1998–2001. In: Proceedings of 13th INTERPOL Forensic
Science Symposium, Lyon, France, 2001
126. Matyáš, R.: Grant of the Ministry of Internal Affairs of Czech Republic, Report RN
20012003003. University of Pardubice, Pardubice (2002)
127. Persons, J., Harbison, G.S.: The 14N quadrupole coupling in hexamethylene triperoxide
diamine (HMTD). Magn. Reson. Chem. 45, 905–908 (2007)
128. Vennerstrom, J.L.: Amine peroxides as potential antimalarials. J. Med. Chem. 32, 64–67
(1989)
129. Girsewald, C., Siegens, H.: Beitr€age zur Kenntnis des Wasserstoffperoxyds. II.
Tetramethylen-diperoxyd-dicarbamid. Berichte der deutschen chemischen Gesellschaft 47,
2464–2469 (1914)
130. Peña-Quevedo, A.J.: Cyclic organic peroxides identification and trace analysis by Raman
microscopy and open-air chemical ionization mass spectroscopy. University of Puerto Rico,
PhD thesis, Puerto Rico (2009)
131. Peña-Quevedo, A.J., Cody, R., Mina-Calmide, N., Ramos, M., Hernández-Rivera, S.P.:
Characterization and differentiation of high energy amine peroxides by direct analysis in
real time TOF/MS. Proc. SPIE 6538, 653828-1, 2007
132. Weale, A., Renfrew, A.: Improvements in or relating to explosive priming compositions. GB
Patent 415,779, 1934
133. Spaeth, C.P.: Ignition composition. US Patent 1,984,846, 1934
Chapter 11
Nitrogen Halides

The nitrogen halides are substances containing three atoms of one of the halogens
bound together with one atom of nitrogen. The most common one is without
question nitrogen triiodide which is often used for demonstration purposes due to
its extreme sensitivity to mechanical impulse and impressive purple cloud formed
as a result of the explosion. Nitrogen trichloride and nitrogen tribromide are both
quite sensitive and explode easily. The last nitrogen halide in the family is a fluorine
analog which does not possess explosive behavior and is therefore not mentioned in
the following sections.

11.1 Nitrogen Trichloride

The earliest report on the preparation of nitrogen trichloride (NCl3) dates back to
the beginning of the nineteenth century and is attributed to Dulong [1, 2]. Sir
Humphry Davy, in his letter to the Royal Society of London, mentioned informa-
tion received from France 12 months earlier (meaning in 1811) concerning a new
compound in the form of a heavier-than-water oil which “explodes by gentle heat
with all the violence of fulminating metals” [3]. The discoverer, not named in this
letter, most likely Dulong, lost an eye and three fingers during the early experiments
with the substance. The details of the discovery and an earlier history of this
dangerous substance are described by Snelders [4].

11.1.1 Physical and Chemical Properties

Nitrogen trichloride forms a bright yellow oily liquid with a density of 1.653 g cm
3.
It is very volatile [5–9] and has a very unpleasant odor sometimes described as
nauseous or pungent [3, 6, 7, 10–12]. The vapors irritate the eyes. In its frozen state, it
exists as a rhombohedral crystalline solid. The melting point is reported between
40

R. Matyáš and J. Pachman, Primary Explosives, 289

DOI 10.1007/978-3-642-28436-6_11, # Springer-Verlag Berlin Heidelberg 2013
290 11 Nitrogen Halides

and
27  C, boiling point 71–73  C [11, 12], and its vapors explode if heated above
93–95  C [6, 9, 10, 13]. In spite of this fact, distillation of nitrogen trichloride in the
open air at 71  C without explosion was reported by Walke [9]. It is insoluble in
water. However, if submerged it slowly decomposes by hydrolysis. In cold water, this
process takes several hours [8, 10]. Solubility is on the other hand relatively good in
solvents such as benzene, chloroform, carbon tetrachloride, ether, carbon disulfide,
and phosphorus trichloride [7, 10, 11]. Sunlight causes the decomposition of nitrogen
trichloride solutions or its reaction with solvents. For example, benzene solution
gives hexachlobenzene when exposed to sunlight; the chloroform solution
decomposes when chlorine, hydrogen, ammonium chloride, and traces of
hexachlorethane form (but no carbon tetrachloride) [14]. Nitrogen trichloride
solutions in diffuse daylight or in darkness can be stored unchanged for weeks [6].
Nitrogen trichloride violently explodes in contact with many substances (espe-
cially with substances which have an affinity for chlorine), such as phosphorus
(even in solution), arsenic, many organic substances (e.g., oils, fats, turpentine,
naphtha), concentrated alkali hydroxides, ozone, solid iodine, and potassium cya-
nide [3, 6, 7, 10, 12, 13, 15]. An interesting laboratory demonstration of the
preparation and later explosion of nitrogen trichloride is described by Rai [16]. In
this experiment, NCl3 is first prepared by reaction of a concentrated solution of
bleaching powder and a saturated solution of ammonium chloride at low tempera-
ture. The reaction product is partly present on the surface of the aqueous solution
and partly, due to its high density, at the bottom of the test tube. Addition of a few
drops of oil or turpentine causes instantaneous explosion of the surface layer of
nitrogen trichloride followed by a second explosion of the product at the bottom
some time later. Explosion of this substance may be caused even by grease from the
fingers [6]. Nitrogen trichloride decomposes in contact with sulfur, acids, and
reducing agents [3, 6, 15]. It can be slowly decomposed by dilute ammonium
chloride solution to give nitrogen and hydrochloric acid [17]. Using a concentrated
solution leads to a rapid decomposition giving the same products.

Nitrogen trichloride is a photosensitive substance which may explode when

exposed to sunlight or magnesium torch light [6, 7, 10, 12]. Photolysis in the
gaseous state [18] or in tetrachloromethane solution [19] yields nitrogen and
chlorine. The use of other solvents usually leads to their chlorination [14]. Nitrogen
trichloride is an interesting chemical agent (aminating and halogenating). Its
chemistry was summarized extensively by Kovacic et al. [20].

11.1.2 Explosive Properties

Nitrogen trichloride is an extremely sensitive substance and it explodes violently

with the slightest impact or friction [7, 12]. The explosion itself is characterized by
11.1 Nitrogen Trichloride 291

a brilliant flash [3]. It is a very hazardous substance in its pure form and caused
serious injuries to early investigators—Mr. Dulong lost three fingers and one eye
[6] and Mr. Davy received severe wounds to an eye when an amount “scarcely as
large as a grain of mustard seed” shattered the glass tube containing it [3]. Although
very sensitive its performance is relatively low [6, 12].
Nitrogen trichloride decomposes to nitrogen and chlorine. Decomposition may
be represented by the following equation [9]:

The volume of gaseous product is 370.5 l per 1 kg of nitrogen trichloride [9].

11.1.3 Preparation

Warning—all equipment that may come into contact with nitrogen trichloride must be
washed by alkali in order to clean it from grease. Not doing so will lead to explosion when
contact between the two occurs.

It is believed that nitrogen trichloride was first obtained accidentally by Dulong

who introduced chlorine gas into a solution of ammonium chloride at 8  C [1–3,
6–8, 16, 21].

Aqueous ammonia may also be used as a starting material; however in this case
concentration and pH are extremely important. The normal reaction between
chlorine and ammonia is obtained only when ammonia is used in stoichiometric
proportions [22]:

In excess ammonia, nitrogen trichloride reacts giving partly free nitrogen and
partly probably ammonium hypochlorite [22]:

The reaction of ammonium chloride or aqueous ammonia with chlorine provide

product in the form of extremely dangerous oily drops at the bottom of the aqueous
phase or as a film on the solution surface. Direct separation of nitrogen trichloride is
a dangerous operation and it is therefore recommended to collect it by extraction.
A suitable solvent for this operation is tetrachloromethane which cannot be further
292 11 Nitrogen Halides

chlorinated and therefore acts as a good inert medium [14]. The extraction from the
aqueous solution into an organic solvent greatly reduces the risk of explosion. Other
ammonium salts may also be used as starting materials instead of aqueous ammonia.
It is however important to note that some ammonium salts are more suitable than
others. The preferred choice among ordinary chemicals is ammonium sulfate since
the reaction between ammonium chloride and chlorine is reported to be reversible
[10, 21, 23]. The effects of various reaction conditions used during preparation of
nitrogen trichloride have been summarized by Mellor [6]. Ammonium nitrate was
the substance of choice of early experimenters such as Mr. Burtom or Mr. Children
who used it in aqueous solution and let it react with chlorine gas [3].

The formation of nitrogen trichloride has also been observed in the gaseous
phase. In this case reaction of gaseous ammonia with chlorine first yields nitrogen
trichloride and later, if there is an excess of ammonia, reacts to form ammonium
chloride [8, 18].

Nitrogen trichloride may also be produced by electrolysis of acidic aqueous

liquids in which ammonium and chloride ions are present [6, 8]. Kolbe found that
electrolysis of a concentrated solution of ammonium chloride gives hydrogen on
the negative pole but neither oxygen nor chlorine on the positive pole. The platinum
positive electrode was however covered by small yellowish oily drops of what
proved later to be nitrogen trichloride [24, 25]. The most favorable conditions for
formation of nitrogen trichloride are high electrolyte concentration, absence of
light, high anodic current density, and separation of anodic and cathodic volumes
by diaphragm [24]. The acidity of the electrolyte further determines the composi-
tion of the product. Nitrogen trichloride is formed in an acidic environment
(hydrochloric acid is recommended) while chloramines (NHCl2 and NH2Cl) are
formed in very weakly acidic, neutral, or alkaline solutions [26]. Nitrogen
trichloride can be removed from the electrolyte by passing air (or other gases)
through the electrolyte with suction applied over the electrolyte [27, 28].

Another method of nitrogen trichloride preparation was published by Balard,

who proved that nitrogen trichloride can be obtained when a solution of
hypochlorous acid comes into contact with aqueous ammonia or ammonium salts
[6, 8, 15, 29]:

Hentschel [30] modified the above-mentioned preparation route of Balard [29] by

replacing hypochlorous acid with sodium hypochlorite and extracting the product
with benzene:
11.2 Nitrogen Tribromide 293

Nitrogen trichloride forms only if the molar ratio of ammonium chloride to

chlorine is equal to or greater than 2:3. Even a ratio of 16:3 is reported to give the
same product. On the other hand, lower amounts of ammonium chloride result in
formation of a solution of chlorine in ammonium chloride instead of the NCl3.

According to Rai [16], nitrogen trichloride can also be prepared by reaction of

bleaching powder (calcium hypochlorite) solution on a saturated solution of ammo-
nium chloride. The reaction is very vigorous and must be carried out at low
temperatures. Ice bath cooling is recommended and the reaction temperature should
not exceed 0  C. The reaction does not require special equipment or extraction of
the product and is therefore suitable for small-scale preparation or class demonstra-
tion of the explosive properties of nitrogen trichloride [16].
Nitrogen trichloride is also formed by passing a mixture of nitrosyl chloride and
phosphorus pentachloride through a tube heated to a high temperature. The nitrosyl
chloride is prepared by heating a mixture of sodium nitrite and phosphorus
pentachloride [31]:

Nitrogen trichloride can be relatively safely stored in solution. It has, however,

been reported that spontaneous explosion of a 12 % solution in di-n-butylether
occurred shortly after preparation and violent decomposition of 12 % solution of
nitrogen trichloride was reported during preparation without cooling (3–5 %
solutions can be prepared safety without cooling) [32]. Solutions of nitrogen
trichloride slowly decompose during storage into nitrogen and chlorine even
when stored in the dark [17].

11.1.4 Use

The extreme sensitivity of nitrogen trichloride, together with its low physical and
chemical stability, prevents it from being used in practical applications as an
explosive. It has, however, been used in its gaseous form as an agent for bleaching
and maturing of flour [5, 33]. It had also been studied as a chemical agent
(aminating and halogenating) for synthesis in organic chemistry [20, 34–39].

11.2 Nitrogen Tribromide

There is very little information about nitrogen tribromide (NBr3) in open literature
and to make the situation even more difficult these literature sources tend to
contradict each other.
294 11 Nitrogen Halides

11.2.1 Physical and Chemical Properties

Nitrogen tribromide (NBr3) is reported as a red, oily, volatile liquid with offensive
odor [6, 8]. From later work it appears, however, that nitrogen tribromide is a solid
substance of a deep red color with nitrogen to bromine ratio 1:3 [40]. This
extremely temperature-sensitive substance “explodes even at
100  C in Nujol-
pentane suspension (1:2.7) with the slightest mechanical disturbance” [40].
It slowly hydrolyses in water and explodes in contact with phosphorus or arsenic [6].
Nitrogen tribromide is soluble in chloroform [41] and at temperatures below
80  C in
polar solvents that do not undergo bromination or oxidation [40]. Nitrogen tribromide
reacts with ammonia instantly giving solid, dark violet monobromamine [40]:

With N-bases (pyridine, urotropine), it directly forms bromine adducts. The step
which would lead to nitrogen tribromide adducts, similar to those observed in
reaction of nitrogen triiodide adducts in the case of the reaction of NI3·NH3 with
tertiary bases, is absent [40].

Iodine reacts with nitrogen tribromide in a dichloromethane solution at
87  C

giving red-brown solid nitrogen dibromideiodide (NBr2I) which is stable up to

20  C [40].

The infrared and Raman spectroscopic characterization of the nitrogen tribromide

is quite problematic due to its high thermal and mechanical sensitivity. It was
reported by Jander [40] that orange-red mixtures of solid nitrogen tribromide and
ammonium bromide or acetate have been evaluated instead of the pure substance.
The gas phase spectra were obtained by Klap€
otke [42].

11.2.2 Preparation

The preparation of nitrogen tribromide, as cited in the oldest literature, is based on

the action of aqueous potassium or sodium bromide on nitrogen trichloride. It is
reported that the initial yellow color slowly changes to red, which becomes deeper
and deeper in tint finally giving a product a dense black oily appearance having a
chlorine-like odor [6, 9, 12, 13, 43]. This product has similar properties to the
nitrogen trichloride (e.g., explodes by contact with phosphorus and arsenic [9]) and
was considered to be nitrogen tribromide. The composition of such product was
however not checked by serious analytical methods. Galal-Gorchev and Morris [41]
11.3 Nitrogen Triiodide 295

therefore raised questions disputing the previously reported formula. Roozeboom

[44] found that the above-mentioned reaction leads to an ammonium tribromide
NH4Br3 in the form of orange crystals. It should however be noted that ammonium
bromide was used instead of the sodium or potassium bromide used in the original
procedure [44].
Galal-Gorchev and Morris reported that they prepared nitrogen tribromide by
reaction of aqueous bromine with ammonia and they confirmed the formation of
NBr3 by extraction into chloroform and analyzed the chloroform solution by UV
spectroscopy [41]. Jander [40] reports that the first preparation of nitrogen
tribromide was achieved by Thiedemann by reaction of an acidic aqueous ammonia
salt solution (pH ¼ 4) with bromine. The UV spectroscopy is mentioned as the
method of the product analysis. The isolation of pure nitrogen tribromide from
these aqueous solutions was done by extraction with ether and subsequent precipi-
tation in Freon 12 at
110  C.
Some other methods of preparation of NBr3 by direct bromination of ammonia
are further summarized by Jander [40]. Another possible way for preparation of
pure solid NBr3 is by reaction of bromine or hypobromus acid with an aqueous
solution of ammonia [41, 45]. The concentration of reaction products is a function
of temperature, acidity, and bromine to ammonia ratio. Nitrogen tribromide, NBr3
forms from neutral solutions when the molar ratio of bromine to ammonia is greater
than 1.5 [45].
Pure solid nitrogen tribromide may be prepared by reaction of bistrimethylsilyl-
bromamine and bromine chloride at
87  C in pentane according to Jander [40]:

According to some more recent investigations by Klap€otke, nitrogen tribromide

also forms by reaction of bromine azide and elemental bromine in gaseous form [42]:

11.3 Nitrogen Triiodide

Nitrogen triiodide adduct with one molecule of ammonia (NI3·NH3) was first
prepared by Bernard Courtois, discoverer of iodine, in 1813. It was among the
first derivatives of iodine ever made [46, 47]. The history of the investigation of
nitrogen triiodide during the nineteenth century is summarized in review by
Chattaway [47].
296 11 Nitrogen Halides

11.3.1 Structure

The generally reported cases of “nitrogen triiodide” mostly refer to one of the
nitrogen triiodide adducts with ammonia. The composition of such a substance can
be summarized by the general formula NI3·xNH3. The number of the ammonium
groups varies depending on the reaction conditions but at least the following
substances are reported to exist: NI3·NH3, NI3·2NH3, NI3·3NH3, NI3·5NH3, and
NI3·12NH3. The ammonium adducts with more than one ammonium group are
stable only at low temperatures and all of them lose ammonia over a period of time
to eventually yield NI3·NH3 as a relatively stable final product. Attempts to remove
the last NH3 group resulted in a complete break-up of the molecule [48].
The above-mentioned facts resulted in a common belief that it is impossible to
prepare pure nitrogen triiodide—NI3 without an ammonium molecule—due to its
low stability. The preparation of pure NI3 is however mentioned in at least two
papers. The first is the work of Cremer and Duncan [46] from 1930. They reported
preparation of nitrogen triiodide by reaction of dry ammonia with less stable
dibromoiodides:

The product they obtained by this reaction contained iodine and nitrogen in
molar ratio 1:3.04 (mass ratio 1:27.54; calc. 1:27.18). The resulting substance can
be sublimed in a vacuum at room temperature and condensed by liquid air [46].
This paper seems almost forgotten as we found only one brief reference to it by
Špičák and Šimeček [12].

In 1990, a second paper reporting the first-ever preparation of “adduct-free

nitrogen triiodide” was published by Tornieporth-Oetting and Klap€otke [49]. The
authors allowed boron nitride to react with iodine monofluoride in CFCl3 at low
temperature (
30  C) which yielded pure nitrogen triiodide according to the
following reaction:

The substance formed was reported to decompose rapidly in solution at 0  C and

within several hours at
60  C; the solid substance was found to be stable at

196  C, [49]. It is reported that the preparation of adduct-free nitrogen triiodide is
possible only in the absence of ammonia which is in disagreement with the previous
method by Cremer [46] and will require further confirmation.

Nitrogen triiodide (NI3·NH3) has a polymeric structure [NI3·NH3]n in which tetra-

hedral NI4 units are corner-linked into infinite chains of
N
I
N
I
(2.15 and
2.30 Å) which in turn are linked into sheets by I
I interactions (3.36 Å) in the
c-direction; in addition, one I of each NI4 unit is also loosely attached to an NH3
11.3 Nitrogen Triiodide 297

Fig. 11.1 Projection of the monoclinic crystal structure of nitrogen triiodide [40]. Reprinted from
Advances in Inorganic Chemistry and Radiochemistry, Volume 19, J. Jander, Recent chemistry
and structure investigation of nitrogen triiodide, tribromide, trichloride, and related compounds,
p. 1–63, Copyright (1976), with permission from Elsevier

(2.53 Å) that projects into the space between the sheets of tetrahedra [40, 50]. The
structure is shown in Fig. 11.1.
The estimate of strength of the bond holding NI3 to NH3 is only 16.7 kJ mol
1.
The strength of the N
I bond is 201 kJ mol
1 [51].

11.3.2 Physical and Chemical Properties

Nitrogen triiodide (NI3·NH3) forms black-colored crystals (see Fig. 11.2) with a
density of 3.5 g cm
3 insoluble in water [11]. Its enthalpy of formation is
146 kJ mol
1 [52]. Light causes decomposition of nitrogen triiodide producing
nitrogen [53]. It also decomposes in hot water [11]. Nitrogen triiodide decomposes
by action of many chemical agents, by action of diluted acids (in the case of sulfuric
and hydriodic acids it forms solid iodine and ammonia salt) and it explodes in
contact with concentrated acids, bromine, chlorine, ozone, and hydrogen sulfide. It
also decomposes in aqueous solutions of alkalis, sulfites, thiosulfates, cyanides, or
thiocyanates [11, 47, 54]. Chattaway pointed out that nitrogen triiodide decomposes
in aqueous ammonia with the decomposition rate depending on concentrations [47].
The NI3 molecule forms adducts similar to those with ammonia also with
N-bases such as pyridine (forming NI3·py) [55], quinoline (NI3·3C9H7N) [56], or
urotropine (NI3·I2·C6H12N4) [57].
298 11 Nitrogen Halides

Fig. 11.2 Star crystals of

nitrogen triiodide (Top—
prepared by diffusion of
iodine solution into aqueous
ammonia, Bottom—prepared
by diffusion of alkali ICl into
aqueous ammonia)

11.3.3 Explosive Properties

Nitrogen triiodide is an extremely sensitive compound when dry. It explodes upon

the slightest stimulus as follows:
• Slightest touch (such as a touch by a feather) [11]
• Upon very mild heating (such as a warm air stream) [11]
• With sufficiently strong light (e.g., an electronic flash [58] or light from a spark
discharge [11])
• By bombardment with a-particles [59, 60] or by other fission products [61, 62]
but not by b-particles [59] and neutrons [61]
• By the sound of a tuning fork [63]
• Even spontaneously [62]
Due to its extreme sensitivity, nitrogen triiodide must be stored only in “wet”
conditions, preferably under ether [11]. It retains its sensitivity to a certain extent
even under water where it can be initiated by friction [13].
From the studies of the relationship between the light energy required for
ignition and time lag between the beginning of the light flash and the beginning
11.3 Nitrogen Triiodide 299

of explosion, it seems that the initiation of NI3·NH3 explosion is caused by a

thermal mechanism when light energy changes to thermal energy [11].
The explosion of NI3·NH3 produces a cloud of purple–brown iodine vapor. For
the mechanism of the NI3·NH3 explosion, two equations were proposed. Explosion
in air was determined using the following equation [11]:

The equation below was published for explosion of NI3·NH3 in a helium

environment [51] or for its thermal decomposition at low pressures [48].

Tudela [52] reported this equation for the explosion of NI3·NH3 without further
details. The enthalpy of NI3·NH3 explosion, according to the second equation, is

99 kJ mol
1 (calculated) [52] and
88.1  4.2 kJ mol
1 (experimental) [51].
Activation energy of this decomposition is 75.4–79.6 kJ mol
1 [11].

The presence of ammonia stabilizes NI3·NH3, because ammonia retards the

decomposition of NI3·NH3 to pure NI3. In a concentrated ammonia solution,
NI3·NH3 cannot be ignited even with a very strong flash. Its stability and sensitivity
are also reduced in an ammonia atmosphere. Removal of the NH3 causes spontane-
ous explosion of nitrogen triiodide [11] and it therefore explodes immediately in
high vacuum when dry [64]. Under pure water local explosions of NI3·NH3 do
occur, but the explosion does not spread to the surrounding material [11, 58].

11.3.4 Preparation

Nitrogen triiodide mono-ammonium adduct is usually prepared by action of aque-

ous ammonia on iodine dissolved in a suitable solvent such as aqueous potassium
iodide [46–48, 51, 61, 64].

Nitrogen triiodide is also formed when iodine is used in the solid state [51–53,
59, 65]. But this method is not very suitable—the iodine, being in particles of some
size, not only reacts slowly, but also becomes surface-coated with the iodide which
is difficult to remove [47]. An alcohol or chloroform solution of iodine can be used
as well [9, 54], however using alcohol solutions of iodine or ammonia is not suitable
according to Chattaway. Alcohol rapidly decomposes the nitrogen triiodide-
forming triiodomethane which is not easy to remove from the product [47].
300 11 Nitrogen Halides

Crystalline nitrogen triiodide can be prepared by reaction of aqueous iodine

monochloride (ICl) alkalized by potassium hydroxide with aqueous ammonia. On
cooling, nitrogen triiodide forms as blackish-brown shiny needles, up to 2 mm long
[54, 66]. Nitrogen triiodide is also formed by addition of ammonia to alkaline
solutions of potassium hypoiodite (KIO) [54]. Other iodizing agents such as iodine
monobromides or dibromoiodides can be used as well [46].
Nitrogen triiodide also forms through an ozonation reaction of KI in an aqueous
solution of ammonia (product contains NHI2 and NH2I side products) [67]. Forma-
tion of gaseous NI3 was observed in the case of reaction of boron nitride with iodine
monofluoride [52].

11.3.5 Use

Nitrogen triiodide has never been used in any practical industrial application due to
its extreme sensitivity. Despite the inherent danger of severe injuries during its
preparation and handling, it is particularly popular with young people who use it as
a pyrotechnic toy that explodes by a simple touch.

References

1. Dulong, M.: Ueber die verpuffende Verbindung des Salz - und Stick - Gases I. Schweigger’s
Journal f€ur Chemie und Physik 8, 302–308 (1811)
2. Dulong, M., Thenard, M.M., Berthollet, C.L.: Sur un Mémoire de M. Dulong, sur une nouvelle
substance détonante. Annales de chimie 86, 37 (1813)
3. Davy, H.: On a new detonating compound. Philos. Trans. R. Soc. Lond. 103, 1–7 (1813)
4. Snelders, H.A.M.: De ontdekking van het stikstoftrichloride. Chemie Techniek revue 22,
457–459 (1967)
5. Baker, J.C.: Improvements in process of bleaching and maturing flour. GB Patent 159,166,
1922
6. Mellor, J.W.: A Comprehensive Treatise on Inorganic and Theoretical Chemistry. Longmans
Green, London (1958)
7. Krauz, C.: Technologie výbušin. Vědecko-technické nakladatelstvı́, Praha (1950)
8. Whiteley, M.A. (ed.): Halides of Nitrogen. Longman, Green, London, (1949)
9. Walke, W.: Lectures on Explosives. Wiley, New York (1897)
10. Patnaik, P.: Handbook of Inorganic Chemicals. McGraw-Hill, New York (2003)
11. Fedoroff, B.T., Sheffield, O.E., Kaye, S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, New Jersey (1960–1983)
12. Špičák, S., Šimeček, J.: Chemie a technologie třaskavin. Vojenská technická akademie
Antonı́na Zápotockého, Brno (1957)
13. Wisser, J.P.: Explosive Materials—The Phenomena and Theories of Explosion. D. Van
Nostrand, New York (1907)
14. Hentschel, W.: Ueber Chlorstickstoff. Berichte der deutschen chemischen Gesellschaft 30,
1434–1437 (1897)
15. Selivanoff, T.: Chlorides and iodides of nitrogen. J. Chem. Soc. 66, 312–313 (1894)
References 301

16. Rai, H.: Note on nitrogen chloride, with a convenient method for its preparation. Chem. News
117, 253 (1918)
17. Dowell, C.T., Bray, W.C.: Experiments with nitrogen trichloride. J. Am. Chem. Soc. 39,
896–905 (1917)
18. Griffiths, J.G.A., Norrish, R.O.W.: Photosensitized decomposition of nitrogen trichloride and
the induction period of hydrogen-chlorine reaction. Trans. Faraday Soc. 27, 451–461 (1931)
19. Bowen, E.J.: The photochemistry of unstable substances. J. Chem. Soc. 123, 1199–1206
(1923)
20. Kovacic, P., Lowery, M.K., Field, K.W.: Chemistry of N-bromamines and N-chloramines.
Chem. Rev. 70, 639–665 (1970)
21. Noyes, W.A.: Inorganic Syntheses. McGraw-Hill Book, New York (1939)
22. Noyes, W.A., Lyon, A.C.: The reaction between chlorine and ammonia. J. Am. Chem. Soc. 23,
460–463 (1901)
23. Noyes, W.A.: The interaction between nitrogen trichloride and nitric oxide. Reactions of
compounds with odd electrons. J. Am. Chem. Soc. 50, 2902–2910 (1928)
24. Kolbe, H.: Beobachtungen € uber die oxydirene Wirkung des Sauerstoffs, wenn derselbe
mit H€ulfe einer elektrischen S€aule entwickelt wird. Journal f€ ur praktische Chemie 41,
137–139 (1847)
25. Kolbe, H.: Observations on the oxidizing power of oxygen when disengaged by means of
voltaic electricity. Mem. Proc. Chem. Soc. Lond. 3, 285–287 (1845)
26. Van der Lee, G.: Process for producing nitrogen trichloride. US Patent 2,248,650, 1941
27. Staudt, E.: Process for the manufacture of nitrogen trichloride. US Patent 2,118,903, 1938
28. Staudt, E.: Process for producing nitrogen trichloride. US Patent 2,199,942, 1940
29. Balard, A.J.: Recherches sur la nature des combinaisons décolorantes du chlore. Annales des
Chimie et des Physique, 225–304 (1834)
30. Hentschel, W.: Ueber die Zusammensetzung des Chlorstickstoffs. Berichte der deutschen
chemischen Gesellschaft 30, 1792–1795 (1897)
31. Noyes, W.A.: An attempt to prepare nitro-nitrogen trichloride, an electromer of ammono-
nitrogen trichloride. J. Am. Chem. Soc. 35, 767–775 (1913)
32. Schlessinger, G.G.: Nitrogen trichloride-ether mix explodes. Chem. Eng. News 44, 46 (1966)
33. Baker, J.C.: Process of producing nitrogen trichloride. US Patent 1,510,132, 1924
34. Coleman, G.H., Craig, D.: Nitrogen trichloride and unsaturated ketones. J. Am. Chem. Soc. 49,
2593–2596 (1927)
35. Coleman, G.H., Craig, D.: Nitrogen trichloride and unsaturated ketones. II. J. Am. Chem. Soc.
50, 1816–1820 (1928)
36. Coleman, G.H., Howells, H.P.: Addition of nitrogen trichloride to unsaturated hydrocarbons.
I. J. Am. Chem. Soc. 45, 3084–3089 (1923)
37. Coleman, G.H., Mullins, G.M.: Nitrogen trichloride and unsaturated acids. J. Am. Chem. Soc.
51, 937–910 (1929)
38. Coleman, G.H., Mullins, G.M., Pickering, E.: Nitrogen trichloride and unsaturated
hydrocarbons. II. J. Am. Chem. Soc. 50, 2739–2741 (1928)
39. Coleman, G.H., Buchanan, M.A., Paxson, W.L.: Reaction of nitrogen trichloride with
Grignard reagent. J. Am. Chem. Soc. 55, 3669–3672 (1933)
40. Jander, J.: Recent chemistry and structure investigation of nitrogen triiodide, tribromide,
trichloride, and related compounds. Adv. Inorg. Chem. Radiochem. 19, 1–63 (1976)
41. Galal-Gorchev, H., Morris, J.C.: Formation and stability of bromamide, bromimide, and
nitrogen tribromide in aqueous solution. Inorg. Chem. 4, 899–905 (1965)
42. Klap€otke, T.: The reaction of bromine azide with bromine. Polyhedron 16, 2701–2704 (1997)
43. Performance-oriented packaging standards; changes to classification, hazard communication,
packaging and handling requirements based on UN standards and agency initiative. Fed. Reg.
55, 52402–52729 (1990)
44. Roozeboom, H.W.B.: Ammonium tribromide. J. Chem. Soc. 42, 140 (1882)
45. Inman, G.W., Lapointe, T.F., Johnson, J.D.: Kinetics of nitrogen tribromide decomposition in
aqueous solution. Inorg. Chem. 15, 3037–3042 (1976)
46. Cremer, H.W., Duncan, D.R.: Nitrogen triiodide. J. Chem. Soc. 2750–2754 (1930)
302 11 Nitrogen Halides

47. Chattaway, F.D.: The constitution of the so-called “Nitrogen iodide”. J. Chem. Soc. 69,
1572–1583 (1896)
48. Meldrum, F.R.: The thermal decomposition of nitrogen iodide. Proc. R. Soc. Lond. A 174,
410–424 (1940)
49. Tornieporth-Oetting, I., Klap€ oke, T.: Nitrogen triiodide. Angew. Chem. Int. Ed. 29, 677–679
(1990)
50. Greenwood, N.N.: Chemistry of the Elements. Elsevier, Oxford (1997)
51. Andrews, M.V., Shaffer, J., McCain, D.C.: Nitrogen-iodine bond strength. Thermochemistry
of nitrogen triiodide ammine. J. Inorg. Nucl. Chem. 33, 3945–3947 (1971)
52. Tudela, D.: Nitrogen triioidide. J. Chem. Educ. 79, 558 (2002)
53. Chattaway, F.D., Orton, K.J.P.: The action of light on nitrogen iodide. Am. Chem. J. 24,
159–167 (1900)
54. Chattaway, F.D., Orton, K.J.P.: The formation and constitution of nitrogen iodide. Am. Chem. J.
24, 342–355 (1900)
55. Hartl, H., Ullrich, D.: Die Kristallstruktur von Stickstofftrijodid-1-Pyridin NI3.C5H5N.
Zeitschrift f€ur anorganische und allgemeine Chemie 409, 228–236 (1974)
56. Jander, J., Bayersdorfer, L., H€ ohne, K.: Nitrogen-iodine compounds. V. Adducts of nitrogen
triiodide with N-bases and their application for constitution determination of nitrogen iodide
[nitrogen to iodine ratio 2:3]. Chem. Abst. CAN 68, 110940 (1968)
57. Pritzkow, H.: Die Kristallstruktur von Stickstofftrijodid-1-Dijod-1-Hexamethylentetramin
NI3.I2.C6H12N4. Zeitschrift f€ ur anorganische und allgemeine Chemie 409, 237–247 (1974)
58. Meerk€amper, B.: Zum Verhalten des Jodstickstoffs beim Belichten mit Strahlung
verschiedener Intensit€at. Zeitschrift f€
ur Elektrochemie und Angewandte Physikalische Chemie
58, 387–416 (1954)
59. Henderson, G.H.: a-Particles as detonators. Nature 109, 749 (1922)
60. Poole, H.H.: The detonating action of a-particles. Sci. Proc. R. Dublin Soc. 17, 93–95 (1922)
61. Bowden, F.P., Singh, K.: Irradiation of explosives with high-speed particles and the influence
of crystal size on explosion. Proc. R. Soc. Lond. A 227, 22–37 (1954)
62. Feenenberg, E.: The detonation of nitrogen iodide by nuclear fission. Phys. Rev. 55, 980–981
(1939)
63. Hanus, M.: Méně známé třaskaviny. Synthesia a.s., VUPCH, Pardubice (1996)
64. Garner, W.E., Latchem, W.E.: Note on the decomposition of nitrogen iodide. Trans. Faraday
Soc. 32, 567–569 (1936)
65. Hambly, G.F., Peters, R.: Explosion of nitrogen triiodide: A safer and cleaner demonstration.
J. Chem. Educ. 70, 943 (1993)
66. B€arnighausen, H., Hartl, H., Jander, J.: Kristalldaten von Stickstofftrijodid-1-Ammoniak NI3.
NH3. Zeitschrift f€ ur Naturforschung. Teil B. Anorganische Chemie, organische Chemie,
Biochemie, Biophysik, Biologie 21, 591 (1966)
67. Chudnov, A.F.: Sposob polucheniya iodictogo azota. SU Patent 1,212,935, 1986
Chapter 12
Acetylides

Acetylides are salts of acetylene, which is, under normal conditions, a gas with a
slightly acidic character (pKa is 25, for comparison pKa of acetic acid is 4.76). Due
to their acidic nature, one or both of the hydrogen atoms can be substituted by a
metal atom. Furthermore, acetylene forms so-called metallo-addition compounds
usually containing the acetylene molecule and an added metal compound
(C2H2·MX) [1].
The acetylides of alkali metals and salts of alkaline earths are reactive
compounds, which violently decompose in contact with water or even in contact
with moisture in the air, releasing acetylene. These acetylides do not have the
characteristics of primary explosives and are widely used in organic synthesis as a
source of the acetylene (ethyn-1,2-diyl) group.
Acetylides of heavy metals (silver, copper, gold, mercury) do not react with
moisture and are stable in contact with air. These acetylides are very sensitive to
mechanical stimuli and have the characteristics of primary explosives. Their explo-
sive power is considered to be the same as that of azides and fulminates [2].

12.1 Silver Acetylides

Silver acetylide comes in either a simple form (Ag2C2), in various double salts or
even more complicated complexes depending on the reaction conditions of the
preparation (mainly presence of other salts in the reacting mixture and pH). The
presence of an oxidizing group (such as nitrate, perchlorate, and also halogens) in
complex acetylides appears to increase the explosiveness, whereas the presence of
poorly or nonoxidizing anions (e.g., phosphate, sulfate, organic acid residues)
appears to decrease the explosiveness [3]. An overview of many complex silver
acetylides is copiously described in the literature [4, 5]. Historically, there are only
two groups of acetylides which have been studied in detail for possible industrial
application (a) silver acetylide itself Ag2C2 and (b) its double salts with silver
nitrate especially Ag2C2·AgNO3, less frequently Ag2C2·6AgNO3 [6].

R. Matyáš and J. Pachman, Primary Explosives, 303

DOI 10.1007/978-3-642-28436-6_12, # Springer-Verlag Berlin Heidelberg 2013
304 12 Acetylides

12.1.1 Silver Acetylide

Ag2C2

Simple silver acetylide was first prepared by Quet in 1858 even before acetylene
itself had been identified. The procedure was based on the introduction of a gas
obtained from decomposition of alcohol by electric discharge into an ammoniacal
solution of silver chloride [5, 7, 8].
In the same year, Vogel and Reischaur obtained silver acetylide by introduction
of coal–gas into a solution of the silver salt [9]. The determination of the exact
structure of the molecule, however, took a relatively long time. The variety of
structures considered and their historical development has been summarized by
many authors including, for example, Keiser [7] or Stettbacher [9].

12.1.1.1 Physical and Chemical Properties

Silver acetylide forms crystals with most likely a hexagonal structure, crystal
density 4.47 g cm
3 [10] and heat of formation 357.6  5.0 kJ mol
1 [11] (as
compared to 36.8 kJ mol
1 for sodium acetylide). Silver acetylide, Ag2C2, is a
white solid substance that is sensitive to light. It darkens on exposure to light and
turns black on exposure to direct sunlight for just a few hours [12]. The rate of
photodecomposition is much greater than for SA [12]. Silver acetylide is practically
insoluble in water and common organic solvents [5, 10, 13]. In solutions of
inorganic acids, depending on the type and concentration of the acid, it undergoes
hydrolysis to acetylene and the appropriate salt [12, 14]. Acetylene is also produced
if it comes into contact with potassium cyanide or sulfite [5, 15]. Action of chlorine,
bromine, or some organic nitrocompounds results in very violent or even explosive
decomposition [12]; it also explodes in contact with hydrogen sulfide [16]. Silver
acetylide easily forms double or triple salts by reaction with concentrated aqueous
solutions of silver salts. With a solution of silver acetylide, based on the reaction
conditions, it produces various double salts of Ag2C2 and AgNO3 [17] (chapter
12.1.2-12.1.4); under the action of a solution of silver perchlorate it forms the
double salt silver acetylide-perchlorate with the following formula:
Ag2C2·2AgClO4·2H2O [18], while the action of silver fluoride solution results in
Ag2C2·8AgF [19]; the triple salt 2Ag2C2.AgF·9AgNO3·H2O is formed by action of
silver acetylide on an aqueous solution of silver nitrate and silver tetrafluoroborate
(molar ratio 1:1) [20]. An overview of many other double salts is given in the
review by Vestin and Ralf [5].

12.1.1.2 Explosive Properties

Simple silver acetylide is generally quite sensitive to mechanical stimuli and

definitely more sensitive than its double salt Ag2C2·AgNO3 [2]. Sensitivity of
12.1 Silver Acetylides 305

Table 12.1 Impact sensitivity of silver acetylides [21]

Ammonia Impact sensitivity
concentration
in reaction Impact height 0.5 kg Recalculated
mixture (m/m %) hammer (cm) energy (J)
Ag2C2 0.57 15 0.74
Ag2C2 2.0 66 3.2
Ag2C2·AgNO3a – 43 2.1
Ag2C2·AgNO3b – 79 3.9
Ag2C2·AgNO3b – 64 3.1
MF – 24 1.1
LA – 43 2.1
a
Prepared in neutral solution.
b
Prepared in acidic solution (nitric acid).

simple silver acetylide is about the same as MF according to Stettbacher [9]. Impact
sensitivity of silver acetylide has been studied in detail by Taylor and Rinkenbach
who found that it is highly affected by reaction conditions, mainly the concentration
of ammonia in the reaction mixture. The results are compared with MF and LA in
Table 12.1 [21].
Friction sensitivity of silver acetylide is generally high and exceeds sensitivity of
most other primary explosives including MF [22] or cuprous acetylide [12] and it is
even slightly more sensitive than LA [21]. K€ ohn [12] reports that significant
decomposition is observed even at friction force of 0.2 N (lowest possible force
of the machine) when using ceramic plates of BAM type. Our measurements
confirm the results of above-mentioned authors. Sensitivity of silver acetylide to
friction is one of the highest compared to other common industrial and improvised
primary explosives (see Fig. 2.19) [23]. Aging further increases the friction sensi-
tivity as explosion of half year old silver acetylide occurred even during sweeping
of sample from ceramic plate by brush (Matyas Unpublished). Friction sensitivity
is, just like the impact sensitivity, influenced by the preparation route [21].
Ignition temperatures of silver acetylide reported in various literature sources
cover a very broad range spanning from 140  C to 200  C. The reason is most likely
reflecting different reaction conditions and hence different products. It is therefore
very important to always check what was really prepared [12]. The summary of
published values of ignition temperatures of silver acetylide in comparison with
silver acetylide–silver nitrate is summarized in Table 12.2.
It was observed by K€ ohn that the ignition temperature changes as the material
ages. Some values determined at heating rate 1  C s
1 are presented in Table 12.3
for acetylides of silver and copper [12]. The results are the lowest values obtained in
a series of measurements. The sensitivity of silver acetylide to impact, friction, and
hot wire does not change with time [12].
The heat of explosion of silver acetylide is 294 kJ mol
1 according to Stadler
[29]. For a long time it was assumed that only solid products form from the
explosion of simple silver acetylide [1]. Later it was, however, shown that some
gaseous products do indeed form (2.4 ml from 1 g of sample according to Stadler
[29]). Eggert found that the gaseous products of explosion contain water, carbon
306 12 Acetylides

Table 12.2 The ignition temperature of simple Ag2C2 compared with the double salt
Ag2C2·AgNO3
Ignition temperature ( C)
Ag2C2 Ag2C2·AgNO3 Conditions of determination References
143–148 a
202 –209 a
Range for heating rate 5–21.5  C min
1 [24]
171–177 200a or 225b Instantaneous explosion or within 1 sc [21]
195–200 197–202 Explosion within 5–10 s [10]
~200 220 Details are not mentioned [25]
– 210a Explosion within 5 s [26]
– 210, 212 Details are not mentioned [27, 28]
220 Instantaneous explosion [26]
a
Prepared in acidic solution.
b
Prepared in neutral solution.
c
Compared with 260  C for MF and 383  C for LA.

Table 12.3 Ignition temperatures of silver and copper acetylides at heating rate 1  C s
1 with
sample size 3 mg [12]
Ignition temperature ( C)
Sample age Ag2C2 Cu2C2
3h 155 110
24 h 158 115
3 days 156 135
8 days 157 142
2 weeks 157 163
3 weeks 157 190
6 weeks 161 184
2 months 163 175
a
2.5 months 169
a
7 months 170
a
16 months 167
a
Explosive decomposition not observed below 200  C.

monoxide, carbon dioxide, hydrogen, and methane. The amount of gaseous

products is about one-tenth of the gaseous products that form during explosion of
Ag2C2·AgNO3 [30]. Taki later reported that 2–5 mol% of Ag2C2 contribute to the
formation of gaseous products during explosion. The composition of these products
is about 30% hydrogen, 50–60% nitrogen, 10–20% carbon dioxide, and small
amounts of methane and ethane. Taki attributed the formation of gases to impurities
in silver acetylide [16].
The explosion of simple Ag2C2 is less violent and far less noisy than explosion
of Ag2C2·AgNO3 or AgN3 [30–32]. Eggert ascribes this to the fact that explosion of
Ag2C2·AgNO3 or AgN3 both produce large amounts of gas while Ag2C2 produces
only a very low amount of these products [30, 32]. Ten grams of Ag2C2 does not
create any cavity in lead block test [29].
McCowan measured detonation velocities of silver acetylides Ag2C2 and
Ag2C2·AgNO3, packed in a trench 1  1  50 mm cut in a perspex plate and
12.1 Silver Acetylides 307

ignited by an exploding wire. Detonation velocity of Ag2C2 was 1,200 m s
1 and
1,980 m s
1 for Ag2C2·AgNO3 [10].
Simple silver acetylide is a relatively “weak” primary explosive [5]; it is less
brisant than its double salt Ag2C2·AgNO3 [2], however, has stronger explosive
properties than cuprous acetylide. Urbański attributes this to an exceptionally high
positive heat of formation [33].

12.1.1.3 Preparation

Silver acetylide forms by reaction of acetylene with a solution of a silver salt

(nitrate, perchlorate, or chloride) in aqueous ammonia. Mixing silver nitrate with
aqueous ammonia results in temporary formation of a brown precipitate which later
dissolves in this solution. After the solution clears, acetylene is introduced and a
gray-white precipitate forms [12]. Several authors describe that a voluminous
yellow precipitate is formed initially, which then rapidly transforms into a white
precipitate with a smaller volume [5, 9]. This phenomenon was discussed in the
Vestin and Ralf review but the composition of the yellow precipitate has not been
identified [5].

Details of silver acetylide preparation are described in the work of K€ohn [12] or
Stettbacher [9], the latter recommending to wash acetylene before introducing into
the solution by passing it through four gas-washing bottles. The first contains
diluted sulfuric acid which absorbs ammonia and possibly other nitrogen containing
bases. The second contains potassium permanganate mixed with sulfuric acid for
oxidation of phosphine and sulfane. The third contains a neutral solution of
potassium permanganate and the last one pure water [9]. Using unpurified acetylene
in the process of silver acetylide preparation leads to a product with a grayish or
brownish tinge [29].

Simple silver acetylide does not form in aqueous potassium cyanide or potas-
sium thiosulfate solutions [1]. Introduction of acetylene into a neutral or acidic
solution of silver nitrate does not lead to the simple silver acetylide salt Ag2C2, but a
complex acetylide Ag2C2·AgNO3. Keiser, however, reports that it is possible to
prepare Ag2C2 in diluted neutral solutions of silver nitrate, while in more
concentrated ones the double salt Ag2C2·AgNO3 is formed [7].
Several authors have reported that explosions can occur during some steps of
silver acetylide preparation. Taki published a risk of explosion during spreading out
of silver acetylide; it can explode when it is pulverized to a fine powder [16]. Vestin
and Ralf reported that explosions of silver acetylide occur rather often (about every
tenth preparation), especially during the evacuation (when the product is dried
under vacuum) [5].
Silver acetylide may spontaneously form when acetylene comes into long-term
contact with metallic silver. This may also be the case of some soldering alloys
where different amounts are allowable depending on the overall composition [12].
308 12 Acetylides

12.1.1.4 Uses

To the best of our knowledge simple silver acetylide has never found any practical
application.

12.1.2 Silver Acetylide–Silver Nitrate

Ag2C2·AgNO3

12.1.2.1 Physical and Chemical Properties

The silver acetylide–silver nitrate forms fine needle and cross crystals [28] as
shown on Fig. 12.1 with density 5.36 g cm
3 [6] or 5.369 (X-ray) [17]. The density
is superior to MF and LA making Ag2C2·AgNO3 a primary explosive with one of
the highest known densities [29]. It decomposes by action of acids liberating
acetylene:

The decomposition by action of concentrated sulfuric acid or nitric acid is

gentle, unlike in the case of simple silver acetylide [9]. Silver sulfite and acetylene
form by action of solutions of alkaline sulfides; decomposition takes place also by
action of alkaline chloride at higher temperature; however, in this case it is rather
slow and incomplete [4]. Potassium cyanide solution decomposes it in a similar
way to simple silver acetylide liberating acetylene quantitatively [5]. Silver
acetylide–silver nitrate is not stable in water and according to Stadler it slowly
decomposes to Ag2C2 with part of the AgNO3 dissolving in water. The composition
of the precipitate corresponds to Ag2C2·AgNO3·Ag0.53C0.52 after 14 h exposure in
distilled water at normal temperature. However, in another section of this chapter,
Stadler reported that the explosive properties of Ag2C2·AgNO3 are not reduced by
3 days exposure to a moist environment at 90  C, or in a moist environment with
66% carbon dioxide or by 3 days exposure to light. Ag2C2·AgNO3 reacts with
gaseous ammonia if stored above aqueous ammonia [29].

12.1.2.2 Explosive Properties

Sensitivity of silver acetylide–silver nitrate to impact and friction is lower than

sensitivity of simple silver acetylide Ag2C2 or mercury fulminate [29]. According to
Taylor and Rinkenbach the reaction conditions (especially pH) have a significant
influence on sensitivity. The impact sensitivity of samples prepared from a neutral
solution is higher than that of Ag2C2·AgNO3 prepared form an acidic solution;
sensitivity of Ag2C2·AgNO3 prepared form a neutral solution is about the same
as sensitivity of LA [21]. Stadler published impact sensitivity for Ag2C2·AgNO3
12.1 Silver Acetylides 309

Fig. 12.1 Needle crystals of silver acetylide–silver nitrate Ag2C2·AgNO3 by SEM

equal to 2.8–3.4 cm for 2 kg hammer in comparison with 3.2 cm for LA and 1.1 for
MF [29].
Friction sensitivity of silver acetylide–silver nitrate (both prepared from acidic and
neutral solutions) is published lower than the sensitivity of mercury fulminate [21].
According to our experiments sensitivity of Ag2C2·AgNO3 is between LA and MF
(see Fig. 2.19) [23]. Silver acetylide–silver nitrate is exceptionally sensitive to flame.
The ignition temperature of Ag2C2·AgNO3 is mostly reported to be higher than
for simple silver acetylide [21, 24] (see Table 12.2). The ignition temperature of the
product is significantly influenced by concentration of nitric acid in the reaction
mixture. It increases with nitric acid concentration from 206  C (without HNO3) to
280  C (for 28% content of HNO3). Similar behavior was observed for concentra-
tion of silver nitrate; ignition temperature increases with silver nitrate concentration
from 203  C (1% AgNO3) to 282  C (for 20% AgNO3). Elaborate analysis of the
measured samples was unfortunately not done before testing and it is therefore hard
to relate molecular structure to sensitivity [29].
The thermal stability of silver acetylide–silver nitrate increases when some
metals are present in the crystalline lattice of Ag2C2·AgNO3. Boldyrev and Pronkin
reported that the addition of cadmium nitrate into the reaction mixture during
Ag2C2·AgNO3 preparation increases the ignition temperature of Ag2C2·AgNO3.
This product is also less sensitive to ultraviolet light [26].
Stadler and Stettbacher suggested for explosive decomposition the following
equation [29, 31]:

The heat of explosion is 774 kJ mol
1 [29]. In earlier work, Eggert reported the
formation of other rather unexpected gaseous products during explosion (water, hydro-
gen, methane, nitrogen, and unspecified nitrogen oxides) [30]. Stadler later published
that 139.4 ml gaseous products (0  C, 101.3 kPa) form during explosion of 1 g
310 12 Acetylides

Table 12.4 Detonation velocity of Ag2C2·AgNO3 compared with LA [29]

Ag2C2·AgNO3 LA
Density (g cm
3) Detonation velocity (m s
1) Density (g cm
3) Detonation velocity (m s
1)
2.51 2,250 1.45 2,120
2.92 2,710 2.16 3,080
3.79 3,320 3.12 4,270
3.96 3,460 3.19 4,540

Table 12.5 Dependence of ignition efficiency of Ag2C2·AgNO3 on preparation conditions and

compared with LA and MF [29]
Ignition efficiency (mg)
Reaction conditions Tetryl TNT
Neutral pH, 5% cold solution AgNO3 50 >150
Neutral pH, 5% hot solution AgNO3 30–50 100
Acidic pH, 13% hot solution AgNO3 20 50–75
LA 20 30
MF 100 120

Ag2C2·AgNO3 with composition 38.7 mol% CO2, 41 mol% CO, and 20.2 mol% N2
[29]. The powder of Ag2C2·AgNO3 measured by a lead block test is on average
136 cm3 for 10 g sample prepared in acidic environment and 120 cm3 for sample
prepared in a neutral environment (compared with 181 cm3 for LA) [29].

Detonation velocity of Ag2C2·AgNO3 has been measured by Stadler. The

dependence of detonation velocity on density is presented in Table 12.4 and
compared with lead azide. The detonation velocity of LA is superior to that for
Ag2C2·AgNO3 at all densities [29].
The brisance of silver acetylide–silver nitrate (determined as the number of
splinters) increases with increasing loading pressure and slightly exceeds that of
LA pressed by 50 MPa. Ag2C2·AgNO3 cannot be dead-pressed by this pressure
level [29].
The initiating efficiency is high. It is reported as being about 4 times more
powerful than MF (0.005 g for PETN, 0.07 for tetryl, and 0.25 for TNT) [13];
Stettbacher determined 0.07 g Ag2C2·AgNO3 for tetryl (compared with 0.29 g for
MF and 0.02 for SA) [9]. Stadler studied the influence of reaction conditions on
ignition efficiency of Ag2C2·AgNO3. The highest ignition efficiency was determined
for Ag2C2·AgNO3 prepared from a hot acidic solution of AgNO3, lower for the
product prepared from a hot neutral solution of AgNO3 and the lowest for the product
prepared from a cold neutral solution of AgNO3. Ignition efficiency of Ag2C2·AgNO3
prepared from a hot acidic solution is approaching that of LA [29] (Table 12.5).
12.1 Silver Acetylides 311

12.1.2.3 Preparation

Silver acetylide–silver nitrate forms when acetylene is introduced into a neutral or

slightly acidic aqueous solution of silver nitrate [5, 13, 31]. The concentration of
silver nitrate solution must be lower than 10% wt. because in more concentrated
solutions silver acetylide–hexanitrate forms [10, 27, 28]. Silver acetylide–silver
nitrate precipitates from the solution in the form of a heavy white powder. Just as in
the case of simple silver acetylide, use of unpurified acetylene results in a product
with a grayish or brownish tinge [29].

The complex salt initially formed from the solution of silver nitrate may be
transformed into a simple silver acetylide if the acetylene pressure at the end of
precipitation exceeds some critical value. The details of the transformation are,
according to Vestin and Ralf [5], described by Chavastelon who observed that
introduction of acetylene into an aqueous solution containing excess of silver
nitrate quantitatively gives a 1:1 complex. This complex also initially forms if
excess acetylene is used. If the reaction is terminated in a reasonable time scale the
precipitate is again the 1:1 complex salt. Silver acetylide, however, begins to form
if the acetylene treatment continues. The change from the complex to the acetylide
is not very fast and even after 40 h there may be some unconverted complex left in
the reaction mixture. It is therefore important to understand that the precipitate may
have a varying composition depending on the transformation extent [5].

Silver acetylide–silver nitrate also forms directly by reaction of calcium carbide

with aqueous silver nitrate [4] and it even forms as a film on the surface of silver
nitrate solution in an acetylene atmosphere [10]. It is also possible to prepare this
substance by adding Ag2C2 into a stirred neutral solution of silver nitrate or by
mixing Ag2C2 with nitric acid (50–60%) [2].

12.1.2.4 Uses

Silver acetylide–silver nitrate is reported as “probably suitable for use in primers and
detonators” [2]. Several patents were published at the beginning of the twentieth
century recommending use of silver acetylides in detonators [34] and as a replace-
ment of MF in impact initiated detonators [35]. Danilov et al. reported in 2001 that
silver acetylide–silver nitrate is not used in practical applications in Russia (referring
to explosive applications) [25].
Silver acetylide–silver nitrate was used in light initiated flying plate generator of
shock wave experiments at Sandia in 1980 [36, 37]. The use in organic synthesis
has been reported by Sladkov and Ukhin [38].
312 12 Acetylides

12.1.3 Silver Acetylide–Silver Hexanitrate

Ag2C2·6AgNO3

Double salt of silver acetylide with six silver nitrate molecules (silver acetylide–-
hexanitrate) forms rhombohedral crystals if acetylene is introduced into a
concentrated solution of silver nitrate (concentration higher than 25%) [28, 39, 40].
The product is very soluble in a solution of silver nitrate (mother liquor) and the
solubility increases with the nitrate concentration [27, 28].
The crystal density of the product formed is 4.090 g cm
3 according to Guo
et al. [17]; 4.79 g cm
3 according to Jin et al. [41], or 4.81 g cm
3 according to
Kung-Tu Chou [40]. The crystal structure of Ag2C2·6AgNO3 has been studied and
is reported in [39–41]. The rhombs of the acetylide–hexanitrate complex decom-
pose in water to Ag2C2·AgNO3 and silver nitrate. They also tend to transform to
Ag2C2·AgNO3 needles in other environments that act to reduce the silver nitrate
concentration of the solution in which the rhombs exist. Hence addition of acety-
lene leads to Ag2C2·AgNO3 while addition of silver nitrate leads to Ag2C2·6AgNO3
[28]. The complex acetylide HgC2·3AgNO3 forms from Ag2C2·6AgNO3 in solution
of mercuric nitrate [42].
When heated, hexanitrate first melts and then decomposes producing nitrogen
oxides. The thermal decomposition is not violent as with Ag2C2·AgNO3. The
decomposition temperature is rather high and significantly exceeds that for
Ag2C2·AgNO3 (308–327  C for hexanitrate vs. 212  C for mononitrate) [27, 28].
According to Shaw and Fisher silver acetylide–hexanitrate is, unlike Ag2C2 and
Ag2C2·AgNO3, a nonexplosive substance [27]; Vestin and Ralf reported, that this
compound can explode, but feebly [5].

12.1.4 Other Salts of Silver Acetylide–Silver Nitrate

Studies of acetylides have proved the existence of a large number of other silver
acetylide–silver nitrate-based complexes. Pentanitrate Ag2C2·5AgNO3 and 5.5
nitrate hemihydrate Ag2C2·5.5AgNO3·0.5H2O are among the more frequently
mentioned ones. Guo, who also described the crystal structure of both complexes,
reports a density of 4.560 g cm
3 for Ag2C2·5AgNO3 and 4.427 g cm
3 for
Ag2C2·5.5AgNO3·0.5H2O [17].
Ag2C2·5.5AgNO3·0.5H2O is prepared by reaction of simple silver acetylide with
a solution of silver nitrate in a water suspension at 80  C. A violent decomposition
is reported for this complex compound when it is heated. The second compound,
Ag2C2·5AgNO3, can be prepared by reaction of Ag2C2 with silver trifluoroacetate.
Moist simple silver acetylide reacts with a concentrated solution of silver trifluor-
oacetate at 80  C and the solution is evaporated in a desiccator above P2O5. A gluey
residue is re-dissolved in water and a small amount of silver nitrate is added at
80  C. The resulting solution is kept at 0  C for several days, after which a mixture
of Ag2C2·5AgNO3 and Ag2C2·6AgNO3 crystallizes. The monoclinic–prismatic
12.2 Cuprous Acetylide 313

crystals of Ag2C2·5AgNO3 can be picked out from among the block-like crystals of
Ag2C2·6AgNO3.

12.2 Cuprous Acetylide

Simple cuprous acetylide was first prepared by Quetem in 1858. The preparation
was based on introduction of the gases (contained acetylene) produced by passing
electric sparks through liquid alcohol into a solution of cuprous chloride in aqueous
ammonia [7, 8].

12.2.1 Physical and Chemical Properties

Cuprous acetylide is a red to brown-red amorphous substance. Its specific color is

determined by the conditions of preparation. The substance prepared by the normal
precipitation of cuprous salts by acetylene forms as a monohydrate [43]. It is
interesting to note in older literature that the molecular formula of cuprous acetylide
monohydrate is often written in a rather unusual form, for example C2H2Cu2O [44].
The water of crystallization is firmly bonded and may not be removed even at 140  C
above phosphorous oxide [43]. Older literature contains procedures for preparation
of the anhydrous salt by drying the monohydrate above sulfuric acid [7].
Cuprous acetylide is not soluble in water, but quite well soluble in bases [2]. In
an oxygen environment it undergoes slow decomposition, according to Klement
and K€oddermann-Gros [43]:

Cuprous acetylide darkens when it is stored in the open. The change of color is
accompanied by a significant increase in its sensitivity to mechanical stimuli. It is
believed that both these phenomena are caused by oxidation of cuprous acetylide to
cupric acetylide by oxygen in the atmosphere [45].

Potassium cyanide decomposes cuprous acetylide and an equivalent amount of

acetylene is produced [46]:

This reaction was proposed by Polyakov for quantitative analysis of copper

acetylides (both cuprous and cupric). In the case of a mixture of cuprous and cupric
acetylide only total acetylide content is determined. The analyzed substance is
dissolved in a solution of potassium cyanide (cupric acetylide is also dissolved
314 12 Acetylides

producing one mol of acetylene) and the acetylene is introduced into a solution of
the cuprous salt. Cuprous acetylide precipitates from the solution and the excess of
cuprous ions is titrated iodometrically.

Klement and K€ oddermann-Gros published a different course for the above-

mentioned reaction [43]:

In solutions of inorganic acids, cuprous acetylide hydrolyzes to acetylene and

the corresponding salt. Hydrolysis rate and its course depend on the type and
concentration of the acid [14]. Acetylene gas is evolved from cuprous acetylide
even by action of hydrogen sulfide and potassium cyanide solution [1]. Some
concentrated acids (nitric acid, sulfuric acid) and oxidizing agents (ozone, perman-
ganate, chlorine, bromine) decompose acetylide explosively [47]. The reaction with
hydrogen peroxide (30%) forms a substance with an aldehydic character [33].
Reaction with aqueous silver nitrate solution quickly leads to silver acetylide and,
using a mercurous nitrate solution leads to mercurous acetylide [48].

Cuprous acetylide further forms complex compounds in a similar way to silver

acetylide. These cuprous complex salts form by the action of acetylene on certain
cuprous salts in a neutral or slightly acidic medium [33].

12.2.2 Explosive Properties

Friction sensitivity of cuprous acetylide prepared by common procedure involving

cuprous chloride (procedure published e.g., by Špičák and Šimeček [49]) is rela-
tively low and is approaching sensitivity of PETN (Fig. 2.19) [23]. Cuprous
acetylide can easily be initiated by electrostatic discharge or hot wire. The sensitiv-
ity to these two types of initiation was the reason why it was used in pyrotechnic
mixtures for blasting cap fuseheads [33]. Brisance is lower than that of silver
acetylide.
The ignition temperature of cuprous acetylide is reported with very wide ranges
due to a strong influence of the reaction conditions on the resulting properties and
the diversity of testing methods. The lowest published ignition temperature is
100  C [44], followed by 120  C [2, 13], 120–123  C [33], 170  C (in vacuum
265  C!) [43] and the highest is in the range 260–270 C [45]. Values published by
other authors are summarized in Table 12.2. Many researchers report that the
ignition temperature changes as the material ages. Interestingly, some of them
12.2 Cuprous Acetylide 315

report a decrease of ignition temperature with time [43, 45], while others suggest an
increase [12]. Morita reports that the changes are caused by atmspheric oxygen and
that the ignition temperature first drops from 260–270  C to 100  C and later again
rises above 200  C [45]. The aging was also studied by K€ohn who found the
opposite trend with the substance first showing an increase in ignition temperature
followed by a decrease and later by complete loss of ability to explode on heating
(see Table 12.3) [12].

12.2.3 Preparation

The reaction of acetylene with an aqueous solution of cuprous chloride may yield a
variety of substances depending on the reaction conditions. The most important
factors are acidity and presence of other inorganic salts. Various complex salts with
coordinated acetylene molecule may form (for example use of an acidic or alcohol
solution results in formation of the complex salt Cu2Cl2·C2H2) [1].
Simple cuprous acetylide forms by reaction of gaseous acetylene introduced into
the aqueous ammonia solution of the cuprous salt. Precipitates of different colors
form depending on the reaction conditions.

Using pure cuprous chloride as a reactant leads to cuprous acetylide precipitated

as a red substance. The precipitate does not form an individual compound, the ratio
of C/Cu being in range 0.94–1.13 (theoretically it should be equal to 1) [50].
Klement and K€ oddermann-Gros analyzed the product prepared in an ammoniacal
environment and found it to be 95% pure [43]. Precipitation carried out in an acidic
environment produced substance which was not sensitive to impact [50].

Early scientists assumed that recovery of the acetylene from the cuprous
acetylide precipitate was quantitative. However, it was soon found that the
regenerated acetylene was not perfectly pure because of the addition reaction of
hydrochloric acid to form vinyl chloride, and also because of the alteration of the
precipitate in air to yield a cuprous compound of diacetylene [1].
In order to limit the oxidation of the cuprous salt to cupric and hence prevent the
formation of cupric acetylide, a number of authors recommend the presence of reducing
agents (e.g., hydroxylamine, sulfur dioxide, hydrazine sulfate, etc.) [1, 14, 33]. The
applicability of certain reducing agents during the preparation of cuprous acetylide was,
however, questioned by Brameld Clark and Seyfang [50]. According to these authors,
the product prepared from ammoniacal solution of cuprous chloride in the presence of
any of hydrazine hydrochloride, hydroxylamine hydrochloride, or formaldehyde has
lower explosive properties than product prepared in the usual way. The probable reason
is the formation of other by-products from the reaction (e.g, the precipitate prepared in
the presence of formaldehyde has the atomic ratio of C/Cu equal to four). The product
prepared in the presence of tin(II)chloride is not explosive [50].
316 12 Acetylides

During the preparation and processing of cuprous acetylide, attention should be

paid to potential contamination by cupric acetylide. This substance is produced by a
reaction of acetylene with certain copper salts which may be present as an impurity
in the initial cuprous chloride. The material is unstable and highly sensitive to
mechanical stimuli, exploding upon heating to 50–70  C (see Sect. 12.3) [33].
Cuprous acetylide may also form spontaneously at places where copper or its
alloys come to contact with acetylene. The acetylide does not form with any alloy
containing copper but only when the content exceeds maximum allowable
copper content specific for the particular alloy. The explosions of laboratory and
industrial apparatuses as a result of copper acetylide formation are a subject of
many reports [12].

12.2.4 Uses

Cuprous acetylide is the only acetylide which has been practically used, due to the
ease with which it can be ignited by hot wire and by electric charges. It was
therefore used as a component of fuse head compositions [13, 33, 51, 52]. Cuprous
acetylide was also designed as a catalyst in ethynylation reactions (direct conden-
sation of acetylene and aldehydes or ketones) [53–57].
The creation of cuprous acetylide has been suggested as a quantitative method
for determination of copper in analytical chemistry [33]. Cuprous acetylide is
produced in ammoniacal environments in the presence of hydroxylamine, even at
very low concentrations of acetylene gas. It is on the basis of the formation of a
brown precipitate of cuprous acetylide that a sensitive method for detection of
acetylene was devised [58].

12.3 Cupric Acetylide

C C
Cu

According to Fedoroff and Sheffield cupric acetylide was first prepared by

S€oderbaum by the introduction of acetylene into ammoniacal copper salts [2, 59].

12.3.1 Physical and Chemical Properties

Cupric acetylide is a gray-black colored substance. Depending on the method of

preparation it may be produced as an amorphous substance, or as the so-called
metallic, an extremely sensitive form. Cupric acetylide explosively decomposes if
12.3 Cupric Acetylide 317

combined with nitric acid [2] or dilute sulfuric acid, and in potassium cyanide
solution it decays slowly [59]. With acids it releases acetylene [1]. With silver
nitrate solution a simple silver acetylide is produced [48]. The action of potassium
cyanide solution causes the release of acetylene:

This reaction was proposed by Polyakov for determination of presence of copper

acetylides (both cuprous and cupric) in mixture with other substances containing
copper (see Sect. 12.2.1) [46].

12.3.2 Explosive Properties

Unlike cuprous acetylide, both forms of cupric acetylide are highly sensitive
substances. Cupric acetylide may be initiated by a weak mechanical stimulus
such as tapping [50]. It retains a high level of sensitivity even under water [45].
Cupric acetylide is further unstable and can explode on heating, even at
temperatures as low as 50–70  C according to Urbański [33] or at 100–120  C
according to Morita [45].

12.3.3 Preparation

Cupric acetylide is prepared by the introduction of acetylene into a solution of

cupric salts. Similar to cuprous acetylide, the properties of the product (color,
sensitivity) are to a large extent dependent on the conditions of the reaction [50].

The product of the reaction forms either as an amorphous substance or as a

crystalline, so-called metallic, form [50]:

• The amorphous form is a black precipitate which forms rapidly from common
copper salts (chloride, sulfate, nitrate).
• The so-called metallic form is created if the reactant is cupric borate in a strongly
alkaline environment, or cupric acetate in an acidic or strongly alkaline environ-
ment. These lustrous metallic looking plates form only when blowing acetylene
through the solution for a long time or on standing in contact with the gas. This
form is extremely sensitive to mechanical stimuli and explodes with a bright
flash on a gentle tap or even on touching under solution.
When using cupric chloride as a reactant and carrying out the reaction in an
alkaline environment, product properties vary significantly depending on the type
of alkali. The product from an ammoniacal environment contains a significantly
318 12 Acetylides

higher proportion of carbon (the ratio of C/Cu corresponds to 2.7–2.8 compared

with a theoretical 2), while in the presence of sodium carbonate and sodium
hydroxide the content of both elements is closer to theory (1.85–2.07). The
acetylide precipitation is, in the latter case, practically immediate, while the rate
of precipitation in ammoniacal environments depends on the concentration of
ammonia; in strongly ammoniacal solutions, the precipitate appears only some
time after the introduction of acetylene [50].
The composition of the product prepared in a neutral environment of cupric
chloride or sulfate is close to theory (the ratio of C/Cu ¼ 1.98). If the reactant is a
cupric tartrate in an acidic environment then cuprous acetylide is the final product
due to the reducing properties of tartaric acid [50]. Cupric acetylide is also
produced directly by the reaction of calcium carbide in aqueous solutions with
cupric salts. Calcium hydroxide and cupric hydroxide, which co-precipitate
together with cupric acetylide, can be dissolved by adding dilute acetic acid [48].
Cupric acetylide (along with cuprous) may inadvertently appear on copper
surfaces or alloys with high copper content when exposed to acetylene. Therefore,
copper should not be used in places where it could come in contact with acetylene.

12.3.4 Uses

Because of its high sensitivity and low stability, cupric acetylide has never been
used in any practical application.

12.4 Mercuric Acetylide

HgC2

12.4.1 Physical and Chemical Properties

Mercuric acetylide is a heavy white amorphous powder with a density of

5.3 g cm
3 (at 16  C) [60, 61]. Its structure was discussed by Malý and Kuča
who, through X-ray analysis, determined the inter-atomic distances in the molecule
HgC2 (length of bond CC is 1.19  0.02 Å, the length of the C–Hg bond is
2.17  0.02 Å) [62].
Mercuric acetylide is insoluble in water, ethanol, and ether. Freshly produced
mercuric acetylide dissolves well in ammonium acetate. It decomposes in solutions
of potassium cyanide and sodium sulfide [14, 60, 61]. In inorganic acid solutions,
mercuric acetylide slowly hydrolyzes to acetylene and the corresponding salt (rate
depends on the type and concentration of the acid) [14]. Hydrochloric acid only has
a slight effect on mercuric acetylide at normal temperatures and at higher
temperatures it decomposes this acetylide to mercuric chloride and acetylene,
12.4 Mercuric Acetylide 319

which is partially hydrolyzed to acetaldehyde [15, 60, 61, 63]. Nitric acid dissolves
acetylide, and dilute sulfuric acid causes a gradual decomposition with mainly the
aldehyde as a product. Concentrated sulfuric acid, chlorine, and bromine react with
mercuric acetylide explosively. Reaction with brominated water yields tetrabro-
moethylene C2Br4. With iodine dissolved in potassium iodide solution diiodoacetylene
C2I2 is produced, or if the reaction takes place at higher temperatures, over a longer
period of time in an excess of iodine, tetraiodoethylene C2I4 forms [61]. With silver
nitrate solution it reacts quickly to form a simple silver acetylide [48].
During slow heating, mercuric acetylide slowly decomposes at 110  C and
above to mercury, carbon, and water [60, 61].
Storing mercuric acetylide in an ethanolic solution of mercuric chloride or even
shortly boiling it in an aqueous solution of mercuric chloride leads to its transfor-
mation into a nonexplosive compound that has the same properties as the product of
bubbling acetylene through a solution of mercuric chloride [60, 61].

12.4.2 Explosive Properties

Mercuric acetylide explosively decomposes to mercury and carbon in an amor-

phous form (like soot) [62]. Nothing else was found about explosive properties of
this compound in an open literature.

12.4.3 Preparation

Acetylene reactions with mercury compounds are different from the analogous
reaction with compounds of silver or copper. Unlike silver nitrate or cupric chlo-
ride, mercuric compounds in neutral solutions catalyze the addition of water to the
acetylene molecule. The acetaldehyde and a few substituted acetylenes therefore
form as a product of this reaction and form either main or side products of the action
of acetylene on mercuric solutions [1].
Based on the comparison with cupric acetylide it could be assumed that mercuric
acetylide will form from the reaction of acetylene with a solution of mercuric
chloride. This reaction gives a white precipitate, which is not HgC2, but some
organomercury compound. To the substance prepared in a neutral environment,
Keiser attributes the formula C2(HgCl)2 [15, 63], Blitz, and Mumm (ClHg)3C–CHO,
Biginelli CHCl¼CHHgCl [1].
Mercuric acetylide HgC2 forms when passing acetylene through Nessler reagent
solution (solution of HgI2 in KI and KOH). The product consists of a white
flocculent precipitate identified by Keiser as HgC2 [15, 63] and later confirmed
by X-ray analysis [62]. However, on the basis of subsequent analysis, Fedoroff and
Sheffield identified the reaction product as 3HgC2·H2O [2].
The effect of the type of mercuric reactant and composition of the reaction mixture
on the yield of mercuric acetylide has been dealt with by Plimpton and Travers.
Freshly precipitated mercuric oxide is suggested as the most appropriate starting
material. It is dissolved in ammonia and, after ammonium carbonate addition,
320 12 Acetylides

acetylene is introduced into the solution. The product forms as a heavy white powder.
Based on the analysis of mercury in the product, the formula 3HgC2·H2O has been
proposed [61]. Babko and Grebelskaya also started with mercuric oxide, but used an
alkaline solution of potassium iodide as the reaction environment [14]. Introduction
of acetylene into solutions of a number of other mercury salts leads to explosive
compounds, probably acetylides, but unfortunately no satisfactory analysis of these
compounds has been published. Exceptionally high sensitivity and brisance was
observed with the precipitate formed by the introduction of acetylene into mercuric
oxide solution in chloric acid [3].
Introduction of acetylene into a saturated solution of mercuric acetate in glacial
acetic acid yields a substance which has an explosive character, but this is quickly
lost during storage (during a week). Ferber with Romero report this substance to be
mercuric acetylide and proposed the formula 2HgC2·H2C2·H2O [64].
An interesting compound, mercury acetylide-silver nitrate complex
HgC2·3AgNO3, forms by introducing acetylene to a concentrated solution of silver
nitrate (about 30%) acidified by nitric acid and followed by addition of mercuric
nitrate. The product precipitates from the solution [42].

12.4.4 Uses

Mercuric acetylide has never been employed in any practical explosive application. It
has, however, found some use in analytical work because formation of the precipitate
of mercuric acetylide (from an alkaline solution of mercuric iodide and potassium
iodide) can be used for the quantitative determination of acetylene [1].

12.5 Mercurous Acetylide

Hg2C2·H2O

Mercurous acetylide is a gray-colored substance. It crystallizes as a

monohydrate insoluble in water [2, 60, 65]. Behavior during heating is described
variously, some authors stating that the substance first separates out the water of
crystallization and subsequently degrades [60], while others, like Burkard and
Travers, describe the substance as unable to release crystal water because heating
to temperatures over 100  C leads to decomposition [65]. Mercurous acetylide is
decomposed to acetylene on treatment with hydrochloric acid [65, 66]. Reaction
with iodine yields mercurous iodide and tetraiodoethylene (C2I4) with a small
proportion of diiodoacetylene (C2I2).
The preparation of mercurous acetylide is not very well described in the litera-
ture. The most complete seems to be the initial work of Plimpton [66] who
suspended freshly prepared mercurous acetate in water (it is insoluble) and passed
acetylene through such suspension. He himself, however, reported that the gray
explosive substance which forms from the acetate was not analyzed. In its
properties the prepared substance resembled acetylides of copper and silver.
12.6 Aurous Acetylide 321

Burkard later tried to clarify the issue of the product composition and based on the
results of elemental analysis concluded that the substance is mercurous acetylide
monohydrate—Hg2C2·H2O [65]. Another not very well described way for prepar-
ing mercurous acetylide is the reaction of cuprous acetylide in aqueous suspension
with mercurous nitrate [48]. Both preparation methods must be also carried out in
the absence of daylight.

12.6 Aurous Acetylide

Au2C2

12.6.1 Physical and Chemical Properties

Aurous acetylide is a yellow compound, it decomposes by boiling in water into its

constituents (acetylene does not form), and it also decomposes by the action of
hydrochloric acid (acetylene and black aurous chloride form). Cold ferric chloride
or cupric sulfate does not decompose it. When the acetylide is heated very gradu-
ally, it decomposes without explosion [67].

12.6.2 Explosive Properties

Aurous acetylide is a highly sensitive substance which explodes, even by brushing

with a camel’s hair “brush” on filter paper [67]; Vincente et al. reported that it
explodes after drying when touched by a spatula [68]. Explosion is also reported
when rapidly heating it. Temperature of ignition is in range 83–157  C (heating in
the air-bath, heating rate was not specified). Solid products, gold and amorphous
carbon, form when gold acetylide explodes [67].

12.6.3 Preparation

Aurous acetylide can be prepared by the reaction of acetylene with sodium aurous
thiosulfate Na3Au(S2O3)2 in a strongly alkaline solution. The product forms as a
yellow flocculent precipitate. Sodium aurous thiosulfate is prepared by reaction of
auric chloride with sodium thiosulfate [67].
Aurous acetylide does not form when passing acetylene through an aqueous
solution of auric chloride. Instead metallic gold precipitates. Precipitation does not
occur when introducing acetylene into a solution of auric chloride alkalized by
potassium hydroxide nor into aqueous or ammoniacal solutions of potassium auric
cyanide [67]. Unwanted formation of aurous acetylide has been reported during
preparation of some alkynylgold(I) complexes [68].
322 12 Acetylides

References

1. Nieuwland, J.A., Vogt, R.R.: The Chemistry of Acetylene. Reinhold Publishing Corporation,
New York (1945)
2. Fedoroff, B.T., Sheffield, O.E., Kaye, S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, New Jersey (1960–1983)
3. Nieuwland, J.A., Maguire, J.A.: Reactions of acetylene with acidified solutions of mercury and
silver salts. J. Am. Chem. Soc. 28, 1025–1031 (1906)
4. Gmelins Handbuch der anorganischen Chemie – Silber, pp. 270–273. Verlag Chemie,
Weinheim (1973)
5. Vestin, R., Ralf, E.: Solver compounds of acetylene. Acta Chem. Scand. 3, 101–143 (1949)
6. Redhouse, A.D., Woodward, P.: Crystallographic data for silver acetylide. Acta Crystallogr.
17, 616–617 (1964)
7. Keiser, E.H.: The composition of the explosive copper and silver compounds of acetylene.
Am. Chem. J. 14, 285–290 (1892)
8. Quet, M.: Note sur un phénomène de polarité dans la décomposition des gaz par ľétincelle
électrique, et sur les produits que ľon obtient en décomposant ľalcohol par ľétincelle électrique
ou la chaleur. Comptes rendus hebdomadaires des séances de l’Académie des sciences 40,
903–905 (1858)
9. Stettbacher, A.: Neuere Initialexplosivstoffe. Zeitschrift f€ ur das gesamte Schiess- und
Sprengstoffwesen 11, 1–4 (1916)
10. McCowan, J.D.: Decomposition of silver acetylide. Trans. Faraday Soc. 59, 1860–1864 (1963)
11. Finch, A., Gardner, P.J., Head, A.J., Majdi, H.S.: The standard enthalpy of formation of silver
acetylide. Thermochim. Acta 180, 325–330 (1991)
12. K€ohn, J.: Untersuchungen € uber die explosiven Eigenschaften von Silberacetylid. Amts- und
Mitteilungsblatt der Bundesanstalt f€ ur Materialpr€ufung 8, 57–62 (1978)
13. Krauz, C.: Technologie výbušin. Vědecko-technické nakladatelstvı́, Praha (1950)
14. Babko, A.K., Grebelskaya, M.I.: Rastvorimost atsetilenidov medi, serebra i rtuti. Zhurnal
obshchey khimii 22, 66–76 (1952)
15. Keiser, E.H.: The metallic derivatives of acetylene. Am. Chem. J. 15, 535–539 (1893)
16. Taki, K.: Reactive species in the explosion of silver acetylide I. Reaction with saturated
hydrocarbons. Bull. Chem. Soc. Jpn. 42, 2906–2911 (1969)
17. Guo, G.-C., Zhou, G.-D., Mak, T.C.W.: Structural variation in novel double salts of silver
acetylide with silver nitrate: Fully encapsulated acetylide dianion in different polyhedral silver
cages. J. Am. Chem. Soc. 121, 3136–3141 (1999)
18. Guo, G.-C., Wang, Q.-G., Zhou, G.-D., Mak, T.C.W.: Synthesis and characterization of
Ag2C2•2AgClO4•2H2O: A novel layer-type structure with the acetylide dianion functioning
in a m6-h1,h1:h2,h2:h2,h2 bonding mode inside an octahedral silver cage. Chem. Commun.
339–340 (1998)
19. Guo, G.-C., Zhou, G.-D., Wang, Q.-M., Mak, T.C.W.: A fully encapsulated acetylenediide in
Ag2C2•8AgF. Angew. Chem. Int. Ed. 37, 630–632 (1998)
20. Wang, Q.-M., Mak, T.C.W.: Coexistence of differently capped trigonal prismatic C2@Ag7
cages in a triple salt of silver(I) acetylide. J. Cluster Sci. 12, 391–398 (2001)
21. Taylor, A.C., Rinkenbach, W.H.: Sensitivities of detonating compounds to frictional impact,
impact, and heat. J. Franklin Inst. 204, 369–376 (1927)
22. Khmelnitskii, L.I.: Spravochnik po vzryvchatym veshchestvam. Voennaya ordena Lenina i
ordena Suvorova Artilleriiskaya inzhenernaya akademiya imeni F. E, Dzerzhinskogo, Moskva
(1962)
23. Matyáš, R., Šelešovský, J., Musil, T.: Sensitivity to friction for primary explosives. J. Hazard.
Mater. 213–214, 236–241 (2012)
24. Tammann, G., Kr€ €
oger, C.: Uber die Verpuffungstemperatur und Schlagempfindlichkeit von
fl€ussigen und festen Explosivstoffen. Zeitschrift f€ ur anorganische und allgemeine Chemie 169,
1–32 (1928)
References 323

25. Danilov, J.N., Ilyushin, M.A., Tselinskii, I.V.: Promyshlennye vzryvchatye veshchestva; chast
I. Iniciiruyushchie vzryvshchatye veshchestva. Sankt-Peterburgskii gosudarstvennyi tekhnolo-
gicheskii institut, Sankt-Peterburg (2001)
26. Boldyrev, V.V., Pronkin, V.P.: Povyshenie termicheskoi ustoichivosti atsetilenida serebra
vvedeniem dobavok kadmiya. Zhurnal vsesoyuznogo khimicheskogo obshchestva im.
D. I. Mendeleeva 6, 476–477 (1961)
27. Shaw, J.A., Fisher, E.: Silver acetylide compound and process of making same. US Patent
2,483,440, 1949
28. Shaw, J.A., Fisher, E.: A new acetylene silver nitrate complex. J. Am. Chem. Soc. 68, 2745
(1946)
29. Stadler, R.: Analytische und sprengstofftechnische Untersuchungen an Azetylensilber.
Zeitschrift f€ur das gesamte Schiess- und Sprengstoffwesen 33, 269–272, 302–305, 334–338
(1938)
€
30. Eggert, J.: Uber Acetylensilber. Chemiker-Zeitung 42, 199–200 (1918)
31. Stettbacher, A.: Z€ undsprengstoffe. Nitrocellulose 11, 227–229 (1940)
€
32. Eggert, J.: Uber einige Vorlesungsversuche mit Acetylen-silber. Berichte der deutschen
chemischen Gesellschaft 51, 454–456 (1918)
33. Urbański, T.: Chemistry and Technology of Explosives. PWN—Polish Scientific Publisher,
Warszawa (1967)
34. Semple, J.B.: Improvements relating to the detonation of explosives. GB Patent 133,393, 1918
35. FR Patent 321,285, 1902
36. Benham, R.A.: Preliminary Experiments Using Light-Initiated High Explosive for Driving
Thin Flyer Plates. Report SAND-79-1847 (1980)
37. Benham, R.A.: Initiation and Gas Expansion Model for the Light-Initiated Explosive Silver
Acetylide-Silver Nitrate. Report SAND-79-1829 (1980)
38. Sladkov, A.M., Ukhin, L.Y.: Copper and silver acetylides in organic synthesis. Russ. Chem.
Rev. 748–763 (1968)
39. Osterlof, J.: Crystal structure of Ag2C2•6AgNO3 and 2CuCl•C2H2. Acta Crystallogr. 7 (1954)
40. Chou, K.-T.: Crystal structure of Ag2C2•6AgNO3. Chem. Abstr. 60, 2399 (1964)
41. Jin, X., Zhou, G., Wu, N., Tang, Y., Huang, H.: Structure determination and refinement of
silver acetylide-silver nitrate (1:6). Chem. Abstr. 113, 88547 (1990)
42. Shaw, J.A., Fisher, E.: Mercury acetylide-silver nitrate complex and process of making same.
US Patent 2,474,869, 1949
43. Klement, R., K€oddermann-Gros, E.: Die Oxydationsprodukte des Kupfer(I)-acetylides.
Zeitschrift f€ur anorganische Chemie 254, 201–216 (1947)
44. Blochmann, R.: Ueber die Vorg€ange bei der unvollst€andigen Verbrennung des Leuchtgases
und €uber das Verhalten desselben in der Hitze bei Abschlufs von Luft. Justus Liebigs Annalen
der Chemie 173, 167–191 (1874)
45. Morita, S.: The effect of oxygen on the explosivity of red cuprous acetylide. Chem. Abstr. 50,
6047 (1956)
46. Polyakov, N.N.: Opredelenie acetilenidov medi v prisutstvii drugikh soedinenii medi. Zhurnal
analiticheskoi khimii 8, 302–305 (1953)
47. Rupe, H.: Zwei Vorlesungsversuche. Journal f€ ur praktische Chemie 88, 79–82 (1913)
48. Durand, J.-F.: Doubles décompositions, en milieu aqueux, entre ses acétylures métalliques et
des sels. Comptes rendus hebdomadaires des séances de l’Académie des sciences 177,
693–695 (1923)
49. Špičák, S., Šimeček, J.: Chemie a technologie třaskavin. Vojenská technická akademie
Antonı́na Zápotockého, Brno (1957)
50. Brameld, V.F., Clark, M.T., Seyfang, A.P.: Copper acetylides. J. Soc. Chem. Ind. 66, 346–353
(1947)
51. Rintoul, W.: Explosives. Rep. Prog. Appl. Chem. 5, 523–565 (1920)
52. Burrows, L.A., Lawson, W.E.: Electric blasting initiator. US Patent 2,086,531, 1937
53. Reppe, W.: Äthinylierung. Justus Liebigs Annalen der Chemie 596, 6–11 (1955)
324 12 Acetylides

54. Reppe, W., Keyssner, E.: Verfahren zur Herstellung von Alkoholen der Acetylenreihe. DE
Patent 726,714, 1937
55. Reppe, W., Keyssner, E.: Production of alkinols. US Patent 2,232,867, 1941
56. Reppe, W., Steinhofer, A., Spaenig, H., Locker, K.: Production of alkinols. US Patent
2,300,969, 1942
57. Reppe, W., Steinhofer, A., Trieschmann, H.-G.: Verfahren zur Ausf€ uhrung katalytischer
Umsetzungen. DE Patent 734,881, 1939
€
58. Pietsch, E., Kotowski, A.: Uber den Nachweis sehr geringer Mengen von Acetylen. Angew.
Chem. 44, 309–312 (1931)
59. S€oderbaum, H.G.: Ueber die Einwirkung des Acetylens auf Cuprisalze. Berichte der deutschen
chemischen Gesellschaft 30, 814–815 (1897)
60. Bagal, L.I.: Khimiya i tekhnologiya iniciiruyushchikh vzryvchatykh veshchestv.
Mashinostroenie, Moskva (1975)
61. Plimpton, R.T., Travers, M.W.: Metallic derivates of acetylene. I. Mercuric acetylide. J. Chem.
Soc. 264–269 (1894)
62. Malý, J., Kuča, L.: Struktura a rozpad acetylidu rtuti. Chemické listy 47 (1953)
63. Keiser, E.H.: Metallic derivates of acetylene. J. Chem. Soc. 61 (1894)
€
64. Ferber, E., R€omer, E.: Uber einige neue Acetylen-Quecksilber-Komplexsalze. Journal f€ ur
praktische Chemie 277–283 (1934)
65. Burkard, E., Travers, W.T.: The action of acetylene on the acetates of mercury. J. Chem. Soc.
81, 1270–1272 (1902)
66. Plimpton, R.T.: Metallic derivates of acetylene. Proc. Chem. Soc. 8, 109–111 (1892)
67. Mathews, J.A., Watters, L.L.: The carbide of gold. J. Am. Chem. Soc. 22, 108–111 (1900)
68. Vicente, J., Chicote, M.-T., Abrisqueta, M.-D., Jones, P.G.: New neutral and anionic alkynylgold(I)
complexes via new synthetic methods. Crystal and molecular structures of [(PPh3)2N][Au
(CCCH2OH)2], [Au(CCSiMe3)(CNtBu)], and [Au(CCR)PR0 3] (R0 ¼Cyclohexyl, R¼CH2Cl,
CH2Br; R0 ¼Ph, R¼SiMe3, tBu). Organometallics 16, 5628–5636 (1997)
Chapter 13
Other Substances

In this chapter, we have decided to summarize substances that are not very well
described in open literature. There are three groups of substances that we consider
interesting enough to mention here—salts of nitramines, organophosphates, and
hydrazine nitrates.

13.1 Salts of Nitramines

Primary nitramines are substances with acidic hydrogen and which therefore easily
form salts. Since many nitramines are high explosives it is logical that their salts,
especially those of heavy metals, were those investigated. Only a small number of
such substances, however, fall into a group of primary explosives.
The heavy metal salts of methylnitramine (MNA) have been reported by Davis
[1] as “primary explosives which had not been extensively investigated.” Searching
more recent literature revealed that there has not been much work published since
the time of World War II.
Silver and lead salts of methylenedinitramine (MEDINA) have, according to
Urbański, sufficient initiating properties to be used practically. The sensitivity to
impact and the ignition temperatures of both salts are summarized in Table 13.1 [2].
Ethylenedinitramine (EDNA) is a powerful secondary explosive patented by
Hale [3]. The two acidic hydrogens of the nitramino group can be relatively easily
replaced with metal ions. Every once in a while speculation arises regarding the
applicability of EDNA salts for use as primary explosives. The sensitivity of the
metallic salts is, however, relatively low. The cupric salt of ethylenedinitramine is
less sensitive than both LA and LS. It follows from Table 13.2 that it is comparable
to secondary explosives. Ignition of CuEDNA occurs at 196
C, DSC onset is at
162
C (10
C min1) [4]. Cupric, ferrous, lead, and potassium salts of EDNA are
more sensitive then RDX but not sensitive enough to qualify for use as primary
explosives. Impact sensitivities obtained by Blatt [5] and summarized in Fedoroff,
Shefield, and Kaye’s [6] are listed in Table 13.3.

R. Matyáš and J. Pachman, Primary Explosives, 325

DOI 10.1007/978-3-642-28436-6_13, # Springer-Verlag Berlin Heidelberg 2013
326 13 Other Substances

Table 13.1 Sensitivity and ignition temperatures of methylenedinitramine salts [2]

Impact sensitivity Ignition
Salt h50; 2 kg weight (cm) temperature (
C)
Ag 10 195
Pb 12 213

Table 13.2 Sensitivity of CuEDNA compared with LA and LS [4]

Impact Sensitivity to electric discharge
sensitivity—h50;
Ball & Disc test Friction sensitivity Standard test Test for sensitive expl.
Compound (cm) (m s1)a (mJ) (No.7) (mJ)
CuEDNA >40 >3.7 >40 >40
LAb 19 1.2 – 2.5
LSb 11 1.8 – 7
a
Emery paper friction test; values are pendulum velocities required to produce a 50 % probability
of ignition.
b
Service material RD 1343 for LA (precipitated from sodium carboxymethylcellulose/sodium
hydroxide) and RD 1303 for LS. Emery paper friction test; values are velocity of pendulum
required to produce a 50 % probability of ignition.

Table 13.3 Impact sensitivity of metallic salts of EDNA [5, 6]

Compound CuEDNA FeEDNA K2EDNA PbEDNA RDX
Impact sensitivity (cm/5 kg hammer) 17 21 43 30 51

The heavy metallic salts (including the cupric salt) of ethylenedinitramine can be
easily prepared by reacting ethylenediamine with the corresponding sulfate via the
sodium salt. In the case of copper, the product precipitates from the solution in the
form of a blue/green solid which tends to form compact material after drying in air
overnight. Such product can be reduced to a powder by gentle grinding in toluene
using a glass rod. The final powdery product is obtained after filtering off the
toluene and drying under vacuum [4]. The same method of preparation has been
reported for the lead salt [7].
+
Na
- -
NH NO2 N NO2 N NO2
H2C H2C H2C 2+
+ NaOH + CuSO4 Cu
H2C H2C - H2C -
NH NO2 N NO2 N NO2
+
Na
EDNA CuEDNA

The cupric salt of ethylenedinitramine has been studied as a potential green

primary explosive replacing LA. Low sensitivity, however, excluded it from such a
use [4].
Another relatively recently investigated group of primary nitramines are salts of
4,6-diazido-2-nitramino-1,3,5-triazine (DANT). These substances have been
13.1 Salts of Nitramines 327

Fig. 13.1 SEM photographs of cesium (left) and rubidium (right) salts of DANT (kindly provided
by Tomáš Musil)

Table 13.4 Sensitivity and DSC data of rubidium and cesium salts [8]
Impact sensitivity Friction sensitivity Small BAM (g) Onset DSC,
Compound Ball drop (mJ) No-fire level Low fire level 20
C min1 (
C)
Rb salt 12 850 900 200
Cs salt 13 175 200 182
LS 25 40 50 290

Table 13.5 Performance of rubidium and cesium salts (witness plate test) [8, 9]
Compound Loading pressure (MPa) Density (g cm3) Average dent in Al block (mm)
Rb salt 69 1.810 0.8
Cs salt 69 2.026 0.5
LA (RD 1333) 69 3.119 37.3

examined while searching for new potential green primary explosives. From the
published results, it seems that the most promising are the cesium and rubidium salts
of DANT. SEM photographs of rubidium and cesium salts are shown in Fig. 13.1.
+ - + -
Rb NNO2 Cs NNO2

N N N N

N3 N N3 N3 N N3

The sensitivity of the cesium and rubidium salts of 4,6-diazido-2-nitramino-

1,3,5-triazine has been published by Hirlinger and Bichay and is reprinted in
Table 13.4 [8].
The performance of these two salts was measured by the plate dent test. Both
salts have a performance which is too low for use as a lead azide replacement
(as follows from Table 13.5) [8, 9].
328 13 Other Substances

Preparation of DANT has been briefly described by Hirlinger and Bichay [8]
Fronabarger et al. [11] and more recently by Musil et al. in detail [10]. Cyanuric
chloride is the starting material that is aminated at low temperature to yield
2-amino-4,6-dichloro-1,3,5-triazine which in turn reacts with sodium azide to
form 2-amino-4,6-diazido-1,3,5-triazine. Finally, the product is nitrated at low
temperature with 100 % nitric acid to produce the final product, 4,6-diazido-2-
nitramino-1,3,5-triazine. The alkali salts are readily formed by reaction with the
appropriate hydroxides in methanol [8, 10, 11].

Cl Cl N3
N N N
NH3 NaN3
N Cl N NH2 N NH2
N N N
Cl Cl N3

N3 N3 N3
+
N N N Rb
HNO3 RbOH -
N NH2 N NHNO2 N NNO2
N N N
N3 N3 N3

The rubidium and cesium salts did not perform well in trials for LA replacement
and were therefore proposed as LS replacements. Using less electropositive metals
may yield candidates for lead azide replacement [8].

13.2 Organophosphates

An interesting and relatively unexpected group of organophosphate compounds has

recently been reported. Two candidates have been mentioned: 4,4,6,6,8,8-
hexaazido-1,3,5,7,2l5,4l5,6l5,8l5-tetrazatetraphosphocine-2,2-diamine (DAHA)
and 7,7,9,9-tetraazido-1,4-dinitro-1,4,6,8,10-pentaaza-5l5,7l5,9l5-triphospha-spiro
[4.5]deca-5,7,9-triene (ENTA) [12]. Surprisingly, there is nothing reported in the
literature about diazido, dinitro, or dinitramino derivates of DAHA in position
2 instead of the amino groups nor about diazido or dinitramino derivates of ENTA
in position 1,4 instead of the nitro groups.
H2N NH2
P
N N N N
N3 N3
O2N NO2
P P P
N N
N3 N3 N3
N N N3
P P P
N
N3 N3 N3 N3

DAHA ENTA
13.2 Organophosphates 329

Table 13.6 Sensitivity and DSC data of ENTA [12]

Impact sensitivity Friction sensitivity Small BAM (g) DSC, 20
C min1 (
C)
Compound Ball drop (mJ) No-fire level Low fire level Onset Peak
ENTA – 300 400 235 266
LS 25 40 50 290 305

Table 13.7 Results of plate dent test of ENTA [12]

Compound Loading pressure (MPa) Density (g cm3) Average dent in Al block (mm)
ENTA 69 1.756 1.3
LA (RD 1333) 69 3.119 37.3

ENTA is described as being a yellow or white [12] or colorless [13] crystalline

solid. Density of ENTA is 1.83 g cm3 [12] and melting point 144–145
C [12, 13].
DAHA forms as a white crystalline material with melting point 72–74
C [14].
The sensitivity of ENTA (Table 13.6) and its performance measured by witness
plate test (Table 13.7) compared to LA and LS indicate its low sensitivity but
unfortunately also its low performance. DAHA is sensitive to hot wire and success-
fully initiates secondary explosives (RDX, CL-20) in a detonator (MK-1) [23].
DAHA is a thermally stable compound despite its low melting point (72–74
C). It
decomposes violently at 230
C (DSC, onset) [14].
Bichay and Hirlinger [12] reported that the detonation ability of ENTA in the
above-mentioned test strongly depends on synthesis conditions. The ENTA sample
reported in the earlier tables failed to detonate (1.3 mm dent) whereas other tested
samples produced detonation (values for those samples were not found). The
authors expected that higher purity and larger crystals would improve the detona-
tion characteristics of ENTA.
The synthesis of ENTA begins with the commercially available starting material
hexachlorocyclotriphosphazene which reacts with 2 equivalents of ethylenediamine to
yield 7,7,9,9-tetrachloro-1,4,6,8,10-pentaaza-5l5,7l5,9l5-triphosphaspiro[4.5]deca-
5,7,9-triene-1,4-diamine (a compound very susceptible to hydrolysis). This compound
can be re-crystallized from methylene chloride or hexane. The second step is nucleo-
philic azide displacement of the residual chloro groups with lithium or sodium azide in
dry acetone. 7,7,9,9-Tetraazido-1,4,6,8,10-pentaaza-5l5,7l5,9l5-triphosphaspiro-
[4.5]deca-5,7,9-triene-1,4-diamine forms a clear gum which slowly crystallizes
under high vacuum. Nitration of 7,7,9,9-tetraazido-1,4,6,8,10-pentaaza-5l5,7l5,9l5-
triphosphaspiro[4.5]deca-5,7,9-triene-1,4-diamine is the last step in ENTA synthesis.
Nitronium tetrafluoroborate in acetonitrile is necessary because 100 % nitric acid in
acetanhydride does not yield any product. More suitable usage of N,N0 -dinitroethy-
lendiamine (EDNA) or its dilithium or disodium salt instead of ethylenediamine is not
possible, probably because of the poor nucleophilicity of the nitramine group [12, 13].
330 13 Other Substances

Cl Cl
N N + -
P H2C NH2 H2N NH2 H2C NH3 Cl
N N Et2O P
+ 2 N N +
Cl Cl + -
P P H2C NH2 Cl Cl H2C NH3 Cl
N P P
Cl Cl N
Cl Cl

N N
H2N NH2 N N
P H2N NH2
N N acetone P
+ 4 LiN3 N N + 4 LiCl
Cl Cl
P P N3 N3
N P P
Cl Cl N
N3 N3 N
N
O2N NO2
NO2BF4 / CH3CN P
N N
N3 N3
P P
N
N3 N3
ENTA

DAHA is prepared from readily available octachlorocyclotetraphosphazene. It is

aminated with ammonium hydroxide in diethylether at low temperature, forming the
intermediate 1,1-diamino-3,3,5,5,7,7-hexachlorocyclotetraphosphazene. DAHA
forms in the second step by nucleophilic azide displacement of the residual chloro
groups with sodium azide in acetone [14, 24].
Cl Cl H2N NH2
P P
N N Cl N N Cl
Cl Cl
Na2SO4
P P + 2 NH4OH P P + 2 NH4Cl
Et2O
Cl Cl Cl N N Cl
N N
P P
Cl Cl Cl Cl

H2N NH2 H2N NH2

P P
N N N N N3
Cl Cl N3
acetone
P P + 6 NaN3 P P + 6 NaCl

Cl Cl N3 N N N3
N N
P P
Cl Cl N3 N3

DAHA

Both substances have been proposed as “green candidates” for new primary
explosives [12, 14, 23]. Details of the results, except the ones in Table 13.7, are not
known.
13.3 Hydrazine Complexes 331

Table 13.8 Form and color of metallic hydrazine nitrates [16]

Formula Color, form
[Cd(N2H4)3](NO3)2a White crystalline powder
[Co(N2H4)3](NO3)2a Brown fine crystalsa
[Mn(N2H4)2](NO3)2 Yellow-brown powder
[Ni(N2H4)3](NO3)2 Rose violet colored fine crystals
[Zn(N2H4)3](NO3)2a White crystalline powder
a
The same colors and shapes have been published by Lao [17] for products containing two
hydrazine ligands.

13.3 Hydrazine Complexes

With bivalent metals, hydrazine nitrate forms coordination compounds that may be
represented by the general formula Me[(N2H4)2 or 3](NO3)2 [6]. The two most often
mentioned substances are nickel hydrazine nitrate (NHN) and cobalt hydrazine
nitrate (CoNH).
These compounds are not typical primary explosives as they have sensitivity and
explosive properties in between that of primary and secondary explosives [15]. The
amount of information about these compounds is rather limited and in some cases
quite inconsistent.
The description of crystal type and color of several metallic hydrazine nitrates
are summarized in Table 13.8. The density of NHN is 2.07 g cm3. Nickel and
cobalt hydrazine nitrate are practically insoluble in common organic solvents (e.g.,
ethanol, acetone) and sparingly soluble in water (0.47 g l1 at 30
C, 2.31 g l1 at
70
C). NHN burns upon the action of 96 % sulfuric acid, but weak acid makes it
decompose more gently; CoHN explodes in contact with concentrated sulfuric acid.
NHN mildly reacts with a 10 % solution of sodium hydroxide and this can be used
for producing a chemical decomposition. NHN is stable on exposure to sunlight and
it hardly reacts at all with common metals. Cobalt hydrazine nitrate is unstable and
decomposes slowly, even in the presence of traces of moisture, changing in color
from brown to greenish [16, 17].
Nickel hydrazine nitrate is not easily detonated by flame or heat in charges of a
few grams even when mixed with lead styphnate, picrate, or RDX. These mixtures
were loaded in a blasting cap and initiated but the best that has been observed was a
deflagration [6, 16]. Other results have been obtained by Talawar et al. [18]. They
made a research of the applicability of NHN in detonators. NHN is ignitable by the
flame of a match, a safety fuse, or a hot wire. Whether it develops detonation
strongly depends on its confinement and its density.
Impact sensitivity and ignition temperature for several metallic hydrazine
nitrates are summarized in Table 13.9.
The detonation velocity of NHN is 3,600 m s1 at 0.8 g cm3 and 6,900–7,000 m s1
at 1.7 g cm3 [16, 21]. To achieve the density of 1.7 g cm3 NHN was pressed by
150 MPa, which shows its good resistance to dead pressing. The dependency of the
detonation velocity on the diameter of the charge at density 0.62 g cm3 is
summarized in Médard and Barlot paper [16].
332 13 Other Substances

Table 13.9 Metallic hydrazine nitrates: ignition temperatures and sensitivity to impact and
friction
Impact sensitivity Friction Ignition
Recalculated sensitivity temperature
Compound As reported to energy (J) (N) (
C) References
[Cd(N2H4)3](NO3)2a ~1.5 m/10 kg 147 – 236–245 [16]
[Co(N2H4)3](NO3)2a ~1.75 m/2 kg 34 – 206–211 [16]
59 cm/2 kg (h50) 11.6 (h50) >60 – [19]
[Mn(N2H4)2](NO3)2 Not sensitive – 150 [16]
[Ni(N2H4)3](NO3)2 1.4 m/2 kg 27.5 – 212–215 [16]
84 cm/2 kg (h50) 16.5 >10 219 [20]
(210 onset)
21 cm/0.4 kg (h0) 0.82 – – [21]
lower than MF 260–270 [17]
96 cm/2 kg (h50) 18.8 (h50) 10 219 [18]
– 72 (F50) 232b Our data
[Zn(N2H4)3](NO3)2a >3 m/10 kg >294 – 310 [16]
a
The same values of impact sensitivities and ignition temperatures are reported by [17] for products
containing two hydrazine ligands.
b
Heating rate 5
C min1 (DTA).

Metallic hydrazine nitrates is prepared by the reaction of the relevant nitrate with
hydrazine in water or alcohol [16, 21]. The product is isolated from the reaction
mixture as a precipitate [6]. The preparation of NHN according to the procedure of
Zhu [21] gives 95 % yield and leads to fine powder shown in Fig 13.2.
 
NiðNO3 Þ2 þ 3 N2 H4 ! Ni ðN2 H4 Þ3 ðNO3 Þ2
Detailed preparation methods for NHN and CoHN have been described by
Chhabra et al. [20]. They used diluted aqueous solutions (4 and 8 %) of nickel
nitrate preheated to 65
C and simultaneously mixed it with a concentrated solution
(>80 %) of hydrazine hydrate. The reaction gave a 90 % yield of NHN. When using
cobalt nitrate the yield was 85 % of CoHN. Reducing the temperature to 25
C led
to yields around 90 % for both complexes; however, the products obtained at lower
temperatures were amorphous and did not flow as well as the granular ones
produced at higher temperatures.
According to Chinese authors [17] researchers outside China use 30 % nickel
nitrate and a 40 % solution of hydrazine hydrate. Using solutions of such a high
concentration leads to the formation of a light pink powder with unsuitable
properties. To obtain good product, the Chinese use lower concentrations in both
nickel nitrate (5–10 %) and hydrazine hydrate (10–15 %). The reaction temperature
is 50–70
C and within 30–40 min yields about 80 % of product in the form of
spherical crystals of NHN with density 1.0 g cm3.
Information about the process is only available to a limited extent. It is believed
that an aqueous solution of nickel salt is placed into the reactor and hydrazine is
slowly added. Most of the time nickel nitrate is used, but some trials using nickel
acetate and sodium nitrate have also been found. Acidity of the nickel solution in
References 333

Fig. 13.2 SEM photograph

of nickel hydrazinium nitrate
(NHN) (kindly provided by
Tom Musil)

the reactor is adjusted by addition of acetic acid which is done before the addition of
the hydrazine. The initiating efficiency of NHN to RDX is 0.17 g and to PETN it is
0.13 g (compared to 0.2 g of MF) [17].
Of all the hydrazine nitrate salts only nickel hydrazine nitrate has been suggested
for practical applications. Although it was first reported more than 50 years ago it
still has not found wider application [22]. Despite the earlier information that nickel
hydrazine nitrate is not reliably initiated in blasting caps [6, 16] it has been recently
suggested as a primary explosive that is suitable as a replacement for lead azide as an
intermediate charge in commercial detonators [15, 22]. Other authors recommended
NHN as a complete replacement for lead styphnate and a partial replacement of lead
azide in detonators [18].
One analog of NHN is a substance with the nitrate group replaced by azide—
nickel hydrazine azide (NHA). Only very limited information is available, includ-
ing a preparation procedure which is practically the same as in the case of NHN.
Aqueous solutions of the nickel salt and sodium azide are placed in a stirred reactor,
acidity is adjusted by addition of acetic acid, the mixture is heated to 50–70
C, and
an aqueous solution of hydrazine hydrate is slowly added. NHA has green poly-
crystalline form with crystal density 2.12 g cm1. Average particle size of product
with good fluidity is around 80 mm and bulk density of such powder is
0.57–0.65 g cm3. The thermal decomposition is a two-step process which starts
at 165–206
C (heating rates from 10 to 30
C min1). The second step starts at
206–400
C. NHA does not become dead pressed by 70 MPa, because it is less
sensitive to impact but more to friction than PETN [19].

References

1. Davis, T.L.: The Chemistry of Powder and Explosives. Wiley, New York (1943)
2. Urbański, T.: Chemistry and Technology of Explosives. PWN—Polish Scientific Publisher,
Warszawa (1967)
3. Hale, G.C.: Explosive. US Patent 2,011,578, 1934
334 13 Other Substances

4. Millar, R.W.: Lead-free Initiator Materials for Small Electro-explosive Devices for Medium
Caliber Munitions. Report QinetiQ/FST/CR032702/1.1, 2003
5. Blatt: Compilation of Data on Organic Explosives, Sensitivities to Impact of K, Fe, Pb and Cu
Salts. Report, Office of Scientific Research and Development, 1944
6. Fedoroff, B.T., Sheffield, O.E., Kaye, S.M.: Encyclopedia of Explosives and Related Items.
Picatinny Arsenal, New Jersey (1960–1983)
7. Franz, A.O.: Explosive compound, process of making same and a composition thereof.
US Patent 2,708,623, 1955
8. Hirlinger, J.M., Bichay, M.: New Primary Explosives Development for Medium Caliber Stab
Detonators. Report SERDP PP-1364, US Army ARDEC, 2004
9. Hirlinger, J., Fronabarger, J., Williams, M., Armstrong, K., Cramer, R.J.: Lead azide replace-
ment program. In: Proceedings of NDIA, Fuze Conference, Seattle, Washington, April 5–7, 2005
10. Musil, T., Matyáš, R., Lyčka, A., Růžička, A.: 4,6-Diazido-N-nitro-1,3,5-triazine-2-amine
(DANT)—synthesis and characterization. Propellants Explosives Pyrotechnics (2012) 37,
275–281 (2012)
11. Fronabarger, J., Sitzmann, M.E., Williams, M.D.: Method for azidotriazole, nitrosoguanazine,
and related compounds. US Patent 7,375,221 B1, 2008
12. Bichay, M., Hirlinger, J.M.: New Primary Explosives Development for Medium Caliber Stab
Detonators. Report SERDP PP-1364, US Army ARDEC, 2004
13. Dave, P.R., Forohar, F., Axenrod, T., Bedford, C.D., Chaykovsky, M., Rho, M.-K., Gilardi, R.,
George, C.: Novel spiro substituted cyclotriphosphazenes incorporating ethylenedinitramine
units. Phosphorus Sulfur Silicon 90, 175–184 (1994)
14. Forohar, F., Dave, P.R., Iyer, S.: Substituted cyclotetraphosphazene compound and method of
producing the same. US Patent 6,232,479, 2001
15. Hariharanath, B., Chandrabhanu, K.S., Rajendran, A.G., Ravindran, M., Kartha, C.B.:
Detonator using nickel hydrazine nitrate as primary explosive. Defence Sci. J. 56, 383–389
(2006)
16. Médard, L., Barlot, J.: Prépatarion et propriétés des nitrates complexes des métaux bivalentes
et de l’hydrazine et d’un styphnate complexe analogue. Mémorial des poudres 34, 159–166
(1952)
17. Lao, Y.-L.: Chemistry and Technology of Primary Explosives. Beijing Institute of Technology
Press, Beijing (1997)
18. Talawar, M.B., Agrawal, A.P., Chhabra, J.S., Ghatak, C.K., Asthana, S.N., Rao, K.U.B.:
Studies on nickel hydrazinium nitrate (NHN) and bis-(5-nitro-2H tetrazolato-N2)tetraamino
cobalt(III) perchlorate (BNCP): Potential lead-free advanced primary explosives. J. Sci. Ind.
Res. 63, 677–681 (2004)
19. Zhu, S., Wang, Z., Li, Y., Zhang, L., Ye, Y.: Performance of NHA and its application. In:
Schelling, F.J. (ed.) Proceedings of 35th International Pyrotechnics Seminar, pp. 201–206,
Fort Collins, Colorado (2008)
20. Chhabra, J.S., Talawar, M.B., Makashir, P.S., Asthana, S.N., Haridwar, S.: Synthesis, charac-
terization and thermal studies of (Ni/Co) metal salts of hydrazine: Potential initiatory
compounds. J. Hazard. Mater. A99, 225–239 (2003)
21. Zhu, S., Wu, Y., Zhang, W., Mu, J.: Evaluation of a new primary explosive: Nickel hydrazine
nitrate (NHN) complex. Propellants Explosives Pyrotechnics 22, 317–320 (1997)
22. Thangadurai, S., Kartha, K.P.S., Sharma, D.R., Shukla, S.K.: Review of some newly
synthesized high energetic materials. Sci. Technol. Energetic Mater. 65, 215–226 (2004)
23. Hirlinger, J.M., Cheng, G.: Investigation of alternative energetic compositions for small
electro-explosive devices for medium caliber ammunition, in, US Army armaments research
WP-1307-FR-01, Picatinny Arsenal (2004)
24. Fincham, J.K., Shaws, R.A.: Phosphorus-nitrogen compounds. Part 62. The reactions of
2,2-diamino-4,4,6,6,8,8-hexachloro- and 2,6-diamino-2,4,4,6.8,8- hexachloro-cyclotetraphospha-
zatetraene with sodium methoxide in methanol. The first example of amino group migration in
the tetramer system. 31P, 1H, and 13C nuclear magnetic resonance spectroscopic investigations of the
products, Phosphorus, Sulfur and Silicon 47, 109–117 (1990)
Index

A C
Acetylides, 303 Cadmium azide, 106, 109
Alkaline fulminates, 63 Cadmium fulminate, 63
2-Amino-4,6-dichloro-1,3,5-triazine, 328 5-Carboxamidotetrazolatopentaaminecobalt
7-Amino-4,6-dinitrobenzofuroxan, 168 (III) perchlorate, 233
Aminoguanidine, 195 CCI Clean Fire, 7
5-Amino-1H-tetrazole (5-ATZ), 194 Charge diameter, 20
Aminotetrazole salts, 194 (3-(Chloromethyl)pentamethylhexoxonane),
1-Amino-1-(tetrazol-5-yldiazenyl)guanidin 271
(GNGT, tetrazene), 4, 6, 26, 189 5-Chlorotetrazole salts, 207
Ammonium fulminate, 63 Cobalt hydrazine nitrate (CoNH), 331
Antimony sulfide, 5 Cobalt perchlorate complexes, 228
Antimony triazide, 110 Compacting pressure, 13
Arsenic triazide, 110 Confinement, 20
Aurous acetylide, 321 Copper azides, 96
Azides, 71 undesired formation, 102
Azides, organic, 110 Copper(II) tetrakis-[1,5-
Azidoformamidine, 195 cyclopentamethylenetetrazol]
5-Azido-1-methyltetrazole, 222 perchlorate (CuL4), 241
5-Azido-1-picryltetrazole, 222 Corazol, 238
5-Azidotetrazoles, 209 CuEDNA, 325
organic derivatives, 222 Cupric acetylide, 316
1-Azido-2,4,6-trinitrobenzene, 111 Cupric azide, 97
Azoimide (hydrazoic acid), 71 Cupric salt of 5-nitrotetrazole, 201
5,50 -Azotetrazole salts, 212 Cuprous acetylide, 313
Cuprous azide, 97
impact sensitivity, 28
B Cuprous salt of 5-nitrotetrazole, 203
Barium styphnate, 149 1-Cyanoformimidic acid hydrazide, 232
Benzo[d][1,2,3]oxadiazole, 157 5-Cyanotetrazole, 231
Benzotrifuroxan (BTF), 167 Cyanuric triazide, 111
Bis(furoxano)-2-nitrophenol (BFNP), 179 1,5-Cyclopentamethylenetetrazole
Bis(2-hydroperoxypropane)peroxide, 255 complexes, 238
Bismuth triazides, 110
Black powder, 5

R. Matyáš and J. Pachman, Primary Explosives, 335

DOI 10.1007/978-3-642-28436-6, # Springer-Verlag Berlin Heidelberg 2013
336 Index

D G
Dead pressing, 11 Glass powder, 5
Deflagrating substances/mixtures (priming Gold fulminate, 63
mixtures, primes), 2 Green initiating substances, 6
Deflagration, 2 Gum Arabic, 5
Deflagration to detonation transition (DDT),
2, 227
Density, 11, 13 H
Detonants, 2, 79 Heavy metals, 7
Detonating substances (primary explosives), 2 Hexaazidotetrazatetraphosphocine-2,2-
Detonators, 1 diamine (DAHA), 328
Diacetone diperoxide (tetramethyltetroxane; Hexamethylene triperoxide diamine
DADP), 256 (diazahexaoxabicyclotetradecane,
5,7-Diamino-4,6-dinitrobenzofuroxan HMTD), 275
(CL-14), 167 Hg free, 7
Diaminohexachlorocyclotetraphosphazene, High-voltage detonator (HVD), 235
330 1-(1H-Tetrazol-5-yl)guanidinium nitrate, 219
1,5-Diaminotetrazole ferrous perchlorate Hydrazine nitrate, 331
complex (DFeP), 245 7-Hydroxylamino-4,6-dinitro-4,7-
4,6-Diazido-2-nitramino-1,3,5-triazine dihydrobenzofuroxan, 175
(DANT), 326
2-Diazo-4,6-dinitrophenol (dinol, diazol,
DDNP, DDNPh, DADNPh), 157 I
Diazophenols, 157 Igniters, 1
Dihydroperoxide 2,2-dihydroperoxypropane, Ignition, reliable, 4
255 Impact sensitivity, 25
4,6-Dinitrobenzofuroxan (4,6-DNBF), 168 Initiating efficiency, 13
Dinitroguanidines, 250 Initiating substances (primaries), 1
Dinitroresorcine (DNR), 133 a-Isocyanilic acid, 37
Dinol (DDNP), 4, 7
Disilver 5-amino-1H-tetrazolium perchlorate
Ag2(ATZ)ClO4, 196 K
KDNBF, 173, 176

E L
Ease of ignition (Bickford fuse) test, 32 LDDS, 148
Electrostatic discharge, sensitivity, 31 Lead azide, 2, 4, 31, 74–89
Environmental hazards, 6 Lead (IV) azide, 88
Ethylene dinitramine (EDNA), 325 Lead dinitroresorcinol, 133, 135
Ethylene tetrazylazide, 222 Lead hypophosphite nitrate, 5
Explosive train, 1 Lead mononitroresorcinol, 131
Lead picrate, 132
Lead salt of trinitroresorcine, 5
F Lead styphnate (LS), 4, 6, 86, 138
Ferrous 5-nitrotetrazole, 199 basic, 145
Flame sensitivity, 32 double salts, 148
Formonitrile oxide, 38 Lead tricinate, 6
Friction initiation/sensitivity, 29
Fulminates, 37
blasting caps, Alfred Nobel, 55 M
Fulminic acid, 37 Mercuric acetylide, 318
Furoxan, 167 Mercuric azide, 105, 109
Index 337

Mercuric salt of 5-nitrotetrazole, Hg(NT)2, 201 Peroxides of acetone, 255

Mercurous acetylide, 320 Picramic acid, 157, 162
Mercurous azide, 105, 108 Picric acid, 131
Mercury fulminate (MF), 2, 4, 39–59 5-Picrylaminotetrazole, 218
Metafulminuric acid, 37 Polynitrophenols, 131
Metallic hydrazine nitrates, 331 Potassium chlorates, 5
Methylenedinitramine (MEDINA), 325 Potassium fulminate, 63
Methyl-5-nitrotetrazoles, 221 Potassium 7-hydroxylamino-4,6-dinitro-4,7-
dihydrobenzofuroxan, 175
Predetonation, 32
N Primary explosives, 2, 4
Nickel hydrazine nitrate, 331 explosive properties, 11
Nitramines, 325 Primer, 1
Nitrogen dibromideiodide, 294 Priming compositions (priming mixtures), 5
Nitrogen halides, 289
Nitrogen tribromide, 294
Nitrogen trichloride, 289 R
Nitrogen triiodide, 295 Reinforcing cap, 20
sensitivity, 23
Nitroglycerine, initiation, 55–56
5-Nitro-1H-tetrazole (HNT), 197 S
5-Nitro-2-picryltetrazole, 222 Secondary explosives, initiation, 22
5-Nitrotetrazolato-N2-ferrate coordination Sensitivity, 23
complexes, 248 electrostatic discharge, 31
5-Nitrotetrazole, cupric salt, 201 flame, 32
cuprous salt, 203 friction, 29
mercuric salt, 201 Sensitizers, priming compositions, 4
organic derivatives, 221 Silver acetylide, 303
silver salt 201 Silver acetylide-hexanitrate, 312
Nitro-2-(2,4,6-trinitrofenyl)tetrazole, 221 Silver acetylide-silver nitrate, 308
5-(N-Nitramino)tetrazoles, 188 Silver azide (SA), 4, 89
NONTOX, 7 explosive properties, 92
preparation, 93
sensitivity, 91
O uses, 96
Organic azides, 110 Silver fulminate, 59
Organic peroxides, 255 Silver salt of 5-nitrotetrazole, 201
Organometallic azides, 111 Simple initiating impulse (SII), 1
Organophosphates, 328 SINOXID, 7
Output charges, 2 SINTOX, 7
2-Oxa-3,4-diazabicyclo[3.2.2]nonatetraene, Smokeless powder, 5
157 Sodium fulminate, 63
Oxidizers, 5 Specific surface, 15, 19
Surface mining blasting, 25

P
PbNATNR, 148 T
Pentaamine(1,5-cyclopentamethylene- TAAT (4,40 ,6,60 -tetra(azido)azo-1,3,5-
tetrazolato-N3) cobalt(III) perchlorate triazine), 116
(PAC), 238, 251 TAHT (4,40 ,6,60 -tetra(azido)hydrazo-1,3,5-
Pentaamine(5-cyano-2H-tetrazolato-N2)cobalt triazine), 116
(III) perchlorate (CP), 228 Tetraacetone tetraperoxide
Pentaamine(5-nitro-2H-tetrazolato-N2) cobalt (octamethyloctaoxacyclododecane,
(III) perchlorate (NKT), 237 TeATeP), 274
338 Index

Tetraaminecarbonatocobalt(III) nitrate Thallous azide, 105

(CTCN), 242 Theoretical maximum density (TMD), 13
Tetraamine-cis-bis(5-nitro-2H-tetrazolato-N2) Toxicity, 6
cobalt(III) perchlorate (BNCP), 241 Triacetone triperoxide
Tetraazido-1,4-benzoquinone (TeAzQ), 121 (hexamethylhexaoxonane, TATP),
Tetraazido-1,4-dinitropentaazatriphosphaspiro 257, 262
[4.5]deca-5,7,9-triene (ENTA), 328 Triazide (cyanuric triazide), 111
Tetrachloropentaazatriphosphaspiro[4.5] Triazidotrinitrobenzene (TATNB, TNTAB),
decatriene-1,4-diamine, 329 111, 118
Tetramethylene diperoxide dicarbamide Tricinate, 6
(tetraoxatetraazacyclotetradecanedione, Trinitroresorcine, 138
TMDD), 280
Tetrazene (GNGT), 4, 6, 26, 189
Tetrazoles, 187 W
organic substituent, 217 WINCLEAN, 7
Thallium fulminate, 63 Wollfenstein’s superoxide (TATP), 257, 262