Practical Handbook of Spectroscopy

941 Pages·2017·106.032 MB·English

by  Robinson, James W

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
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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 information obtained from authentic and highly regarded sources. Reprinted material is
quoted with permission, and sources are indicated. A wide variety of references 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 314).
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/cm2) at which the Electron
Energy Has Fallen from Its Initial Energy, Vo • to the
K-Shell Ionization Energy in Targets of Atomic
Number Z .......................................................... 171
Table 9 The Mass-Range ps (g/cm2 at which the Electron
)
Energy Has Fallen from Its Initial Energy, Vo • to the
L -Shell Ionization Energy in Targets of Atomic
111
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) ....................... 431
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 .................................................................. 481
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 ................................................................. 515
Table 1 Absorption Maxima Recommended for Calibration
Purposes ........................................................... 515
Spectral Slit Width of a Grating Monochromator ................................ 518
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 .......................... 518
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
Measurement 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 .................. 551
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