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Practical Handbook of
Spectroscopy

Edited by

J. W. Robinson, Ph.D., D.Sc., F.R.C.S.

Department of Chemistry
Louisiana State University
Baton Rouge, Louisiana

0 ~'~~/:~;,~~"'
Soca Raton London New York

CRC Press is an imprint of the

Taylor & Francis Group, an informa business
Library of Congress Cataloging-in-Publication Data

Practical handbook of spectroscopy/edited by J. W. Robinson.

p. cm.
Includes bibliographical references and index.
ISBN 0-8493-3708-9
I. Spectrum analysis--Handbooks. manuals. etc. I. Robinson .
James W. , 1923-
QD95.P73 1991
543' .0858--dc20 90-48265
CIP

This book represents informat ion obtained from authentic and highly regarded sources. Reprinted material is
quoted with permission, and sources are indicated. A wide variety of re ferences are listed . Every reasonable effort
bas been made to give reliable data and information, but the authors and the publisher cannot assume responsibility
for the validity of all materials or for the consequences of their use.

All rights reserved . This book. or any parts thereof. may not be reproduced in any form without written consent
from the publisher.

Direct all inquiries to CRC Press, Inc. , 2000 Corporate Blvd. , N.W., Boca Raton , Florida, 33431.

c 1991 by CRC Press. Inc.

International Standard Book Number 0-8493-3708-9

Library of Congress Card Number 90-48265

 PREFACE
This handbook is a distillation of the CRC Handbook of Spectroscopy, Volumes I, 11 ,
and Ill, reduced in size to be presented in one convenient volume.
The principal objective is to provide a readily accessible source of information on the
major fields of spectroscopy. Specifically, these fields are X-ray spectroscopy; ESCA ; atomic
spectroscopy (atomic absorption, emission spectrography, flame photometry, and inductively
coupled plasma); infrared and Raman spectroscopy; ultraviolet absorption spectroscopy;
electron spin resonance; mass absorption coefficients; appearance potentials; activation anal-
ysis; neutron cross-sections; wavelength standards; and diatomic molecules of astrophysical
importance.
The book will provide some theoretical information, but is mostly dedicated to providing
a reference for the spectroscopic data available on the most important materials in the
particular field.
The handbook will be of maximum value to the practicing spectroscopist. Many scientists
are experts in one or two fields of spectroscopy, but relative novices in other similar fields.
This handbook will be invaluable to people wishing to get information about these "other
fields."
It will be of particular use to analytical and organic chemists or to spectroscopists wishing
to identify materials or compounds. The book will indicate to them which techniques may
provide useful information and what kind of information the techniques will provide and
will not provide. In short, it will be a companion to those spectroscopists who have a need
to broaden their horizons into the major fields discussed.

J. W. Robinson
Louisiana State University
 THE EDITOR
J. W. Robinson, B.Sc., Ph.D., D.Sc., F.R.C.S., earned his degrees at the University
of Birmingham, England. He is Professor of Chemistry and Chairman of the Analytical
Division at Louisiana State University, Baton Rouge, Louisiana.
He has authored more than 177 publications and has written 3 books, Undergraduate
Instrumental Analysis, Atomic Absorption Spectroscopy, and Atomic Spectroscopy. He is
Editor of the international journals Spectroscopy Letters and Journal of Environmental
Science and Health and Assistant Editor of Applied Spectroscopy Reviews. He is a past
Gordon Conference Chairman, a Guggenheim Fellow, and a recipient of the Honor School
of the American Institute of Chemistry.
 ACKNOWLEDGMENTS

Materials in this book were derived from new material and Volumes I , Il, and HI of
the CRC Handbook of Spectroscopy, edited by J. W. Robinson:

Section 1. X-Ray Spectroscopy: derived from X-Ray Spectroscopy, Volume I (pages 3 to

154, 230 to 231 , and 238 to 254).

Section 2. ESCA- Photoelectron Spectroscopy: derived from ESCA Photoelectron Spec-

troscopy, Volume I (pages 257 and 512 to 752).

Section 3. Atomic Spectroscopy: derived from Atomic Spectroscopy, Volume I (pages 809
to 815).

Section 4. Emission Spectroscopy: derived from new material and Emission Spectroscopy,
Volume I (pages 847 to 868).

Section 5. Infrared Spectroscopy: derived from Infrared Spectroscopy, Volume ll (pages

3 to 16, 18, 24 to 36, 50 to 72, 76, 96 to 99, and IOJ to 102).

Section 6. Raman Spectroscopy: derived from Raman Spectroscopy, Volume II (pages

107 to 130).

Section 7. Ultraviolet Absorption Spectroscopy: derived from Ultraviolet Absorption Spec-

troscopy, Volume ll (pages 133 to 214).

Section 8. Electron Spin Resonance: derived from new material and Electron Spin Res-
onance, Volume II (pages 217 to 229, 232 to 233, 235 to 238, 240 to 241, 243 to 244,
249, 252 to 254, 259 to 261 , 268, 275 to 276, and 287 to 3 14).

Section 9. Mass Photoelectric Absorption Coefficients: derived from Mass Photoelectric

Absorption Coefficients, Volume III (pages 1 to 78).

Section 10. Appearance Potential Spectroscopy: derived from Appearance Potential Spec-
troscopy, Volume III (pages 79 to 93).

Section 11. Thermal Neutron Cross Sections and Resonance Integrals for Activation
Analysis: derived from Thermal Neutron Cross Sections and Resonance Integrals for Ac-
tivation Analysis, Volume Ill (pages 95 to I 23).

Section 12. X-Ray Fluorescence and Coster-Kronig Yields for the K-, L-, and M-Shells:
derived from Tables of Experimental Values of Fluorescence and Coster-Kronig Yields for
the K-. L-, and M-Shells, Volume ill (pages 125 to 139).

Section 13. 14 MeV Neutron Activation Cross Sections: derived from 14 MeV Neutron
Activation Cross Sections, Volume lii (pages 141 to 162).

Section 14. Wavelength Standards in Visible, Ultraviolet, and Near-Infrared Spec-

troscopy: derived from Wavelength Standards in Visible, Ultraviolet, and Near-Infrared
Spectroscopy, Volume Ill (pages 163 to 173).

Section 15. Wavelength-Dependent and Electronic System OsciUator Strengths for Free
Diatomic Molecules of Astrophysical Importance: derived from Wavelength-Dependent
and Electronic System Oscillator Strengths for Free Diatomic Molecules of Astrophysical
Importance, Volume Ill (pages 193 to 205).
 TABLE OF CONTENTS

SECTION 1. X-RAY SPECTROSCOPY

X-Ray Spectroscopy .............................................. . .......... . ............ 3
I. Characteristic X-Ray Emission Lines .............................................. 3
Table I Wavelength, Probable Error in Last Digit of Wavelength,
and Energy of Some Characteristic Emission Lines .................. 4
References ........................................................................ 22
Il. Characteristic X-Ray Absorption Edges ............................. . ............. 23
Table 2 X-Ray Absorption Edges ...... .. .. ... ................... . ...... . .... 24
References .. . .................................. .. .............................. . .. 27
Ill. Mass Attenuation and Absorption Cross Sections for 94 Elements;
0.1 keY to l MeV ................................. . ................... .. ......... 28
Table 3 Mass Attenuation and Absorption Cross Sections for
94 Elements; 0.1 keY to I Me V .................................... 28
TV. Approximate Jump Factors for K and L Absorption Edges ...... . ............... 155
Table 4 K-Edge Jump Factors ..... ......................... . ... . ........... !55
Table 5 L-Edge Jump Factors ............................. . . .. .............. 155
V. Schematic Energy Level Diagram Showing the X-Ray Lines ................. . .. 156
VI. Crystals and Multilayer Langmuir-Blodgett Films Used as Analyzers
in Wavelength-Dispersive X-Ray Spectrometers ............................... . . !57
Table 6 Crystals and Multilayer Langmuir-Biodgett Films Used
as Analyzers in Wavelength-Dispersive X-Ray
Spectrometers ..... . ................ ... ............................. !58
Vll. Cross Sections for Ionization of K- and L-Shells by Electrons ................. . 167
VUI. Electron Range and Electron Stopping Power ................................... 168
Table 7 A The Stopping Power for Electrons of Energy V in
Targets of Atomic Number Z ...................................... 169
Table 7B The Stopping Power for Electrons of Energy V in
Targets of Atomic Number Z ............... . .................... . . 170
Table 8 The Mass-Range ps (g/cm 2) at which the Electron
Energy Has Fallen from Its Initial Energy, Vo• to the
K-Shell Ionization Energy in Targets of Atomic
Number Z ....................... . ...................... . . .......... 17 1
Table 9 The Mass-Range ps (g/cm 2 ) at which the Electron
Energy Has Fallen from Its Initial Energy, Vo• to the
L111-Shell Ionization Energy in Targets of Atomic
Number Z . .. ....................................................... 172

SECTION 2. ESCA - PHOTOELECTRON SPECTROSCOPY

ESCA - Photoelectron Spectroscopy ....................... ..... ...................... 177
Table l X-Ray Molecular Orbital Spectra .................................. 178
Table 2 X-Ray Core Spectra ....................... . ........................ 183
References . . ..... . .... ... ..................... .. .............................. 416

SECTION 3. ATOMIC SPECTROSCOPY

Atomic Spectroscopy .......................................................... . ........ 421
I. Oscillator Strengths (/-Values) of Interest in Atomic Absorption
Spectroscopy .... .. . ........ ............................. ........ ..... ..... ...... 421
Table 1 Oscillator Strengths (f- Values) of Interest in Atomic
Absorption Spectroscopy ............................... . ... ....... . 421
II. Doppler Half-Widths of Atomic Spectral Lines (Table 2) ... . . .. .............. . .422
fii. Ionization Potentials of the Elements, i.e. , the Energy Required
for the Process M ~ M+ + e - ..................................... . ........... 423
Table 3 Ionization Potentials of the Elements ............................... 423
IV. Dissociation Energies of Diatomic Oxide Molecules ............................. 424
Table 4 Dissociation Energies of Diatomic Oxide Molecules ............... 424
V. Properties of Premixed Flames Used in Atomic Spectroscopy ...... . ............ 425
Table 5 Properties of Premixed Flames Used in Atomic
Spectroscopy ....................... . ................. . . ... . ........ 425
VI. Efficiences of Atomization of Metals in Flames ................... . ........... . .425
Table 6 Efficiencies of Atomization of Metals in Flames ..... . ........... . . 426
References ............. .. .. ........... ...... .... . ............... . ............ . 426
VII. Measured Degrees of Ionization of Metals in Flames .. .. . . .. .. . . . ....... ... . . . . . 427
Table 7 Measured Degrees of Ionization of Metals in Flames .............. 427
Table 8 Salts Suitable for Preparing Calibration Curves .................... 428
Table 9 Primary Wavelengths and Sensitivities for Flame
Atomic Absorption Analysis ........................ . . .. . .......... 429
Table 10 Detection Limits Using Plasma MS Analysis ..................... .430
Table 11 Sensitivities (I% Absorption) and Detection Limits
for Carbon Rod Atomizer (Mini-Massmann) ....................... 43 1
Table 12 Zeeman Background Correction Data for P.E. 5000 .... . ..... .. . . . 432

SECTION 4. EMISSION SPECTROSCOPY

Emission Spectroscopy ............ .. ................. ... ... ............. ............ ... 437
I. Comparison of Some Experimentally Determined Emission-Spectroscopic
Detection Limits . . . .... ... . ..... .. .. . ... . ...... .. ......................... ...... .437
Table I Comparison of Some Experimentally Determined
Emission-Spectroscopic Detection Limits ........... . ...... . .. .. ... 437
II. Reported Relative Detection Limits for Arc Excitation . ........... . . .. . ......... 438
Table 2 Reported Relative Detection Limits for Arc Excitation ............. 438
lli. Relative Detection Limits for Spark Excitation of Solids ........................ 440
Table 3 Relative Detection Limits for Spark Excitation of Solids .. . . ... . .. . 441
IV. Detection Limits for Liquid Samples (tJ-g/ml) ........ ... . ...... ... . .............. 442
Table 4 Detection Limits for Liquid Samples ................ . ... . ... . .... .. 442
V. Detection Limits for Micro or Residue Samples (ng) ............ . .... .. ..... .. .. 444
Table 5 Detection Limits for Micro or Residue Samples.. ... . .. ... . ........ 444
VI. Detection Limits with the Laser Microprobe (tJ-g/g) .............. . ... ......... .. 446
Table 6 Detection Limits with the Laser Microprobe ........ . .............. 446
VII. Preconcentration-Separation Procedures Used for Emission
Spectrometric Analyses . ... . ........... ... . ....................... . ... .. .. ...... .447
Table 7 Preconcentration-Separation Procedures Used for
Emission Spectrometric Analyses ............................... . .. 447
References ..................... . ... . .. .... ............ .. . .. .. . . ............... 447
VIII. Sensitive Lines for Use in Atomic Emission Spectrometry ...... . ... . ....... .... 448
Table 8 Sensitive Lines for Use in Atomic Emission Spectrometry .. . .... .. 448
IX . Wavelengths Commonly Recommended for Use in Plasma Emission .. . . ....... .460
Table 9 Wavelengths Commonly Recommended for Use in
Plasma Emission ...... ..... ... .. . .. ........ ..... . ..... .. . ....... ... 460
X. Prominent Lines Used in Plasma Emission ................ .. .................... 462
Table 10 Prominent Lines Used in Plasma Emission with
Detection Limits and Elements Which May Cause
Spectral Interference .............................. . ..... . .......... 462
XI. Comparison of Detection Limits for AES, AAS, and AFS ...................... 469
Table ll Comparison of Detection Limits for Atomic-Emission (AES),
Atomic-Absorption (AAS), and Atomic-Fluorescence
Spectroscopy (AFS) ........ . .. ....................... .. . .. ......... 469
XlJ . Wavelength Used in Flame Emission ......... ............ ................. .. . ... 472
Table 12 Wavelengths of Emission Lines Used for the Detection
and Determination of Some Common Elements ......... .. ... ...... 472
XIII. Sensitivity Results Obtained with Nitrous Oxide-Acetylene Flames . . ........... 474
Table 13 Sensitivity Results Obtained with Nitrous Oxide-Acetylene
Flames ............... .. ............................................ 474
XIV. Results Obtained with Shielded Burners ............................ .. ........... 475
Table 14 Results Obtained with Shielded Burners ........................... 475
XV. Relative Sensitivities Detection Limits .. ... .. ..................... . .. .. ......... .476
Table 15 Relative Sensitivities Detection Limits .......... ...... . .. .. . ...... .476

SECTION 5. INFRARED SPECTROSCOPY

Infrared Spectroscopy ... ...... . .. .. . .................. .. .. .. .. . ....... . ..... . . .. . ...... 48 1
I. Sampling ................. ............. ........................... . ..... .. ....... 481
Properties of Common Window Materials ................... .. ... . .............. 481
Properties of Common Solvents .. ....... ........................................ 495
Spectra of Common Solvents ..... .. . ... ........................................ . 496
11 . Calibration: Secondary Standards for Wavelengths ............. . .. ... ........... 509
Ill. Spectrometer Operation ............... . ................... .. . . .... .. ............. 512
The Coblentz Society Specifications for the Evaluation of Infrared
Reference Spectra: Class IJ Spectra ..... . ... .. . ............ ............. ......... 512
Class Ill Spectra .. .. ..... . . . .. ................. .... . ............ ........... . .... . 5 15
Table 1 Absorption Maxima Recommended for Cal ibration
Purposes ........ .. . ....... ...................... . ...... ..... ....... 515
Spectral Slit Width of a Grating Monochromator ..................... .... ....... 5 18
Relationship Between Noise (N), Slit Width (s), and
Response Time (T) ................. ..... ......................................... 518
Determination of Scan Speed from the Spectrometer Time
Constant and the Half-Band Width ..... ........................... .. .. . ......... 518
Theoretical Transmittance of Mylar Beamsplitter Foils .......................... 5 18
I V. Interpretation .................................................................... 519
Common Spurious Absorption Bands and Their Origin ........... . . . .......... . . 519
Wavelength-to-Wavenumber Conversion Tables and Refractive
Index of Standard Air, 2-20 IJ.m ... . ....... ......................... .. .. . ...... 520
Numbering of Fundamental Vibrational Frequencies in Molecules ...... ......... 523
Infrared Correlation Charts and Tables .. ........................................ 524
Correlation Chart of Infrared Group Frequencies ................ . .. . ............ 529
V. Quantitative Analysis ............... .. ............................ . .............. 534
Absorption Laws ................................................................ 534
Determination of Stray Radiation ................................................ 534
To Minimize Errors in Quantitative Analysis .................................... 534
References ....................... . . . ............. ... .. ...... ........ ........ . . 535
Measure ment of Absorbance . . ..... . ................ ....... . ... ............ ...... 535
SECTION 6. RAMAN SPECTROSCOPY
Raman Spectroscopy .................. ...... .. ... ..................... ......... ........ 539
I. Instrumentation ................................................... .. ............. 539
Sources .......................................................................... 539
Table I Major Wavelengths for Some Common Gas Lasers ................ 539
 Monochromators ................... .. ................................. .. ......... 539
Detector and Amplification ........ ...... .......................... ...... ........ 539
11 . Spectrometer Operation .......... . .. .. ............................ ... ............ 539
Monochromator Parameters ................................. ......... ............ 539
Table 2 Possible Spurious Lines due to Emission from the
Laser Plasma When an Argon Laser is Being Used as
the Raman Exciting Source . ... .. .. ..... .. .. ....................... 540
Spectrometer Calibration ........... .. .... ...................... .. . ......... . .... . 542
Resolution Check ................................................................ 543
Intensity Dependencies ............... .. ................................. .. ...... 543
Table 3 Calibration of Laser Raman Spectrometers for
Helium-Neon Excitation ............................................ 546
Table 4 Calibration of Raman Spectrometers for Argon
Ion Laser Excitation .. .. ............................................ 546
Depolarization Ratios ............. . ................................ .. ............ 547
Ill . Sampling and Geometry ........... ....... . .. ....... . ... .. .. .... .. .. ............. 547
Conventional Solid and Liquid Phase Geometry .................... ... .......... 547
Table 5 Routine Calibration of the Laser Raman Spectrometer
with Indene ........................................................ 549
Table 6 Chlorine Isotope Bands .............................. ..... ......... 549
Special Geomet:ries ................ ... ........................................... 549
Table 7 Comparison of Different Laser Excitation Frequencies ............. 550
Microsampling ................. ......... ......................................... 550
IV . Interpretation .................................................. . .......... . . ..... 550
V. Representative Raman Spectra ................................................... 550
Table 8 A Summary of Characteristic Raman Frequencies .... . ..... . .. ..... 55 1
VI. The Documentation of Raman Spectra .... .... . ...... .......... . ... .. ....... .. ... 556
Recommendation for the Presentation of Raman Spectra for Cataloging
and Documentation in Permanent Data Collections ................ .. ............ 556
Recommendations ................ ... ............................. ..... .......... 562
References ...................... .. ....................................... . ....... 562

SECTION 7. ULTRAVIOLET ABSORPTION SPECTROSCOPY

Ultraviolet Absorption Spectroscopy ........ .. .. .. ......................... .. .......... 565
I. Ultraviolet: Spectral Data Index ...... ...................... .. ... .. .............. 565

SECTION 8. ELECTRON SPIN RESONANCE

Electron Spin Resonance ............... ....... ....................... .... . .. ........... 649
I. Introduction ...................................................................... 649
ll . Physical Constants and Conversion Factors ...................................... 650
Table 2- 1 Conversion Factors ................................................. 650
Table 2-2 Energy Conversion Factors ......................................... 650
Table 2-3 Nuclear Spins, Abundances, Moments and Hyperfine
Couplings for Some Common Magnetic Nuclei .................... 651
Ill . Instrumentation ............. ..... . .......... .................. . .. .. . ..... .... . ... 653
Block Diagram of Superheterodyne Spectrometer ... .... .................... . .... 653
Sensitivity .......................... . ............................. ... ............ 653
Resonance Cavities ....... . .......... . ............................. ..... ......... 655
Table 3-1 Electrical Properties of Several Metals, Where f Is
in the Units Hz ..................................... .. .............. 655
Table 3-2 Dielectric Properties of Materials Sometimes
Encountered Inside Cavitjes ........................................ 660
IV. Theory ........................................................................... 661
The Spin Hamiltonian ........................................................... 661
Crystal Fields . .................. .............. ............. .. ..... ....... ........ 66 1
Spin Orbit Interaction ............................................................ 662
Zero Field Splittings .............................................. . .. . ..... . ..... 662
Table 4- 1 Coefficients C4 and 0 6 for Three Coordinations .... . ............... 662
Table 4-2 List of Operator Equivalents to Some Commonly Occurring
Functions Within a Manifold of Given J, the Summation
Being Over the Coordinates of the Magnetic Electrons .... ........ 664
Quadrupole Interaction .......................................................... 667
V. Transition Ions ................................................................... 668
Table 5- 1 ESR Data for Transition Group Ions in
Magnesium Oxide (MgO) .......................................... 669
Table 5-2 ESR Data for Transition Group Ions in
Spinels (AB 20 4) •.•••. • ••.••••••. • .••••••. •• ••••••••• •• ••• • .••••• • •• 672
Table 5-3 ESR Data for Transition Group Ions in
Corundum (AI 20 3) •••.•....•..•• .. .. •••••••• •••••••••••••••••.••••• 673
VI. Free Radicals .................................................................... 675
Table 6-1 Hyperfine Characteristics of Typical Ions and
Radicals in the Liquid Phase ....................................... 676
Table 6-2 Variation in g Values for DPPH at Room Temperature ............ 677
VII. Relaxation ....................................................................... 677
Introduction ...................................................................... 677
Bloch Equations ................................................................. 677
Modified Bloch Equations .. . .. . ................ ....... ...................... . ... 677
Exchange ...................... ... . . . . .......................... . . . .............. 678
Motional Effects on Relaxation .............................. ... ................. 678
Relaxation in Solids ............................................................. 678
Saturation Method of Measuring Relaxation Times ....... .................... ... 679
Table 7-1 Typical Temperature and Field Dependence Fonnulas
for the Spin-Lattice Relaxation Time T 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . 681
Table 7-2 Characteristics of Relaxation Times in Solids and Liquids ......... 681
Pulse Techniques and Spin Echos ............................................... 682
VIII. Lineshapes ....................................................................... 685
Lorentzian and Gaussian Lineshapes ........ . ... .. ............ . .............. . .. . 685
Table 8- 1 Comparison of Gaussian and Lorentzian Lineshapes ............... 687
Zero Field Powder Pattern Lineshape ............................................ 688
Dipolar Lineshapes ................. . ............................................ 688
Anisotropic g-Factor and Hyperfme Tensors ..................................... 688
Inhomogeneous Lines ........... ............... ............... : . ............. .... 689
IX . Electron Nuclear Double Resonance ............. .............. ................ .. 69 1
Acknowledgments ...................................................................... 693
References .............................................................................. 693
SECTION 9. MASS PHOTOELECTRIC ABSORPTION COE FFICIENTS
Mass Photoelectric Absorption Coefficients ....................... . ..... .. ............. 70 I
Introduction ...................... .. . .. ...... . ... . .... .. ............ . ........ .. ... 70 I
Table of Mass Absorption Coefficients for K Alpha I Lines .................. 702
Table of Mass Absorption Coefficients for K Beta I Lines ................... 714
Table of Mass Absorption Coefficients for L Alpha I Lines .. . ...... ......... 724
Table of Mass Absorption Coefficients for L Beta I Lines .................... 743
Table of Mass Absorption Coefficients for M Alpha Lines ................... 762
Table of Mass Absorption Coefficients for M Beta Lines ............. . .. ..... 77 1
SECTION 10. APPEARANCE POTENTIAL SPECTROSCOPY
Appearance Potential Spectroscopy .. .. ................ ...... .. . .. ..... .. . .............. 78 J
Introduction .............. . .. . ................ . ...... . .......... .. ..... . .......... 781
Introduction to Table of Atomic Energy Levels ...... . . . . . ....... . ... . ..... . .... 782
Table I Atomic Energy Levels . .......... ... ............ .. ..... . ........... 783
References .... . ................. . ....... . ............................ . ... . ....... 793

SECTION 11. THERMAL NEUTRON CROSS SECTIONS AND RESONANCE

INTEGRALS FOR ACTIVATION ANALYSIS
Thermal Neutron Cross Sections and Resonance Integrals for
Activation Analysis . .............. .. . .. .. . ........... . .. . .... . .. . .... . ............... .. . 797
Introduction ..................... . ............................. . .................. 797
References .......................... . ... . .............. . ...... . ...... .. .. .... .... 797
Table I Thermal Neutron Cross Sections and Resonance
Integrals ............................................................ 798

SECTION 12. X-RAY FLUORESCENCE AND COSTER-KRONIG YIELDS FOR

THE K-, L-, AND M-SHELLS
Tables of Experimental Values of X-Ray Fluorescence and Coster-Kronig
Yields for the K- , L-, and M-Shells .................................. . ............... .. 829
Introduction ...... . ...... . ................................... . .. . ........ . ..... . .. 829
Description in Terms of the Altered Vacancy Distributions (Vn ................. 830
Description in Terms of the Primary Vacancy Distributions (Ni) .... ........ .... 830
Transformation Equations Relating the Two Descriptions . ..... ................. 831
Table J Experimental Values of Low-Z K X-Ray Fluorescence
Yields .......................... . ........ . ...................... . ... 834
Table 2 Experimental Values of K-Shell X-Ray Fluorescence
Yields ........................................... . ... . .............. 835
Table 3 L-Subshell Fluorescence Yields .... ....... ..... ..... ..... . ..... .... 837
Table 4 Coster-Kronig Transition Probabilities in the L-Subshells .......... 838
Table 5 Average L-Shell Fluorescence Yields ...... . ... . .. .. . . ... . .... . ... . 839
Table 6 M-Shell Fluorescence and Coster-Kronig Yields ........... . ... . .. . 840
References .. .. .............. .. ... . ... . ......................... . ... . ............. 843

SECTION 13. 14 MeV NEUTRON ACTIVATION CROSS-SECTIONS

14 Me V Neutron Activation Cross-Sections ............................... .... ......... 847
Introduction ..... ..... .... .. .. ....... . ........................ . ........ ... ...... .. 847
Activation Cross-Section Data .. .. ............................. . ..... . . .. . . ...... 848
Table I Activation Cross-Sections for the Formation of 14.5 MeV
Neutron-Induced Major Nuclear Reaction Radioactive
Products .......... .... . .... ........................... ... ..... ...... 850
References ................................................ . . ............ . ....... . 867

SECTION 14. WAVELENGTH STANDARDS IN VISIBLE, ULTRAVIOLET, AND

NEAR-INFRARED SPECTROSCOPY
Wavelength Standards in Visible, Ultraviolet , and Near-Infrared
Spectroscopy ....... .. .. .. ....... . .................................. . .. . ..... . .......... 871
Primary Standard ... . .... . . ........... .... ..... ... ... .. . . ........................ 871
Secondary Standards ....... . .. . ....................... .. . ....................... . 871
Vacuum-Ultraviolet Standards ................ .. ...... . .. .... .................... 871
Table 1 Class A Secondary Standards of Wavelength ...................... 872
 Table 2 Class B Secondary Standards of Wavelength Lines
of the Iron Arc in Air . . ................................. . .......... 872
Table 3 Proposed Secondary Standards of Wavelength: Lines
of Krypton-86 .. . .. .. . ..... . .. ................. . ... . .. .. .. .. ........ 873
Table 4 Vacuum Wavelengths of Mercury-198 Lines .. .. . ....... . .. . .. . . ... 878
Interconversion of Wavelengths Measured in Air and in Vacuum . . ...... ... . ... 878
Table 5 Ritz Standards of Cu ll in the Vacuum Ultraviolet . . .. . . . ....... ... 879
Table 6 Standard Wavelengths of Si I in the Vacuum Ultraviolet. . . ........ 879
Table 7 Refractive Index of Standard Air and Vacuum Correction
for Wavelengths Measured in Air .................... ... ........... 88 1
References ....................... . .............................. .. . . ............. 881

SECTION 15. WAVELENGTH-DEPENDENT AND ELECTRONIC SYSTEM

OSCILLATOR STRENGTHS FOR FREE DIATOMIC MOLECULES OF
ASTROPHYSICAL IMPORTANCE
Wavelength-Dependent and Electronic System Oscillator Strengths for
Free Diatomic Molecules of Astrophysical Importance ... . .... .. .. .. .. ... . ... . .. .. .. . . . 885
Introduction ..................... . . .... .............................. .. ...... . .... 885
Nomenclature and Symbols ... . . .. . ... ...................... . .... .. .. . ... . ....... 885
Absorption and Emission Spectroscopy ...................... . .. . ... .. . . ......... 886
Detailed Balance ................................................................. 887
Lifetime Measurements .......................................................... 887
Ab Initio Calculations .......... . ... . . . ............................ . .............. 888
Building-Up Concepts .... . ......... . ............................................ 888
More Nomenclature ............ . .. .... . .. .... . .............. . ... .. . .... . .. .. . . . .. 890
Factoring the Transition Moment . . .. .. .. ... . .......... . ..... . . ..... ............. 890
R, and f,1 (A) as Functions of Wavelength . .. .. .. ..... . ... . .... .. . .. . . ... . .. ... . . 89 1
Approximate Relationship Between f,1 (A) and f:~ .......... . . ... .. .. ... . ........ 892
Still More Notation and f6 •••••. ..• . • • . •••••••••••••••••••••••...• . •••••••••••••• 892
Relations Between Band and Band-System Oscillator Strengths ................. 893
Numerical Data ................... . .. . ........................................... 894
Acknowledg ments .................................................. . ............ 894
Table lA Statistical Weight w1 in Equation 14 ................ .. ... . ......... 895
Table I B Statistical We ight w21 in Equation 19 ............. . ... . ............. 895
Table 2 Notations for Strengths and Oscillator Strengths .. .. ... . ... ........ 896
Table 3 Notations for Wavelength-Dependent Oscillator Strength
as Used in This Chapter. . . .... ... . ... ... .... .. ... .. . ... . .... . . ... . . 896
References .. ..................... . .. .. .................. . ...... . ... . ............. 897

Index ....... . ............................. .. ..... . ...................................... 90 1

Section 1
X-Ray Spectroscopy
 Section I: X-Ray Spectroscopy 3

X-RAY SPECfROSCOPY

L. S. Birks, Naval Research Laboratory

I. CHARACTERISTIC X-RAY EMISSION The precision with which a quantity can be

LINES measured is often as important as the measure-
ment itself. The table has been constructed with
A/ex Burr, New Mexico Stare University strict attention to the number of significant figures
The following table contains the wavelength, recorded. The number in the column after the
precision of measurement. and energy of the most wavelength represents the probable error assigned
useful characteristic x-ray lines for each element. to the last digit of the wavelength. A rough idea ,
In the table the first column lists the element, the good for most purposes, of the precision of the
characteristic line, and the atomic levels involved energy reported can be obtained from th~ number
in the production of the x-ray photon. The middle of significant figures in the energy. If a better
columns give the wavelength (in A* units) and the estimate of precision is required , it can be ob-
precision of measurement in the form of the tained from the wavelength error. In the case of a
probable error in the last digit. The last column few lines with a wavelength precision of the order
gives the energy of the line in kiloelectron of 10 ppm, it must be remembered that the
volts. uncertainty of the conversion factor between A*
The A* wavelength unit is the unit of the x-ray units and keY is about I 0 ppm and must be added
wavelength scale in which all the more precise to the uncertainty in the wavelength measurement.
x-ray wavelengths are measured. It was designed to Again, this last complication will be of interest
be as close to the angstrom unit as possible. The only to those who need the utmost accuracy.
A* wavelength unit is completely defined by The primary source of this table is an article by
Bearden,' and some comments on the x-ray Bearden4 which reported the most probable value
wavelength scale in general are given by Thomsen of every measured characteristic x-ray line based
and Burr. 2 Later advances 3 in the measurement of on a critical review of all known measurements of
atomic constants have shown that the A* unit is that line. An extensive report 5 lists each measure-
20 ppm smaller than the angstrom unit. Thus. for ment which was considered in this review and
almost all the lines listed in the following table. no discusses in considerable detail the process
error will be created if A* is read as angstrom. followed in arriving at the results. In a few cases.
However, in those rare cases where the utmost notably the Ma and Mtl lines of the lanthanides. 6
precision is required, the differ~nces must be values measured after the above mentioned study
considered. had been completed are given here.
4 Practical Handbook of Spectroscopy

TABLE 1

Wavelength, Probable Error in Last Digit of Wavelength, and

Energy of Some Characteristic Emission Lines

P.E. in Last
Line Wavelength A* Wavelength Digit Energy keY

3 Lithium
KaKL 228.0 0.0543

4 BeryUium
KO:KL 114.0 0.1085

5 Boron
KaKL 67.6 3 0.1833

6 Carbon
KaKL 44.7 3 0.277

7 Nitrogen
KaKL 31.6 4 0.3924

8 Oxygen
KaKL 23.62 3 0.5249

9 Fluorine
Ka KL 2 ,> 18.32 2 0.6768

10 Neon
Ka KL 2 · ' 14.610 3 0.8486
KPKM 14.452 5 0.8579

11 Sodium
Ka KL 1 , 3 11.9101 9 1.0410
KPKM 11.575 2 1.0711

12 Magnesium
KaK L, , > 9.8900 2 1.25360
KPKM 9.521 2 1.3022

13 Aluminum
Ka 2 KL , 8.34173 9 1.48627
Ka, KL, 8.33934 9 1.48670
K!lKM 7.960 2 1.5574

14 Silicon
Ka, KL 2 7.12791 9 1.73938
Ka, KL, 7.12542 9 1.73998
K!lKM 6.753 1.8359

15 Phosphorus
Ka, KL, 6.160 2.0127
Ka, KL, 6.157 2.0137
K!lKM 5.796 2 2.1390

16 Sulfur
Ka, KL 2 5.37496 8 2.30664
Ka, KL, 5.37216 7 2.30784
KP, KM 5.0316 2 2.4640
 Section 1: X-Ray Specrroscopy 5

TABLE I (continued)

Wavelength , Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines

P. E. in last
Line Wavelength A• Wavelength Digit Energy keY
17 Chlorme
Ka, KL, 4.7307 I 2.62078
Ka, Kl , 4 .7278 I 2.62239
KtlKM 4.4034 3 2.8156
Lnl,M, 67.33 9 0.1841
UIL,M, 67.90 9 0.1826

18 Argon
Ka, KL, 4. 19474 5 2.95563
Kc., KL, 4. 19180 5 2.95770
Ktl, ·'KM,,, 3.8860 2 3.1905
LTl L, M, 55.9 0.22 17
LQ L, M, 56.3 0.2201

19 Potassium
Ka, KL, 3.7445 2 3.3111
Ka, KL, 3.7414 2 3.3138
Ktl, ,, KM,,, 3.4539 2 3.5896
LTl L,M , 47.24 2 0.2625
L2 L, M, 47.74 0.25971

20 Calc•um
Ka, KL, 3.36166 3 3.68809
Ka, KL, 3.35839 3 3.69168
Ktl, ,, KM, ,, 3.0897 2 4.0127
Ln L 2 M1 40.46 2 0.3064
LQL,M, 40.96 2 0.3027
La L, M•. s 36.33 2 0.341 3

21 Scandium
Ka, KL, 3.0342 4.0861
Ka, KL, 3.0309 I 4.0906
Ktl, ,, KM,,, 2.7796 2 4.4605
LTl L, M, 35.13 2 0.3529
Ltl, L, M. 31.02 2 0.3996
LQ L, M, 35.59 3 0.3483
La L, M. ·' 31.35 3 0.3954

22 Titanium
Ka, KL, 2.75216 2 4 .504 86
Ka, KL , 2.74851 2 4 .51084
Ktl, ,, KM,,, 2.51391 2 4.93181
Ln L,M, 30.89 3 Q.40 13
UJ, L, M. 27.05 2 0.4584
LQL, M, 31.36 2 0.3953
la L,M. ,1 21 .42 2 0.4522

23 Vanadium
Ka, KL, 2.50738 2 4.94464
Ka, KL , 2.50356 2 4.95220
Ktl,,, KM,,, 2.28440 2 5.42729
LTl L,M, 27.34 3 0.4535
Ltl, L, M. 23.88 4 0.5192
U>L,M, 27.77 I 0.4465
Lii L, M.,, 24.25 3 0.51 13
6 Practical Handbook of Spectroscopy

TABLE I (continued)

Wavelength, Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines
P. E. in Last
Line Wavelength A• Wavelength Digit Energy keV

24 Chromium
K<1 1 KL, 2.293606 3 5.40551
K<1 1 KL, 2.28970 2 5.4 1472
KP, , 3 KM, ,3 2.084 87 2 5.94671
l !'ll, M, 24.30 3 0.5102
LP, L, M. 21.27 0.5828
LQ L,M, 24.78 I 0.5003
Ui L, M. ,s 21.64 3 0.5728

25 Manganese
K.a, KL, 2. 10578 2 5.88765
K<1 1 KL, 2.101820 9 5.89875
KP, ,> KM,,, 1.91021 2 6.49045
l l'l L, M, 21 .85 2 0.5675
LP, L, M. 19.1 I 2 0.6488
U L, M, 22.29 0.556 3
La L, M. ,s 19.45 0.6374

26 Iron
K<1 1 KL, 1.939980 9 6.39084
Ke1 1 KL, 1.936042 9 6.40384
KP,,, KM, ,, 1.75661 2 7.05798
l l'l L, M, 19.75 4 0.628
Ul, L, M. 17.26 0.7185
LQ L, M, 20.15 I 0.6152
La L, M. ,s 17.59 2 0.7050

27 Cobalt
Ka, Kl, 1.792850 9 6.9 1530
Ka, KL, 1.788965 9 6 .93032
KP,,, KM ,,, 1.62079 2 7.64943
ll'l L, M, 17.87 3 0.694
LP, L, M. 15.666 8 0.791 4
U L, M, 18.292 8 0.6778
l u L, M• . s 15.972 6 0.7762

28 N1ckd
Ka, Kl , 1.661747 8 7.46089
Ka, KL, 1.657910 8 7.478 15
KO, , 1 KM , .> 1.500 135 8 8.26466
ll'l L, M, 16.27 3 0.762
LO, L, M. 14.271 6 0.8688
Ll L, M, 16.693 9 0.7427
La L, M•. , 14.561 3 0.8515

29 Copper
Ka, KL , 1.544390 2 8.02783
Ka, KL, 1.540562 2 8.04778
KO,,, KM ,,, 1.392218 9 8.90529
Ll'l L, M, 14.90 2 0.832
LP, L, M. 13.053 3 0.9498
U L, M, 15.286 9 0.8111
La L, M. ·' 13.336 3 0.9297
 Section 1: X-Ray Spectroscopy 7

TABLE 1 (continued)

Wavelength, Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines

P. E. in Last
Line Wavelength A• Wavelength Digit EnerJY keY

30 Zinc
Ka, KL, 1.439000 8 8.61578
Ka, KL, 1.435155 7 8.63886
K.a, ,> KM,,, 1.29525 2 9.5720
L11 L,M, 13.68 2 0.906
LIJ, L, M. 11.983 3 1.034 7
L!1 L,M, 14.02 2 0.884
LO: L,M. ,s 12.254 3 1.0117

31 Gallium
Ka, KL 2 1.34399 1 9.22482
Ka, KL, 1.340083 9 9.25174
I<Jl, KM, 1.20835 5 10.2603
KO, KM, 1.20789 2 10.2642
L11 L, M, 12.597 2 0.9842
LIJ, L, M. 11.023 2 1.1248
LQL, M, 12.953 2 0 .9572
La: L,M. ,s 11.292 1.09792

32 Germanium
Ka 1 KL, 1.258011 9 9.85532
Ka, KL, 1.254054 9 9.88642
I<Jl, KM, 1.12936 9 10.9780
I<Jl,KM, 1.12894 2 10.982 1
L11 L,M, 11 .609 2 1.0680
LO, L1 M4 10.175 1.2185
U! L, M, 11.965 4 1.0362
LO: L, M. ,, 10.436 1 8 1.18800

33 Arsenic
Ka, KL 1 1.17987 10.50799
Ka, KL, 1.17588 I 10.54372
I<Jl, KM, 1.05783 5 11.7203
KO, KM, 1.05730 2 11.7262
L11L 2 M, 10.734 I 1.1550
LIJ, L, M4 9.4141 8 1.3170
U1 L 3 M, 11 .072 I 1.1198
Ui L, M. ,s 9.6709 8 1.2820

34 Selenium
Ka, KL, 1.10882 2 I 1.1814
Ka, KL 3 1. 10477 2 11.2224
K.a, KM, 0.99268 5 12 4896
K.a, KM, 0.992 18 3 12.4959
L11 L,M, 9.962 I 1.2446
LIJ, L1 M. 8.7358 5 1.41923
LQ L,M, 10.294 I 1.2044
LO: L, M.,s 8.9900 5 1.37910

35 Bromine
Ka 2 KL, 1.04382 2 11.8776
Ka, KL, 1.03974 2 11.924 2
KP, KM, 0.93327 5 13.2845
8 Practical Handbook of Spectroscopy

TABLE I (continued)

Wavelength, Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines

P. E. in Last
line Wavelength A • Wavelength Digit Energy keV

KJJ, KM, 0.93279 2 13.2914

L'l L,M, 9.255 I 1.3396
LtJ, L,M. 8.1251 5 1.52590
UL,M, 9.585 1.2935
Ui L,M.,, 8.3746 5 1.48043

36 Krypton
Ka, KL, 0.9841 12.598
Ka, KL, 0.9801 12.649
KJJ, KM, 0.8790 14. 104
KtJ, KM , 0.8785 I 14 .112
LtJ, L, M. 7.576 3 1.6366
Lii L, M• •s 7.817 3 1.5860

37 Rubidium
Ka, KL, 0.92969 I 13.3358
Ka, KL, 0.925553 9 13.3953
KtJ, KM, 0.82921 3 14.9517
KJJ, KM, 0.82868 2 14.9613
L'l L2 M, 8.0415 4 1.54177
LP, L, M. 7.0759 3 1.75217
U L,M, 8.3636 4 1.48238
La, L1 M4 7.3251 3 1.69256
La, L,M, 7.3183 2 1.69413

38 Strontium
Ka, KL, 0.87943 I 14.0979
Ka, KL, 0.87526 I 14. 1650
KJJ, KM , 0.78345 3 15 .8249
KJJ, KM, 0.78292 2 15.8357
L'l L,M, 7.5171 3 1.64933
LIJ, L,M. 6.6239 3 1.87172
UL,M, 7.8362 3 1.58215
La1 L3 M4 6.8697 3 1.80474
La, L, M, 6.8628 2 1.80656

39 Yttrium
Ka, KL, 0.83305 14.8829
Ka, KL, 0.82884 I 14.9584
KJJ, KM, 0.74126 3 16.7258
KJJ, KM, 0.74072 2 16.7378
L'l L, M, 7.0406 3 I. 76095
LP, L,M. 6.2120 3 1.99584
U! L, M, 7.3563 3 1.68536
LC11 L, M. 6.4558 3 I. 9204 7
La, L1 M1 6.4488 2 1.92256

40 Zirconium
Ka, KL, 0. 79015 I 15.6909
Ka, KL, 0.78593 I 15.7751
KJJ, KM, 0.70228 4 17.654
KtJ, KM, 0.70173 3 17.6678
 Section 1: X -Ray Spectroscopy 9

TABLE I (continued)

Wavelength, Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines

P. E. in Last
Line Wavelength A• Wavelength Digit Energy keY

L'l L, M, 6.6069 3 1.87654

LIJ, L 3 M. 5.8360 3 2.1244
U! L,M, 6.9185 3 1.79201
La, L,M. 6.0778 3 2.0399
La, L,M, 6.0705 2 2.04236
L(J 2 · ' , L,N. ,s 5.5863 3 2.2194

41 Niobium
Ka, KL, 0.75044 16.5210
Ka, KL 3 0.74620 I 16.6151
KIJ, KM, 0.66634 3 18.6063
Kfl, KM, 0.66576 2 18.6225
L'l L,M, 6.2109 3 1.99620
Lfl, L, M. 5.4923 3 2.2574
LQ L 3 M, 6.5176 3 1.90225
La1 L,M. 5.7319 3 2.1630
La, L3 M, 5 7243 2 2.16589
L(J 2 · ' , L3 N4 ,s 5.2379 3 2.3670

42 Molybdenum
Ka 1 KL, 0713590 6 17.3743
Ka, KL, 0.709300 I 17.47934
K,a, KM, 0.632872 9 19.5903
K.a, KM, 0.632288 9 19.6083
L11 L1 M, 5.8475 3 2.1202
LP, L,M. 5.17708 8 2.39481
L2 L,M, 6.1508 3 2.01568
La1 L,M. 5.41437 8 2.28985
La, L,M, 5.40655 8 2.29316
L(l, ,Is L, N. ,s 4.9232 2 2.5183

43 Technetium
Ka,KL 2 0.67932 3 18.2508
Ka, KL 3 0.67502 3 18.3671
KP, KM, 0.60188 4 20.599
K.a, KM, 0.60130 4 20.619
L(l, L,M. 4.8873 8 2.5368
La, L,M, 5.1148 3 2.4240

44 Ruthenium
Ka, KL, 0.647408 5 19.1504
Ka, KL, 0.643083 4 19.2792
KP, KM, 0.573067 4 21.6346
KP, KM, 0.572482 4 21.6568
LnL,M, 5.2050 2 2.38197
LP, L,M. 4.62058 3 2.68323
LQ L,M, 5.5035 3 2.2528
La 2 L,M. 4.85381 7 2.54431
La, L3 M, 4.84575 5 2.55855
LP, ,Is L, N.·' 4.3718 2 2.8360
10 Practical Handbook of Spectroscopy

TABLE 1 (continued)

Wavelength, Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines

P. E. in Last
Line Wavelength A • Wavelength Digit Energy keV

45 Rhodium
Ka, KL, 0.617630 4 20.0737
Ka 1 KL, 0.613279 4 20.2161
KP, KM, 0.546200 4 22.6989
K(l 1 KM, 0.545605 4 22.7236
Ln L,M, 4.9217 2 2.5191
Ul, L2 M4 4.37414 4 2.83441
LQ L 3 M1 5.2169 3 2.3765
La, L,M. 4.60545 9 2.69205
La, L 3 M1 4.59743 9 2.69674
Ul, ,as L,N. ,s 4.1310 2 3.0013

46 Palladium
Ka, KL, 0.589821 3 21.0201
Ka, KL3 0.585448 3 21.1771
KP, KM, 0.521123 4 23.7911
KP, KM, 0.520520 4 23.8187
Ln L2 M, 4 .6605 2 2.6603
Ul, L,M. 4. 14622 5 2.99022
UL 3 M1 4.9525 3 2.5034
La, L,M. 4.37588 7 2.83329
La, L,M1 4.36767 5 2.83861
Ul, ,,s L, N. ,s 3.90887 4 3.17179

47 Silver
Ka, KL, 0.563798 4 21.9903
Ka, KL 1 0.5594075 6 22.16292
KP, KM, 0.497685 4 24.9115
KP, KM, 0.497069 4 24.9424
Ln L,M, 4.4183 2 2.8061
Ul, L,M. 3.93473 3 3.15094
LQ L,M, 4.7076 2 2.6337
La, L,M. 4 .16294 5 2.97821
La, L3 M1 4 15443 3 2.98431
Ul,,, s L,N.,1 3.70335 3 3.34781

48Cadmium
Ka 2 KL 1 0.539422 3 22.9841
Ka, KL, 0.535010 3 23.1736
KP, KM, 0.475730 5 26.0612
KP, KM, 0.475105 6 26.0955
Ln L,M, 4.19315 9 2.956 75
LP, L,M. 3.73823 4 3.31657
LQ L,M, 4.48014 9 2.76735
La, L,M. 3.96496 6 3.12691
La, L,M 1 3.95635 4 3.13373
LP, •' I L,N. ,s 3.51408 4 3.52812

491ndium
Ka, KL, 0.516544 3 24.0020
Ka, KL, 0.512113 3 24.2097
 Section I: X-Ray Spectroscopy 11

TABLE 1 (continued)

Wavelength, Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines

P. E. in Last
Line Wavelength A• Wavelength Digit Energy keV

K/3 3 KM, 0.455181 4 27.2377

K/3, KM, 0.454545 4 27.2759
Ll'l L,M, 3.98327 9 3.11254
L13, L,M. 3.55531 4 3.48721
LQ L3 M, 4.26873 9 2.90440
La, L3 M4 3.78073 6 3.27929
La, L,M, 3.77192 4 3.28694
L(J, ·', L,N. ,s 3.33838 3 3.71381

50 Tin
Ka, KL, 0.495053 3 25.0440
Ka, KL 3 0.490599 3 25.2713
K(3, KM, 0.435877 5 28.4440
K/3, KM 3 0.435236 5 28.4860
Ll'l L,M, 3.78876 9 3.27234
L(J, L, M. 3.38487 3 3.66280
LQL,M, 4.07165 9 3.04499
La, L 3 M4 3.60891 4 3.43542
La, L,M, 3.59994 3 3.44398
LP, , 1 , L, N. ,s 3.17505 3 3.90486

51 Antimony
Ka, KL, 0.474827 3 26.1108
Ka , KL 3 0.470354 3 26.3591
KP, KM, 0.417737 4 29.6792
Ki3, KM 3 0.417085 3 29.7256
L11 L, M, 3.60765 9 3.43661
LP, L, M. 3.22567 4 3.84357
L!1 L,M, 3.88826 9 3.18860
La, L,M. 3.44840 6 3.59532
La, L,M, 3.43941 4 3.60472
L(J, •' s L,N. •' 3.02335 3 4.10078

52 TeUurium
Ka, KL, 0.455784 3 27.2017
Ka, KL, 0.451295 3 27.4723
K/3 3 KM, 0.400659 4 30.9443
KJJ, KM, 0.399995 5 30.9957
LI'IL,M, 3.43832 9 3.60586
L(J, L,M. 3.07677 6 4.02958
Ul L 3 M, 3. 71696 9 3.33555
La, L3 .M 4 3.29846 9 3.7588
La, L,M, 3.28920 6 3. 76933
L13,,,, L,N.,, 2.88217 8 4.3017

53 Iodine
Ka, KL, 0.437829 7 28.3172
Ka, KL, 0.433318 5 28.6120
K/3 3 KM, 0.384564 4 32.2394
K13, KM 3 0.383905 4 32.294 7
L11 L,M, 3.27979 9 3.7801
L(J, L,M. 2.93744 6 4.22072
LQ L,M, 3.55754 9 3.48502
12 Practical Handbook of Spectroscopy

TABLE 1 (continued)

Wavelength, Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines

P. E. in Last
Line Wavelength A • Wavelength Digit Energy keV

La 2 L,M. 3.15791 6 3.92604

La, L3 M, 3.14860 6 3.93765
LP 2 , 1 s L, N. ,s 2. 75053 8 4.5075

54 Xenon
Ka 2 KL 2 0.42087 2 29.458
Ka, KL, 0.41634 2 29.779
Kil, KM 2 0.36941 2 33.562
Kil, KM, 0.36872 2 33.624
La, L,M, 3.0166 2 4.1099

SS Cesium
Ka 2 KL, 0.404835 4 30.6251
Ka, KL 3 0.400290 4 30.9728
Kil 3 KM, 0.355050 4 34.9194
Kil, KM 3 0.354364 7 34.9869
Ln L,M, 2.9932 2 4.1421
Lil, L2 M. 2.6837 2 4.6198
U! L,M, 3.2670 2 3.7950
La 2 L,M. 2.9020 2 4.2722
La, L,M, 2.8924 2 4.2865
LP,,, s L,N.,, 2.5118 2 4.9359

56 Barium
Ka 2 KL 2 0.389668 5 31.8171
Ka, KL, 0.385111 4 32.1936
KP 3 KM, 0.341507 4 36.3040
KP, KM 3 0.340811 3 36.3782
Ln L,M, 2.8627 3 4.3309
Lil, L2 M4 2.56821 5 4.82753
UL,M, 3.1355 2 3.9541
La 2 L 3 M4 2.78553 5 4.45090
La, L,M, 2.77595 5 4.46626
LP,,,, L,N 4 ,, 2.40435 6 5.1565

57 Lanthanum
Ka, KL, 0.375313 2 33.0341
Ka, KL, 0.370737 2 33.4418
Kil, KM, 0.328686 4 37.7202
KP, KM, 0.327983 3 37.8010
Ln L2 M1 2.740 3 4.525
Lil, L,M. 2.45891 5 5.0421
LI1L 3 M, 3.006 3 4.124
La, L,M. 2.67533 5 4.63423
La, L3 M, 2.66570 5 4.65097
Lil 2 , 1 , L,N.,, 2.3030 3 5.3835
MPM.N, 14.573 5 0.8508
MaM,N, ,, 14.859 5 0.8344

58 Cerium
Ka 2 KL 2 0.361683 2 34.2789
Ka, KL, 0.357092 2 34.7197
KP, KM 1 0.316520 4 39.1701
 Section 1: X-Ray Spectroscopy 13

TABLE I (continued)

Wavelength , Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines

P. E. in Last
Line Wavelength A• Wavelength Digit Energy keY

KP, KM , 0.315816 2 39.2573

Lfl L, M, 2.6203 4 4.731 5
LP, L,M. 2.3561 3 5.2622
L2 L,M, 2.8917 4 4.2875
La, L,M. 2.5706 3 4.8230
La, L,M, 2.5615 2 4.8402
LO,," L,N.,, 2.2087 2 5.6 134
MP M4 N6 13.786 5 0.8993
Mii M, N6 , 1 14.078 5 0.8807

59 Praseodymium
Ka, KL , 0.348749 2 35.5502
Ka, KL, 0.3 44140 2 36.0263
KP, KM, 0.304975 5 40.6529
KP, KM, 0.304261 4 40.7482
LflL,M , 2.512 3 4.935
LO, L, M. 2.2588 3 5.4889
U L, M, 2.784 1 4 4.4532
La, L,M. 2.4729 3 5.0135
La, L , M ~ 2.4630 2 5.0337
LP,·', L, N. ,s 2.1 194 4 5.850
MP M.N. 13.056 5 0.9496
Ma M, N•. 7 13.339 5 0.9295

60 Neodymium
Ka, KL, 0.3364 72 2 36.8474
Ka, KL, 0.331846 2 37.3610
KP, KM , 0.294027 3 42.1665
KP, KM, 0.293299 2 42.2713
Lfl L, M, 2.4094 4 5.1457
LO, L, M. 2. 1669 2 5.7216
LQ L,M , 2.6760 4 4.6330
La: L,M. 2.3807 3 5.2077
La, L,M, 2.3704 2 5.2304
Ul,_,. L,t.: •. , 2.0360 3 6.0894
MP M. N. 12.399 5 0.9999
Ma M.N • . , 12.667 5 0.9788

6 1 Promethium
t\a 1 KL : 0.324803 4 38.17 12
Ka, t\L, 0.320160 4 38.7247
KP, i'M , 0.28363 4 43.713
KP, KM, 0.28290 3 43.826
LO, L: M• 2.0797 4 5.961
La, L, M. 2.2926 4 5.4078
La, L,M , 2.2822 3 5.4325
LO ,,,. L,N.,, 1.9559 6 6.339

62 Samarium
Ka, J.:L, 0.3 13698 2 39.5224
J.:a, KL, 0.309040 2 40. 1181
KP, KM , 0.27376 2 45.289
KJJ, KM, 0.27301 2 45 .413
14 Practical Handbook of Spectroscopy

TABLE I (continued)

Wavelength, Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines
P. E. in Last
Line Wavelength A• Wavelength Digit Energy keV

Ln L,M 1 2.21824 3 5.5892

Ul, L,M. 1.99806 3 6.2051
UL 3 M1 2.4823 4 4.9945
La, L, M. 2.21062 3 5.6084
La 1 L,M , 2.1998 2 5.6361
Ul,, 1 s L,N.,, 1.88221 3 6.5870
MP M. N, 11.249 5 1.1022
MiiM,N,,, 11.485 5 1.0795

63 Europium
Ka, KL, 0.3031 18 2 40.9019
Ka, KL 3 0.298446 2 41.5422
KP, KM, 0.264332 5 46.9036
KP, KM, 0.263577 5 47.0379
Ln L,M, 2.1315 2 5.8166
Ul, L,M. 1.9203 2 6.4564
U! L,M, 2.3948 2 5.1772
La, L,M. 2.1315 2 5.8166
La, L, M, 2.1209 2 5.8457
Ul,, , , L, N• ., 1.8118 2 6.8432
MP M. N, 10.736 5 1.1548
Mii M, N, ,, 10.955 5 1.1317

64 Gadolinium
Ka, KL, 0.293038 2 42.3089
Ka, KL 3 0.288353 2 42.9962
KP, KM, 0.25534 2 48.555
KP, KM , 0.25460 2 48.697
Ln L, M, 2.0494 1 6.0495
Ul, L,M. 1.8468 2 6.7 132
LQ L, M, 2.3122 2 5.3621
La, L,M. 2.0578 2 6.0250
La, L,M, 2.0468 2 6.0572
Ul, ,, s L~ N.·' 1.7455 2 7.1028
Mtl M. N. 10.249 5 1.2097
Mii M, N•. , 10.469 5 1.1843

65 Terbium
Ka, KL, 0.283423 2 43.7441
Ka, KL, 0.278724 2 44.4816
Ktl, KM, 0.24683 2 50.229
KIJ 1 KM 3 0.24608 2 50.382
Ln L, M, 1.9730 2 6.2839
Ul, L,M. I. 7768 3 6.978
LQ L ~M, 2.2352 2 5.5467
La, L,M. 1.9875 2 6.2380
La, L,M, 1.9765 2 6.2728
Ul,,,, L, N., , 1.6830 2 7.3667
Mtl M. N. 9.787 5 1.2668
Mii M, N, ·' 10.014 5 1.2381

66 Dysprosium
Ka, KL, 0.274247 2 45.2078
 Section I: X-Ray Spectroscopy 15

TABLE 1 (continued)

Wavelength, Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines

P. E. in Last
Line Wavelength A• Wavelength Digit Energy keV

Ka, KL, 0.269533 2 45.9984

Ktl, KM, 0.23862 2 51.957
KP, KM, 0.23788 2 52.119
L11 L, M, 1.89743 7 6.5342
~. L,M. 1.71062 7 7.2477
L2 L,M, 2.15877 7 5.743 1
La, L,M. 1.91991 3 6.4577
La, L,M, 1.90881 3 6.4952
1.62369 7 7.6357
~'·" L,N.,,
MP M.N, 9.359 5 1.3247
Mil M, N, ,, 9.589 5 1.2930

67 Holmium
Ka, KL, 0.265486 2 46.6997
Ka, KL, 0.260756 2 47.5467
Ktl, KM, 0.23083 2 53.7 11
Ktl, KM , 0.23012 2 53.877
L11 L,M, 1.8264 2 6.7883
~. L,M. 1.64 75 2 7.5253
UL,M, 2.0860 2 5.9434
La, L, M. 1.8561 2 6.6795
La, L,M, 1.8450 2 6.7198
~'·" L,N.,, 1.5671 2 7.911
MP M4 N6 8.959 5 1.3839
MilM,N,,, 9.193 5 1.3486

68 Erbium
Ka, KL, 0.257110 2 48.2211
Ka, KL, 0.252365 2 49.1277
Ktl, KM, 0.22341 2 55.494
Ktl, KM, 0.22266 2 55.68 1
L11 L,M, 1.7566 1 7.0579
~. L,M. 1.5873 I 7.8109
UL,M, 2.015 1 6.152
La, L, M. 1.7955 2 6.9050
La, L, M, 1.78425 9 6.9487
1.51399 9 8.1890
UJ, ·" L,N • . s
MP M.N, 8.584 5 1.4443
MilM,N,,, 8.822 5 1.4054

69 Thulium
Ka, KL, 0.249095 2 49.7726
Ka, KL, 0.244338 2 50.7416
KP 3 KM, 0.21636 2 57.304
Ktl, KM , 0.2 1556 2 57.5 17
L11 L,M, 1.6963 2 7.3088
UJ, L,M. 1.5304 2 8.101
U1 L, M, 1.9550 2 6.3419
La, L, M. 1.7381 2 7.1331
La, L,M, 1.7268 2 7. 1799
UJ, ,, , L,N. ·' 1.4640 2 8.468
MP M.N, 8.238 5 1.5050
MilM,N,,, 8.475 5 1.4629
16 Practical Handbook of Spectroscopy

TABLE I (continued)

Wavelength, Probable Error in Last Digit of Wavelength, and Energy of

Some Characteristic Emission Lines

P. E. in Lut
Line Wavelength A• Wavelength Digit Energy keV

70 Ytterbium
Ka, KL, 0.241424 2 51.3540
Ka, KL, 0.236655 2 52.3889
KP, KM, 0.2096 I 59.14
KP, KM, 0.20884 8 59.37
Ln L, M, 1.63560 5 7.5802
LO, L, M, 1.47565 5 8.4018
U1 L,M, 1.89415 5 6.5455
La, L,M, 1.68285 5 7.3673
La, L, M, 1.67189 4 7.4156
LO, ·' s L, N, . s 1.41550 5 8.7588
MP M,N, 7.9 12 5 1.5670
MaM, N6 • 1 8.141 5 1.5229

71 Lutetium
Ka, KL, 0.234081 2 52.9650
Ka, KL, 0.229298 2 54 .0698
KP, KM, 0.20309 4 61 .05
KP, KM , 0.20231 3 61.283
Ln L, M, 1.5779 I 7.8575
LP, L, M, 1.42359 3 8.7090
LQL, M, 1.8360 I 6 .7528
La, L, M, 1.63029 5 7.6049
La, L, M, 1.61951 3 7.6555
LO,s L, N, 1.3715 I 9.0395
LO, L, N, 1.37012 3 9.0489
MP M, N, 7.601 2 1.6312
Mil Ms N6 • 1 7.840 2 1.5813

72 Hafnium
Ka, KL, 0.227024 3 54.6114
Ka, KL, 0.222227 3 55.7902
KP, KM, 0.19686 4 62.98
KP, KM , 0.19607 3 63.234
Ln L,M, 1.52325 5 8.1393
LP, L,M, 1.37410 5 9.0227
LQ L, M, 1.78145 5 6.9596
La, L, M, 1.58046 5 7.8446
La , L3 M, 1.56958 5 7.8990
LO, s L, N, 1.32783 5 9.3371
LO, L, N, 1.32639 5 9.3473
MP M, N. 7.303 1.6976
Ma M, N,,, 7.539 1.6446

73 Tantalum
Ka, KL, 0.220305 8 56.277
Ka, KL, 0.215497 4 57.532
KP, KM , 0.190890 2 64.9488
KP, KM, 0. 190089 4 65.223
Ln L, M, 1.4 7 106 5 8.4280
LO, L, M, 1.32698 3 9.3431
LVL, M, 1.72841 5 7. 1731
La, L, M, 1.53293 2 8.0879
Another Random Scribd Document
with Unrelated Content
practice of the Patent Office. In the Scientific American, of December 16
and 23, 1854, in a most interesting series of articles on the reaper, the
Hussey machine is fully described. The first public trial was on July 2,
1833, before the Hamilton County Agricultural Society, near Carthage, O.,
and its success was attested by nine witnesses. Great stress was laid by
Mr. Hussey on the double finger bar, i. e., a finger bar having one member
above and the other below the knife. The Scientific American said the
machine was a success from the first; that “in 1834 the machine was
introduced into Illinois and New York, and in 1837 into Pennsylvania, and
in 1838 Mr. Hussey moved from Ohio to Baltimore, Md., and continued to
manufacture his reapers there up to the present time.”
In 1836 Hussey was invited by the Maryland Agricultural Society for the
Eastern Shore to exhibit his machine before them. On July 1 he did so,
and made practical demonstration of its working to the society at Oxford,
Talbot County, and again on July 12 at Easton. On the following Saturday
it was shown at Trappe, and it was afterwards used on the farm of Mr.
Tench Tilghman, where 180 acres of wheat, oats and barley were cut with
it. The report of the Board of Trustees of the society was an unqualified
commendation of the practicability, efficiency and value of the machine,
and a handsome pair of silver cups was awarded to the inventor. The
report was signed by the following well-known residents of the Eastern
Shore: Robert H. Goldsborough, Samuel Stevens, Samuel T. Kennard,
Robert Banning, Samuel Hambleton, Sr., Nichol Goldsborough, Ed. N.
Hambleton, James L. Chamberlain, Martin Goldsborough, Horatio L.
Edmonson, and Tench Tilghman.
Hussey made and sold his machine for years. In the American Farmer, of
October, 1847, an agricultural journal printed at Baltimore, the
advertisement of his machine appears with full price lists of the different
sizes of machines, and also of an improvement in the manner of disposing
of the grain, which was the invention of Mr. Tench Tilghman, and was
adopted by Hussey on his reaper.
 FIG. 151.—THE McCORMICK REAPER OF 1847.

While Hussey was at work at his reaper, McCormick also was busily
engaged with his, and he took his second patent January 31, 1845, No.
3,895. This related to the cutter bar, the divider, and reel post.
McCormick’s next patent was dated October 23, 1847, No. 5,335, and in
this the raker’s seat was to be mounted on the platform as shown in Fig.
151. McCormick’s last named patent also covered the arrangement of the
gearing and crank in front of the drive wheel, so as to balance the weight
of the raker. In the same year Hussey took out his patent of August 7,
1847, No. 5,227, for the open top and slotted finger guard, which is an
important part of all successful cutter bars.
The rivalry between the McCormick and Hussey machines continued for
many years, and they were frequently in competition both in America and
England. The stimulus of this rivalry doubtless had much to do with the
development and success of the reaper. Both Hussey and McCormick
asked for extensions of their patents, but they failed to get them. In 1848,
pending McCormick’s extension proceedings, facts were introduced by him
to show that his invention of the reaper antedated Hussey’s, and that he
had made his machine as early as 1831, and had used it then on the farm
of Mr. John Steele, in Virginia. This claim to priority was supported by the
publication of a description of the machine, and certificate of its use, in
the Union, a newspaper published at Lexington, Va., September 28, 1833,
and although no adjudication was ever made on this issue, this fact,
together with Mr. McCormick’s success in the contest in England in 1851,
and his subsequent persistence and activity in improving, developing and
introducing the reaper, has so distinguished him in this connection, that
to-day his name is as commonly associated with the reaper as is Fulton’s
with the steamboat, or that of Morse with the telegraph. To Mr. McCormick
more than to anybody else the perfection of the reaper is due. In the
spring of 1851 McCormick placed his reaper on exhibition at the World’s
Fair in London. Hussey also had his machine there, and they were the only
ones represented. The machines were tested in the field, and astonished
all who saw them operate. The Grand Council medal, which was one of
four special medals awarded for marked epochs in progress, was given to
McCormick, and the judges referred to the McCormick machine as being
worth to the people of England “the whole cost of the exposition.” It is
only fair to state that Hussey was not present to direct the trial of his
machine, and that in a subsequent trial another jury decided in his favor,
and His Royal Highness, Prince Albert, ordered two of Hussey’s machines
in 1851—one for Windsor and the other for the Isle of Wight. The Duke of
Marlborough also gave his personal testimonial to Mr. Hussey as to the
excellence of his machine. In 1855, at a competitive trial of reapers near
Paris, three machines were entered. The American machine cut an acre of
oats in twenty-two minutes, the English machine in sixty-six minutes, and
the Algerian in seventy-two. In 1863, at the great International Exposition
at Hamburg, the McCormick reaper again took the grand prize. While in
Paris in 1878 Mr. McCormick was elected a member of the French
Academy of Sciences as “having done more for the cause of agriculture
than any living man.” Mr. McCormick continued to the end of his days, in
1884, to devote his entire energies to the development of the reaper, and
well deserved the princely fortune that resulted from his indefatigable
labors, a good portion of which fortune he spent during his life in the
cause of education and acts of philanthropy. The inventory of his estate,
filed in the Probate Court of Cook County, Ill., showed $10,000,000 as the
reward of his genius and industry, and is an object lesson of the reward of
merit for the ambitious youth of the Twentieth Century.
FIG. 152.—THE MANN HARVESTER OF 1849.

FIG. 153.—THE MARSH HARVESTER OF 1858.

 FIG. 154.—THE CHAMPION REAPER.

In the development of the reaper one of the first deficiencies to be

supplied was automatic mechanism for taking the grain from the platform.
In November, 1848, F. S. Pease took out patent No. 5,925 for a rake
whose teeth projected up through slots in the platform, and moved back
and forth to deposit the grain upon the ground. On June 19, 1849, J. J. &
H. F. Mann took out patent No. 6,540 on a machine employing the
principle of an endless band for carrying the cut grain to the side of the
machine, where it passed up an inclined plane and accumulated in a
receptacle to form a gavel, which was clumped upon the ground. This
machine is shown in Fig. 152. On July 8, 1851, W. H. Seymour took out
patent No. 8,212 for a self-raker, and this machine marks the beginning of
the era of self-raking reapers, which for a quarter of a century in various
modifications continued to be used, until displaced by subsequent
improvements in binding devices. In 1853 the Sylla and Adams machine
was brought out, the patents for which were bought by the Aultmans, and
the Aultman and Miller, or “Buckeye” harvester, was manufactured
thereunder. The general form of the modern harvester has followed along
the lines of the Mann machine of 1849. The development began by
replacing the gavel receptacle on the right of that machine (Fig. 152) with
a platform on which stood men who rode on the machine as they bound
the grain. An early and important example of a harvester of this class is
given in the Marsh machine, patented August 15, 1858, No. 21,207, and
shown in Fig. 153. To this type of machine the self-binding devices were
subsequently applied, but before they materialized many other
improvements in self-rakers were made and applied, among which may be
mentioned the combined rake and reel of Owen Dorsey, of Maryland
(1856), sweeping horizontally across the quadrantal platform; the
McClintock Young revolving reel, carrying a rake; the Henderson rake
(1860) used on the Wood machine; the Seiberling dropper (1861), which
consisted of a slotted platform which moved to discharge the gavel; and
the various improvements covered by Whiteley’s patents, which were
embodied in the Champion reaper, of Springfield, O., and which is shown
in Fig. 154. This machine had a combined rake and reel of the Dorsey
type, whose arms moved over a circular inclined and stationary cam, and
whose rakes had a horizontal sweep over the platform, and a vertical
return over the wheels.

FIG. 155.—THE LOCKE WIRE BINDER OF 1873.

The next step, and, perhaps the most important one, in the development
of the reaper, was in providing automatic devices for binding the gavels of
grain into sheaves. John E. Heath, of Ohio, in patent No. 7,520, of July 22,
1850, was the pioneer, and he used cord. Watson, Renwick & Watson, in
patent No. 8,083, of May 13, 1851, and C. A. McPhitridge, in patent No.
16,097, of November 18, 1856, quickly followed in the attempt to provide
such a device, the former using cord and the latter wire. But the problem
was not an easy one to solve. On November 16, 1858, W. Grey took out
patent No. 22,074, for starting the binding mechanism by the weight of
the bundle. Probably the first to complete a binding attachment that was
partly automatic, and to attach it to a reaping machine, were H. M. & W.
W. Burson, of Illinois. On June 26, 1860, and October 4, 1864, W. W.
Burson patented a cord binder, and in 1863 one thousand machines were
built. These machines, however, used wire, and being assisted in their
operations by hand labor, were not truly automatic. On February 16, 1864,
Jacob Behel, of Illinois, obtained a patent, No. 41,661, for a very
important invention in binders. He showed and claimed for the first time
the knotting bill, which loops and forms the knot, and the turning cord
holder for retaining the end of the cord. On May 31, 1870, George H.
Spaulding took out patent No. 103,673 for a binder which automatically
regulated the bundles to a uniform size. Sylvanus D. Locke, of Wisconsin,
was the next inventor who undertook to solve the problem. He took out
patents No. 121,290, November 28, 1871, and No. 149,233, March 31,
1874, and many others. In 1873 he associated himself with Walter A.
Wood, and they built and sold probably the first automatic self-binding
harvester that was ever put upon the market. The Locke wire binder of
1873 is shown in Fig. 155. The use of wire, however, for binding grain,
involved certain objections in that it required a special cutting tool for
cutting the sheaves at the thresher, and it was not easy to remove the
wire, and parts of it were likely to go through the thresher. Inventors
accordingly concentrated their attention on the use of twine or cord.
Marquis L. Gorham, of Illinois, built a successful twine binder, and had it at
work in the harvest field in 1874. This machine, covered by patent No.
159,506, February 9, 1875, not only bound by cord, but produced bundles
of the same size. The grain in this machine is delivered by the elevator of
the harvester upon a platform, where it is seized by packers and carried
forward into a second chamber, where it is compacted by the packers
against a yielding trip, so that when sufficient grain is accumulated, the
trip will yield and start the binding mechanism into operation. The ball of
cord carried on the machine has one end threaded through the needle
and fastened in a holder. The grain is forced against the cord by the
packers, and when the binder starts the needle encircles the gavel,
carrying the cord to a knotting bill, and the end is again seized by the
rotating holder, the loop formed, the ends of the band severed, and the
bound bundle is discharged from the machine. A gate, which has in the
meantime shut off the flow of grain, is now drawn back, and the operation
is repeated. On February 18, 1879, John F. Appleby took out a patent, No.
212,420, for an improvement on the Gorham binder. In Fig. 156 is shown
a modern automatic self-binding reaper which embodies the fundamental
principles of McCormick and Hussey, the inclined elevator and platform
shown by Marsh, and the automatic binding devices of Behel, Gorham and
Appleby.

FIG. 156.—MODERN AUTOMATIC SELF-BINDING REAPER.

This machine, under favorable conditions, with one driver, cuts twenty
acres of wheat in a day, binds it, and carries the bound bundles into
windrows, and with one shocker, performs the work of twenty men, and
does it better, the saving in the waste of grain over hand labor being
sufficient to pay for the twine used in binding. It is said that the self-
binding reaper has reduced the cost of harvesting grain to less than half a
cent a bushel.
It is estimated that more than 180,000 machines of the self-binding type
are now produced yearly, the manufacturers in Chicago alone turning out
more than three-fourths of this number. It is not possible to do justice to
all the worthy workers in this great industry. Nearly 10,000 patents have
been granted on reaping and mowing machines, and the conspicuous
names of Whiteley, Wood, Atkins, Manny, Yost, and Ketchum, in addition
to those already mentioned, are only a small part of the great army of
inventors who have contributed to the development and perfection of the
reaper.
In 1840 it is said there were but three reapers made. To-day the total
number of self-binding harvesters, reapers and mowers in use is estimated
to be two millions. The growth of this industry in the four earlier decades
is as follows (the relatively small increase between 1860 and 1870 being
accounted for by the Civil War):

1840. 1850. 1860. 1870. 1880.

Machines made 3 3,000 20,000 30,000 60,000

Immediately succeeding this period the automatic cord binder was put
into use, and within five years the increase in output of reapers and
mowers was very great. In 1885 more than 100,000 self-binding
harvesters and 150,000 reapers and mowers were built and sold. In 1890
two manufacturing establishments in Chicago made more than 200,000
machines, half of which were self-binders and the other half reapers and
mowers, and these two institutions alone employed in their various
branches of manufacturing and selling 10,000 employees. In 1895 the
output of the largest of these manufacturing establishments was 60,000
self-binding harvesters, fitted with bundle carriers and trucks, 61,000
mowers, 10,000 corn harvesters, and 5,000 reapers, making 136,000
machines in all. In 1898 the output of this one factory for the year was
74,000 self-binding harvesters, 107,000 mowers, 9,000 corn harvesters,
and 10,000 reapers, amounting to 200,000 machines. This output,
together with 75,000 horse rakes, also made, averaged a complete
machine for every forty seconds in the year, working ten hours a day. The
estimated annual production of all factories in this class of agricultural
implements is 180,000 self-binding harvesters, 250,000 mowing machines,
18,000 corn harvesters, and 25,000 reapers.

FIG. 157.—STEAM HARVESTER AND THRESHER.

 The wheat is headed, threshed, cleaned and sacked by this machine in one
continuous operation.—
Cutter, 26 feet wide; Capacity, 75 acres per day.

FIG. 158.—FIFTY HORSE POWER STEAM PLANTING COMBINATION.

Traction engine pulling sixteen 10-inch plows, four 6-foot harrows, and a drill.

There were exported in the year 1880 about 800 self-binding harvesters,
2,000 reapers, and 1,000 mowers. In 1890 this was increased to 3,000
self-binding harvesters, 4,000 reapers, and 2,000 mowers. The total value
of mowers and reapers exported in 1890 was $2,092,638. The growth
subsequent to 1890 is well attested by the exports for 1899, which for
mowers and reapers was $9,053,830, or more than four times what it was
in 1890. These exported machines harvest the crops of the Argentine
Republic, Paraguay, and Uruguay, of South America; carry their labor-
saving values to Australia and New Zealand; traverse the wheat fields
along the banks of the Red Sea and the Volga, and are used throughout
all the continent of Europe.

FIG. 159.—A WESTERN HARVEST SCENE (LEFT SECTION OF VIEW).

 FIG. 159.—A WESTERN HARVEST SCENE (RIGHT SECTION OF VIEW).

With the self-binding harvester performing the work of twenty men,

cutting and binding the grain, and arranging the bundles in windrows, it
would seem that perfection in this art had been reached, but the tendency
of the age is to do things on a constantly increasing scale, and so the
latest developments in harvesters comprise a mammoth machine (Fig.
157) propelled across the grain fields by steam, and which by the same
power cuts a swath from 26 to 28 feet wide, threshes it at once as it
moves along, blows out the chaff, and puts the grain in bags at the rate of
three bags per minute, each bag containing one hundred and fifteen
pounds, and requiring two expert bag sewers to take the grain away from
the spout, sew the bags, and dump them on the ground. Seventy-five
acres a day is its task. A companion piece to this machine is illustrated in
Fig. 158, which shows the same power utilized for planting. A powerful
steam traction engine of fifty horse power hauls across the field a planting
combination of sixteen ten-inch plows, four six-foot harrows and a seeding
drill in the rear. Such great reaping machines only find useful application in
the enormous wheat fields of California and the Pacific Coast States,
where the dry climate permits the grain to ripen and dry sufficiently while
standing in the field. Moreover, only the heads of the grain are cut, the
straw being left standing. Some conception of the enormous scale upon
which grain is raised in the Western States may be gotten from the
dimensions of the farms. It is said that Dr. Glenn’s wheat farm comprises
45,000 acres; the Dalrymples’, in North Dakota, 70,000; and Mr. Mitchell,
in the San Joaquin Valley, in California, has 90,000 acres. The Dalrymple
farms in 1893 had 54,000 acres in wheat, and employed 283 self-binding
reapers to harvest the crop. There is a single unbroken wheat field on the
banks of the San Joaquin River, near the town of Clovis, in Madera County,
California, which comprises 25,000 acres, or nearly forty square miles of
wheat—a veritable sea of waving grain. The field is nearly square; each
side is a little over six miles long. If its shape were changed to the width
of one mile, the field would then be forty miles long. It has been said of
the grain fields of the West, that the men and teams eat breakfast at one
end of a furrow, take dinner in the middle of the row, and at night camp
and sup at the end of the same row. With a field of such proportions it is
not difficult to see how this may be true. The cultivation and garnering of
crops from such vast areas can only be appreciated by comparisons. If it
were one man’s work to plow such a field, even with a double gang plow,
cutting a furrow twenty-four inches wide, he would travel 105,600 miles,
which would be equivalent to going around the world four times. If he
plowed twenty miles a day, it would take 5,280 days. To harrow would
require as long, and to plant would take about the same time, or about
forty-three years altogether. A full lifetime would be required to plant the
crop, and a second generation would be required to reap it. But great
results require great agencies, and so great labor-saving machines,
operated by armies of men, are brought into requisition, and with these
the crop is both planted and reaped. A long procession of self-binding
harvesters, following close one behind the other, makes quick work of it,
and before the weather changes this great field is mowed, its crop
garnered, and bread supplied for the hungry of all lands.
The exports of wheat to foreign lands in 1898 were 148,231,261 bushels,
worth $145,684,659, and the exports of wheat flour for the same year
were 15,349,943 barrels, worth $69,263,718. The total yield of wheat in
the United States for 1898 was 675,148,705 bushels.
With the fertile earth, and its prolific inventors, the United States has
become the richest country in the world. What its future is to be no man
may say, but its destiny is not yet fulfilled, and it is pregnant with potential
possibilities.
 CHAPTER XVII.
Vulcanized Rubber.

Early Use of Caoutchouc by the Indians—Collection of the Gum—Early Experiments

Failures—Goodyear’s Persistent Experiments—Nathaniel Hayward’s Application of
Sulphur to the Gum—Goodyear’s Process of Vulcanization—Introduction of His
Process Into Europe—Trials and Imprisonment for Debt—Rubber Shoe Industry—
Great Extent and Variety of Applications—Statistics.

ost all important inventions have grown into existence by slow

M stages of development, and by successive contributions from

many minds, not a few having descended by gradual processes of
evolution from preceding centuries. Vulcanized rubber, however, is
not of this class. It belongs exclusively to the Nineteenth Century,
and owes its existence to the tireless energy of one man. The value of
the crude gum had been previously speculated upon, and for years
attempts had been made to utilize it, but not until Goodyear invented his
process of vulcanizing it did it have any real value. This process was an
important, distinct and unique step, entirely the work of Mr. Goodyear,
and it has never been superseded nor improved upon to any extent.
Charles Goodyear was born in New Haven, December 29, 1800, and his
life, beginning two days in advance of the Nineteenth Century, furnishes
an extraordinary illustration of the struggles and trials of the inventor
against adverse fortune, and is a pathetic example of self denial,
indefatigable labor, and unrequited toil. Of feeble health, small stature,
poor, and frequently in prison for debt, he made the development of this
art the paramount object of his life, and with a pious faith and unfaltering
courage for thirty years he devoted himself to this work. Money he cared
nothing for, except in so far as it was necessary to carry on his work, and
he died July 1, 1860, poor in this world’s goods, but rich in the
consciousness of the great benefit conferred by his invention upon the
human race.
 FIG. 160.—COLLECTING THE GUM.

India rubber, or caoutchouc, as it is more properly called, is a

concentrated gum derived from the evaporation of the milky juice of
certain trees found in South America, Mexico, Central America and the
East Indies. The South American variety is called Jatropha elastica, and
the East Indian variety the Ficus elastica. The South American Indians
called it cahuchu. The province of Para, south of the equator, in Brazil,
furnishes the largest part and best quality of gum. The tree from which
the gum exudes grows to the height of eighty, and sometimes to one
hundred feet. It runs up straight for forty or fifty feet without a branch.
Its top is spreading, and is ornamented with a thick and glossy foliage.
The gum is collected by chopping through the bark with a hatchet and
placing under each series of cuts a little clay cup formed by the hands of
the workman. About a gill of the sap accumulates in each cup in the
course of a day, and it is then transferred to receiving vessels and taken
to camp. The first use of the gum was made by the South American
Indians, who made shoes, bottles, playing balls and various other articles
from it. Their method for making a shoe was to take a crude wooden last,
which they covered with clay to prevent the adhesion of the gum. It was
then dipped in the sap, or the latter was poured over it, which gave it a
thin coating. It was then held over a smoky fire, which gave it a dark
color and dried the gum. When one coating became sufficiently hard
another was added, and smoked in turn, and so successive coatings were
applied until a sufficient thickness was obtained. When the work was
completed it was exposed for some days in the sun, and while still soft
the shoes were decorated as the fancy or taste of the maker suggested.
The clay forms were then broken out, and the shoe stuffed with grass to
keep it in shape for use or sale. In 1820 a pair of these clumsy shoes was
brought to Boston and exhibited as a curiosity. They were covered with
gilding, and resembled the shoe of a Chinaman. Subsequently
considerable numbers of these shoes were brought from South America,
and being sold at a large price, they served to stimulate Yankee ingenuity
into devising methods of making them from the raw material, which
being brought as ballast in the ships from Brazil, could be had cheaply. In
France some attention had been given to the material, and the rubber
bottles of the Indians had been cut into narrow threads which were
woven into strips of cloth to form suspenders and garters. In England an
application of it in thin solution had been made by a Mr. Macintosh, who
spread it between two thicknesses of thin cloth to form Macintosh water-
proof coats. The first practical use of the gum on a large scale was
instituted by Mr. Chaffee in Roxbury, Mass., about 1830. He dissolved the
gum in spirits of turpentine and invented steam-heated rolls for spreading
it upon cloth. Companies were formed to exploit the products, and in the
fall and winter of 1833 and 1834 many thousands of dollars’ worth of
goods were made by the Roxbury Company, but the business proved a
total failure, for in the summer the goods melted, decomposed and
became so offensive as to be worse than useless, while the cold of winter
rendered them stiff and liable to crack. With a knowledge of these facts
and conditions Charles Goodyear commenced his experiments, believing
that there was a great future for this material if it could only be
prevented from melting in summer and stiffening in winter. He tried
mixing it with many materials, first using magnesia, which, however,
proved ineffective. On June 17, 1837, he took out patent No. 240, in
which he proposed to destroy the adhesive properties of caoutchouc by
superficial application of an acid solution of the metals, nitric acid with
copper or bismuth being specially recommended. He also claimed the
incorporation of lime with the gum to bleach it. Under this process Mr.
Goodyear made various articles in the form of fabrics, toys and
ornamental articles, using the fabric to make clothing for himself, which
he wore to demonstrate its value and wearing qualities. A striking word
picture of Mr. Goodyear at this time is given by the reply of a gentleman
who, being asked by a man looking for Mr. Goodyear as to how he might
recognize him, replied, “If you meet a man who has on an India rubber
cap, stock, coat, vest, and shoes, and an India rubber money purse in his
pocket, without a cent of money in it, that is he.”
Many useful and artistic articles were made under this first patented
process, including maps, surgical bandages, etc., and were brought by
Mr. Goodyear to the notice of President Jackson, Henry Clay and John C.
Calhoun, from whom he received very encouraging letters. His efforts,
however, to introduce his process commercially were not attended with
success. Capitalists and manufacturers had been rendered so
conservative by the large loss of money in the Roxbury Company, that
they were disinclined to have anything further to do with it. Practically
alone he was obliged to continue his work. By the kindness of Mr. Chaffee
and Mr. Haskins he was allowed the use of the valuable machinery
standing idle in their factory at Roxbury, and he made shoes, piano
covers, table cloths and carriage covers of superior quality, and from the
sale of these, and of licenses to manufacture, he for the first time was
able to support his family in comfort. Mr. Goodyear had not yet
discovered, however, the process of vulcanization, upon which the rubber
industry is founded. In 1838 Mr. Nathaniel Hayward, of Woburn, Mass.,
who had been employed in the bankrupt rubber company, discovered
that the stickiness of the rubber could be prevented by spreading a small
quantity of sulphur on it. The same result had also been noticed by a
German chemist. On Feb. 24, 1839, Mr. Hayward procured the patent,
No. 1,090, on his process, and assigned it to Mr. Goodyear. The patent
covered a process of dissolving sulphur in oil of turpentine and mixing it
with the gum, and also included the incorporation of the dry flowers of
sulphur with the gum, the product afterwards being treated by Mr.
Goodyear’s metallic salt process. This was the starting point of
vulcanization, for vulcanization consists simply in admixing sulphur with
the rubber, and then subjecting it for six to eight hours to a temperature
of about 300°. Its effect is to so change the nature of the gum to prevent
it from melting or becoming sticky under the influence of heat, or of
hardening and becoming stiff under the influence of cold, the vulcanized
gum remaining elastic, impervious, and unchangeable under all ordinary
conditions. This great discovery of the influence of heat on the sulphur
treated gum was quite accidental and wholly unexpected. Heat above all
things was the agency which in all previous observations was most to be
feared, for it was this more than anything else that melted down,
decomposed and destroyed all of his manufactured articles. While sitting
near a hot stove engaged in an animated discussion concerning his
experiments, a piece of the gum treated with sulphur, which he held in
his hand, was, by a rapid gesture, thrown upon the stove. To his
astonishment, he found that this relatively high heat did not melt it, as
heretofore, and while it charred slightly, it was not made at all sticky. He
nailed the piece of gum outside the kitchen door in the intense cold, and
upon examining it the next morning found it as perfectly flexible as when
he put it out. Goodyear had discovered the process which afterwards
came to be known as “vulcanization.” The discovery was made in 1839,
but was not accepted by those to whom it was submitted as possessing
any importance. Prof. Silliman, of Yale College, however, in the fall of
1839 testified to the results claimed for it by Mr. Goodyear—that it did not
melt with heat, nor stiffen with the cold. On June 15, 1844, Mr. Goodyear
took out his celebrated patent, No. 3,633, covering this process, in which
he not only used sulphur, but added a proportion of white lead. The
proportions named were 25 parts of rubber, 5 parts of sulphur, and 7
parts of white lead, the ingredients either to be ground in spirits of
turpentine, or to be incorporated dry between rolls. The odor imparted by
the sulphur was to be destroyed by washing with potash or vinegar. This
patent was reissued in two divisions Dec. 25, 1849, and again on Nov. 20,
1860, and was extended for seven years from June 15, 1858, which was
the end of the first term. Under this patent two kinds of rubber were
made and sold—“soft rubber,” containing only a small proportion of
sulphur, while the other, known as the “vulcanite,” “ebonite,” or “hard
rubber,” had from 25 to 35 per cent. of sulphur and was subjected to a
longer heat.
The history of this patent is a remarkable one. Immensely valuable as it
was, Goodyear reaped but a small share of the profit, for in the midst of
his poverty and necessities he was obliged to sell licenses and establish
royalties at a figure far below the real value of the rights conveyed. Some
idea of the great value of the business which Mr. Goodyear had
developed may be had from the fact that the companies who held rights
under the patent for the manufacture of shoes paid at one time to Daniel
Webster the enormous fee of $25,000 for defending their patent
interests.
With the idea of extending his invention Mr. Goodyear visited England in
1851, where he found that Thomas Hancock, of the house of Macintosh
& Co., had forestalled him, although not the inventor. A peculiar provision
of the English patent law, which gives the patent to the first introducer,
permitted this. Nothing daunted, however, he organized a magnificent
exhibit for the Great International Exhibition held in Crystal Palace at
Hyde Park, London, in 1851. This exhibit cost him $30,000, and he called
it the Goodyear Vulcanite Court. It comprehended an elegantly
constructed suite of open rooms made of hard rubber ornamented with
handsome carvings, and furnished with rubber furniture, musical
instruments, and globes made of rubber, and it was also carpeted with
the same material. For his exhibit he received the “Grand Council Medal,”
which was one of the highest testimonials of the exposition. This exhibit
was afterwards moved from London to Sydenham, where it was exposed
and used as an agency for some years for the sale of rubber goods.
 FIG. 161.—MACHINE FOR GRINDING AND WASHING CRUDE
RUBBER.

Mr. Goodyear had obtained a French patent for his invention, and at the
Exposition Universelle in Paris, in 1855, he fitted up at an expense of
$50,000 two elegant courts with India rubber furniture, caskets and rich
jewelry, and for this exhibit he had conferred upon him by the Emperor
Napoleon the “Grand Medal of Honor” and the “Cross of the Legion of
Honor.” It was a singular instance of the irony of fate that the decoration
of the “Cross of the Legion of Honor” should have been conveyed to him
while imprisoned for debt in “Clichy,” the debtors’ prison in Paris. The
lofty courage of the man was well illustrated at this time in his reply to
his wife’s solicitous inquiries as to how he had spent the night while in
prison. He said, “I have been through nearly every form of trial that
human flesh is heir to, and I find that there is nothing in life to fear but
sin.” The declining years of his life were full of sorrow, pain and affliction,
and at his death in 1860 his estate was $200,000 in debt. He lived long
enough, however, to see his material applied to nearly five hundred uses,
giving employment in England, France and Germany to 60,000 persons,
and producing in this country alone goods worth $8,000,000 a year.
 FIG. 162.—MAKING RUBBER CLOTH.

The greatest of all applications of rubber are to be found in the

manufacture of boots and shoes. The number of attacks of cold,
rheumatism, and death-dealing diseases from wet feet, that have been
averted by the use of rubber shoes, can never be estimated, but perhaps
it is safe to say that the rubber shoe has done more to conserve the
health of the human family than any other single article of apparel.
In the manufacture of shoes the finest quality of rubber is received in
wooden boxes 4 × 2 × 11⁄2 feet, containing about 350 pounds in lumps
of 1 to 75 pounds. These lumps are cut to suitable size, and are then
ground and washed in the machine shown in Fig. 161, water and steam
being sprayed on the rubber during the operation. It is then worked into
sheets or mats between rolls. From the grinding room the sheets are
taken to the mixing room, where lampblack, sulphur and other
ingredients are added, and worked into it by being passed many times
between heated rolls, the sheets being finally reduced to a thickness of
less than 1⁄32 of an inch. The rubber sheets are then applied to a cloth
backing by cloth calendering rolls, shown in Fig. 162, which are steam
heated and by great pressure serve to incorporate the sheets of rubber
and cloth into intimate and inseparable union. Out of this rubber fabric,
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