Analytical Flame Spectroscopy Selected Topics by C. Th. J. Alkemade, R. Bleekrode, J. C. Burger, C. C. Butler, P. G. Cath, V. A. Fassel, P. T. Gilbert, W. Gillies, R. Herrmann, R. N. Kni

ANALYTICAL FLAME SPECTROSCOPY
PHILIPS TECHNICAL LIBRARY
ANALYTICAL FLAME SPECTROSCOPY

SELECTED TOPICS
by
C. Th. J. Alkemade, R. Bleekrode, J. C. Burger, C. C. Butler, P. G. Cath, V. A. Fassel,

P. T. Gilbert, W. Gillies, R. Herrmann, R. N. Kniseley, R. Mavrodineanu, O. Menis,
W. Muller-Herget, M. Pinta, T. C. Rains, R. Smith, J. B. Willis, J. D. Winefordner,
and G. K. Yamasaki
Edited by R. Mavrodineanu
MACMILLAN EDUCATION
ISBN 978-1-349-01010-3 ISBN 978-1-349-01008-0 (eBook)
DOI 10.1007/978-1-349-01008-0
© N.V. Philips' Gloeilampenfabrieken 1970

Softcover reprint of the hardcover 1st edition 1970 978-0-333-11800-9
All rights reserved. No part of this publication may
be reproduced or transmitted, in any form or by
any means, without permission
Published by
MACMILLAN AND CO LTD
London and Basingstoke
Associated Companies in New York, Toronto,
Melbourne, Johannesburg and Madras
PHILIPS
Trademarks of N.V. Philips' Gloeilampenfabrieken
No representation or warranty is given that the matter treated in this book is free
from patent rights; nothing herein should be interpreted as granting, by implication
or otherwise, a licence under any patent rights
FOREWORD
Analytical procedures based upon the ability of combustion flames to emit, absorb,
or re-emit specific radiations originating from the chemical species under investigation
are already well established and have provided valuable measuring tools in a variety
of fields and a large number of applications. The scientific principles on which these
procedures are based, and even some of their earlier analytical applications, have been
well understood and developed for many years. It is, however, due to the works of
Henrik Lundegardh, Allan Walsh, and James Winefordner that flame emission, atomic
absorption, and atomic fluorescence spectroscopy have realised their full potential
as analytical techniques.
The scientific literature available to the analyst who wishes to use these spectroscopic
techniques is extensive, comprising well over 5000 publications, and it provides valuable
information on every aspect of the theory and application. A number of books covering
both theory and practice are available.
This book covers a number of selected subjects on specific aspects of analytical flame
spectroscopic techniques, and includes the fields of: Flame Emission, Atomic Absorption
and Atomic Flame Fluorescence. Some of the subjects were chosen because of their
general and long-term interest, for example, excitation and interference phenomena in
flames; other subjects were selected because of their relative novelty, such as the use
of low pressure flames, the detection and determination of nonmetals, and the determin-
ation of rare earths. Other subjects, such as the principles of electronic and optical
design in their application to flame spectrophotometric purposes, were selected because
it was felt that they needed a more detailed discussion. The detection and measuring
sensitivity together with the accuracy and precision of analytical flame spectroscopic
techniques, which is a subject of permanent interest and of fundamental value to the
analyst, has been included in this collection together with a critical review of two of the
widest fields of application of the technique: biochemical and agricultural applications.
The flourishing fields of atomic absorption and atomic flame fluorescence require an
uninterrupted survey, while the closely related topic of hollow cathodes, which thus far
has not received full attention, is discussed in detail.
The volume ends with a collection of more than 2000 references to works on flame
spectroscopy, selected with special regard to analytical applications and covering the
last several years.
The organization of the various topics on analytical flame spectroscopy discussed in
this book presents to the reader a fairly consistent sequence of subjects. Nonetheless,
every chapter constitutes in itself a well defined subject which can be read individually;
consequently, a certain amount of repetition is unavoidable.
Any merit in this book must be attributed to the efforts of the individual contributors,
each an authority in his field. The editorial work on the manuscripts was kept to a
minimum; in this manner, the personality of each author is reflected in his chapter.
The editor hopes that the subjects selected and the scientific information contained
in this volume will be helpful to the analyst.
May 1969 R. Mavrodineanu

LIST OF CONTRmUTORS
1. C. Th. Alkemade
Fysisch Laboratorium
Rijks-Universiteit
Utrecht, Netherlands
2. R. Bleekrode
Philips Research Laboratories
Eindhoven, Netherlands
3. J. C. Burger
Electronic Tube Division
Westinghouse Electric Corporation
Elmira, New York, U.S.A.
4. C. C. Butler
Institute for Atomic Research
Ames Laboratory
Iowa State University
Ames, Iowa, U.S.A.
5. P. G. Cath
Keithley Instruments, Inc.
Cleveland, Ohio, U.S.A.
6. V. A. Fassel
Ames Laboratory
Ames, Iowa, U.S.A.
7. P. T. Gilbert
Spinco Division
Beckman Instruments Inc.
Palo Alto, California, U.S.A.
8. W. Gillies
Westinghouse Electric CorporatIon
9. R. Herrmann
Department of Medical Physics
University of Giessen
Giessen, West Germany
10. R. N. Kniseley
Ames Laboratory
Ames, Iowa, U.S.A.
11. R. Mavrodineanu Present address: Analytical Chemistry Division

Philips Laboratories National Bureau of Standards
Briarcliff Manor, New York, U.S.A. Washington, D.C., U.S.A.
12. O. Menis
Analytical Chemistry Division
National Bureau of Standards
Washington, D.C., U.S.A.
13. W. Milller-Herget
Philips Laboratories
Briarcliff Manor, New York, U.S.A.
14. M. Pinta
Office of Scientific and Technical Research Overseas (ORSTOM)
93-Bondy, France
15. T. C. Rains
Washington, D.C., U.S.A.
16. R. Smith
Department of Chemistry
University of Florida
Gainesville, Florida, U.S.A.
17. J. B. Willis
CSIRO
Chemical Research Laboratories
Division of Chemical Physics
Clayton, Victoria, Australia
18. J. D. Winefordner
19. G. K. Yamasaki
CONTENTS
Foreword V
List of Contributors VI
C. TH. J. ALKEMADE
Chapter 1 FROM SAMPLE TO SIGNAL IN EMISSION FLAME PHOTO-
METRY; AN EXPERIMENTAL DISCUSSION 1
1.1 Introduction................... 1
1.2 Brief outline of the basis of emission flame photometry 2
1.2.1 General principle and analytical advantages 2
1.2.1.1 General principle 2
1.2.1.2 Analytical advantages . . . . . 4
1.2.2 The nebulizer and burner system. . . . . 4
1.2.2.1 Chamber-type nebulizer with separate burner 5
1.2.2.2 Total-consumption nebulizer-burner 6
1.2.3 The flame. . . . . . . • . . . 6
1.2.3.1 Laminar premixed flame. 6
1.2.3.2 Turbulent un-premixed 7
1.2.3.3 Excess flame radicals 8
1.2.4 The spraying efficiency . . . . 9
1.2.4.1 Definition.. . . . . 9
1.2.4.2 Experimental methods of determination. 10
1.2.4.3 Experimental results .. . . . . . . . . 11
1.2.4.4 The metal vapour as a trace component ofthe flame gas. 12
1.3 Desolvation of spray in the flame. . . . . . . . . . . . . . . 13
1.3.1 The rate of desolvation . . . . . . . . . . . . . . . 13
1.3.2 Experimental methods for testing incomplete desolvation 13
1.4 Volatilization of desolvated aerosol. . . . . . . . . . . . . . 15
1.4.1 The composition and rate of volatilization of desolvated aerosol
particles. . . . . . . . . . . 15
1.4.1.1 Particle composition . . . . . . . . . . . . . 15
1.4.1.2 Rate of volatilization. . . . . . . . . . . . . 17
1.4.2 Experimental methods for testing incomplete volatilization. 19
1.5 Dissociation of molecular metal species . . . . . . . . . . . . . 24
1.5.1 Some important molecular metal species in flame photometry 24
1.5.2 The degree of dissociation. . . . . . . . . . . . . . . . 25
1.5.2.1 Equilibrium dissociation; the mass-action-Iaw . . . 25
1.5.2.2 Non-equilibrium dissociation; excess flame radicals. 28
1.5.3 Experimental methods for testing incomplete dissociation . . 30
1.5.3.1 Case of metal compounds containing a constituent of
the solution sprayed . . . . . . . . . . . . . . . 30
1.5.3.2 Case of metal compounds containing a constituent of
the flame gas. . . . . . . . . . . 31
1.6 Ionization of metal species . . . . . . . . . . . . 33
1.6.1 Ionic species of interest in flame photometry. 33
CONTENTS IX
1.6.2 The degree of ionization . . . . . . . . . 34

1.6.2.1 Equilibrium ionization; Saha's law . 34
1.6.2.2 Non-equilibrium ionization . . . . 35
1.6.3 Experimental methods for testing partial ionization. 36
1.7 Excitation of metal vapor to light-emission. . . . 38
1.7.1 Equilibrium excitation. . . . . . . . . . . . . . 38
1.7.1.1 Thermal radiation intensity in the absence of self-
absorption; the Boltzmann distribution law . 38
1.7.1.2 Thermal radiation intensity in the presence of self-
absorption; Kirchhoff's law 40
1.7.2 Suprathermal chemiluminescence . . . . . . . . . . 41
1.7.2.1 G e n e r a l . . . . . . . . . . . . . . . . . 41
1.7.2.2 Types of suprathermal chemiluminescence in flames. 41
1.7.2.3 Experimental methods for testing non-thermal excitation 42
References . 44
O. MENIS, T. C. RAINS
Chapter 2 SENSITIVITY, DETECTION LIMIT, PRECISION AND ACCUR-
ACY IN FLAME EMISSION AND ATOMIC ABSORPTION
SPECTROMETRY 47
2.1 Introduction. 47
2.2 Definition of terms . 48
2.2.1 Detection limits 48
2.2.2 Sensitivity. 52
2.2.3 Precision 52
2.2.4 Accuracy. 52
2.3 The optimization of components . 53
2.3.1 Source 53
2.3.2 Nebulizer-burner systems 55
2.3.2.1 Total consumption burner. 55
2.3.2.2 Sheath burner . 55
2.3.2.3 Absorption tube . 56
2.3.2.4 "Premix" burner . 57
2.3.2.5 Helium-glow discharge 58
2.3.2.6 Furnace 59
2.3.3 Optics. 59
2.3.4 Selection of wavelength . 61
2.3.5 Detection system. 61
2.3.5.1 Electric circuit . 61
2.3.5.2 Multiplier phototubes 62
2.4 Control of analyte environments . 62
2.4.1 Water-miscible solvent 63
2.4.2 Nonaqueous solvents . 63
2.4.2.1 Elimination of matrix effects. 64
2.4.2.2 Direct analysis of organic samples 64
2.4.2.3 Pre-concentration techniques. 64
2.4.3 Phenomenon of overexcitation or chemiluminescence 66
x CONTENTS
2.5 Criteria for improvement of precision and accuracy. 69

2.5.1 Integration of the signal 70
2.5.2 Differential method . . . . . 70
2.5.3 The role of ionization buffers . 73
2.5.4 Procedure for standard addition 73
2.5.5 Internal standardization. 74
2.6 Conclusion 75
References. . . 75
W. MULLER-HERGET
Chapter 3 SOME CONSIDERATIONS ON OPTICAL DESIGN AND SELEC-
TION OF SPECTROSCOPIC INSTRUMENTS 79
3.1 Introduction....... 79
3.2 The compensation principle 79
3.3 The collimator. . . . . . 86
3.3.1 General remarks. 86
3.3.2 Lens collimators . 87
3.3.3 Mirror collimators 88
3.3.4 The collimator pharoid 89
3.3.5 Optimum slid width. 90
3.4 The dispersing element . . 91
3.4.1 General remarks . . 91
3.4.2 The prism. . . . . 92
3.4.2.1 Prisms with flat faces. 93
3.4.2.2 Prisms with curved surfaces 93
3.4.2.3 Liquid prisms . . . . . . 95
3.4.3 The dispersion grating. . . . . . . 95
3.4.3.1 Types of gratings and performance 96
3.5 The camera system . . . . . . . . . . . . . . . . 102
3.6 Illumination of spectroscopic instruments. Luminosity and astigmatism 105
3.6.1 Stigmatic instruments. . . . . 106
3.6.2 Astigmatic instruments . . . . • 108
3.6.2.1 Stigmatic illumination . 109
3.6.2.2 Astigmatic illumination . 110
3.6.3 Sampling and absorption cells . . 111
3.7 Monochromators and double-monochromators. 114
A-I The Fery system . . . • . . . 117
A-2 The Desvignes monochromator 118
A-3 The Czerny-Turner system 119
A-4 The Ebert-Fastie system 121
B-1 Instruments for flame photometry 126
B-2 Manufacturers of instruments for atomic absorption 138
References. . . . . . . . . . . . . . . . . . . . . . 140
P. G. CATH
Chapter 4 PRINCIPLES OF ELECTRONIC INSTRUMENTATION 145
4.1 Introduction........... . . . . . . . . . . . . 145
CONTENTS XI
4.2 Analog circuits. . . . . . . . . . . 146

4.2.1 Amplification....... 146
4.2.1.1 Drift-free amplifiers 149
4.2.1.2 Chopper-stabilized amplifiers 150
4.2.2 Mathematical operations 150
4.2.2.1 Integration . . . . 152
4.2.2.2 Signal averaging . . 153
4.2.2.3 Non-linear functions 154
4.2.3 Noise . . . . . . . . . . . 155
4.2.4 Synchronous detection . . . 156
4.2.5 Applications to spectroscopy 158
4.2.5.1 Emission spectroscopy 158
4.2.5.2 Absorption spectroscopy 159
4.3 Digital circuit techniques . 161
4.3.1 Basic circuits. . . . 161
4.3.1.1 Flip-flop.. 162
4.3.1.2 Pulse gate. 163
4.3.1.3 Logic gates 165
4.3.1.4 Logic inversion. 167
4.3.1.5 NOR and NAND gates. 169
4.3.2 Counters . . . . . . . . . . 170
4.3.2.1 Number representation 172
4.3.3 Analog-to-digital conversion. 173
4.3.4 Digital-to-analog conversion. 175
4.3.5 Sequencing control. 176
4.4 On-line computer control 177
References. . . . . . . . . . . . 180
P. T. GILBERT
Chapter 5 NONMETALS . . . . . . . . 181
5.1 Introduction........... 181
5.1.1 Importance of the old work 182
5.1.2 Overexcitation.... 184
5.2 Hydrogen.......... 186
5.2.1 Direct flame emission. 186
5.2.2 Indirect flame emission 188
5.2.3 Electric discharges . 188
5.3 Boron 188
5.3.1 The flame spectrum. 188
5.3.2 Origin of the fluctuation bands 194
5.3.3 The bands of boron monoxide . 195
5.3.4 The line spectrum . . . . . . 195
5.3.5 Detection of boron by the flame color or visual spectroscopy 196
5.3.6 Semiquantitative visual and spectroscopic methods 202
5.3.7 Determination of boron by flame photometry . . 204
5.3.8 Flame spectography of boron . . . . . . . . . 204
5.3.9 Flame-spectrophotometric determination of boron 205
XII CONTENTS
5.3.10 Flame-emission monitoring of boron 212

5.3.11 Indirect flame-emission determination. 212
5.3.12 Atomic absorption spectroscopy 213
5.3.13 Electric discharges and other sources 213
5.4 Carbon. 214
5.4.1 Atomic carbon 214
5.4.2 Molecular carbon, C 2 213
5.4.3 Methine, CH 215
5.4.4 Other bands . 215
5.4.5 Determination by direct flame emission 216
5.4.7 Electric discharges 218
5.4.8 Laser excitation 219
5.5 Silicon 219
5.5.1 The flame spectrum. 219
5.5.2 The visible flame bands . 219
5.5.3 The ultraviolet bands of silicon monoxide . 221
5.5.4 The line spectrum 223
5.5.5 Emission flame spectrophotometry 225
5.6 Nitrogen 228
5.6.1 The band spectra 228
5.6.2 Detection of nitrogen by flame spectroscopy . 232
5.6.3 Flame spectrophotometry of nitrogen . 232
5.6.4 Indirect flame emission . 233
5.6.6 Flame ionization. 237
5.7 Phosphorus . 238
5.7.1 The flame spectrum 238
5.7.2 The green flame of HPO. 239
5.7.3 Current work on the HPO spectrum 241
5.7.4 Origin of the HPO spectrum. 247
5.7.5 Mechanism of the HPO emission. 248
5.7.6 The bands of phosphorus monoxide. 252
5.7.7 The phosphorus continuum . 255
5.7.9 Detection of phosphorus by flame spectroscopy. 256
5.7.10 Flame spectrophotometry of phosphorus 257
5.7.13 Flame ionization . 267
5.8 Arsenic. 269
5.8.1 The line spectrum. 269
5.8.2 The bands of arsenic monoxide. 272
5.8.3 The arsenic continuum 273
CONTENTS XIII
5.8.4 Flame spectrophotometry of arsenic. 273

5.8.7 Flame ionization . 276
5.9 Oxygen. 276
5.9.1 Direct flame emission. 276
5.10 Sulfur 278
5.10.1 The flame spectra. 278
5.10.2 The bands of molecular sulfur, S2 279
5.10.3 Modern work on the S2 spectrum 281
5.10.4 The bands of carbon monosulfide. 283
5.10.5 Mechanism of sulfur emission . 283
5.10.6 The sulfur continuum. 288
5.10.7 Flame-spectrophotometric determination of sulfur 288
5.11 Selenium 296
5.11.1 The flame band spectra . 296
5.11.2 The spectrum of selenium monoxide 296
5.11.3 The spectrum of molecular selenium, Se 2 299
5.11.4 The visible flame spectrum 301
5.11.8 Atomic fluorescence spectroscopy 308
5.12 Tellurium. 308
5.12.1 The flame band spectra . 308
5.12.3 Flame spectrophotometry of tellurium. 317
5.12.5 Atomic absorption spectroscopy . 319
5.12.6 Atomic fluorescence spectroscopy 320
5.13 Fluorine. 320
5.13.1 Flame spectra . 320
5.13.2 Flame spectrophotometry of fluorine 321
5.13.3 Indirect flame spectrophotometry 322
5.14 Chlorine 323
5.14.1 Flame colors 323
5.14.2 Nonmetallic flame spectra of chlorine. 324
5.14.3 The bands of cuprous chloride . 324
5.14.4 CuCI as an impurity spectrum . 326
5.14.5 Flame spectra of other metallic chlorides 328
5.14.6 Sensitized flame detectors . 329
XIV CONTENTS
5.14.7 The Beilstein test. . . . . . . . . . . . . . 340

5.14.8 Copper-sensitized solution methods for chlorine 343
5.14.9 Flame emission methods with other sensitizers. 344
5.14.10 The indium burner. . . . . . . . . 344
5.14.11 Nonsensitized indirect flame emission. 349
5.14.13 Ionization detectors 350
5.14.14 Electric discharges . . . . 350
5.15 Bromine. . . . . . . . . . . . . 351
5.15.1 Nonmetallic flame spectra. 351
5.15.2 Metallic bromide spectra . 351
5.15.3 Detection by sensitized flame emission. 352
5.15.4 Other methods for bromine 353
5.16 Iodine . . . . . . . . . . . . . 353
5.16.1 Nonmetallic flame spectra. 353
5.16.2 Metallic iodide spectra . . 354
5.16.3 Detection by flame emission 355
5.16.4 Other methods for iodine 356
5.17 The noble gases 356
References . . . . . . . . . . . . . 357
R. N. KNISELEY, v. A. PASSEL, C. C. BUTLER

Chapter 6 ATOMIC EMISSION AND ABSORPTION SPECTROMETRY OF
THE RARE EARTH ELEMENTS. 379
6.1 Introduction............. 379
6.2 Atomic and molecular emission spectra . 379
6.3 Production of free atoms . . . . . 382
6.4 Analytical applications . . . . . . . . 387
6.4.1 Flame emission spectrometry. . 387
6.4.2 Atomic absorption spectrometry 392
A-J Emission spectra of the rare earth elements 393
References . . . . . . . . . . . . . . . . . 410
R. BLEEKRODE
Chapter 7 SOME RECENT SPECTROSCOPIC INVESTIGATIONS OF
LOW-PRESSURE OXYACETYLENE FLAMES 411
7.1 Introduction....... 411
7.2 Experimental information. . . . 412
7.2.1 Flames........ 412
7.2.2 Spectroscopic equipment 413
7.3 Emission........... 414
7.3.1 Molecular bands. . . . 414
7.3.2 Seeded flames: Fe and Pb emission. 416
7.4 Absorption....... 419
7.4.1 Molecular bands. 419
7.4.2 Seeded flames . . 422
CONTENTS xv
7.4.2.1 Fe absorption with a continuum source . 422
7.4.2.2 Fe absorption with a line source . 424
7.5 Special topics . . . . . . . . . . 425
7.5.1 Zeeman scanning 425
7.5.2 Temperature measurements 426
7.6 Conclusion........ 427
A-I Absorption from a continuum 428
References . . . . . . . . . . . 429
M. PINTA
Chapter 8 AGRICULTURAL APPLICATIONS OF FLAME PHOTOMETRY. 431
8.1 Introduction....................... 431
8.1.1 Natural media . . . . . . . . . . . . . . . . . . 431
8.1.2 Elements which can be determined by flame photometry 431
8.1.3 Analytical methods. 432
8.1.4 Sample preparation 432
8.1.5 Calibration methods 433
8.1.6 Equipment. . . . . 434
8.1. 7 Comparison with other methods . 436
8.2 Analysis of rocks and soils. . . . . . . . 437
8.2.1 General problems. . . . . . . . 437
8.2.2 Determination of the major elements 437
8.2.2.1 Aluminium . . . . . . . 438
8.2.2.2 Iron . . . . . . . . . . 441
8.2.2.3 Sodium, potassium, calcium, magnesium. 443
8.2.3 Trace elements . . . . . . . . . . 447
8.2.3.1 Lithium, rubidium, caesium . . . . . . 447
8.2.3.2 Strontium, barium . . . . . . . . . . 448
8.2.3.3 Manganese, copper, chromium, thallium. 449
8.2.3.4 Miscellaneous methods: Atomic fluorescence spec-
trophotometry; determination of zinc, cadmium, mer-
cury, gallium, thallium and indium 451
8.3 Analysis of plants . . . . . . . . . . . . . . . . . . 452
8.3.1 General problems. . . . . . . . . . . . . . . 452
8.3.1.1 Preparation of samples; general method. 453
8.3.1.2 The chemical composition of plant media 454
8.3.2 Determination of the major elements . . . . . . 454
8.3.2.1 Potassium, calcium, magnesium, sodium 454
8.3.2.2 Sulphur. . 458
8.3.2.3 Chlorine.. . . . . . 459
8.3.2.4 Phosphorus. . . . . 460
8.3.3 Determination of trace elements 460
8.3.3.1 Lithium, rubidium, caesium 460
8.3.3.2 Strontium, barium . . . 461
8.3.3.3 Manganese, iron, copper 462
8.3.3.4 Boron. 464
8.4 Analysis of water 464
8.4.1 General details 464
XVI CONTENTS
8.4.2 Determination of the major elements: sodium, potasSIum,

calcium, magnesium . . . . . . . . . . . . . . . . . . . 466
8.4.3 Determination of the trace elements lithium, rubidium, caesium,
barium and strontium . . . . . . . 469
8.4.3.1 Lithium, rubidium, caesium . . . . . . . . . . . . 469
8.4.3.2 Barium, strontium . . . . . . . . . . . . . . . . 470
8.4.4 Determination of the trace elements iron, nickel, cobalt, copper,
manganese, chromium, aluminium 470
8.4.4.1 Iron, cobalt, nickel, copper .. 470
8.4.4.2 Aluminium 472
8.4.4.3 Chromium. 472
8.4.4.4 Manganese 472
8.5 Analysis of fertilizers. . . . 473
8.5.1 Determination of potassium . 473
8.5.2 Determination of other elements . 474
References. 474
R. HERRMANN
Chapter 9 THE APPLICATIONS OF FLAME PHOTOMETRY IN BIOLOGY
AND MEDICINE . . . . . . . . . . . . . . . . . . . . . . 479
9.1 The history of the biological and medical applications of flame photometry. 479
9.2 Emission or absorption methods in flame photometry? 479
9.2.1 Detection limit 480
9.2.2 Precision . . . . . . . . 480
9.2.3 Bias . . . . . . . . . . 480
9.2.4 Scanning the spectral range 481
9.2.5 Concentration range covered. 481
9.2.6 Elements with high dissociation energies. 481
9.2.7 Simplicity of the reference solution . . . 482
9.2.8 Requirements to be met by the monochromator 482
9.2.9 Requirements to be met by the operating personnel. 482
9.3 The choice of the instrument. . . . . . 483
9.3.1 The elements to be determined. 483
9.3.2 Detection limit . . . . . 483
9.3.3 Amount of sample required 483
9.3.4 Precision........ 484
9.3.5 Bias . . . . . . . . . . 484
9.3.6 Qogging and encrustation. 485
9.3.7 Operating costs and automation 485
9.4 Properties of the starting material in medical and biological investigations. 486
9.4.1 State of aggregation. . 486
9.4.2 Chemical composition. 486
9.4.3 Surface tension . . . 487
9.4.4 Viscosity . . . . . . 488
9.4.5 Interference due to chemical reaction with other substances 489
9.4.6 Interference due to physical reaction with other substances. 489
CONTENTS XVII
9.5 Sample preparation and execytion of the method. 489

9.5.1 Introduction. 489
9.5.2 Choice of the l>pectral line . 490
9.5.3 Sample preparation 490
9.5.3.1 Taking and preserving the sample 490
9.5.3.2 Dilution 493
9.5.3.3 Deproteinization . 494
9.5.3.4 Calcination 495
9.5.3.5 Extraction 496
9.5.3.6 Precipitation reactions. 497
9.5.3.7 Ion exchange. 497
9.5.4 The spectral lines or bands used for the analysis of particular
elements. 497
9.5.4.1 Potassium. 498
9.5.4.2 Sodium. 499
9.5.4.3 Calcium 499
9.5.4.4 Magnesium 500
9.5.4.5 Strontium. 500
9.5.4.6 Copper. 500
9.5.4.7 Lithium. 501
9.5.4.8 Beryllium. 501
9.5.4.9 Iron 501
9.5.4.10 Lead. 501
9.5.4.11 Rubidium. 502
9.5.4.12 Sulphate. 502
9.5.4.13 Chlorine. 502
9.5.4.14 Chromium. 503
9.5.4.15 Caesium. 503
9.5.4.16 Nitrogen 503
9.5.4.17 Phosphorus 503
9.5.4.18 Silicon 503
9.5.4.19 Zinc 504
9.5.5 The preparation of reference and blank solutions 504
9.5.5.1 The blank. 504
9.5.5.2 The check solution . 505
9.5.5.3 Reference solutions. 506
9.5.5.4 Intermediate standards 506
9.5.6 Special analytical considerations 507
9.5.6.1 Automation. 507
9.5.6.2 Micro- and ultramicro methods 508
9.6 Interference and way to reduce it . 509
9.6.1 Interference with the zero level. 510
9.6.2 Non-specific effects. 511
9.6.3 Specific effects. 512
9.6.3.1 Temperature effects 512
9.6.3.2 Ionization effects. 513
9.6.3.3 Evaporation effects. 514
References. 516
xvm CONTENTS
J. B. WILLIS
Chapter10 ATOMIC ABSORPTION SPECTROMETRY . 525
10.1 Introduction. 525
10.2 Theoretical . . . . . 526
10.3 Instrumental 531
10.3.1 Light sources 531
10.3.1.1 Spectral lamps . 531
10.3.1.2 Hollow-cathode lamps 531
10.3.1.3 High-intensity hollow-cathode lamps 533
10.3.1.4 Selectively modulated hollow-cathode lamps. 534
10.3.1.5 Other line sources . 534
10.3.1.6 Continuous sources . . . . . . . 534
10.3.2 Atomization of the sample . . . . . . . . 535
10.3.2.1 Non-flame methods of atomization. 535
10.3.2.2 Flames . . . . . . . . . . . . . 536
10.3.3 Wavelength selectors . . . . . . . . . . . 539
10.3.3.1 Conventional filters and monochromators . 539
10.3.3.2 Resonance monochromators. . . 540
10.3.4 Detectors, amplifiers and readout systems. . . 541
10.3.5 Complete instruments . . . . . . . . . . . 543
10.4 Atomic absorption spectrometry and flame photometry. 544
10.4.1 Scope and limitation of the two techniques. 544
10.4.2 Use of different flame types . . . . . . . . . 545
10.4.2.1 General considerations. . . . . . . 545
10.4.2.2 Low and medium-temperature flames . 546
10.4.2.3 High-temperature flames. 548
10.4.3 Nebulization conditions. . . . . 548
10.4.3.1 Drop-size in spray . . . 548
10.4.3.2 Efficiency of nebulization 549
10.4.3.3 Effect of solvent . . . . 549
10.4.3.4 Efficiency of atomization in flame 550
10.4.4 Interferences . . . . . . . . . . . . . 551
10.4.4.1 Spectral or radiation interference. 551
10.4.4.2 Excitation interference 552
10.4.4.3 Ionization interference 552
10.4.4.4 Chemical interference. 555
10.4.4.5 Background effects. . 557
10.5 The technique of atomic absorption spectrometry 558
10.5.1 Selection of optimum experimental conditions . 558
10.5.1.1 Choice of lamp current. 558
10.5.1.2 Choice of slit width. . . . 560
10.5.1.3 Choice of absorbing line. . 560
10.5.1.4 Choice of flame conditions. 561
10.5.2 Methods of increasing sensitivity. 561
10.5.2.1 Optical means . . 561
10.5.2.2 Electronic means. . . . 562
10.5.2.3 Chemical means . . . . 563
10.5.3 Preparation and handling of samples 564
CONTENTS XIX
10.5.4 Calibration and measuring techniques 564

10.5.5 Development and assessment of specific analytical procedures 566
10.6 Application to individual elements 567
10.6.1 Aluminium 568
10.6.2 Antimony. 568
10.6.3 Arsenic 568
10.6.4 Barium 568
10.6.5 Beryllium . 568
10.6.6 Bismuth. 569
10.6.7 Boron. 569
10.6.8 Cadmium. 569
10.6.9 Calcium. 569
10.6.10 Cerium. 570
10.6.11 Cesium. 570
10.6.12 Chlorine 570
10.6.13 Chromium. 571
10.6.14 Cobalt 571
10.6.15 Copper. 571
10.6.16 Dysprosium. 572
10.6.17 Erbium. 572
10.6.18 Europium. 572
10.6.19 Fluorine. 572
10.6.20 Gadolinium . 572
10.6.21 Gallium 572
10.6.22 Germanium . 573
10.6.23 Gold. 573
10.6.24 Hafnium 573
10.6.25 Holmium. 573
10.6.26 Indium. 573
10.6.27 Iridium. 574
10.6.28 Iron 574
10.6.29 Lanthanum 574
10.6.30 Lead. 574
10.6.31 Lithium. 575
10.6.32 Lutetium. 575
10.6.33 Magnesium 575
10.6.34 Manganese 576
10.6.35 Mercury. 576
10.6.36 Molybdenum 577
10.6.37 Neodymium. 577
10.6.38 Nickel 577
10.6.39 Niobium 578
10.6.40 Osmium 578
10.6.41 Palladium. 578
10.6.42 Phosphorus 578
10.6.43 Platinum 579
10.6.44 Potassium. 579
10.6.45 Praseodymium. 579
XX CONTENTS
10.6.46 Rhenium 579

10.6.47 Rhodium. 580
10.6.48 Rubidium. 580
10.6.49 Ruthenium 580
10.6.50 Samarium. 580
10.6.51 Scandium. 580
10.6.52 Selenium 580
10.6.53 Silicon 581
10.6.54 Silver. 581
10.6.55 Sodium 581
10.6.56 Strontium . 582
10.6.57 Sulphur . 582
10.6.58 Tantalum. 582
10.6.59 Tellurium. 582
10.6.60 Terbium. 582
10.6.61 Thallium 583
10.6.62 Thorium 583
10.6.63 Thulium. 583
10.6.64 Tin. 583
10.6.65 Titanium 583
10.6.66 Tungsten 584
10.6.67 Uranium 584
10.6.68 Vanadium. 584
10.6.69 Yttrium. 584
10.6.70 Ytterbium. 585
10.6.71 Zinc 585
10.6.72 Zirconium 585
References 585
Addendum 595
J. D. WINEFORDNER, R. SMITH
Chapter 11 ATOMIC FLUORESCENCE FLAME SPECTROMETRY. 599
11.1 Theoretical considerations. . . . . . . . 599
11.1.1 Mechanism of atomic fluorescence . . . . . . . . . . 599
11.1.2 Intensity of atomic fluorescence . . . . . . . . . . . 600
11.1.3 Variation of atomic concentration in flame, and solution con-
centration. . . . . . . . . 602
11.1.4 Fluorescence power efficiency 604
11.1.5 Shape of analytical curves. . 604
11.1.6 Limits of detection. . . . . 605
11.1.7 Optimization of experimental conditions 606
11.2 Basic instrumentation. . . . . . . 606
11.2.1 Optics and monochromator 606
11.2.2 Detector/amplifier systems. 608
11.3 Sources of excitation . . . . . . 608
11.3.1 Metal vapour arc lamps. . 609
CONTENTS XXI
11.3.2Hollow cathode discharge lamps. . . . . . . 609

11.3.3Electrodeless discharge tubes. . . . . . . . . 610
11.3.3.1 Types of electrodeless discharge tubes. 611
11.3.3.2 Power requirements . . . . . . . . 611
11.3.3.3 Stabilization of electrodeless discharge tubes. 613
11.3.4 Continuous sources . . . . . . . . . . . 613
11.4 Flame cells . . . . . . . . . . . . . . . . . . . 613
11.4.1 Turbulent flames/total consumption burners. 614
11.4.2 Laminar flames/aspiration chamber burners 614
11.4.3 Non-flame cells. . . . . . . • . . . . . 615
11.5 Comparison with other flame spectrometric methods 615
11.5.1 Theory...... 615
11.5.2 Limits of detection 616
11.5.3 Analytical curves. . 616
11.5.4 Selectivity and interferences 616
11.5.4.1 Spectral interferences. 616
11.5.4.2 Non-specific interferences 617
11.5.4.3 Specific interference 617
11.6 Future studies in atomic fluorescence . 618
Acknowledgement 618
References. 619
Appendix. . . . 621
J. C. BURGER, W. GILLIES, G. K. YAMASAKI

Chapter12 HOLLOW CATHODE DISCHARGE DEVICES 625
12.1 Introduction. . . . . . . . . . 625
12.2 Early history . . . . . . . . . 625
12.3 Development of sealed-off devices 626
12.4 Design parameters . . . . . . . 627
12.4.1 Window type and envelope structure 627
12.4.2 Cathodes........ 628
12.4.3 Gas fill and pressure . . . 632
12.5 Operation of hollow cathode devices 633
12.5.1 Volt-ampere characteristics 633
12.5.2 Power supply . . 634
12.5.3 Current limits . . . . . 635
12.5.4 Warm-up and life . . . 636
12.5.5 Pulsed or A-C operation 638
12.5.6 Device life. . . . . . • 640
12.6 Application of hollow cathode devices to atomic absorption spectroscopy. 640
12.6.1 Line broadening . . . . . . . . . . 640
12.6.2 Line interference and resolution . . . 641
12.6.3 Factors affecting signal-to-noise ratio. 644
12.6.4 Photomultiplier saturation 645
12.6.5 Electronics ........ 646
12.7 Current status of hollow cathode devices 646
References . . . . . . . . . . . . . . . . 649
XXII CONTENTS
R. MAVRODINEANU
Chapter 13 BIBLIOGRAPHY ON FLAME SPECTROSCOPY -ANALYTICAL
APPLICATIONS. 651
13.1 Emission . . . . . . 653
13.1.1 Early works. 653
13.1.2 Books.. 654
13.1.3 Theses... 654
13.1.4 Reviews 655
13.1.5 Bibliographies. 656
13.1.6 Chapters in books and related material 656
13.1.7 Fundamental works. . 657
13.1.8 Instrumentation... 678
13.1.9 Analytical procedures. 684
13.1.10 Less familiar flames . 713
13.2 Atomic absorption spectroscopy 715
13.2.1 Atomic absorption. . 715
13.2.2 Hollow cathode discharge tubes 741
13.3 Electrical discharges having the aspect of combustion flames 745
13.3.1 The radio-frequency discharge. 745
13.3.2 Plasma arcs . . . . . 748
13.3.3 Arc-and-spark-in-flame 752
Subject Index . . . . . . . . . . . . . 755

CHAPTER 1
FROM SAMPLE TO SIGNAL IN EMISSION FLAME

PHOTOMETRY; AN EXPERIMENTAL DISCUSSION
C. Th. J. Alkemade
Fysisch Laboratorium
Rijks-Universiteit, Utrecht
1.1 Introduction
This chapter deals with the problem of obtaining an emission signal from the sample, and
with the associated processes in analytical flame photometry. Except for the excitation
process, all the processes discussed are relevant both to emission flame photometry
and to absorption or fluorescence flame photometry (also called: atomic absorption and
atomic fluorescence spectroscopy).
Emphasis is laid on the experimental rather than the theoretical or analytical aspects
of the subject. Experimental results are presented for illustration, and the experimental
methods used to obtain these results are described briefly. In this respect the intent as well
as the contents of this chapter are complementary to Chapter 4 in Reference [1], which
deals largely with the same subject but considers it from a more fundamental point of
view. Both these chapters, however, can be read independently of one another.
The analytical implications of the processes studied (such as sensitivity, form of ana-
lytical curves, interference effects) are not discussed here per se. They are dealt with more
or less extensively in the usual textbooks on emission flame photometry (see for in-
stance [2,3, 4, 5, 6, 7]; see also the textbooks on atomic absorption analysis, quoted
in Chapter 13 by Mavrodineanu in this book). For a better theoretical understanding of
the processes in nebulizer and flame that are relevant to flame photometry, we refer to
the specialized literature (e.g., [8, 9, 10, 5, 6, 11] where also references to more general,
theoretical works are found). Instrumental aspects of the flame photometer are also
described in some detail in Reference [8]. We shall not cite these references again in
the following sections.
As a background to the problems treated, we shall first present in Section 1.2 a
brief outline of emission flame photometry as a tool of spectrochemical analysis. The
function and characteristics of some essential parts of the flame photometer will be
described and some important concepts will be introduced. A survey is also given of
the different stages through which the sample has to pass when it is converted from a
liquid solution into an optically radiating vapor. These stages are separately discussed
in more detail in the subsequent Sections 1.3 up to 1.7. Attention is given mainly to the
sample transformations which take place in the high-temperature environment of the
flame itself. Sample preparation, aspiration and nebulization are not as such of primary
importance in this chapter, which is mainly concerned with the role played by the
flame.
2 FROM SAMPLE TO SIGNAL IN EMISSION FLAME PHOTOMETRY [1
1.2 Brief outline of the basis of emission flame photometry
1.2.1 GENERAL PRINCIPLE AND ANALYTICAL ADVANTAGES
1.2.1.1 General principle
Emission flame photometry is a method of spectrochemical analysis that is based on the

transformation of the sample into the vapor state and its subsequent excitation in a chemi-
cal flame. The spectrum of the radiation emitted by the vapour state is characteristic of
the kind of metal(s) contained in the sample (qualitative analysis). The intensity of a
spectral line is a measure of the concentration ofthe metal emitting that line (quantitative
analysis). Elements such as Na that are present as cations in a solution, often give a suffi-
ciently strong emission to be determined by flame photometry. Elements such as CI or S
normally do not radiate in the flame. Under certain conditions, however, compounds
containing these elements, such as InCI and HPO, may give a spectral emission that is
strong enough for analytical purposes. In general, flame photometry yields no informa-
tion on the kind of chemical compound in which the element analyzed was present in the
sample (as salt or in complexed form). This is a consequence of the high temperature and
of the occurrence of chemical reactions in the flame. The original chemical bond of the
element is broken and sometimes replaced by new bonds with other constituents in the
flame.
--
Fuol
t
Sample
solution
Compressed air
Fig. 1.1 Simplified diagram of a filter flame photometer equipped with a chamber-type nebulizer
and a premixed flame. Compressed air is used to aspirate and nebulize the solution to be analyzed.
The larger spray droplets are collected on the wall and are drained at the bottom of the spray-
chamber. Air (with spray) and fuel gas are mixed in a Meker burner and produce a flame colored
by metal vapour. The analysis line is selected from the flame spectrum by a spectral filter. Its in-
tensity is measured by a photocell connected to a read-out meter.
Reprinted from: C. Th. J. Alkemade, A. M. Hoogenboom, J. A. Smit, "Inleiding tot Fysische
Meetmethoden", 1970, figure 111.26, by courtesy of N .V. Oosthoek's Uitgeversmaatschappij,
Utrecht.
1.2] BASIS OF EMISSION FLAME PHOTOMETRY 3
A simplified diagram of an emission flame photometer is shown in Fig. 1.1. The sample
to be analyzed is usually converted to liquid form, for instance as a solution in
water. This solution is aspirated into a pneumatic nebulizer and dispersed as a fine spray
of droplets. This spray is carried into the flame by the gas that operates the nebulizer. The
flame is produced on a burner by combustion of a fuel gas (e.g., C 2 H 2 ) with an oxidant
gas (e.g., air). Under the influence of the high temperature of the flame the solvent eva-
porates and the remaining dry aerosol particles volatilize from the solid or molten state
into the gaseous state. In this state the element to be analyzed (e.g., Ca) may be present
as free neutral atoms (Ca) or molecules (CaO), or as positive ions (CaOH+ and Ca+).
Whereas desolvation and volatilization are irreversible processes, reversible reactions
and processes usually set up a certain balance between the atomic, molecular, and ionic
metal species in the gaseous state.
These sample transformations and the related processes are summarized in Fig. 1.2
Imolecules I c
.g
o
'5
:I~[ j:1
:il
:I
otoms I
l
'c
.2
l~us '"
decomposition atomization l ight omission
Fig. 1.2. Transformation of a liquid sample into an optically radiating vapour in emission flame
photometry. The processes acting in the different stages of this transformation are indicated. The
decomposition, atomization, and light-emission are discussed in the text.
The successive stages are denoted by: fragmentation, decomposition, and atomization (i.e.,
formation of free atoms by molecular dissociation or ion recombination, and vice versa).
In the vapour state the metal species are excited whereupon they may emit atomic or ionic
spectral lines, or molecular spectral bands in the near infra-red, visible, or ultraviolet
parts of the spectrum. The flame temperature plays an important role in the excitation
and usually in the atomization of the sample. Occasionally it is also an important factor
in the decomposition of the sample.
A suitable line or band of the element is selected from the flame spectrum by a spectral
filter or monochromator, and it is detected by means of a photocell (e.g., barrier-layer cell
or photomultiplier tube). The photocurrent of the cell is often amplified by electronic
means before it is measured by a read-out meter or recorder.
The stationary meter deflection obtained for a constant rate of sample flow to the ne-
4 FROM SAMPLE TO SIGNAL IN EMISSION FLAME PHOTOMETRY [l
bulizer is a measure ofthe metal concentration (e.g., in mg/l or parts-per-million, p.p.m.).

IntegIation of the meter deflection or photocurrent over a certain time-interval yields a
measure of the absolute amount of analyte (e.g., in (Jog) contained in the sample that was
aspirated during this interval. The meter deflection is calibrated in concentration units
by aspirating a series of standard solutions with varying but known metal concentrations.
An analytical or calibration curve is constructed by plotting the meter deflections vs.
the known standard concentrations. This curve is then used to deduce unknown sample
concentrations from the corresponding meter deflections measured under the same ex-
perimental conditions as the deflections of the standard solutions. Flame photometry is
thus essentially a relative method of analysis.
The spectral apparatus should not only select the analysis line or band from the radia-
tion of other elements in different parts of the spectrum, but it should also reduce the
interference from the flame background emission whose more or less continuous spectrum
underlies the analysis line. The fluctuations in this background emission add to the noise
in the measuring apparatus and limit the detectability of low metal concentrations in the
solution. In order to get a good sensitivity, i.e. a low detection limit, the emission signal
of the analysis line should be as large as possible compared to the fluctuations in this
background emission (and to the instrumental noise).
1.2.1.2 Analytical advantages
The advantages of emission flame photometry compared to chemical methods of analysis

are its sensitivity (the best detection limits of some 70 elements range from 10- 5 to 10 2
p.p.m., according to Winefordner and Veillon [12]), its precision (1 % or better), and rapidi-
ty (especially in routine analyses). Although emission flame photometry has been
applied to more than 70 elements of the periodic table, its usual application is restrict-
ed to the metallic elements such as alkali or alkaline-earth metals, Cu, Ag, TI, etc. Another
advantage is often the rather simple construction and operation of the flame photometer
compared with other physical methods of analysis. The possibility to analyze simulta-
neously two or more elements in the same sample, or to analyze minute quantities of
sample material should also be mentioned.
A possible disadvantage, in some cases, is that the sample must be converted into
a liquid solution. Special means, however, have been developed to analyze solid samples
directly in the flame. Interference effects in the analysis of samples with a complex and
varying composition, which effects arise when the emission signal for a given concentra-
tion of analyte also depends on the presence and concentration of concomitants in the
solution, such as HCI or other metallic elements, may also be a problem. They need not
lead to errors, however, if the composition of the standard samples closely resembles
that of the sample to be analyzed, or if appropriate corrections are applied.
1.2.2 THE NEBULIZER AND BURNER SYSTEM
There are two main types of nebulizer and burner systems, if some intermediate but
less common types are ignored.
1.2.2.1 Chamber-type nebulizer with separate burner
An example of this type is shown schematically in Fig. 1.1. It is usually used with air
as the oxidant gas. Compressed air is led at high speed through a capillary into the
nebulizer chamber. According to Bernoulli's law, a low pressure (usually about 1O-100cm
of water below 1 atm) exists at the outlet of this capillary. This low pressure is used to
aspirate the solution through a separate capillary from the sample container outside the
nebulizer. The rate of solution aspiration (in ml/min) can be calculated from the viscosity
of the liquid and the length and inner bore size of the liquid capillary, using the Hagen-
Poiseuille law. This law seems to be more applicable to usual types of nebulizer with
small bore sizes [13]. Apart from the suction pressure and the other factors mentioned,
the difference in height between the outlet of the capillary and the surface level of the
solution in the container, as well as the density of the solution play a (secondary)
role.
The liquid flowing from the capillary is instantaneously c disrupted by the air jet
and nebulized into a fine spray of separate droplets. The size distribution of these droplets
and in particular the mean droplet diameter depend, among other things, on the surface
tension of the liquid, the relative speed of the liquid with respect to the air jet, and the
mutual position and inner bore sizes of the capillaries for the liquid and air flow. The
rate of solution aspiration is also an important factor. An increase in this rate prod-
uces a coarser size distribution of the droplets.
Instead of the perpendicular orientation of the two capillaries shown in Fig. 1.1, a con-
centric construction is often used, and this seems to produce better dispersion. In this
case the liquid capillary is centered at the axis of a cylindrical, tapered nozzle with a
slightly larger diameter. The gas flowing through this nozzle then surrounds the
emerging liquid flow.
Measurements of size distribution have frequently been reported (see, for example
[14,15,16]). A typical order of magnitude for the mean droplet diameter is 10 [LIl1for sonic
velocity of the air jet. Liquid capillaries with smaller inner bore size usually produce a more
uniform spray distribution with smaller mean droplet diameter [15].
The size distribution produced at the outlet of the liquid capillary strongly deviates
from the size distribution of the spray that actually enters the flame. Firstly, the coarser
droplets will be caught by the walls of the expansion chamber (also called spray chamber)
of the nebulizer because of centrifugal effects. The analyte contained in these droplets will
be lost for excitation in the flame. Secondly, on their way through the expansion chamber,
the air conduit, and burner housing, the spray droplets will (partly) evaporate until the
air becomes saturated with vapour. The resulting reduction in droplet diameter may,
however, partly be counteracted by coagulation or recombination of the droplets on
their way to the burner [17].
Chamber-type nebulizers are usually combined with premix burners in which fuel gas
and air (with spray) are thoroughly mixed before combustion takes place. The unburnt
gas-mixture leaves the burner housing through a vertical tube or through a top plate in
which many small holes are drilled close together (Meker burner). The small diameter of
these holes prevents flash-back of the flame. If the holes are sufficiently long, the flow of
gas-mixture inside them will be laminar, and this helps to produce a stable flame.
Premix burners are normally used for gas-mixtures which do not have a very high
burning velocity (because of the danger of flash-back of the flame into the burner housing).
This restricts their use to the cooler flames burning with air, although the hot C 2 H r N 20
flame can also be safely produced by a premix burner.
1.2.2.2 Total-consumption nebulizer-burner
This nebulizer-burner system, which may also be called a direct-injection burner, combines
the functions of nebulizer and burner in one unit. The capillary for the liquid intake is po-
sitioned concentrically inside the nozzle for the oxidant gas (usually O 2 ). The latter nozzle
is, in tum, placed concentrically in a somewhat wider, separate nozzle for the fuel gas.
From these nozzles fuel and oxidant gas stream freely out at high speeds. The outlets of
these nozzles thus form the tip of the burner; no mixing offuel gas and oxidant gas takes
place before they leave the burner. The compressed Orflow aspirates and nebulizes the
liquid. Turbulent mixing of the Orflow and spray with the fuel gas is achieved above the
burner tip. Combustion takes place at some distance from this tip, where the mixing has
proceeded sufficiently far.
All aspirated liquid is thus introduced into the flame ("total-consumption"). There is
no rejection of the larger droplets and no time is available for partial evaporation of the
spray droplets before entering the flame. The size distribution of the spray entering the
flame is thus much coarser here than in the case of a chamber-type nebulizer. This has
some far reaching consequences which will be discussed in the following sections.
Some advantages of the direct-injection burner over a premix burner with chamber-
type nebulizer, are (see also Table l.I in Section 1.2.3):
(i). there is no loss of analyte due to precipitation of the larger spray droplets in the
expansion chamber and burner housing;
(ii). fuel-oxidant mixtures such as C 2 H 2 -0 2 or H 2 -0 2 , which have higher burning
velocities, can be safely used; these mixtures usually produce hotter flames;
(iii). combustible liquids such as gasoline can be safely sprayed.
They have also some practical and analytical disadvantages. In particular, interference
effects connected with incomplete volatilization may be more pronounced in flames burn-
ing with direct-injection burners than with premix burners.
1.2.3 THE FLAME
The character of the flame is typically different when a premix burner with chamber-
type nebulizer or a direct-injection burner is used. Both types of flame are described in
the following sections.
1.2.3.1 Laminar premixed flame
This flame can be easily realized with the aid of a Meker burner and it is generally char-
acterized by its stable appearance and homogeneous properties. Three zones can be
clearly distinguished:
(i). The primary combustion or reaction zone (or inner cone) where the fuel-oxidant mixture
that has left the burner is ignited. With a Meker burner this zone is split up into a
number of little cones, one for each cylindrical hole in the burner top. In this very thin
zone (thickness is of the order of 0.1 mm) the combustion reactions proceed rapidly to
near completion, as far as sufficient oxygen is available in the supplied gas-mixture. In this
zone, i.e. during the combustion, thermal and chemical equilibrium do not exist, so that
a general temperature cannot meaningfully be defined here. Its strong emission in hydro-
carbon flames stems from chemiluminescent spectral bands emitted by short-lived radi-
cals such as C 2 and CH.
(ii). In the intermediate zone above and immediately adjacent to the reaction zone, the
flame gases are usually found in a state of thermal and chemical equilibrium. They attain
here, practically, their final temperature, which depends on the kind of fuel and oxidant
gases used and on their mixture strength. A maximum temperature is usually attained
when the gas-oxidant ratio is slightly above the stoichiometric ratio. Maximum theoretical
temperatures are typically 2200 K for propane-air, 2600 K for acetylene-air, and 3250 K
for acetylene-nitrous oxide mixtures. The actual maximum temperature is often somewhat
lower owing to heat losses, incomplete combustion, etc. [18]. For a fuel-rich premixed
acetylene-nitrous oxide flame a temperature of 2880 K has been measured [98]. This in-
termediate zone is mostly (but not exclusively) used in flame photometric work.
(iii). The latter zone is surrounded by the secondary combustion or reaction zone (or outer
cone) where the flame comes into contact with the ambient air. The infusion of air and its
turbulent mixing with the flame gas causes on the one hand a cooling effect and on the other
hand, the additional, gradual supply of fresh oxygen gives rise to further combustion of
the flame gases. This secondary combustion takes place in a rather diffuse zone at the flame
border, whose width increases with height in the flame. Its presence can usually be recog-
nized by a gradual increase in flame background emission when moving from the flame
axis towards the flame border. The extent of this secondary combustion and the heat li-
berated by it are larger, the more oxygen-lean (or fuel-rich) the primary gas-mixture in the
burner was.
1.2.3.2 Turbulent un-premixed flame
A flame of this kind is produced when a direct-injection burner is used. The turbulent
character is connected with the high flow speed at which the gases emerge from the burner
nozzles. This turbulence promotes the mixing of fuel and oxidant gases, but it also causes
a strong intermixing of the flame gases with the ambient air. It has even proved possible
to produce a flame of H 2 - and Ar-gas that burns completely when the gases mix with
oxygen supplied by the surrounding air [19].
Consequently, flames of this type are noisy, often have no clearly distinct structure, and
are inhomogeneous with respect to the local temperature, chemical composition, metal
concentration, and gas-velocity.
The turbulence increases markedly when a solution is sprayed; at the same time the form
of the flame may change, too. Part of the spray droplets which are blown into the border
of the flame are hurled outside the hot region by the turbulent motion of the gases.
The maximum theoretical temperatures obtainable with C 2 H r 0 2 and H r 0 2 mixtures
are around 3400 and 2950 K, respectively. The actual temperatures attained with direct-
injection burners are often considerably lower for these gas-mixtures owing to mixing
with the ambient air, incomplete combustion, etc. Spraying of water may also strongly re-
duce the flame temperature, unless the rate of aspiration is kept low (say less than 1 mlf
min; see [20]). In general, the quantity and the composition of the solution sprayed have
definitely a more pronounced effect on the flame temperature and composition with direct-
injection burners than with premix burners and chamber-type nebulizers. This applies
especially when the solution contains organic material.
For comparison, the different properties of laminar premixed and turbulent un-
premixed flames are summarized in Table 1.1.
TABLE 1.1.
COMPARISON OF PROPERTIES OF A PREMIXED FLAME WITH CHAMBER-TYPE NEBULIZER AND OF AN
UN-PREMIXED FLAME WITH DIRECT SPRAY INJECTION
Property Premixed flame Un-premixed flame
structure distinct zones blurred zones

character of gas flow laminar turbulent
noise no yes
mixing with ambient air moderate strong
homogeneity good bad
equilibration of the flame gas fairly good fairly good
suitable for gas-mixtures with high
burning velocity no yes
spraying efficiency * 1-15% 10-100%
influence of spraying on flame properties weak marked
suitable for spraying inflammable solvents no yes
desolvation of droplets in flame (nearly) complete (usually) incomplete
* see Section 1.2.4
1.2.3.3 Excess flame radicals
Radicals such as H, OH, and 0 may be found in excess concentrations in and Gust)
above the reaction zone of H2- and C 2H 2-air flames. These radicals which are products
of the combustion reactions, are produced in large concentrations in the primary com-
bustion zone. They may persist in higher concentrations than their chemical equilibrium
concentrations in the flame region adjacent to this zone, owing to the slowness of their
recombination reactions. The recombination of Hand OH, for instance, proceeds by a
thermolecular reaction
(1)
where Z is a third partner (usually a flame molecule) that carries off part of the chemical
energy released in the recombination. This third partner is necessary to stabilize the
reaction product, H 2 0. In absence of a third partner, H 20 would be formed in a state
of high excitation, from which it would disintegrate again. The presence of a third
partner explains the slowness of the reaction rate and the slow relaxation in the establish-
ment of radical equilibrium in the flame above the primary combustion zone. The longer
the time spent by these radicals in the flame, i.e. the larger the vertical distance from the
combustion zone, the closer the radical concentrations will approach their final equili-
brium values.
The bulk concentrations of the stable flame molecules such as N 2, CO 2, and H 2 0 are
usually not much disturbed by the chemical disequilibrium of these radicals. This is true
because these radicals are usually minor constituents of the flame, being present there at
partial pressures below 0.01 atm. The deviation of their concentrations from chemical
equilibrium, however, can still have some pronounced effects on the dissociation, ioniza-
tion, and excitation of metal species in the flame. These effects are produced by reac-
tions in which the metal species and one or more of these flame radicals take part.
Radical disequilibria may thus give rise to some deviations from thermodynamic equilibri-
um in the state of the metal vapor. The latter deviations are generally more pronounced
the lower the flame temperature is. At lower temperatures the equilibrium values of the
radical concentrations are also low and it takes more time before the actual radical con-
centrations have decayed by recombination to their final (low) values. Since the extent
of radical disequilibrium decreases with increasing height in the flame, the state of the
metal vapor will then also change with increasing height.
1.2.4 THE SPRAYING EFFICffiNCY (8)
1.2.4.1 Definition
In order to obtain a high sensitivity, the fraction of aspirated analyte that is actually con-
verted into the vapour state should be as high as possible in a given flame. This fraction is
determined by the efficiency of the fragmentation and decomposition of the sample in
nebulizer and flame (see Fig. 1.2). The efficiency of volatilization often depends strong-
lyon the specific properties of the analyte and the other concomitants in the solution
(see Section 1.4). For a given solvent, however, the efficiency of nebulization and eva-
poration of the spray droplets depends mainly on the properties of the nebulizer-flame
system alone. We now define the spraying efficiency 8 for a given solvent (usually distilled
water) as a characteristic constant of the flame photometer, by putting e equal to the
fraction (in %) of analyte aspirated per second, that passes in the desolvated state (i.e.,
either as dry aerosol or as vapor) through a given total cross-section of the flame.
With chamber-type nebulizers a significant fraction of the spray is usually lost in the
expansion chamber and in the conduits to the flame. Thus 8 will be significantly less than
100% here. The remaining droplets that enter the flame are often so small that they are
practically all desolvated immediately at the flame base. In this condition 8 is inde-
pendent of the height of observation in the flame. Assuming further that no droplets are
lost at the rim of the burner top, where they might disappear into the relatively cool outer
layer of the flame, we have that 8 is a property of the nebulizer (and air conduit) alone.
There are, however, indications that this assumption is not always valid (see [14]). The
value of 8 depends also on the properties of the solvent, such as the surface tension and
saturated vapor pressure at room temperature. It is also a function of the rate of aspira-
tion; an increase in this rate as such is usually accompanied by a decrease in 8 [14, 92].
This is explained by the influence of this rate on the dispersion properties of the spray
formed (compare Section 1.2.2.1). A recent critical study of the operation of a chamber-
type nebulizer is found in [92].
With total-consumption nebulizers, all aspirated liquid enters the flame base. However,
incomplete desolvation and losses of droplets that are hurled outside the turbulent flame
often make 8 lower than 100%. Since the extent of droplet evaporation will increase with
increasing height in the flame (corresponding to an increased residence time of the

droplets) 8 may be a function of height in this case. It is in fact a property of the
nebulizer and flame together, and may also vary with the kind of solvent.
1.2.4.2 Experimental methods of determination
With chamber-type nebulizers an upper limit for 8 can be found by comparing the quantity
of solution drained per sec from the chamber with the solution aspiration rate. The value
found is an upper limit, as an additional fraction of analyte may be lost in the air
conduit and burner housing or at the rim of the burner top. A correction should also be
made for the fact that the concentration of analyte in the drained solution may exceed
that in the aspirated solution owing to partial evaporation of the liquid in the chamber.
In a more direct way, 8 can be determined from a measurement of the absolute atomic
concentration, N a , of the sprayed element in the flame. If this element is completely v ola-
tilized and does not form molecules or ions in the gaseous state, we have according to the
definition of 8, to a good approximation (see also [21])
(2)
whereNa is the number of atoms per cm 3 of the flame gas; Vu and VI are the volume flow
of the unburnt gases supplied to the burner at 298 K, and of the aspirated solution, res-
pectively (both expressed in the same units, e.g., cm 3 per sec); 'fJ is the number of moles of
burnt gases produced per mole of unburnt fuel-oxidant mixture; T is the flame temperature
in OK; C is the solution concentration in moles of metal per litre; NAY is Avogadro's
number. An absolute determination of Na can be made by absolute intensity or absorption
measurements at a (resonance) line of the metal with known oscillator strength (see also
[11,12]). The absolute flame temperature should be known accurately, when intensity
measurements are used.
Fully atomized standard elements, i.e. elements that fulfill the above conditions as re-
gards their complete volatilization and full atomization in the gaseous state, are, for in-
stance, Cu, Na, and Zn [11]. Possible partial ionization of Na can be easily suppressed
by adding an excess of an easily ionizable element, such as Cs, to the solution (see Section
1.6.3 sub iv).
If the rise-velocity, Vb, of the burnt flame gases (in cm per sec) and the cross-sectional
area, 0, of the flame column coloured by metal vapor (in cm 2 ) have been determined ex-
perimentally, we can also find 8 from [14,22]
8 = 103NaVbO/(VICNAY). (3)
A new method of determining Vb by means of entrained carbon particles has recently been
reported by Rann [23].
It should be noted that molecular diffusion of the metal vapor out of the flame has
been disregarded here. It could affect the value of Na in thin flames. The extent of this
effect depends on the diffusion constant and thus on the kind of metal considered.
With total-consumption nebulizer-burners producing inhomogeneous flames with cy-
lindrical symmetry, 8 can be determined by measuring the absolute concentration of,
e.g., Cu-atoms as a function of radial distance to the flame axis, at a given height in the
flame. Since not only the metal concentration, but also the local temperature may be
sensitive to the distance from the flame axis, absorption measurements are in this case
to be preferred over absolute intensity measurements (for a more extensive discussion
see [24] and [25]). Replacing N.O in Eq. (3) by the integral of N. over the flame cross-
section and taking for Vb an average value, we can again find e. It may be noted that
Eq. (2) cannot be used here, as these turbulent un-premixed flames are diluted by a con-
siderable, but unknown amount of ambient air.
An indirect method of evaluating the effect of incomplete desolvation on e in turbulent
flames is based on the assumption that desolvation becomes practically complete in the
limiting case of V, -- 0 [26]. This is a reasonable assumption, because the dispersion of
the spray becomes finer, the lower the aspiration rate is. A finer dispersion again entailS a
more rapid and thus more complete desolvation of the spray droplets. It is possible to con-
trol V, with the aid of a pump that forces the liquid to flow at an adjustable rate into the
nebulizer, without changing the 02-flow. When the relative concentration of, e.g., Cu-
atoms at a fixed place in the flame is measured as a function of V, for a given solution
concentration, the diminution of e with increasing V, can be evaluated from the on n-pro-
portional relationship between the Cu-concentration and V,.
Parsons and Winefordner [27] have developed a third method of determining e in
turbulent flames, that utilizes the reflection of an intense light beam by unevaporated
droplets. It could be shown that only droplets with diameters larger than the wavelength of
the light contribute significantly to the reflection. It is thus possible to compare the total
number of droplets with diameter larger than, say, 1 (lm, that is found with the flame
burning and not burning, respectively. From this comparison the so-called dispersion
efficiency is calculated. This is the fraction of droplets whose diameter is reduced to below
1 (lm because of evaporation in the flame. It has been found experimentally that this
fraction is approximately equal to the spraying efficiency, e.
One problem in this method is that the reflected light intensity is not only deter-
mined by the number of droplets exceeding a critical size, but also by their average surface
area. The latter quantity is also reduced when the flame is burning. A reduction in
surface area by, say, a factor of two, does not necessarily imply that 50 % of all analyte is
converted into a dry aerosol.
1.2.4.3 Experimental results
Values of e lie generally in the range 1-15 % for chamber-type nebulizers and aqueous sol-
vents [14,22,28,29,30,31,92]. For a solvent consisting of 91 % methanol e seems to
ecxeed the value for water by a factor of three [32]. In general e is considerably enhanced
when the chamber wall is heated or the spray is irradiated by infrared radiation [33,34].
An increase in e can also be obtained by increasing the air-flow that operates the nebu-
lizer, while the aspiration rate is kept the same (finer dispersion; better evaporation be-
cause the air becomes less readily saturated with water vapor). However, when a fixed
volume of the flame is viewed by the spectrophotometer, it is rather the value of N. and
not of e that matters in determining the absolute strength of the analysis signal. It is seen
from Eq. (2) that the effect of increased e on N. is then counteracted by the simultaneous
increase in V u , brought about by the increase in Oz- and gas-flow, all other factors being
supposedly the same.
With turbulent un-premixed Hz-0 2 flames (Beckman burner) and aspiration rates of
about 0.5-2 ml water per min, measured values of e lie in the range of 10 to 100% [24,26,
27, 35]. In one case the value of e appeared to increase by nearly a factor of two over a
height interval of 1-5 cm above the burner tip [27]. For solvents containing 90% acetone
e-values of approximately 100 % have been reported near the base of the flame
[26, 36]. When e ~ 100%, the transport of metal vapour per sec integrated over the
flame cross-section should be independent of the height of observation. This holds true
at least if the volatilization of the desolvated aerosol is also complete.
1.2.4.4 The metal vapor as a trace component of the flame gas
It may be interesting to compare the range of metal concentrations to be expected in the

flame in analytical applications with the total concentration of flame molecules. From an
experimental value of e = 4.7% and an aspiration rate of 3.0 cm 3 /min, de Galan and
Winefordner [22] have calculated for their premixed C 2 H 2 -air flame with a chamber-type
nebulizer a concentration of 6.10 14 metal atoms per cm 3 of flame gas, when a solution of
1 mole of metal per litre is sprayed. This holds if the metal species is fully atomized in the
flame (as is the case for, e.g., Cu). The volume flow of unburnt gas-mixture, Vu , was in
their case 330 cm 3 S-1. When the metal is present in different forms in the gaseous
state (molecules, atoms, or ions), the value of 6.10 14 cm - 3 calculated above refers to the
total metal concentration in the flame.
On the other hand, the total concentration of flame molecules in this flame is about
3.10 18 cm - 3. Clearly, even for such a high solution concentration, the total partial
pressure of the metal vapor is only 2.10- 4 atm.
In an un-premixed turbulent Hz-O z flame (with Beckman total-consumption burner
and with V. = 225 cm 3 per sec), Simon [24] has found a maximum Na-value for Na equal
to 2.10 15 cm- 3 on the flame axis for a solution of 1 mole of Na per litre. The expected
total concentration of flame molecules here amounts to 2.7.10 18 cm- 3 • The partial
pressure of this element (which is almost fully atomized) is thus less than 10- 3 atm
in the flame.
It appears that in usual analytical applications with direct-injection nebulizer-burners as
well as with chamber-type nebulizers, the metal vapour is only a trace component of the
total flame gas. A direct influence of the presence of metal vapours on the flame tempera-
ture (see also Chapter 4 in [1]) and composition is thus not to be expected.
Also any direct interaction between two (neutral) species of one or two different kinds
of metal in the flame is likely to be swamped by the interactions of each species with the
bulk flame molecules or radicals. Assuming gas-kinetic cross-sections for these inter-
actions, it can be calculated that a given metal atom A collides about 106 times with a
flame molecule, when it stays for I ms in the flame. During this time interval the flame gas-
es, with metal vapor, rise over a vertical distance of about 1 cm. When a second metal, B,
is present in the solution at a concentration of 10- 3 mole/l, the probability that a given
metal atom A collides with an atom or molecule of species E, is at most of the order of
one in the considered time interval. This follows directly from the partial pressures of
the metal vapor calculated above for a solution of 1 mole/I.
These order-of-magnitude estimations should be borne in mind, whenever mutual in-
terference effects between two kinds of metals are explained by direct reactions or inter-
actions between these species in the gas phase in the flame.
1.3] DESOLVATION OF SPRAY IN THE FLAME 13
1.3 Desolvation of spray in the flame
1.3.1 THE RATE OF DESOLVATION
When the spray droplets enter the flame, they are rapidly heated to the boiling tempera-
ture (Tb ) of the solvent. The rate at which the solvent evaporates is then determined by the
rate at which heat is transferred from the ambient flame gas (temperature = T) to the
boiling droplet. This heat is consumed by the evaporation of the solvent (with specific heat
of vaporization = L) as well as by the heating of the vapour (with average specific heat at
constant pressure = Cp) to the final flame temperature. The vapour pressure drops from
1 atm at the droplet surface, almost to zero at a large distance from the droplet. The
vapour pressure as a function of distance from the droplet adapts itself in such a way
that the transport of vapour from the surface by diffusion just balances the rate of eva-
poration determined by the heat transport.
Assuming that heat is transferred to the droplet mainly by conduction through the
ambient gas (with average thermal conductivity = A), we have for the loss of droplet mass
per unit time [37]
(4)
where r is the droplet radius. We note that according to Eq. (4) the evaporation rate is
proportional to r (and not to the surface area!). By using the proportionality of droplet
mass m to r3, the rate at which the surface area decreases per unit time can be shown
to be independent of r. Consequently, the total time required for complete desolvation
of a droplet is proportional to its initial surface area.
Calculations show that water droplets with initial diameter equal to 1 [Lm require approxi-
mately a time of 3 [Ls for complete evaporation in the flame. If the vertical rise velocity
of the flame gas equals 10 3 cm/s, all droplets with diameter of at most 1 [Lm will be com-
pletely evaporated before they have travelled over a distance of 0.03 mm. However, the
analyte contained in water droplets with initial diameter exceeding 30 [L, will not contri-
bute to the flame emission, when the height of observation is less than 30 mm.
Because of some simplifications made in the derivation of Eq. (4), the evaporation time
calculated from it is only an approximation. It may be adequate for order-of-magnitude
calculations. For combustible solvents and turbulent media an extension of this equation
has been given [6, 37].
1.3.2 EXPERIMENTAL METHODS FOR TESTING INCOMPLETE DESOLVATION
Using Eq. (4) we can calculate the fraction of spray that is completely desolvated at a
given height in the flame, if the drop size distribution of the spray at the flame base and
the rise-velocity are known. Dean and Carnes [16] have measured this distribution by
collecting the spray drops leaving the burner (with flame off) on a glass slide coated, e.g.,
with magnesium oxide. The diameters of the drops can be derived from their impact im-
pressions on the slide, which can be measured with a microscope.
Experiments with a total-consumption nebulizer-burner (Beckman Model 4030) re-
vealed that for water only 32 % of the total spray mass was contained in droplets with
initial diameter less than 25!J.m [16]. For chloroform this fraction was found to be 48 %.
In combination with the above estimates for the time of evaporation, it can be seen
that an appreciable fraction of the spray will not contribute to the emission in the flame,
when the height of observation is restricted to a few cm above the burner tip. This loss
is larger for water than for chloroform (or other organic solvents) under otherwise identi-
cal conditions.
Size distributions of droplets produced by chamber-type nebulizers have also been
analyzed. In one series of experiments the maximum diameter of spray droplets leaving
the spray-chamber was found to be about 20!J.ID [14]. The droplets emerging from the
Mcker burner appeared in the reported case to have diameters below 1 !J.ID, because of
further evaporation in the air conduits and burner housing. It is evident that under these
conditions practically all droplets entering the flame will be desolvated immediately. One
may even expect that part of them are already desolvated during their passage through
the thin primary combustion zone.
An experimental method that yields information about the extent of desolvation more
directly is based on the scattering of an intense light-beam by the spray droplets in the
flame (see also Section 1.2.4.2). The incomplete desolvation of water droplets in a Hz-O z
flame with a direct-injection burner has been established in this way by Piischel, Simon and
Herrmann [25] and by Gibson, Grossman and Cooke [36]. The presence ofunevaporated
droplets even outside the flame has also been detected by this method. These authors
found that complete desolvation occurs in this flame when the solvent consists of 90 %
acetone. The favourable effect of acetone may be ascribed to its low specific heat of
vaporization and, perhaps, to the heat released in the combustion of its vapour. The
low surface tension of this solvent mixture also favours the dispersion of the spray. The
dispersion of the spray can also be influenced, independently, by varying the bore size
of the liquid capillary. A narrower bore size gives a smaller rate of aspiration, from
which a better dispersion generally follows.
Light-scattering by spray droplets in the flame is often observed in atomic fluorescence
analysis with direct-injection burners [38, 39]. It is in general absent when chamber-type
nebulizers or volatile organic solvents are used.
Quantitative measurement of the dispersion efficiency by using light-scattering have
already been mentioned in Section 1.2.4.2 as a method of determining the spraying
efficiency e with direct-injection burners. The experiments carried out by Parsons and
Winefordner [27] demonstrated the improvement in the desolvation of aqueous spray
droplets, which was obtained with these burners when the height of observation above
the burner tip was increased. They have also shown that a gain in spray desolvation
could be obtained by using a burner with a smaller bore size. A gain resulted, too, when
the flow rate of oxygen that aspirates and nebulizes the liquid was raised.
Indirect evidence about the (in-)completeness of desolvation can be gained from relative
photometric measurements of the atomic metal concentration in the flame, as a function
of height. If the width and rise-velocity of the flame is constant over the total height inter-
val considered, and if the metal is fully atomized (see Section 1.2.4.2), incomplete desol-
vation would make the atomic metal concentration become larger with increasing height.
This increase reflects the gradual progression of spray evaporation with time. It is assum-
ed here that volatilization ofthe desolvated aerosol particles takes place instantaneously,
so that its effect on the metal vapor concentration can be disregarded (compare Section
1.4). When the radial distribution of the metal concentration and the flame-width vary
considerably with height, the integral of the atomic metal concentration over the
1.4] VOLATILIZATION OF DESOLVATED AEROSOL 15
whole flame cross-section should be considered in the above experimental check (compare
Section 1.2.4.2).
In homogeneous premixed flames with a separate spray-chamber, it has often been
checked by similar measurements that practically all the analyte contained in the spray
is released at the flame base. For instance, in a premixed cylindrical C 2 H r air flame with
constant rise-velocity of about 10 3 cm/s and a width of 1.6 cm, the Na-concentration
measured in absorption appeared to be constant within 5 % up to a height of 7 cm
[14, p. 70]. Ionization was negligible in this measurement.
Distributions of the Na-concentration have been measured in absorption by Rann and
Hambly [40] for inhomogeneous elongated and premixed flames produced by a slot bur-
ner and fed by a chamber-type nebulizer. These measurements seem to indicate again that
practically all Na is released in the vapour state at the flame base.
Concentration distributions for Na have also been measured by Simon [24] in an in-
homogeneous H r 0 2 flame with direct-injection burner. They have already been discussed
in Section 1.2.4.3 in relation to the determination of the spraying efficiency. The latter
quantity is known often to be limited in this kind of flame by incomplete desolvation.
1.4 Volatilization of desolvated aerosol
The question how and at what rate desolvated metal saIt or oxide particles volatilize
in the flame is still open to speculation. It is, nevertheless, an urgent question in
flame photometry, as incomplete volatilization of the particles during their limited time
of residence in the flame gas, may cause annoying interferences and side-effects. In this
section we present a qualitative, or at best a semi-quantitative, discussion of the rate of
volatilization. This rate depends on the properties of the chemical compound formed in the
aerosol particles. A brief discussion of the possible kinds of compounds formed will thus
be included. Since theory alone largely fails in predicting the degree of volatilization in
flames, some experimental methods will be described below to check whether volatilization
is complete or not.
1.4.1 THE COMPOSmON AND RATE OF VOLATILIZATION OF DESOLVATED AEROSOL PARTICLES
1.4.1.1 Particle composition
In the simple case of a pure NaCl-solution in water, one Na Cl-particle will be formed
from each dehydrated spray droplet introduced into the flame. We disregard the possible
disintegration of each spray droplet into a number of smaller droplets during the boiling
process. Explosive disintegration seems to occur when the solvent is a mixture of com-
ponents with widely varying boiling points or when it contains perchloric acid [36];
it may also occur in the last stage of desolvation when a molten drop of solute
encloses a trace of solvent [99].
Since the boiling point of liquid NaCl (1750 K) is usually below the temperature of
the flame, these NaCI-particles will be readily volatilized, i.e. converted into the gaseous
phase. It is noted that the (initial) mass of each salt particle is usually smaller by several
orders of magnitude than the mass of a spray droplet.
The metal compound formed in the final stage prior to volatilization is, however, not
necessarily identical to the metal salt present in the solution. Reactions in the aqueous
phase or in the solid or molten state, partial decomposition at high temperature, etc., may
result in the formation of a different compound (with different melting or boiling point).
For a given metal salt this compound may also depend on the kind of solvent and on the
constituents of the solution.
Table 1.II summarizes schematically way some typical reactions and compounds
that may be formed in the condensed phase. The original metal salt is represented by
MX. Examples of actual reactions that are important in flame photometry are also
included. The conversion of Mg-, Ca-, and AI-salts into the corresponding oxides (see
Table I.II) is important, since these refractory oxides have high melting points and are
thus difficult to volatilize at usual flame temperatures. The conversion of AI-nitrate into
AI-fluoride by addition of HF is important, since the fluoride is much more volatile than
the oxide which would be formed if the nitrate were present alone. The enhancement of
the absorption signal of Zr upon addition ofHF may similarily be explained by the forma-
tion of a more volatile ZrOF 2 compound [94]. The formation of Ca-(pyro-)phosphate
from CaCl 2 and the phosphate ion results, conversely, in a less volatile particle than when
CaCl 2 was present alone. This explains the depression of Ca-signal by the addition of
phosphoric acid. The binding of Mg to organic complexes such as EDTA or oxine (see
Table l.II) promotes the quick volatilization of this element which would otherwise form
a stable oxide. These organic ligands are easily decomposed at high temperature.
Interelement compounds may result when, e.g., AICl 3 is added to a solution containing
CaCI 2 • A rather involatile Ca-aluminate is then formed in the condensed phase. This ex-
plains the depressing effect of AICl 3 on the Ca-signal. Rather volatile interelement com-
pounds between Mg and Ca have been suggested by Halls and Townshend [41,42] to ex-
plain the enhancement of Mg-signal by the addition of Ca.
TABLE 1. II.
FORMATION OF METAL COMPOUNDS IN AEROSOL PARTICLES PRIOR TO VOLATILIZATION
Type of compound Melting

No. Examples point Referen-
(and formation reaction) (K)
ces
1 MX NaCI 1075
2 MX -+ MxO v '" MgCl 2 'H 2 0 -+ MgO ... 3070 [41]

(+ H 2 O)
MgS04 - MgO ... 3070 [9] [41]
CaC 2 0 4 -+ CaO ... 2850 [84]
AI(N03h - Al 2 0 3 ... 2320 [9]
3 (MX; HY) -+ MxYy ... (AI(N03h; HF) - AIF3 ... 1310 [85]
(CaCI 2 ; H3P04)-Ca3(P04h· .. 1940 [5] [9]
4 (MX; organ.)-M·organ .. (MgCI 2 ; EDTA)-+ Mg·EDTA ... (d) [86]

(MgCI 2 ; oxine)-+Mg·oxine ... (d) [87]
5 (MX; NY) ->- MxN y ••• (CaCI 2 ; AICI 3 ) -+ CaAI 2 0 4 · .. 1820 [5] [9]
<+H20)
Legend: M and N are metals; X and Yare anions; 0 is oxygen; H is hydrogen. Analyte is dissolv-
ed as MX in the solution. (d) denotes decomposition at high temperature.
1.4] VOLATILIZATION OF DESOLVATBD AEROSOL 17
Not only the components present in the evaporating spray droplet determine the
kind of particle that is formed in the final stage before volatilization. The composition
of the flame gases, in particular the existence of reducing or oxidizing conditions, seem
to have an influence. It has been reported that non-volatilized CrO-particles exist in much
larger concentration in a stoichiometric Hrflame than in a fuel-rich flame [43]. In a re-
ducing flame these refractory oxide particles are apparently reduced into a more volatile
compound.
A characteristic feature of the compounds formed from, e.g., Ca and phosphate [44],
or Ca and silicate [45], is that the formation of these compounds saturates for a certain
concentration ratio of Ca and phosphate, etc., in the solution. This concentration ratio
is of the order of unity and apparently corresponds with the stoichiometric ratio of the
elements present in the compound.
A typically different volatilization interference can occur when a large excess of a se-
cond metal salt is present as concomitant in the sample. The analyte will then be dispersed
as a trace component in the matrix formed by this concomitant after desolvation. The vo-
latilization of this matrix then sets a lower limit for the time needed for complete re-
lease of analyte in the flame [46]. If a volatile analyte (e.g., CaCh) is occluded in an invola-
tile matrix (e.g., Ah03), a depression of the analysis signal results. If, however, the matrix
itself is easily decomposed, the dispersion of an involatile analyte in this matrix would
lead to quicker volatilization of analyte. This dispersion results namely in finer analyte
particles after decomposition of the matrix. Finer particles generally l€;ad to more effective
volatilization (see below).
1.4.1.2 Rate of volatilization
The rate at which a particle consisting of a given compound volatilizes, depends on many
different factors. The saturation pressure, p., of the vapour at the surface ofthe solid or
molten particle is the most important factor. This pressure depends on the (surface)
temperature, T p , of the particle in the flame. Consequently, a comparison of the melting,
sublimation, and (or) boiling points with the flame temperature T, may lead to a classi-
fication of the compounds with respect to their volatility in a given flame.
The saturation pressure, the particle radius is also an important factor. The larger
the particle size, the more time it takes before volatilization is completed. For a fixed
size distribution of the spray droplets formed at the tip of the nebulizer, the mass
and volume of the desolvated particles increase proportionally to the solution concentra-
tion. On the other hand, for a fixed solution concentration, the average particle size also
increases when the dispersion of the spray becomes more coarse. A given quantity of ana-
lyte is then distributed over a smaller number of droplets (and particles).
The influence of the particle diameter on the extent of volatilization has been demon-
strated by measuring the reduction in absorbance of the Mg line due to the addition of a
relative excess of aluminum sulphate [93]. The mean particle diameter was estimated from
the known composition of the solution and the mean initial diameter of those droplets
that enter the flame. A pneumatic and an ultrasonic nebulizer were used in this experiment
and the solution composition as well as the rate ofliquid flow were varied. An unambi-
guous relationship appeared to exist between the reduction in Mg absorbance and the
mean particle diameter.
If we disregard saturation of the metal vapor in the flame (at a large distance from the
aerosol particles), then volatilization proceeds irreversibly. The larger the time the
particles have spent in the flame, the larger the relative extent of volatilization will be.
Since the particles move upwards with a speed practically equal to the rise-velocity, Vb' of
the flame gas, the time, t, spent in the flame is related to the height of observation, h,
above the flame base by: Vbt = h. This holds if the spray droplets are already desolvated
at the flame base. In turbulent flames with direct-injection nebulizers the time required
for desolvation may be comparatively large (see Section 1.3). This time should then
be subtracted from the above t-value. In general, the choice of a greater height of ob-
servation or of a lower rise-velocity leads to a more complete volatilization.
The choice of a greater height in a turbulent flame with a direct-injection nebulizer,
does not necessarily result in a lessening of volatilization interference effects in flame
photometry [46]. Owing to a retardation in complete evaporation of the larger drop-
lets in these flames, their contribution to the analysis signal will be comparatively less at a
low height than at greater heights. Larger droplets generally produce larger particles
after desolvation, which are more difficult to volatilize. Suppose now that the analyte and
its concomitant form an involatile compound, so that the analysis signal is depressed in the
presence of the concomitant. The relative depression will then be stronger at greater heights
where the larger droplets are comparatively more important. This might explain why the
Ca-depression by In has been found to be relatively stronger higher in the flame than near
the flame base when a total-consumption burner is used [47].
L'vov has given in his book [9] a semi-quantitative treatment of the rate of volatiliza-
tion of molten particles below their boiling point. He considers a molten drop of a metal
compound, with mass m and radius r. The equation used for describing the, loss of
particle mass per second by volatilization is the same as that for an evaporating water
droplet below the boiling point. This equation is
-dm/dt = 4nrMDps/(RT), (5)
where M is the molecular weight of the volatilizing substance, D is the coeffiCient of diffu-
sion of the vapour in the ambient flame gas, and R is the gas constant. It is assumed that
the average vapor pressure throughout the flame is small compared to Ps. This is a reason-
able assumption when the maximum partial pressures of metal vapor, estimated in Section
1.2.4.4, are considered. This equation is based on the simplifying assumption that the
rate of volatilization is limited by the rate at which the vapour is transported from
the particle surface by diffusion.
Assuming that Ps is independent of r, one deduces from Eq. (5) that the rate at which
the surface area of the drop decreases per second, is independent of r. A similar conclusion
was drawn for boiling water droplets from Eq. (4) in Section 1.3.1. The total time, T, required
for complete volatilization of a molten particle with initial radius ro and density el is
then given by
(6)
The saturation pressure, P .. is a function of the surface temperature, T p , of the (molten)
particle in the flame. In the case considered where the boiling point lies well above the
flame temperature, T, the stationary value of (T - Tp) is related to Ps by [9]
T- Tp = LMDps/(). RT). (7)
HereL and). have the same meaning as in Section 1.3.1 for an evaporating water droplet.
The difference in temperature calculated from Eq. (7) is required to supply the heat of
1.4] VOLATIUZATION OF DESOLVATED AEROSOL 19
volatilization by conduction in the ambient gas. It is noted that (T- Tp) does not depend
explicitly on the particle radius.
The relation between P. and Tp according to Eq. (7) may be plotted in a graph for a
given compound and flame. When the thermodynamic function p.(Tp } is also plotted
in the same graph, the expected values ofp. and Tp can be found from the intersection of
both plots. For median values of the quantities occurring in Eq. (7) (i.e. L = 500 cal/g;
M = 100 gjmol; D = 10 cm 2 js; it = 6'10- 4 cal/cm.s.degree), L'vov derives from Eq. (7)
the following approximate relation for flame temperatures of about 3000 K
T-Tp ~ 3.6ps. (8)
Here T is expressed in K andps in mm Hg. For involatile compounds withps ;: 1 mm Hg,
Tp is practically equal to the flame temperature.
It should be remarked that the actual particle temperature may not attain the stationary
value predicted by Eq. (7), if the available time in the flame is too short to heat the particle
to this value. This could be the case in turbulent flames where high rise-velocities may occur.
Consider the special case that the volatilization of the analyte is inhibited by its
occlusion in a non-volatile matrix of a concomitant element (compare the above). The
fraction of analyte released for a given time of residence, t, in the flame, is then a function
of the initial mass, mo, of the matrix. If t is considerably smaller than the time, T, required
for complete volatilization, we have approximately for this fraction, using Eq. (5)
(mo - m!)jmo -+ Idmjdtl (tjmo) ex: tjm02/3, (9)
since mo ex: r03. When NaCI is occluded by a large excess of Ca-salt in a cool flame, the
fraction of Na released and thus the Na-signal should vary as the minus 2j3-power of the
Ca-concentration in the solution. This would hold at least for large Ca-concentrations
where the fraction of element released is small compared to unity.
As was noted by L'vov, the equations given so far have been derived under simplified
conditions. In particular, the dependence of Ps on r and the heat transport by radiation
have not been considered. In addition, the size-distribution of the particles formed after
desolvation should be taken into consideration, too. However, in combination with
estimated average values of the parameters involved, these equations will permit order-of-
magnitude calculations (see below). This holds at least under the condition that the
particles volatilize from the molten state. When the melting point is above the flame
temperature, complications in the theoretical treatment might arise from the non-spherical
and inhomogeneous structure of the solid particles, etc.
When the boiling point is lower than the flame temperature and P. is of the order of
1 atm, application of Eq. (5) and (7) is no longer permitted. * The rate of volatilization
may then be described more appropriately by the analogue of Eq. (4) for a boiling water
droplet.
1.4.2 EXPERIMENTAL METHODS FOR TESTING INCOMPLETE VOLATILIZATION
We discuss here several methods to check whether volatilization of a given metal species in
a given flame is complete or not.
*) In particular, the difference between the temperature of a boiling droplet and the flame
temperature does not have to obey Eq. (7) anymore (compare, however, Ref. [9]).
If the chemical composition of the desolvated particles can be specified and if these
particles occur in the molten state with a known (average) initial diameter, the time need-
ed for complete volatilization can be estimated by the theory in Section 1.4.1. This is
possible at least, if certain parameters (saturation pressure, etc.) are known as a function
of the temperature. The rise-velocity of the flame should also be approximately known in
order to convert time-values into height-values. Further, a possible delay in the complete
desolvation of the spray droplets in the flame should also be taken into account (see Sec-
tion 1.3).
The (average) initial diameter of the molten particles may be calculated from the
(average) initial size of the spray droplets formed at the tip of the nebulizer and arriving
in the flame. This initial droplet size, together with the solution concentration, directly
gives the amount of solute per particle as well as the particle diameter, if the density of the
molten substance is known. We assume that additional break down of spray drop-
lets, caused by explosive evaporation in the flame, does not occur (see Section 1.4.1). An
experimental method of determining droplet size distributions was described in Sec. 1.3.2.
The size of the desolvated particles may also be found more directly by collecting these
particles on a plate of quartz held in the flame. It might be difficult, however, to collect
and analyze particles with diameters far below 1 (Lm. Electron microscopy has success-
fully been used to measure the size of minute CrO particles collected from a flame
[99].
L'vov [9], for instance, has calculated a value of2.3 [Lmfor the initial diameter of molten
Al 2 0 3 -drops (melting point = 2320 K) that are formed from spray droplets with assumed
initial diameter of20 fLID and with an AI-concentration of 0.12 %. By extrapolating vapour
pressure data from the literature, he calculates: T = 5.6.10- 4 s at a temperature of
3100 K. During this time the particles may have travelled over a vertical distance of ap-
proximately 0.5 cm. The difference in temperature of the flame and of the Al 2 0 3 -particles
with a saturated total vapour pressure of 10 mm Hg, is almost negligible in this case
(compare Eq. (8)).
By similar calculations L'vov [9] estimates that in a C 2 H r 0 2 flame with T R:! 3000 K
and for solution concentrations of 5 %, complete volatilization may be obtained within
3.10- 4 s for most of the metal chlorides. Elements that form refractory oxides such as
A1 2 0 3 , BeO, CaO, and MgO, are, however, expected to be incompletely volatilized
during this period. In these calculations the initial diameter of the spray droplets was
again assumed to be 20 [Lm.
Although Ah03 has a considerably lower melting point than, e.g., CaO or MgO,
atomic absorption analysis shows that atomic AI-vapour is much more difficult to
produce in cool flames than atomic Ca- or Mg-vapour. De Galan and Winefordner [22]
have found that the fraction of free atomic Al in a C 2 H r air flame with chamber-type
nebulizer, was less than 10- 5. For Ca and Mg this fraction was 0.14 and 0.59, respectively.
This large difference in atomization fractions cannot easily be explained by taking into
account only the lower degree of dissociation of AIO-molecules into free AI-atoms in the
gaseous phase (see Table 1.UI in Section 1.5.2.1). A strong inhibition of the volatiliza-
tion of the AI-particles in the flame might be a more plausible explanation. But this,
again, is difficult to understand if Al is present as Al 2 0 3 in the condensed phase, which
has a comparatively low melting point.
Instead of calculating the extent of volatilization from theory by starting from an assum-
ed or measured particle-size distribution, we can also use the following, more direct ex-
perimental methods.
(i). If for a given metal salt concentration in a simple solution, the concentration of metal
vapour in the flame appears to be independent of the kind of anion, complete volatilization
is likely to occur.
(ii). If the total amount of metal vapour passing per second through a horizontal cross-
section of the whole flame increases with height above the burner, incomplete volatiliza-
tion may take place. This holds good, at least, if incomplete desolvation can be excluded.
The latter condition may be checked by observing the absence of any light-scattering
when a blank solution is sprayed (see Section 1.3.2). The variation with height ofthe total
metal concentration in the vapour phase can be deduced from observations of the relative
variation of atomic line intensity. A correction should then, of course, be made for the
variation of line excitation, or molecule formation with height. Ionization effects can
usually be suppressed by addition of a second, easily ionizable element that acts as a
de-ionizer. The effect of line excitation is eliminated when the metal line is observed in
absorption.
(iii). Incomplete volatilization may also be concluded, when the total absolute metal con-
centration in the vapour phase is less than the value calculated from the spraying efficiency,
solution concentration, rate of intake, etc. (see Section 1.2.4.2). This metal concentration
can be deduced from absolute intensity measurements of an atomic metal line, if corrections
are made for the fraction of metal that is bound as a molecule or that is ionized (compare
ii). More simply, one can compare the total vapour concentration of the metal
investigated relative to that of another metal that is known to be completely volatilized.
For equal molar solution concentrations, these vapour concentrations should be the same,
if volatilization is complete for both metals. De Galan and Winefordner [22] have shown
by a similar test the large deficiency of Sn- and AI-vapor concentrations when compared
to the Ca- and Mg-vapor concentrations (see the above).
(iv). Non-volatilized, incandescent solid particles may raise the intensity of the continuous
spectrum emitted in the flame. In particular, when the solution contains salts of, e.g., U,
V, or Al at high concentrations, such continuous spectral emission may become conspic-
uous. With laminar flames burning on a Meker grid the glowing particles may be bundled
together as separate luminous streams rising upwards from each hole in the burner grid
[48]. This is explained by the relatively large mass of these particles, which prevents their
sidewards diffusion in the flame.
(v). The existence of non-volatilized particles can also be concluded from the Rayleigh
scattering observed when the flame is irradiated by an intense light-source. The contribu-
tion of unevaporated spray droplets to the light-scattering can be corrected for by ob-
serving the scattering while spraying a blank solution. Veillon, Mansfield, Parsons and
Winefordner [39] have observed Rayleigh scattering when solutions of Ca, Ba, Ga, and
Ni were sprayed into a Hz-O z flame. When the incident light-beam was polarized, the
scattered light appeared to be polarized, too.
(vi). A test for complete volatilization can also be made by checking the linearity of
the analytical curve under conditions that would not be expected to produce ionization
or self-absorption (see Sections 1.6 and 1.7). An increase in metal concentration in a
simple solution leads naturally to an increase in initial particle mass. This again results
in a lowering of the fraction of element released, if the available time is not sufficient for
complete volatilization (compare Eq. (9». Under these conditions the metal vapor con-
centration in the flame will increase less than proportionally to the solution concentra-
tion. This causes a curvature of the analytical curve towards the concentration axis.
Such curvature has indeed been found for the Ca-emission bands in the range of high
Ca-concentrations (see, for instance, [49] and [50]). These bands are practically free
from self-absorption, so that this curvature points to incomplete volatilization effects.
Ionization is usually not important at these high concentrations.
The doubling-test introduced by Fischer [51] and Kropp [29] is based on similar consi-
derations. When the solution concentration is doubled, the metal vapor concentration will
increase by less than a factor of two, if the volatilization is incomplete. These authors
have checked in this way that volatilization in a turbulent Hz-0 2 flame with direct spray
injection is complete for KCI, MgCl z, and CaClz-solutions with concentrations up to
1000 ppm of K and Mg, and up to 100 ppm of Ca, respectively. These concentration
limits still depend, of course, on the experimental conditions and instrumental com-
ponents chosen in the test. It should be added that this doubling test does not prove the
(in-)complete desolvation of the spray droplets.
In composite solutions incomplete volatilization can be caused by the formation of an
involatile compound between the analyte and its concomitant, or by the occlusion of
analyte in an involatile matrix of the concomitant. The doubling-test should then be per-
formed by doubling both the analyte and the concomitant concentration. When in the
presence of a constant amount of, e.g., AI-nitrate, only the Ca-concentration is varied,
the analytical curve for Ca may show a concave curvature towards the ordinate axis. This
holds because the relative depression of the Ca-signal by Al usually diminishes when the
Ca : Al ratio is raised. A doubling ofthe Ca-concentration alone then leads to an increase of
Ca-signal by more than a factor of two. This is clearly seen in Fig. 1.3 where the "appa-
rent" Ca-concentration is plotted in absence as well as in presence of AI-nitrate. The
"apparent" Ca-concentration in the solution is defined here as the concentration value
that would be found from the Ca-band emission at 620 nm, if no correction were made for
the depressing effect of AI-nitrate. As expected, this depressing effect appears to be smaller
at a greater height in the flame (see Fig. 1.3).
It is easily checked from the curves in Fig. 1.3 that when both the Ca- and the Al-concen-
meq/I,.,.-,-r--r-r-....,,..,;-r-,-r-r-r--.""T'"7!
75
751----\----+---+--7"'1
5 - 15mm height
.~ ----~5mmheight
1850r----+---~~~~~~~
I
8
25 50 75meqfl
Co - concentration
Fig. 1.3. "Apparent" Ca-solution concentration (see text) is plotted as a function of the actual
Ca-concentration in an aqueous solution of CaCI 2 and AI(N03h, for varying AI-concentrations.
Solid and broken curves refer to a height of observation of 15and45mm, respectively, in a laminar,
premixed C 2 Hz-air flame.
Reprinted from [53], page 402, by courtesy of Springer Verlag, Berlin-Gottingen-Heidelberg-
New York.
tration are doubled in the solution, the "apparent" Ca-concentration (Le., the Ca-emis-
sion signal) increasad by less than a factor of two.
(vii). When formation of an involatile compound between the analyte (e.g., Cal and a
concomitant (e.g., phosphoric acid) occurs in a composite solution, a typical depression
curve may be found. In the curve relating the Ca-signal to the P-concentration for fixed
Ca-concentration in the solution, there is often an initial linear decrease of Ca-signal
with increasing P-concentration. Beyond a certain P:Ca ratio of the order unity, the Ca-
signal remains unaffected by P and a plateau can be seen in the curve.
The appearance of a plateau can be explained as follows (see also [5]). Beyond a certain
P:Ca ratio, all the Ca present is initially bound to P in the desolvated aerosol particles.
The excess phosphorus that is not bound to Ca, should volatilize almost immediately
at the base of the flame. Thus an aerosol particle is left, whose mass is determined only by
the quantity of Ca in the spray droplets, independently of the excess quantity ofP. The frac-
tional release of Ca-vapour from this particle increases with increasing height in the flame.
This increase is again independent of the excess P-concentration, since the initial particle
mass is independent of it. The Ca-signal which was zero at the flame base, thus attains at a
given height a constant value in the whole range of excess P-concentrations. A plateau is
then seen in the curve relating the Ca-signal to the P-concentration for a fixed Ca-concen-
tration.
When the absolute Ca-concentration in the solution is reduced, the initial mass of the
Ca-phosphate particles formed in the presence of excess Pwill be correspondingly smaller.
The fractional release of Ca in a given height interval is then enhanced, and the relative
depression of the Ca-signal at the plateau is less severe.
The relative height of the plateau in the depression curves for Ca is usually different for
different kinds of concomitants. This suggests that these depression effects cannot all be
explained by the formation of involatile CaO-particles alone. There seems to be a
tendency to the formation of specific, involatile compounds of Ca and each anion (e.g.,
Ca-phosphate). The different rates of volatilization of these compounds then explain the
different plateau values at a given height in the flame. At zero height, the plateau value will
be close to zero for all concomitants; Ca is then fully bound to Ca-phosphate in the pre-
sence of excess phosphorus, etc. The gradual release of Ca with increasing height and
the increase in Ca-signal then depend specifically on the kind of compound formed.
L'vov [9] assumes that the formation of involatile CaO explains the depression of Ca
by sulphate as well as by nitrate. However, Rocchiccioli and Townshend [52] have re-
ported that the plateau values of the Ca-depression by these anions (and by phosphate)
are markedly different from one another. It is thus not likely that this depression is based
on the formation of involatile CaO in all three cases.
(viii). An obvious condition for the occurrence of volatilization interference effects in
composite solutions, is when analyte and concomitant are found together in the same spray
droplet. When, e.g., Ca and P are introduced separately into the same flame by means of
two separate sprayers in parallel, no depression is observed [53,54,55,56]. This so-called
dual-nebulizer test is a powerful method for revealing volatilization interference effects.
(ix). The existence of incomplete volatilization may also be caused by the dependence of
the observed effects on the flame temperature and on the dispersiveness of the spray. The
analogous influence of these instrumental factors on the extent of desolvation has already
been discussed in Section 1.3. Hotter flames (e.g., the C2Hz-N 20 flame with T> 3000K)
are often recommended for the reduction of volatilization interference effects. FlJr instance,
Amos and Willis [57] have found an absence of Mg-depression by Al in the latter flame,
whereas the Mg-absorbance was reduced by more than a factor of 4 in the presence of
excess Al in the cooler C 2H 2-air flame. Willis [92] has observed a convex bending of the
analytical curve for Mo in atomic absorption analysis for the C2Hz-air flame, but not for
the hotter C2HZ-N20 flame. This curvature appeared to be more pronounced when the
rate of solution aspiration was increased.
Fassel and Becker [58] have reported that in their premixed hot C2HZ-02 flame the
depression of alkaline-earth metals by Al or P is markedly less than in cooler premixed
flames. Slavin, Venghiattis, and Manning [59] and Manning [60] have corroborated the
great advantages of the C2HZ-N 20 flame with respect to the possible depression of alka-
line-earth elements by P, etc.
In turbulent flames with direct-spray injection these volatilization effects are often
more pronounced than in flames of comparable temperature, equipped with a separate
spray-chamber. This is explained by the elimination of the larger droplets in the spray
chamber. Venghiattis [95] has found with a premixed flame that the Ca-depression by P
becomes more severe when the spray-chamber is heated. As a consequence of heating,
larger droplets will be able to reach the flame, after their evaporation, and the average
size of the Ca-P particles will be increased.
When involatile oxides are formed, * the use of fuel-rich flames is advantageous because
reducing conditions prevail here. Also the Ca-depression by P seems to be lessened when a
fuel-rich C 2H 2-air flame is used [61].
*) Particles of erO have been collected by Kelly and Padley [99] on carbon-coated copper
grids passed through H2 flames into which chromic acid was sprayed. This directly proves the
existence of incomplete volatilization, since desolvation may be assumed to be complete,
because a spray-chamber was used.
1.5 Dissociation of molecular metal species
1.5.1 SOME IMPORTANT MOLECULAR METAL SPECIES IN FLAME PHOTOMETRY
Part of the metal element introduced into the flame reacts chemically to form molecules
in the gaseous state. The partner with which the metal element is associated may be pro-
vided by the flame gas components, as in the case of CaO. The partner may also be pro-
vided by a constituent of the solution sprayed, as in the case of BaCl. Most metal com-
pounds are diatomic molecules, but some poly-atomic molecules such as LiOH may also
be important. More complex molecules, such as NaN0 3 , or organometallic molecules
are not stable at the high temperature of the flame. Because the absolute metal concen-
tration is usually quite low in the flame, dimers such as CS 2 are not an important species.
Some elements (for instance: Na, Cu, n, Ag, and Zn) are, virtually,fully atomized. They
occur mainly as free atoms in the flame. Some of them may be partially ionized in the
hotter flames, but this ionization can be easily suppressed by addition of a suitable element
as de-ionizer to the solution (see Section 1.6.3 sub iv). But when a large concentration ofa
halogen compound is present in the solution, some of these elements (e.g., Na) may be
partially bound in the flame as halide.
Most of the alkaline-earth elements are usually in molecular form in the flame. The
concentration of their monoxides often exceeds that of the free atoms, especially so in
1.5] DISSOCIATION OF MOLECULAR METAL SPECIES 25
stoichiometric and fuel-lean flames. In particular Ba has a strong tendency to form monox-
ides. An appreciable proportion of these elements may also be present as monohydroxides
(e.g., CaOH) or even as di-hydroxides (e.g., Sr(OHh), at least in flames containing hydro-
gen as a major component. When excess halogen is introduced into the flame, the emis-
sion bands of their mono halides may be seen in the spectrum.
Some elements form refractory oxides that are hard to dissociate under normal flame
conditions. To this group belong, among others, La, B, Si, Sc, V, U, and Ti. In fuel-rich,
hot flames and under abnormal conditions such as those which prevail in the reaction
zone, their oxides may be sufficiently dissociated to yield an appreciable fraction of free
atoms.
Significant proportions of some alkali elements may be bound as monohydroxides in
flames that contain hydrogen as a major component. The tendency to form hydroxides
is especially strong for Li whose atomic fraction is often reduced to below 10 %. This ten-
dency is much less strong for Cs, Rb, and K. The formation of NaOH is usually negligible.
1.5.2 THE DEGREE OF DISSOCIATION
1.5.2.1 Equilibrium dissociation; the mass-action-law

We consider the equilibrium between a metal compound MX (M is a metal atom) and its
dissociation products, M and X, denoted by
MX~ M + X. (10)
At a given place in the flame the concentrations of these partners have a stationary value.
We now define the degree of dissociation, bd , by
bd = [M]/([M] + [MX]), (11)
where [ ] denotes the concentration in cm - 3 of the considered species in the gaseous state.
The value b d = 1 corresponds to complete dissociation. When b d = 0, no free metal
atoms occur. In general, each metal atom will spend, on the average, a fraction equal to
b d of its time of residence in the considered part of the flame, as a free atom. We disregard
here side-reactions and ionization.
When there is chemical equilibrium at flame temperature T, the dissociation and reverse
association reactions are balanced. The concentrations of the reaction partners are then
mutually related through the mass-action-law
[M] [X]/[MX] = KiT). (12)
The dissociation constant, KlT), depends only on T and on the kind of molecule consider-
ed. The larger KlT) is, the more complete the dissociation of the molecule is. Its value
can be calculated from a general formula derived from Statistical Mechanics. This formu-
la may be written in the form
(13)
where fd(T) is a function of temperature, and contains certain atomic and molecular
parameters of the species involved. The dependence of Kd on temperature (expressed here
in OK) is mainly governed by the exponential factor in the right-hand side of Eq. (13),
which also contains the dissociation energy, Do (expressed here in electronvolts per mole-
cule). Do is, formally, the energy required to dissociate one molecule in the gaseous state
at 0 K. The stability of metal compounds is characterized mainly by the value of Do. For
metal compounds of interest in flame photometry Do ranges from a few to nearly 10 eV.
When Do is less than say 3.5 eV, molecular formation is usually not important; when Do
exceeds 5 eV, a large proportion of the metal is usually in molecular form in the flame.
For median values, T = 2500 OK and Do = 5 eV, the exponential factor increases by
a factor of 10 when Tis increased by about 250°C. A difference in Do-value of -0.5 eV
has a similar effect on the magnitude of this factor. This dependence of Kd on T and Do is
characteristic for the endothermic nature of the dissociation reaction.
Combining Eq. (11) and (12) one finds
(14)
Appreciable dissociation of MX thus occurs only if [X] is at the most the same order of
magnitude as KiT) (here expressed in cm - 3). When X is a flame constituent, for instance
0, its equilibrium concentration can be calculated from the chemical equilibria in the
flame at known temperature and known composition of the supplied gas-mixture. The
consumption of free O-atoms by metal oxide formation can always be neglected in this
calculation.
This independence of [0] of the amount of metal introduced into the flame, has an im-
portant consequence. It follows from Eq. (14) that bd then should be independent of the
metal concentration in the solution, too. In other words, the fractional loss of free metal
atoms due to oxide formation is the same for high and low solution concentrations. A si-
milar conclusion can usually also be drawn in the case of hydroxide and chloride forma-
tion. Owing to the strong binding of chlorine as HCI in the flame, metal chloride forma-
tion is important only if the solution contains halogen compounds in bulk concentrations
(say, 1 mol/lor larger). Normally, the total amount of halogen introduced into the flame
then greatly exceeds the total amount of metal introduced. Consequently, the concentra-
tion of free chlorine atoms in the flame will be practically unaffected by the extent of metal
chloride formation.
It follows from Eq. (14), for given values of [0] and KiT), that bd and thus the ratio
[M]/[MO] must be independent of any other factor that could affect [M] and/or [MO].
Incomplete volatilization or partial ionization may affect the sum of [M] and [MO] but
not their ratio. When concomitants in the solution interfere with the total quantity of
analyte delivered to the flame in the gaseous state, the effects will again be relatively the
same for [M] as for [MO].
As an illustration, Table 1.III lists the ratio [M]/[MO] calculated under equilibrium
conditions for some metals of interest. This ratio follows from the mass-action-Iaw, if [0]
and T are specified. Some typical flames with measured temperature and specified com-
position of the unburnt gas-mixture, were chosen from the literature to calculate the
equilibrium value of [0]. Some dissociation energies used are rather uncertain.
It is seen from Table l.UI that FeO (with a rather low Do-value) is largely dissociated
in all flames considered, whereas the dissociation of BaO (with higher Do-value) amounts
to at best a few per cent. When comparing the atomic to oxide concentration ratios for a
given element in different flames, one must take into account the variation in T as well as
in [0]. The gain in oxide dissociation expected in the hot stoichiometric H r 0 2 flame
no. 3, when compared to the much cooler stoichiometric Hrairflame no. 1, is largely com-
TABLE 1.1II.
CALCULATED EQillLIBRIUM VALUES OF [0] AND [M]/[MO] FOR SEVERAL EXPERIMENTAL FLAMES *
[M]/ [MO]
Flame [0]
No. specification Reference (in cm- 3 ) Fe Ca Mg Al Sn Ba element (M)
dissoc.
4.3 4.0 4.5 5.5 ** 5.5 5.0
energy (eV)
Hrair, [88] 1.8'10 13
1 stoichiom. 4 0.75 0.09 0.003 0.0021 0.002
2018 oK
C 2 H r air, [88] 6.4.10 14
2 fuel-rich 6 0.8 0.16 0.016 0.009 0.006
2400 oK
Hr 0 2, [89,90]
3 1.2'10 16 2 0.25 0.06 0.009 0.006 0.003
stoichiom.
2650 oK
Hz-0 2 , [89, 90] 1.3'1015
4 fuel-rich 20 2.5 0.6 0.09 0.06 0.03
2640 oK
C2 H r O z [90]
5 1.1'10 16 8 0.9 0.25 0.08 0.03
fuel-rich 1 0 .015
2840 oK
* According to calculations performed by Dr P. J. Th. Zeegers at the Physical Laboratory,

University, Utrecht.
*'" A more recent value is: 5.3 eV (cf. P. J. Kalff and C. Th. J. Alkemade, J. Chern. Phys.,
1970, to appear).
pensated, or even overcompensated by the strong increase in [0] in the former flame. On
the other hand we see by comparing the stoichiometric and the equally hot fuel-rich
H 2-0 2 flames no. 3 and no. 4, respectively, that at least a factor of 10 can be gained in the
dissociation by the reduction of [0]. The relatively high value of [0] that exists even in the
fuel-rich, hot C Z Hz-0 2 flame no. 5, makes this flame not much better than the cooler,
fuel-rich C2Hz-air flame no. 2 as far as oxide dissociation in equilibrium is concerned. *
The concentration ratios in this table were calculated by assuming equilibrium conditions
and neglecting the secondary oxygen supplied from the surrounding air. In the thick la-
minar and premixed air-flames no. 1 and 2, burning on a Meker burner, these conditions
are reasonably well fulfilled above the reaction zone. In the turbulent, un-premixed Oz-
flames entrainment of air and deviations from dissociation equilibrium near the (diffuse)
reaction zone could be important. These disturbing effects may become more serious as
the fuel-oxidant ratio is raised. Entrainment of air can of course be avoided by using a
chimney that shields the flame from the surroundings [62]. When organic solvent-mixtures
are sprayed directly into these turbulent flames, the lowering of free oxygen content
caused by the combustion of the organic component, may also have an appreciable effect
on the metal oxide dissociation.
*) Cowley, Fassel and Kniseley [100] have recently compared the capabilities of the fuel-rich
CaHa-air and C2Ha-Oa flames as regards the free-atom population of elements that form stable
oxides. When the oxide dissociation energy exceeds 6 eV, the latter flame is definitely superior.
1.5.2.2 Non-equilibrium dissociation; the role of excess flame radicals
In the primary reaction zone of hydrocarbon or hydrogen flames certain flame radicals,
e.g., C, C 2, CH, H, 0, and OH, may exist far in excess over their equilibrium concentra-
tions which would be expected at the final flame temperature. They are products of the
chain reactions by which the combustion proceeds. Some of these radicals, viz. H,
0, and OH, may also persist above the reaction zone in excess concentrations (see Section
1.2.3.3). This applies in particular to flames of moderate or low temperatures (say, T";;
2500 K).
The presence of excess radicals in and above the reaction zone may strongly enhance
the degree of dissociation of metal compounds. This degree can then no longer be calcu-
lated by applying equilibrium laws. In the reaction zone strong dissociation can even
occur for refractory oxides. A possible dissociation reaction may be here [63, 64, 65]
MO + C-'>- M + CO. (15)
Free C-atoms may occur when very fuel-rich hydrocarbon gas-mixtures are used. Kirk-
hright, Peters and West [66] [96] believe that in the lower part of fuel-rich, premixed
C 2H 2-N 20 flames, long-lived radicals, viz. CN and NH, playa role in the excessive re-
duction of some metal oxides.
Reactions of metal species in the reaction zone are particularly important in un-pre-
mixed, turbulent flames. In these flames the reaction zone tends to spread out to greater
heights than in premixed flames. Incandescent, un-premixed as well as premixed C 2H 2-0 2
flames that are fed by a large excess of fuel gas, are able to produce a large proportion of
free atoms for elements that normally occur as stable oxides [64, 65, 67, 68, 69]. The
region where these free atoms are produced is extended as the fuel-oxidant ratio is raised.
The abnormally strong dissociation of SnO in fuel-rich but cool H 2-air flames, observed
by Gibson et al [36], Slavin [70], and Amos [71], makes this type of flame better suited
for the analysis of Sn by atomic absorption than the hotter C 3 H s -air or C2Hz-air flame.
A definite explanation has not yet been given.
The presence of excess H, OH, and 0 radicals above the reaction zone of hydrogen-
air and hydrocarbon-air flames shifts the degree of dissociation of hydroxides such as
LiOH and BaOH. One might expect that the presence of excess OH-radicals would de-
press the LiOH-dissociation. The reverse holds true, however. This is because LiOH is
actually not formed by recombination of Li and OH, but by the rapid binary exchange re-
action
(16)
This reaction is balanced in the flame, so that a partial equilibrium is set up between the
concentrations of its reactants and products. The presence of excess H-radicals shifts
this partial equilibrium towards a stronger dissociation of LiOH. Since the concentration
of H decays with increasing height to its equilibrium value, the degree of LiOH-dissocia-
tion and thus the atomic Li-concentration will likewise fall off gradually until they have
reached their final equilibrium values.
This decrease of atomic Li-concentration with increasing height above the cones of the
combustion zone is shown in Fig. 1.4 for a premixed, laminar and cylindrical C 2H 2-air
flame. For comparison, the atomic Li-concentration is also shown as a function of height
relat.units
10 --t---t--+----t--+--+--'T--~-.:t.-+----
..- - - - ;
9 \ "dry"stoichiometric
air-CO flame
C ITmax "'2200 Kl
8 §
I
7 :::J
u
"E
6 1J
'iChiometric
air- C2 H2 flame
ITmax "'2500 Kl
~ height above cones
6cm
Fig. 1.4. Relative atomic Li-concentration in the flame is shown as a function of height above the
reaction zone for a C2H r air flame (T"'" 2500 OK) and a dried CO-air flame (T"'" 2200 K),
respectively. Both premixed, laminar and cylindrical flames were produced on a Meker burner and
had about the same rise-velocity. The decay of Li-concentration in the former flame is due to the
gradual shift in the degree of LiOH-dissociation, caused by the decay of excess H-concentration.
Reprinted from [49], fig. 24.
for a (dried) laminar CO-air flame with about equal rise-velocity. In the latter flame where
practically no hydrogen species occur, the atomic Li-concentration remains, indeed, con-
stant. The Li-concentration was derived here in arbitrary units from the intensity of the
atomic Li-line at 670.8 nm. A correction was made for the effect of varying flame tempe-
rature on the excitation.
The dissociation of alkaline-earth oxides seems to be undisturbed by the presence of
excess O-radicals, as was shown by Hollander [49]. This can be explained by assuming
that these oxides are dissociated and formed mainly by the following reactions [72]
M + C02~MO + CO (17)
and/or
(18)
Since there is only a moderate change in enthalpy in these reversible reactions, it is reason-
able to expect that they proceed at a high rate in both directions. A partial equilibrium is
thus set up between the concentrations of reactants and products. The concentrations of
the flame molecules involved are usually but little affected by radical disequilibrium. This
holds because these radicals occur mostly as minor constituents in the flame. Consequent-
ly, the ratio [M]/[MO] and the degree of metal oxide dissociation will likewise be close to
their equilibrium values, irrespective of the deviation in O-concentration.
1.5.3 EXPERIMENTAL METHODS FOR TESTING INCOMPLETE DISSOCIATION
1.5.3.1 Case o/metal compounds containing a constituent o/the solution sprayed
We consider, for example, the case that metal chlorides are formed in the gaseous state
when the solution contains HCI as a concomitant. Not only theoretical calculations (see
Section 1.5.2), but also experimental observations may yield information on the occur-
rence and degIee of dissociation of metal chlorides. Whenever a depressing effect of
HCI is found on the metal line intensity, the following additional observations may help
to explain the role played here by the formation of chlorides. For convenience, we
assume that the effect of self-absorption on the line intensity can be neglected.
(i). In case of chloride formation the relative depression increases with increasing HCI-
concentration. More exactly: the reciprocal of the atomic line intensity should be a linear
function of the HCI-concentration which is proportional to [CI] in the flame (see Eq. (14)).
The depression is the same for the emission intensity (and absorbance) of all spectral lines
of the metal considered. This observation excludes the possibility that the depression
might be caused by an alteration of flame temperature owing to a change in physical pro-
perties of the solution sprayed.
(ii). The relative depression is the same, in the case of chloride formation, when instead of
HCI, other chlorine compounds such as NH 4 CI, are added to the solution in equal mola-
rity. This observation excludes the possibility that the depression is caused by a change in
spraying efficiency due to a change in the physical properties of the solution (see Section
1.2.4.1). These properties would in general be different for different chlorine compounds
in the solution.
(iii). Whenever a depression results from the combined effect of metal chloride formation
and of an alteration in spraying efficiency, simultaneous observations of the effect of
HCI on two different metals may be instructive. It is possible to distinguish between the
two competing effects, if the chloride dissociation energies and thus the degIees of disso-
ciation are different for the two elements [14, 73]. The unknown part played by the com-
mon spraying effect can then be eliminated.
(iv). Spraying effects can also be excluded by checking the depression when the analyte
(without HCI) and a blank solution with HCI, are sprayed separately by two identical
sprayers into the flame (dual-nebulizer test; see also Section 1.4.2). This experiment also
eliminates possible interferences of HCI with the volatilization of the desolvated aerosol
particles. Such interferences might perhaps have played a role in the enhancement of
atomic Zr-concentration by added HCI, observed by Slavin et al. [59].
(v). A possible interference of HCI with the ionization of the analyte can be excluded or
eliminated by the suppression of ionization through the addition of a suitable element
as de-ionizer. Whenever possible, observation of the HCI-effect on both the intensities of
an atomic and an ionic metal line is also instructive.
(vi). Absence of ionization effects can also be concluded if the relative depression is found
to be the same at high and at low concentrations of the analyte. At low concentrations,
ionization effects would be markedly more pronounced (see Section 1.6.2.1), whereas the
relative effect of chloride formation is independent of the analyte concentration (see
Section 1.5.2.1).
(vii). Metal chloride formation may be also checked by observing the dependence of the
depression on the flame temperature and on the dissociation energy for different metal
elements (see Section 1.5.2.1).
(viii). Ceteris paribus, chloride effects will be more pronounced in flames with direct
spray injection than in flames with chamber-type nebulizers. This holds because the deli-
very of chlorine into the flame is larger in the former case for a given RCI-concentration
in the solution (see Section 1.2.4.3).
(ix). Occasionally the appearance of metal chloride bands (e.g., BaCI-bands) may point
to the formation of chloride molecules.
The interpretation of the experimental results may be complicated when the element
considered is partially bound to other constituents in the flame, too. The formation of a
large proportion of LiOR-molecules, for instance, appears to have a stabilizing effect on
the atomic Li-concentration, when LiCI is formed.
1.5.3.2 Case of metal compounds containing a constituent of the flame gas

The occurrence and the degree of dissociation of metal compounds containing flame con-
stituents (e.g., CaO), can also be deduced from experimental observations. The following
methods may be of interest in flame photometry. They are typically different from those
mentioned in the foregoing section. This holds, since we cannot compare here as easily the
atomic line intensity in the absence and in the presence of the other partner, respectively.
(i). The appearance of molecular emission bands may sometimes give a clue as to the
kind of metal compound(s) formed. Not all metal compounds, however, emit visible or
ultraviolet bands in the flame. Moreover, the identification of the bands emitted is some-
times uncertain. This applies in particular to some bands of the alkaline-earth elements.
The absolute intensity of the bands usually does not yield much information on the con-
centration of the emitting molecules. The pertinent optical transition probabilities are of-
ten poorly known.
(ii). Additional information about the degree of dissociation can be obtained from ob-
servations of the relative variation of line and/or band intensities with varying conditions
in the flame. These intensity variations can be converted into relative variations of atomic
and/or molecular concentrations, if the variation of temperature and the temperature de-
pendence of the excitation are known. Any effect on the light intensity caused by a con-
current variation in the delivery of metal vapour to the flame, in the flame thickness, etc.,
can be corrected for by comparison with the simultaneous variation in light intensity of a
fully atomized element (e.g., Cu; see Section 1.5.1). Suppose, for instance, that in two
flame situations characterized by the same temperature but different fuel-oxidant ratios,
the molecular band intensity of the considered element, as well as the Cu-line intensity
are found to be practically the same for given solution concentrations. One may then con-
clude that the molecule emitting the band is a dominant species of this element in the two
flame situations. That is, its concentration is practically equal to the total concentration of
element (atoms + molecules) in the flame, so that Od must be negligibly small. Conversely,
when in different flame situations the atomic line intensity varies with varying temperature
in accordance with Boltzmann's law (see Section 1.7.1.1), molecule formation is negligible.
Otherwise the variation in the degree of dissociation with temperature would be an addi-
tional factor in the temperature dependence of the atomic line intensity.
Measurements of relative atom distributions in inhomogeneous flames may here be of
interest, too. Relative atomic concentrations are preferably measured by the atomic ab-
sorption method, since the variation in local flame temperature does not interfere with
such measurements in practice. Atom distributions have been measured in absorption by
[' II
3
2 2
E E
~
u u
:;: .c
~ .~
.c
..L -'- -'- .J...

Rich Lean Rich Leon
a-Sodium b - Barium
Fig. 1.5. Atom distributions measured in absorption are shown for Na (a) and Ba (b) in a fuel-
rich and a fuel-lean, premixed C2 H 2 -air flame burning on a slot burner. Distributions are shown
in a plane perpendicular to the slot. Successive contours correspond t 0 intervals of 0.1 absorbance;
maximum absorbance is found in the centre. The decay of atomic Ba-concentration with height in
the lean flame is due to the formation of Ba-molecules. Na forms practically no molecules in either
flame.
Reprinted from [401, page 881, by courtesy of the American Chemical Society.
Rann and Hambly [40] in premixed C 2 Hz-air flames burning ona lOcm slot burner. The
distributions ofNa- and Ba-atoms in a typically fuel-rich and fuel-lean flame are shown in
Figs. 1.5a and 1.5b. The Na- and Ba-solution concentration was adjusted in such a way
that the highest absorbance measured was about 1.0. The peak absorbances obtained in
the rich and lean flame, respectively, were in the ratio of 1.4 for Ba and 0.8 for Na. For
Ba there is a marked difference between the two flames, in that the atomic concentration
rapidly falls off with height in the lean flame. For Na the atomic concentration remains
fairly constant in both flames. This depletion of Ba-atoms with height points to a pro-
gressive formation of Ba-molecules (oxides or hydroxides) in the lean flame. The theoreti-
cal interpretation is complicated, however, by retardation of the volatilization process
for some metals, by the large vertical temperature gradient above a height of 0.5 cm, and
by the dilution of this thin flame with ambient air (see [40]).
(iii). The degree of dissociation, bd , can be derived quantitatively from the measured ratio
of atomic concentrations of the investigated element and of a fully atomized element, for
equimolar solution concentrations. Assuming that the investigated element forms only
one kind of compound, that ionization effects can be disregarded and the volatilization
is complete, one may set bd equal to this ratio. This holds because for equimolar so-
lution concentrations the total content of element (molecules and atoms) in the flame is
the same for either element. Instead of using a fully atomized element for reference, one
can find bd, too, by comparing the absolute value of atomic metal concentration with
the absolute total concentration of the same element, calculated from the spraying
efficiency, etc. (compare also Section 1.4.2 sub iii). For a fuller discussion and for the
application of these methods to the determination of dissociation energies, we may refer
to [11]. We mention here only that a comparison of the atomic concentrations of two
1.6] IONIZATION OF METAL SPECIES 33
elements (e.g., Ca and Sr) forming mainly oxides in a flame, may lead to a determination
of the difference of their oxide dissociation energies [10, 49]. The actual O-concentration
in the flame drops out in this comparison, but the flame temperature must be known.
1.6 Ionization of metal species
1.6.1 IONIC SPECIES OF INTEREST IN FLAME PHOTOMETRY
In the flame, neutral atoms or molecules may be split, giving a positive ion and a free
electron (or a negative ion). The higher the flame temperature and the lower the ionization
energy, the larger will be the proportion of ions produced. The ionization energy is the
minimum amount of energy required to remove an electron from the atom or molecule.
As a consequence of ionization, the fraction of element present as neutral species will be
reduced and the spectral lines emitted by this species will be weakened. With some ele-
ments the ionic species may also emit spectral lines in the flame, but these occur at wave-
lengths other than those of the neutral species. Double ionization, i.e. stripping of two
electrons from one neutral atom or molecule has not yet been reported in commonly
used flames.
The tendency to form ions is especially strong for most of the alkali atoms; this ten-
dency decreases in the order: Cs, Rb, K, Na, and Li, corresponding to an increase in
ionization energy in the same order from 3.89 to 5.39 electronvolt (eV). The alkaline-
earth atoms Ba, Sr, and Ca have ionization energies ranging from 5.21 to 6.11 eVand
are less easily ionized than most of the alkali atoms. In flames containing hydrogen, mole-
cular ions such as CaOH+ and BaOH+ may occur, too. Their concentration often exceeds
that of the atomic ions Ca + or Ba +. In the hot C 2H r N 20 flame (T > 3000 K) elements
with higher ionization energy, such as Nb (6.88 eV), may also be noticeably ionized [74].
The above discussion refers mainly to the flame gas with metal vapour above the reac-
tion zone. In the latter zone even Pb-atoms with an ionization energy as large as 7.42 eV
may be ionized. This excessive ionization does not correspond to a state of equilibrium and
it therefore tends to decay above the reaction zone. A necessary condition for metal
ionization in this zone is, of course, that metal atoms are found there in the vapour state.
Negative ions such as CI- may be found when a solution containing HCI is sprayed
into the flame. The electron affinity of chlorine atoms (3.8 eV) is sufficiently high to pro-
duce these ions in significant amounts. Under usual conditions in flame photometry,
however, the great majority of negative species consists of free electrons. In the absence
of strong electric fields we have generally that the local concentration of these electrons
(plus negative ions) equals that of the positive ions, because of charge balance.
When no solution is sprayed, positive ions and free electrons may still be found in hy-
drocarbon, but not in pure CO- or H 2-flames. These so-called natural flame ions are form-
ed in large excess and in great variety in the reaction zone, as side-products of the com-
bustion reactions. Of these natural ions H30+ seems to be the only species that can even
persist above the reaction zone. Its concentration, however, falls off from a peak value of
the order of 10 11 _10 12 cm- 3 near the reaction zone, by several orders of magnitude higher
up in the flame. In any case the concentration of flame ions in equilibrium should be
negligibly small, since the ionization energies of the flame molecules and radicals are
high (> 8 eV). The presence of negative flame ions such as OH- is now considered to
be negligible above the reaction zone.
1.6.2 THE DEGREE OF IONIZATION
1.6.2.1 Equilibrium ionization; Saha's law
Let us consider a neutral metal atom, M, that can be split into a positive ion, M+, and a
free electron, e. The ionization and reverse recombination process are formally described
by
M~M+ + e. (19)
At a given place in a stationary flame the concentrations of these species will have station-
ary values which are denoted here by [M], [M+], and [e], and are expressed in cm- 3 or
partial pressures. The degree of ionization, (J t, is now defined by
(20)
The atomic fraction of element is then given by: 1 - (J i. If we disregard the formation of
other molecular or ionic species of the element considered, we have that: [M+] + [M] =
[M]t where [M]t is the total concentration of element in the vapour state. Complete ioni-
zation is characterized by: (J i = 1; absence of ionization corresponds to: (J i = O.
In equilibrium at the flame temperature T, the ionization and recombination processes
represented by (19) are balanced and we have according to Saha's law
(21)
Here KlT) is the ionization constant which depends only on T and the kind of metal con-
sidered. Its value can be calculated from a general formula derived from statistical me-
chanics, which can be written in the form
(22)
if we express the ionization energy, Et, in eV, and Tin K. The pre-exponential factor
fi(T) involves certain atomic and ionic parameters, and depends (but not strongly) on T.
A discussion similar to that given in Section 1.5.2.1 for the dissociation constant,
applies here to the dependence of the ionization constant on E j and T.
Combining Eqs. (20) and (21), and assuming: [M+] = [e], we get
(23)
When Kj(T) = [M]t (both quantities being expressed in the same units), we find from this
relation: (Ji = 0.61, which corresponds to a state of appreciable ionization. Using Ki(T) =
5.4 . 1011 cm- 3 for Kat T = 2500 K (Ei = 4.34 eV), we expect ionization effects to be-
come apparent when the K-solution concentration is of the order of 1 millimoljl (see
also the data on the metal concentration in the flame, given in Section 1.2.4.4). It follows
from Eq. (23) that for lower K-concentrations (Ji will rise, whereas for higher K-concen-
trations the fractional ionization will decrease (for more extensive calculations see, for
instance, [75]).
When the element exists partly as neutral molecules, the relative reduction in atomic
concentration caused by ionization will be less than when that the same number of
free atoms, but no molecules are present. Adequate equations have been presented
by Mavrodineanu and Boiteux [8, Section 22-2-6]. The larger the molecular to atomic
concentration ratio, $, is, the less the atomic concentration is affected by ionization for
fixed total metal concentration [M]t (molecules + atoms + ions). Only when [M]t ~
K,(T)/tP, will ionization effects become apparent, while in the limiting case: [M]t- 0, all
metal element will be present in the form of ions only.
In the literature, calculations of the partial ionization of aIkaline-earth metals are often
presented without taking into account this stabilizing effect of molecule formation. Be-
sides, the formation of molecular ions should also be allowed for with this group of ele-
ments (see Section 1.6.1).
The variation of 15 1 with total metal concentration, [M]h and thus with solution con-
centration, C, has consequences for the analytical curve. Assuming: [M+] = [e] and
neglecting molecule formation, we have for [M]t ;;;. 10 2 K,(T), that 15, '" 0.1 and thus
[M] ~ [M]t. In this range of concentrations [M] is therefore practically proportional to
C. It further follows from Eq. (23) that [M +] should vary ex: V[M]t ex: VC. For [M]t '"
10- 2 K,(T) we have: 15, ;;;. 0.99 and thus from Eq. (23): [M] ex: [MV ex: C2. In this case
we further find to a good approximation: [M+] ~ [M]t ex: C. Consequently, the analytical
curve for the atomic line intensity shows a concave curvature towards the intensity axis in
the range of relatively low solution concentrations. It merges into a straight line for higher
solution concentrations (if we disregard self-absorption). Upon extrapolation this straight
line should pass through the origin. The concave portion of the curve lies below this extra-
polated straight line.
When natural flame ions are present, it may occur that [e]» [M+] for low concentra-
tions of the metal considered. It follows from Eq. (21) that [M+]J[M] is then practi-
cally independent of C. Consequently, the analytical curve again becomes a straight
line passing through the origin, in the considered range of low solution concentrations.
The slope of this line is, however, smaller than that of the line that would be obtained if
ionization were completely suppressed. Complete suppression in practice occurs when
[e] ;;;. 10 2 K,(T) (see Eq. (21».
The presence of a second, ionizable metal element in the flame can also raise the value
of tel, and shift the ionization equilibrium given by (19), to the left for the original
element, M. The resulting reduction in the degree of ionization can be calculated if we
apply Saha's law (Eq. (21» to both elements separately. In this case [e] must be put
equal to the sum of both ionic concentrations. When the electrons produced by the second
element greatly outnumber those produced by the original element, the same situation
arises as that discussed above for excess flame ions.
The occurrence of CI- ions in the flame has exactly the opposite effect: it reduces the
value of [e] and thus enhances 15" which results in a depression of the atomic line
intensity (see [29]).
1.6.2.2 Non-equilibrium ionization
When natural flame ions are present, the degree of metal ionization, 15 1, calculated from
Eq. (21), will be lower than that expected in complete thermodynamic equilibrium (which
corresponds to a negligible concentration of flame ions). Since the concentration of these
ions decays continuously with increasing height, 15, will increase with height, all other para-
meters such as Tbeing supposedly independent of height. Consequently, the atomic metal
concentration drops with increasing height until a final value corresponding to ionization
equilibrium is attained asymptotically. This disturbing effect of natural flame ions on the
metal ionization will be unimportant for metal concentrations in the flame that are much
higher than the concentration of these ions.
A gradual asymptotic approach towards ionization equilibrium with increasing height
may also occur under other conditions, namely when the rates of the metal ionization and
recombination processes are themselves comparatively slow. If the vapour enters the
flame mainly in the form of neutral atoms, it will take some time before sufficient metal
ions are formed (e.g., by collisional ionization) to bring the degree of ionization in accord-
ance with Saha's law. The ionization and recombination processes represented by (19) are
then not balanced low in the flame and Eq. (21) does not hold there.
The relaxation time for establishment of ionization equilibrium amounts to about
10- 2 S for Na-atoms at T = 2500 K in CO-air and H 2 -air flames [76, 77]. This time
corresponds to a height interval of the order of 10 cm in the usual flames. The atomic Na-
concentration will then continuously decrease with height until at a height of 10 cm Saha
equilibrium is, approximately, attained. The flame temperature here is again supposed to
be independent of height. For other alkali atoms with lower ionization energy, and in
hotter H 2 - and CO-flames, the relaxation time can be markedly shorter. In hydrocarbon
flames at comparable temperatures the establishment of Saha equilibrium seems to pro-
ceed with less delay for the alkali atoms. Hofmann and Kohn [78] have demonstrated ex-
perimentally that Saha's law is obeyed in premixed C 2 H r air flames at T = 2500 K for
the alkali metals as well as the alkaline-earth metals, within a time-delay of at most
5 ms. Recently de Galan and Winefordner [20] have confirmed that the ionization of
alkaline-earth metals agrees reasonably well with Saha's law in un-premixed C 2 H 2 -0 2
and H 2 -0 2 flames at a height of 2 cm above the burner tip. The flame temperature deter-
mined by them from the observed ionization using Saha's law, was found to agree, apart
from random errors of about 100 to 200 °C, with the temperature derived by other means.
There is further experimental evidence which suggest that ionization equilibrium is
established rapidly for alkaline-earth metals in Hrair flames too. An efficient chemi-
ionization process in which MOH+-ions are involved, seems to help the attainment of
ionization equilibrium here. On the other hand deviations of the flame radical concentra-
tions from dissociation equilibrium (see Section 1.5.2.2) may again disturb the ioniza-
tion equilibrium as some of these radicals playa role in the chemi-ionization process.
1.6.3 EXPERIMENTAL METHODS FOR TESTING PARTIAL IONIZATION
Apart from theoretical calculations based on Saha's law, the existence of partial ionization
of metal vapours can also be proved by the following experimental methods. For the sake of
simplicity we shall assume in discussing these methods, that Saha's law is obeyed at the
height of observation.
(i). The observation of a concave portion in the analytical curve in the range of low
metal concentrations in a simple solution, usually points to partial ionization (compare
Section 1.6.2.1). The same curvature should be found with all atomic lines as well as
molecular bands emitted by the metal vapour. Self-absorption is neglected here. The simi-
lar behavior of the atomic lines and molecular bands is a consequence of the mass-action-
law which predicts a constant ratio of the atomic to molecular concentrations irrespective
of the occurrence of partial ionization (see Section 1.5.2.1). A concave curvature will also
be seen in the analytical curve in atomic absorption analysis. Natural flame ions (and
possibly ionizable impurities in the flame gas) may, however, straighten out the concave
curvature. When a relaxation occurs in the establishment of Saha equilibrium for the
metal atoms, the concave curvature as predicted by Saha's law may not develop fully.
(ii). Partial ionization may also be concluded for some metals from the appearance of
ionic lines in the spectrum. The relative dependence of ionic line intensity on solution con-
centration has already been discussed in Section 1.6.2.1. It is typically different from that
for the atomic lines.
(iii). An important clue to the occurrence of partial ionization may be found in the ob-
servation of mutual enhancement of the atomic line intensities when two ionizable metals
are present together. The free electron concentration in the flame is then higher than in the
case when either element is present alone. This results in an enhancement of the intensity
as well as the absorbance of the atomic lines of either metal. The same relative enhan-
cement also occurs for the molecular bands if any are present. At the same time the ionic
line intensities are depressed. At fixed solution concentration ofthe element being analysed,
the relative enhancement of analysis signal increases with increasing concentration of the
concomitant element. Concomitants with a low ionization energy, such as Cs and K,
will in general cause a larger enhancement than those with a higher ionization energy,
such as Na. For a fixed ratio of solution concentrations of both elements, the relative
enhancement is more pronounced, the lower these concentrations are. This holds if we
disregard again the buffering effect of flame ions or ionization relaxation effects.
(iv). The enhancement of atomic line intensity discussed in (iii), asymptotically reaches a
saturation value when the concentration of the added, ionizable element is raised to
higher and higher values (compare Section 1.6.2.1). Saturation takes place when the ion-
ization of the element being analysed is reduced so much that it is present almost as neutral
atoms (and molecules) only. A further enhancement by ionization repression is then clearly
no longer possible. This saturation effect is often used to suppress ionization of an element
under investigation, by adding a sufficiently large quantity of Cs-salt to the solution.
This and some other alkali elements such as Rb or K may act as efficient de-ionizers
because of their low ionization energies. The factor by which the saturated line intensity
1.8 r-----=:::=======t
0.4
0.2
%~--+---~2--~3~==4~==t===i6
M 110+3 RbCI Added
e I~ 255 340 4~5
RI¥TI. Rb Added
Fig. 1.6. Relative variation of atomic and ionic line intensities of three alkaline-earth elements
is shown as a function of Rb-concentration in the solution. An unpremixed C 2 H 2 -0 2 flame was
used. The concentration of the alkaline-earth metals (present as chlorides in the solution) was
20 ppm. Legend: • Ba-atomic line at 554 nm; ... Sr-atomic line at 461 nm; • Ca-atomic line
at 423 mfL; open circles refer to the general behavior observed for the ionic lines of Ba at 455 nm,
of Sr at 408 nm, and of Ca at 394 nm.
Reprinted from [90], p. 2035, by courtesy of the American Chemical Society.
exceeds the undisturbed line intensity is the larger, the lower the solution concentration
is. When saturation is (nearly) complete, the analytical curve is again a straight line
through the origin.
The saturation effect is clearly seen in Fig. 1.6 where the atomic and ionic line intensi-
ties of three alkaline-earth metals are plotted as a function of added Rb-concentration, in
an un-premixed C 2 H r 0 2 flame. As expected, the ionic line intensity drops nearly to zero
when saturation of the atomic line intensities takes place. In the quantitative interpreta-
tion of these plots, however, the possible stabilizing effect of molecule formation on the
atomic metal concentration should be taken into account (compare Section 1.6.2.1). The
tendency to form molecules is especially large for Ba which on the other hand also has
the lowest ionization energy of this group of elements.
(v). The mutual enhancement and saturation effects described in (iii) and (iv) are still
observed when simple solutions of each metal are sprayed into the same flame by two sepa-
rate nebulizers in parallel. This experiment excludes any affect of the added element on
the transport and volatilization of the sample.
(vi). All phenomena described above will in general be more pronounced in hotter
flames. It should further be realized that for equal flame temperature and solution concen-
trations, these phenomena will be less marked in flames with total-consumption nebulizers
than in flames with chamber-type nebulizers. This holds because in the latter flames the
metal concentration is comparatively much smaller.
1.7 Excitation of metal vapour to light-emission
1.7.1 EQUILIBRIUM EXCITATION
In this section a concise survey is presented of some general notions and facts from radia-
tion theory, as far as they are directly relevant in emission flame photometry. For the sake
of simplicity we shall assume that the flame has a uniform temperature and metal distri-
bution in that part of its cross-section where metal vapour is present. Furthermore, only
metal atoms emitting an easily isolated spectral line at a distinct wavelenth A.o = c/'JIo
(c is the light-velocity) will be considered. Molecular band emissions are not discussed. The
excitation energy of the upper atomic level involved in the optical transition, is denoted by
E 1 ; that of the lower level is denoted by Eo. This lower level need not necessarily be the
ground state. We generally have: E 1 - Eo = h'JIo, if h is Planck's constant and both E and
h'JI are expressed in the same units.
1.7.1.1 Thermal radiation intensity in the absence of self-absorption; the Boltzmann distri-
bution law
In thermodynamic equilibrium at the flame temperature T, the fraction [M*]/[M] of
metal atoms that occur in the excited state with energy Eh is given by the Boltzmann
distribution law
(24)
Here Eland T are expressed in eV and K, respectively; g 1 is the statistical weight of the
excited state and Z is the partition function of the atom. Often Z may be approximated by
the statistical weight of the ground state. The intensity, I, of the spectral line emitted from
this excited state, is obtained from Eq. (24)
1.7] EXCITATION OF METAL VAPOUR TO LIGHT-EMISSION 39
1= (hllo/4n) [M*]A 1 -+ 0 1 = (hllo/4n) (gl/Z)A 1-+0 1[M]1O- 5040 EltT

erg.cm - 2. S - l.sterad - 1. (25)
In this most fundamental equation of emission flame photometry, I denotes the flux of
radiation energy per unit of solid angle and per cm 2 surface area, in a direction perpen-
dicular to the flame surface. The transition probability per second of the considered
emission line is denoted by A 1_->- o. The thickness of the coloured flame section along the
axis of observation is given by I (in cm). The concentration of metal atoms, [M], is ex-
pressed in em - 3, and the photon energy, hll 0, in erg.
Eq. (25) enables us to calculate the radiation flux received by the detector, if we know
the solid angle under which the flame is viewed, as well as the flame surface area observed
and the transmission losses of the optical system. In emission flame photometry this radia-
tion flux is ultimately the optical signal that carries all information on the concentration
of the element to be analyzed.
The application of Eq. (25) presupposes that all the photons emitted inside the flame by
downward transitions of excited atoms, actually escape from the flame. The case where this
condition is not fulfilled owing to self-absorption, will be dealt with in Section 1.7.1.2.
It is also supposed in accordance with common practice, that the spectral transmission
bandwidth of the monochromator or filter used, is markedly larger than the line-width.
The intensity I represents, in fact, an integration over the whole width of the spectral
line. The spectral line shape itself plays no role in the result of this integration.
Under the conditions assumed, I varies proportionally to [M]. It follows from Eq. (25)
that lines originating from levels with El being twice as large as that of the yellow Na-line
(with El = 2.1 eV), are about 104 times as weak. This holds under the condition that
T R:i 2500 OK and that all other parameters are the same. This result makes it clear why
under equilibrium conditions ultraviolet lines are usually weak in the flame spectrum.
Inspection of Eq. (25) further shows that a small relative variation in T results in a large
relative variation in I. Upon differentiating I with respect to T one gets
(ill/I) = (11,500 E 1 /T) (ilT/T). (26)
A variation of 25°C in T at 2500 K, thus leads to a variation of about 10% in I for the
yellow Na-line. For lines with higher El this relative variation will be correspondingly
stronger. A constant temperature is thus an essential requirement in emission flame photo-
metry. When in analytical work an external standard is used, Tshould at least be constant
within say 0.1 % during the time interval in which the unknown sample solution is com-
pared with the standard solution.
The detailed, microscopic excitation mechanisms are seen to play no role in the ex-
pression for I which contains only atomic parameters and the macroscopic flame tempera-
ture. The rate of excitation (i.e. the number of metal atoms per cm 3 raised per second to
the excited state, e.g., by collisions with flame molecules) does, paradoxically, not affect
[M*]. This can be understood when it is realized that in equilibrium this rate is always
balanced by the equally large rate of the inverse de-excitation process (principle of detailed
balance). A de-excitation occurs when an excited atom returns to a lower state upon col-
lision with a flame molecule that takes up the excitation energy.
Apart from the possibility of supra thermal chemiluminescence which will be discussed in
Section 1.7.2, Boltzmann's law for equilibrium applies usually in good approximation
for normal flames above the reaction zone. The question of which detailed (de-)excitation
processes actually occur, is then mainly of academic interest and need not be discussed
here (see [5, 6, 8, 97] and chapter IV in [1]).
1. 7.1.2 Thermal radiation intensity in the presence of self-absorption; Kirchhoff's law

Resonance lines for which the ground state forms the lower level, may not only appear in
emission, but also in absorption at exactly the same wavelength. Part of the photons
emitted by a downward transition to the ground state, may thus be absorbed again in the
flame by other atoms of the same metal in the ground state. This phenomenon is known as
self-absorption; its occurrence as such has nothing to do with the presence of a compara-
tively cool outer layer in the flame, a fact that is often misunderstood. The atoms absorb-
ing these photons are thereby raised to the excited state, from which they mostly return to
the ground state by a radiationless transition in a quenching collision with a flame mole-
cule. In this transition the atomic excitation energy is converted into kinetic energy. The
energy of the absorbed photon is thus ultimately converted into heat and the photon is
lost. The fractional loss of photons and the corresponding weakening of the outgoing
radiation, increases with increasing concentration of atoms in the ground state (which is
proportional to the number of all atoms present per cm 3). It also increases with in-
creasing distance over which a photon has to travel, on the average, before it leaves the
flame on its way to the photometer. This distance is proportional to I. For fixed value of I,
I will thus increase less than proportionally with increasing [M]. This holds at least in
the range of high [M]-values where the effect of self-absorption becomes noticeable. The
outgoing radiation intensity is then no more described by Eq. (25), although Boltzmann's
distribution law for [M*]/[M) still remains valid.
The thermal radiation intensity can now be derived from the general Kirchhoff law
(27)
where I is expressed in the same units as in Eq. (25). Here J p is the spectral radiance of a
black-body at the flame temperature, T, and the optical frequency Vo, which is given by the
universal Planck radiation law. The factor At is the so-called integral absorption of the line
and it is expressed in Hz if the spectral radiance J p is expressed per Hz as unit of spectral
interval. The same factor At occurs in the equation for the radiation energy that is absorb-
ed by the metal line when a radiation beam from an external source with a continuous
spectrum traverses the flame. This factor is a function of the product [M]I and depends
on the spectral line shape (i.e. the absorption coefficient as a function of optical frequency).
It also contains the same atomic parameters that occur in Eq. (25) which is in fact an
asymptotic expression of Eq. (27) in the limit for [M]/-. O. In general, At varies only slight-
ly with T, so that the temperature dependence of I for self-absorbed and not self-absorbed
lines is practically the same (compare Eq. (25) and (27».
The dependence of I on [M] is governed by the variation of At with [M). For low con-
centrations where self-absorption is negligible, At varies as ex: [M]. For large concentra-
tions with strong self-absorption, At varies as ex:V[M]. This explains the well-known
square-root dependence of emission intensity on solution concentration, C, in the upper
branch of the analytical curve for resonance lines.
All considerations given so far hold true for flames with homogeneous radial tempera-
ture distribution. When the flame temperature drops with increasing radial distance from
the flame axis, self-reversal of the spectral line may appear in addition. The line intensity
will then grow less than proportionally to Vein the upper branch of the analytical curve.
1.7] EXCITATION OF METAL VAPOUR TO LIGHT-EMISSION 41
1.7.2 SUPRATHERMAL CHEMILUMINESCENCE
1.7.2.1 General
Chemiluminescence occurs when, e.g., a metal atom is excited to light-emission as a result
of a chemical reaction in which part of the chemical energy released is directly converted
into atomic excitation energy. It is not always realized that the occurrence of chemilumi-
nescent reactions does not lead per se to suprathermal excitation. It does so only if the
concentrations of the reactants exceed their chemical equilibrium values derived from the
mass-action-law. In equilibrium the chemiluminescent excitation rate is just balanced by
the reverse chemical quenching rate. The fraction of excited metal atoms is then invariably
given by the Boltzmann distribution law.
The absolute intensity of suprathermal chemiluminescent emission does not only de-
pend on the excess concentrations of the reactants involved. It also depends on the rela-
tive probability that an excited atom returns to the lower state by emission of a photon
and not by a radiationless transition in a quenching collision (compare also Section 1.7.1.2).
This probability is usually small compared to unity and depends on the type and concen-
tration of the collision partners in the flame as well as on T. Typical values are of the order
of a few per cent in flames diluted with N 2.
Suprathermal chemiluminescence may be preferentially observed in cooler flames and
for lines with higher excitation energies, because the thermal radiation intensity drops
strongly with increasing Eland decreasing T. The strength of suprathermal chemilumines-
cence can formally be described by defining an effective radiation temperature, Terr, such
that Eq. (25) gives the true value of I for the considered line, if we replace T by
Terr (> T). This definition also applies to the metal emission in the reaction zone where a
general definition of T cannot be given (see also [S]).
1.7.2.2 Types of suprathermal chemiluminescence in flames

Two types of suprathermal chemiluminescence of atomic lines should be distinguished in
flames (see also [79]). Chemiluminescent emission of spectral bands of metal compounds
such as CuOH, may also occur in flames but will not be discussed here [79]. Both types
are connected with the occurrence of flame radicals in excess of their equilibrium concen-
trations.
(i). "Soft" suprathermal chemiluminescence may occur in, as well as above, the reaction
zone of H 2 -, CO-, and hydrocarbon flames. It is generally based on recombination re-
actions of flame radicals, in which the metal atom to be excited plays the role of a stabiliz-
ing third partner (compare Section 1.2.3.3). Typical reactions are
H+ (O)H + M-- H 2 (O) + M* (2Sa)

CO + 0 + M--C0 2 + M*. (2Sb)
The recombination energy released in these reactions is sufficient to excite atomic lines
with excitation energies up to about 5 eV. To this category belong the suprathermal chemi-
luminescent excitation of the 32S.0 nm line of Ag above the reaction zone of HrO r N 2
flames [SO], or that of the blue K-doublet at 404 nm above the reaction zone of a C 2 H r
air and CO-air flame [49,73]. Sugden [SI] estimates that above the reaction zone of
Hz-flames suprathermal chemiluminescent excitation by radical recombination will

dominate over collisional excitation for lines with El ;> 3.5 eV at T = 2000 oK, The
latter excitation will dominate for lines with El <: 2 eV. Since the excess concentrations of
H- and OH-radicals decay with increasing height above the reaction zone, the strength of
suprathermal chemiluminescence is also a function of height.
(ii). "Hard" suprathermal chemiluminescence. This second type of chemiluminescence is
able to affect emission lines with excitation energies even up to about 8 eV. It is confined
to the reaction zone of hydrocarbon flames (CzHz-air or CzHz-O z ) where the uv lines
of many metal atoms such as Fe show anomalous excitation. It does not occur in pure
Hz- or CO-flames. However, Hz-flames that are also fed by a trace of CzHz or by a
spray of, e.g., methanol, are able to produce this type of chemiluminescence, too [64].
A definitive explanation of all the observed effects has not yet been given. There seems
to be a correlation with the occurrence of CH-radicals and with the excessive ionization
general-Iy found in the reaction zone of hydrocarbon flames [79, 82]. Free C-radicals are
also believed to be involved in fuel-rich, incandescent flames. Postulated chemiluminescent
reactions are, e.g., (see also [8])
CH + 0 + M ---+ CHO + M* (see [36]) (29a)
and
C + MO---+ CO + M*. (see [64]) (29b)
In reaction (29b), chemiluminescent excitation occurs in combination with dissociation of
the metal oxide. An anomalous emission intensity of the atomic lines may then be based
on suprathermal excitation as well as on excessive dissociation of the metal oxides in the
reaction zone.
1. 7 .2.3 Experimental methods for testing non-thermal excitation

The following experimental methods may be followed to prove the occurrence of non-
thermal excitation in flames. With some of these methods self-absorption of the resonance
lines, varying with [M]l, might complicate matters. For simplicity's sake we shall disregard
it here.
(i). When for a single resonance line the effective radiation temperature, T err , (see Section
1.7.2.1) is found to exceed T, suprathermal excitation occurs. Terr can be found from
Eq. (25) by combining an emission and an absorption measurement which refer to I and
[M], respectively. Such combined measurement of Terr can be performed most con-
veniently by the method of line-reversal, which will not further be explained here (see, for
instance, [8] and [83]). The true flame temperature, T, can be determined by measuring the
line-reversal temperature for a suitable thermally excited resonance line with low excita-
tion energy. Fig. 1.7 shows values of Terr measured by de Galan and Winefordner [20]
by the line-reversal method for different metal lines. These measurements were made in
un-premixed, turbulent H 2 -0 2 as well as H 2 -air flames at a distance of several em above
the base of the flame. The mutual consistency found in the former flame proves the exist-
ence of thermal excitation. The increase of Terr with increasing excitation energy, E 1, in the
latter flame, points to suprathermal excitation. This is probably caused by the persistence
of excess radicals at large distances from the base of the flame in un-premixed H 2 -air
flames [20].
(ii). When for a set of neighbouring Fe-lines with known values of El and Al-+O' relative
1.7] EXCITATION OF METAL VAPOR TO UGHT-EMISSION 43
J
3000
.
~
2500
0
0
H2- 0 2
/
x
k'5
2000 r-
I ~.
/
2 __ 3~- H2 -olr
20000 25000 30000 35000

E. em-'
Fig. 1.7. Effective radiation temperature (measured by the method ofline-reversal) is plotted as a
function of the excitation energy E of the emission line observed, for an un-premixed HrO z and
H 2 -air flame, respectively. Legend: 1. Na 589.0 nm; 2. Sr 460.7 nm; 3. Ca 422.7 nm; 4. Fe 372.0
nm; Cu 324.7 nm; x is Fe-excitation temperature derived from relative intensities of some
Fe-lines with E F:d 34000 cm -1 (see Section 1.7.2.3 sub ii). E = 10,000 cm -1 corresponds to 1.24
eV.
Reprinted from [20], page 711, by courtesy of Pergamon Press Ltd.
intensities are measured, a plot ofln (A 1-+0 g 1 'VolI) vs. E 1 should yield a straight line with
slope determined by T, in case of thermal excitation (see Eq. (25». Deviations from a
straight line or the appearance of a different slope point to non-thermal excitation. Note
that in Fig. 1.7 the Fe- excitation temperature determined from the slope of such a plot,
agrees well with the true, line-reversal temperature for the H 2 -0 2 flame. It deviates, how-
ever, from the true temperature determined by Na line-reversal for the Hrair flame.
(iii). The occurrence of (non-)thermal excitation above the reaction zone may also be
demonstrated by relative intensity measurements of the spectral line considered under
different flame conditions with known temperatures. If [M]i remains the same and E 1 is
known, the validity of Eq. (25) can directly be checked. Any possible difference in [M]i
may be corrected for by relative absorption measurements, or by relative intensity mea-
surements of another line of the same metal, which is known to be thermally excited.
A special case of method (iii) is the measurement of relative line intensity as well as true
flame temperature as a function of height above the reaction zone. When strong supra-
thermal excitation occurs owing to the presence of excess flame radicals, the variation of
I follows the decay of these radicals with height, rather than the variation in T.
(iv). The existence of (supra-)thermal excitation above the reaction zone may also be
proved by measuring the relative variation !JIll caused by a variation in T, for a set of
different lines of the same atom. A plot of !JIll versus E1 should yield a straight line
through the origin, if all the lines are thermally excited (see Eq. (26». The transition prob-
abilities need not be known in this test. A possible variation in metal concentration
also drops out, when (!JlfI)- (!JIll). is plotted against (E1 - E.), where the subscript s
refers to an arbitrary standard line.
Some of the methods described can be easily applied in analytical flame photometry
and may be recommended whenever the thermal character of metal line excitation is investi-
gated. These methods may be used, for instance, to decide whether the anomalous emis-
sion strength of Sn-lines in H 2 -air flames with aqueous and organic solvents, is due to
suprathermal excitation and (or) excessive dissociation of SnO-vapor (compare [64]).
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81. T. M. SUGDEN, discussion on: P. J. Th. Zeegers and C. Th. J. Alkemade, Xth Symposium
(International) on Combustion, Cambridge, England, 1964, The Combustion Institute,
Pittsburgh, 1965, p. 33.
82. E. M. BULEWICZ and P. J. PADLEY, Combustion & Flame,S, 331 (1961).
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CHAPTER 2
SENSITIVITY, DETECTION LIMIT, PRECISION AND

ACCURACY IN FLAME EMISSION AND ATOMIC
ABSORPTION SPECTROMETRY
O. M enis and T. C. Rains

Washington D.C. , U.S.A.
2.1 Introduction
This chapter deals primarily with the practical aspects of achieving low detection limits,
high sensitivity, precision and accuracy in the fields of flame emission and atomic absorp-
tion. Emphasis is placed on the role of the various components of the instrument and
on the control of experimental variables that govern the selection of optimum conditions
for attaining these goals. It includes for quidance tables of some of the current results
which other workers have achieved in this field. It also discusses the definitions of these
terms, but it focuses mainly on the description of techniques and on the instruments
which an analyst requires to use these techniques more effectively.
~~~R-~~~M~~==~
SOURCE ~
NEBULIZER- ,.-..:::0......_.,
FLAME
Fig. 2.1. Schematic diagram of atomic absorption instrument.
The sections dealing with the many facets of this methodology are perhaps best in-
troduced by the schematic diagram shown in Fig. 2.1. For atomic absorption the instru-
mental components are: a spectral light source, a chopper system, a flame, a nebulizer,
a monochromator, a detector with its power supply, and lock-in amplifier system con-
nected to a suitable readout, either a recorder or a digital integrator. For flame emis-
sion, the instrument is operated without the light source and the chopper system is
located between the flame and the monochromator. All three components will be dealt
Contribution from the National Bureau of Standards; not subject to copyright.
48 SENSITIVITY, DETECTION UMIT, PRECISION AND ACCURACY [2
with separately. Under optimum operating conditions this instrument can handle a
large number of samples and more than 70 elements have been determined with a
relatively high degree of precision and accuracy. One of the major achievements of this
technique has been the ability to detect nanogram and picogram quantities of given
constituents in a variety of matrices as well as the ability to determine major com-
ponents with great precision.
2.2 Definition of terms
A brief discussion of the definition of terms, in line with some of the terminology or
practices reported in the literature, is given. Among the papers which have appeared
recently on the subject of detection limits and sensitivity. those by Ramirez-Muiioz [1] and
Kaiser [2] are especially helpful. In this section we shall try to relate these views to our
own and to those of others in a form which should serve as a useful guide to the ex-
perimental analyst.
2.2.1 DETECTION LIMITS
An analyst is frequently requested to analyze a given sample and to state whether he can
detect a specific element. Fundamentally, his decision depends on his knowledge of
the systematic and random error of the method. The random error is expressed in terms
of the statistically derived standard deviation of a single determination, "a". In reporting
his findings he selects certain probability levels 84. 97.5. 99.9, etc.• corresponding to a.
20', 30', NO', above the background to express the degree of confidence he has in making
his statement. The value NO' is the detection limit of the analyte (where N depends
on the risk taken). The real dilemma is what to select as the "blank" or background
"noise", above which to measure the signal output from the analyte (element sought).
For an example, in reporting the detection of lithium in a matrix of sea water, the syn-
thetic blank from sea water differs significantly from that of distilled water. There is the
inherent problem of the effect of the matrix and the problem of availability of high purity
material to prepare a realistic blank.
To overcome this difficulty a procedure is recommended in which an analyst establishes
the measure of random error, a, on a synthetic sample containing the element in sufficient
concentration to yield a signal which is five times (or similar multiple) as large as the
background. The derived value of "a" of this signal is in most cases much more conser-
vative than that obtained from a pure water blank. The detection limit then becomes the
20' (or NO') magnitude above the mean obtained from a background or a matrix blank.
In any event, whenever detection limits are reported in the literature, the author should
indicate clearly the method used in establishing them.
Winefordner and coworkers [3-5] have also derived theoretical equations for the cal-
culation of the detection limits based on instrumental and spectral constants. However,
the values of these parameters are generally not well known, and in practice have so
far been of limited use.
The highest sensitivity and/or detection limits reported in the literature for atomic
absorption and flame emission spectrometry are given in Table 2.1. These values were
obtained with a variety of instruments, burners-nebulizers, oxidant fuels, and associated
electronics.
2.2] DEFINITION OF TERMS 49
TABLE 2.1
DETECTION LIMITS REPORTED FOR VARIOUS ELEMENTS BY FLAME EMISSION

AND ATOMIC ABSORPTION SPECTROMETRY
Wavelength Detection Limit, fLg/ml

Element A AAS (2) Ref.
FES (1) Ref.
Ag 3281 0.3 6 0.005 a 7

3383 .02b 7
A1 3093 .1 d 8
3962 .1b 7
As 1937 .2 9
2350 2.2 10
Au 2676 .5 b 7 .01- 7
B 2497 15 8
547 0 .3 b 7
Ba 5536 .01 11 .1 d 8
Be 2349 .003 d 8
Bi 2231 3.3 10 .02 8
Ca 4227 .0009 11 .003 d 8
Cd 2288 4.2 10 .00lc 7
Ce 5699 lOb 6
Co 2364 .007c 8
3427 .01 b
Cr 3579 .1 6 .005 8
4254 .01 b
Cs 8521 .002 7 .05 f 8
Cu 3248 .1 7 .005 8
3274 .01 12
Dy 4211 .1 6 .2d 8
573 0 .1b 7
Er 4008 .3 b 6 .2d 8
5040 .1 b 7
Eu 4594 .003 b 6 .2d 8
Fe 2483 .01 8
3720 .01 b 7
Ga 2874 .07 8
4172 .05 b 7
Gd 3684 4d 8
4520 2b 6
464 0 .1b 7
Ge 2651 .6 6 2d 8
Hf 3072 15 d 8
3682 7S 6
Hg 2537 2.5 10 .21 8
50 SENSITIVITY, DETECTION LIMIT, PRECISION AND ACCURACY [2
Wavelength Detection Limit, fLg/ml

Element
A PES (1) Ref. AAS (2) Ref.
Ho 4104 .1 6
4163 .3 d 8
566 0 .lb 7
In 3039 .05 8
4511 .01 b 7
Ir 2850 4d 8
3800 100 6
K 7665 .0002 7 .005 f 8
La 3928 80 d 8
5791 1 6
743 0 .lb 7
Li 6708 .000003 6 .005 8
Lu 3312 .2 6 50 d 8
468 0 .05 7
Mg 2852 .02 7 .0005 8
Mn 2795 .005 8
4031 .008 b 7
Mo 3133 .1 8
Na 5890 .0001 7 .005 8
Nb 4059 6 20 d 8
Nd 4634 2d 8
4883 1 6
4924 1 6
700 0 .2b 7
Ni 2320 .01 e 8
3525 .01 b 7
Os 4420 10 6
Pb 2170 .01 e 8
2833 .02 7
4058 .lb 7
Pd 2476 .5 8
3635 .04b 7
Pr 4939 2 6
4951 10 8
Pt 2659 .5 8
Rb 7800 .001 7 .005 f 8
Re 3460 6 1.5 d 8
Rh 3435 .03 8
3692 .3 6
Ru 3499 .3 8
3728 .07 b 7
Sb 2598 .35 10
2176 .2 8
2.2] DBFlNITlON OF TERMS 51
Wavelength Detection Limit, (Lg/ml

Element A FES (1) Ref. AAS (2) Ref.
Sc 3912 .07 6 .2d 8

607 0 .Olb 7
Se 1961 .5 8
Si 2516 .2d 8
Sm 4297 5d 8
4884 .6 6
652 0 .Ib 7
Sn 2246 .Ih 8
Sr 4607 .002 7 .01 8
Ta 2715 6d 8
Tb 3901 4 6
4326 2d 8
535 0 .Ib 7
Te 2143 .3 8
Th 5761 150 6
Ti 3643 .Id 8
3653 .5 6
3999 .5 6
Tl 2768 .2 8
3776 .OOO5 b 7
Tm 4094 .3 6 .Id 8
4106 .2 6
4940 .1 7
U 3585 30d 8
V 3184 .Id 8
4379 .3 6
W 4008 4 6 3d 8
Y 4077 .3 6 .3d 8
5970 .02b 7
Yb 3988 .Olb 7 .04 8
Zn 2139 .002 8
Zr 3601 5d 8
(1) - Flame emission
(2) - Atomic absorption
a - Laminar flow burner with preheater
b - Organic solvent
c - Quartz tube
d - Nitrous oxide-acetylene flame
e - High-brightness lamp
f - Osram lamp
g - Mercury germicidal lamp
h - Air-hydrogen flame
2.2.2 SENSITIVITY
There is less ambiguity and confusion in defining the term sensitivity. Ramirez-Muiioz [1]
has described techniques for determining qualitatively and quantitatively the sensitivity
in flame photometry. Since there is a proportionality between absorbance and concen-
tration as expressed by the equation A = mC, where A is the absorbance and m is the
factor or slope of the line, and C is the concentration, one can express sensitivity in terms
of the concentration which is required to produce a 1 % absorption, or an absorbance
equal to 0.0044 absorbance units. In this manner, the sensitivity is expressed as that con-
centration of an analyte in a solution which results in an emission-producing signal that
is 1 % above that of the flame or sample background. As a corollary it is evident that
the steeper the slope, m, the more sensitive is the method, and the smaller differences in
concentration can be detected.
2.2.3 PRECISION
As in all measurements, the imprecision of a method is a composite of the random errors

arising from the various components of the measurement. These include weighing of the
sample, preparation of the final volume, the reproducibility of the nebulization, flame
condition, instrumental settings, and, finally, the stability of the electronic circuitry. The
precision is best established by running replicate solutions of a given element in a given
matrix and expressing it in terms of the standard deviation of a single determination.
To date, most reports in this field claim a precision corresponding to a relative standard
deviation of one to two percent. The best precision that has been so far attained is of
the order of 0.1 to 0.2 percent. These improved precisions have been obtained only
in the analysis of certain materials by resorting to more elaborate techniques. These
procedures will be described more fully later in the text.
2.2.4 ACCURACY
The absolute evaluation of "accuracy" assumes that we are capable of determining the
true value of a given substance. We can make progress along these lines and improve
the accuracy of our value through the refinement of experimental procedure and better
understanding of the systematic and random error. In some cases, this can be attained
by having carefully characterized standards. In flame emission spectrometry this is
often difficult since standards in a solution of a given matrix are difficult to prepare. A
knowledge of the systematic errors can be of help, as in any instrumental method, in
evaluating the relative accuracy of the method and in establishing the absence of a
bias. Without this information, and because of the characteristic effects of the matrix on
the flame emission and absorption of many elements, another approach is the use of a
standard addition method or the application of an internal standard technique. These
techniques for evaluating accuracy will be discussed in detail later in the text.
2.3] THE OPTIMIZATION OF COMPONENTS 53
2.3 The optimization of components
The various components and techniques used in flame emission and atomic absorption
will be discussed individually for the purpose of evaluating the various criteria for
optimizing the control of these variables. They are detailed individually in the following
sections: (1) sources, (2) nebulizer-burners, (3) optics, (4) selection of wavelengths, and
finally (5) the detection and recording system. They relate to the process in atomic
absorption in which the sample is introduced into the nebulizer-burner where the analyte
is dried and dissociated into atoms. A source, usually of monochromatic light, is focused
onto the flame and then to a monochromator, which separates out the desired radiation. A
decrease in radiant intensity of the source due to absorption is then detected by a multi-
plier phototube, amplified, and finally recorded on some readout device. This process is
quantitative through the application of Beer's law:
A = 10glo(Iofl) = klC,
where A is the absorbance, 10 is the incident and I is the transmitted light, k is a constant
for the given wavelength, 1 is the path length of the flame, and C is the concentration.
2.3.1 SOURCE
As the width of the absorption line in the flame is approximately 0.1 A, the source must
produce sharp lines in order to attain the maximum absorption [3]. Various factors
such as Doppler and pressure broadening cause undesirable broadening of the line.
The Doppler broadening is caused by thermal motion of the atoms. The line sources
most suitable for atomic absorption spectrometry are the hollow-cathode, Osram, and
the electrodeless discharge lamps.
Hollow-cathode lamps are normally used because of their stability and convenience.
If these lamps are operated at the proper current, as recommended by the manufacturer,
to minimize the effect of line broadening, an absorption line width of less than 0.02 A
is obtained. While considerably more intensity can be obtained from most lamps by
increasing the current, the analyst runs the risk of the phenomena of self-reversal. Recent-
ly, a new hollow-cathode lamp has been introduced by Sullivan and Walsh [14]; this uses a
pair of auxiliary electrodes immediately above the cathode. The auxiliary electrodes are
powered by an independent high-current power source which excites the metal atoms that
have been sputtered. This process produces a more intense source of light. Cartwright,
Sebens and Slavin [15] have made a comparison of the two types of nickel lamps. The
high-brightness lamp increased the intensity of the resonance line, 2320 A, by a factor
of 8. Also, the adjacent nickel ion line at 2316 A was observed to be suppressed in the
high-brightness lamp. With many monochromators these two lines are not resolved,
and this results in a nonlinear curve for nickel. By means of the high-brightness lamp,
which yielded an increase in the linearity of the working curve, these authors were
able to extend the detection limit for nickel to 0.01 [Lg/ml. The sensitivity attained
with the high-brightness lamp was also slightly improved.
Osram lamps have been limited as sources to the more volatile elements such as the
alkali metals and mercury. These lamps are a source of stable light, but they must be
operated at a low current to prevent self-reversal.
Electrodeless discharge lamps of the type used by Meggers and Westfall [16] have been
used only briefly as a source in atomic absorption spectrometry. Rann and Hambly [17]
used an electrodeless discharge lamp which operated at 15 MHz to determine selenium.
They report a detection limit of 1 fLg/ml. Recently Marshall and West [18] described
an electrodeless discharge lamp powered by a 2450 MHz magnetron unit to excite the
resonance lines of iron. The iron source was more intense than the normal hollow-
cathode lamp, which permitted the use of narrow slits. The narrow slit eliminated the
interference of non-absorbing iron lines. Under those conditions the sensitivity and
linearity of the calibration curve is increased. Ivanov et al. [19] used discharge lamps for
In, Ga, Bi, Sb, TI, Pb, Mg, Ca and Cu and they achieved about the same sensitivity as
with the hollow-cathode lamp.
Menis and Rains used the electrodeless discharge lamp with an Evenson cavity to
determine arsenic in high-purity selenium and cast iron. Since the resonance lines of
arsenic are below 2000 A, the source of radiation must be of high intensity to overcome
the absorption due to air. The electrodeless discharge lamp in an Evenson cavity was
found to offer a source of intense radiation. The lamp was slightly less stable (a drift
of approximately 5 % per hour) than the hollow-cathode lamp. With lower voltage on
the multiplier phototube a higher degree of scale expansion could be used with the
electrodeless lamp.
To secure additional sensitivity for arsenic an argon (entrained air)-hydrogen flame has
been used with a Zeiss (total consumption) burner. The detection limits obtained for the
three resonance lines of arsenic at 1890, 1937 and 1972 A were 0.2, 0.2 and 0.4 fLg/mI,
respectively. Table 2.II gives a comparison of the precision of the hollow-cathode and
electrodeless lamp. While different scale expansions were used in this study, the relative
standard deviation was the same.
The electrodeless lamp is an excellent source of radiation for many elements. With the
use of a beam splitter and two precision lock-in-amplifiers, a ratio recording system could
be made to correct for any instability in the lamp. This approach has not yet been ex-
ploited commercially; however, it appears feasible and would offer a method for high
sensitivity and precision.
TABLE 2.11
COMPARISON OF PRECISION OF HOLLOW CATHODE AND ELECTRODELESS
DISCHARGE LAMP
Std. Rei. Std.
As, fLg/ml Absorbance Av.
Dev., %
I Dev.
Hollow Cathode 2 .100 .110

.117 .116
.102 .108 .109 .007 6
10 .374 .407
.405 .374
.412 .391 .394 .017 4
Electrodeless Lamp 2 .241 .282
.288 .276
.282 .273 .274 .018 6
10 .878 .909
.965 .908
.912 .990 .927 .038 4
2.3.2 NEBULIZER-BURNER SYSTEMS
The nebulizer-burner system is probably the most important component of the flame
emission or absorption instrument. It is the function of the nebulizer-burner to produce
the atomic vapour from the analyte in the sample solution. This process includes many
steps such as the dispersion of solution in the form of small drops (aerosol), evaporation
to dryness, decomposition of salt or oxide, formation of metal vapour, excitation of the
atoms and emission. The extent to which these steps occur within the flame will depend
upon the analyte, matrix, type of nebulizer-burner, oxidant and fuel gases. The ideal
nebulizer-burner system, to assure maximum sensitivity and reproducibility should
have the following characteristics: (1) high degree of flame stability with little or no
apparent noise contribution to the detector system, (2) no memory effect even from
highly concentrated solutions, (3) ease of introducing the sample, (4) a fast response
time, (5) freedom from internal corrosion, (6) a constant nebulization rate of the solu-
tion, (7) capability of using a wide choice of fuel gases, (8) ability to introduce the
largest number of fine droplets into the flame per unit time. Mavrodineanu and Boiteux
[23] present a thorough discussion of oxidants, fuel gases and burner designs.
In flame emission, a total consumption burner is usually used, while the premix or
laminar-flow slot burner is used in atomic absorption. The conditions for maximum
sensitivity in emission or absorption will depend upon each individual element. To
increase the sensitivity for atomic absorption for any given element, one effective way
is to increase the length of the flame path. Another effective way is to use a system of
multiple passes. This can be done with any burner system provided that the intensity of
the source is sufficient to overcome the reflection losses of the mirrors.
2.3.2.1 Total consumption burner
In flame emission, the total consumption or sprayer burner such as the Beckman integral
burner is used by most workers to secure the maximum detection limits. Since all the
droplets are introduced directly into the flame, the radiant intensity of the analyte is
controlled by the various parameters associated with the nebulizer-burner system. The
advantages of this type of system are: high efficiency of nebulization, the ability to
use various fuels and oxidants with complete safety, the use of combustible solvents,
ease of cleaning and the attainment of high sensitivity.
The major disadvantages of this burner system are: gas flow must be carefully con-
trolled to insure reproducible results, interferences from the condensed phase, i.e., alumi-
nium, phosphate, etc. are more pronounced and there is the discomfort of the loud noise
of the flame.
Kniseley et al. [20] have modified the Beckman burner into a premix type which has
overcome some of its disadvantages. The modification of the burner decreases noise
and results in a gain in sensitivity of an order of a magnitude for many elements.
However, for satisfactory operation the sample solution must be at least 50 percent
ethanol or some other flammable solvent.
2.3.2.2 Sheath burner
In an effort to increase the sensitivity of flame emission for many elements, Gilbert [21]
proposed the use of a sheath for the Beckman burner. Additional oxygen is made to flow
in the sheath and around the flame and this prevents nitrogen in the air from cooling the
flame. The enhancement resulting from use of a sheath of our own similar design in the
analysis of aqueous and organic solvent solutions of several elements is shown in Table
2.III. This enhancement factor was obtained under the same experimental conditions
except for the addition of oxygen through the sheath. The greater enhancement with the
sheath for the organic solvent would indicate an over excitation condition in the flame.
An even higher enhancement factor was obtained when methyl isobutyl ketone was
used.
TABLE 2.III
ENHANCEMENT RESULTING FROM USE OF SHEATH ON
THE NEBULIZER-BURNER
(Additional O 2 flow through sheath, 0.06 ft 3 /min)
Wavelength Enhancement Factor
I
Analyte
A Aqueous Solution 50 vol. % Methanol
Ag 3383 4.5 8.0

Ba 4554 8.7 11.8
5536 1.2 3.0
Ca 4227 2.0 5.1
Fe 3720 4.3 6.9
Mn 4034 4.4 9.1
Sr 4607 1.8 4.3
The oxygen-sheath principle has been applied in a slightly different way in the Chaffee-
Keyes burner. The fuel (hydrogen or acetylene) is used as the nebulizer. The sample
capillary tube is on the outside of the burner and can be interchanged for various size
capillary tubing. The manufacturers' claim of two-fold enhancement over the conventional
burner has not been borne out by the experience of one of the authors. The flame burns,
however, very quietly. The burner can be used in a premixed mode when used with oxy-
acetylene. By premixing the gases the white inner cone of the oxyacetylene flame is
eliminated with a reduction in flame background.
2.3.2.3 Absorption tube
Fuwa and Vallee [24], with a quartz tube into which the aerosol is aspirated, obtained
a vast increase in sensitivity in atomic absorption by virtue of an increase in the absorbing
path. They have investigated the effect of tube size as well as various other parameters
associated with this type of arrangement [25]. Table 2.1V shows data comparing the
detection limit of zinc for various diameter tubes and burner arrangements. The choice
of tube diameter, matrix, and length vary with different investigators. Silica or quartz
tubes which insure a high reflectance are often chosen. Ceramic tubes (sintered corundum)
have been used, but they must be heated up slowly. The best results are obtained when
ceramic tubes are used in connection with a furnace. In this manner Rubeska and Stupar
[26] have obtained an increase in sensitivity for some noble metals over the quartz tube
arrangement of Fuwa and Vallee. While the preheating of the tube with a furnace did
not increase the sensitivity, it did minimize some interferences and extended the life of
TABLE 2.IV
ATOMIC ABSORPTION ENHANCEMENT OF SENSITIVITY FOR ZINC ANALYSIS
Log loll = 0.1 Detection limit Zn detectable

[Lg/ml [Lg/ml g
1. Elongated burner * 7.5 0.3 3 x 10- 7

2. Beckman burner
a. Vertical flame 8.2 0.3 3 x 10- 8
b. Horizontal flame 1.0 0.04 4x10- 9
c. Asbestos tube 0.3 0.01 1 x 10- 9
d. Vycor tube 0.16 0.006 6xlO- 1O
Diameter 2.6 cm
e. Vycor tube 0.016 0.0006 6x 10- 11
Diameter 1 cm
f. Vycor tube 0.01 0.0004 4xlO- 11
Diameter 1 cm MgO sheath
g. Vycor tube 0.005 0.0002 2 x 10- 11
Diameter 1 cm MgO sheath
Higher Pressure
*) Hilger-Watts Ltd., attachments No. H909 and H1090.

Reprinted from Ref. [25] by courtesy of Analytical Chemistry.
the tube. Feldman and Dhumward [27] have also described a T-shaped stainless steel
tube for the determination of mercury. Other workers [28, 29] have further investigated
various tube sizes and arrangements for particular elements.
2.3.2.4 "Premix" burner
The principal difference between the premix or laminar flow burner and the total con-
sumption burner is the way in which the gases and samples are mixed and introduced
into the flame. In the "premix" burner, the sample is aspirated into a mixing chamber
which effectively separates the large droplets from the fine spray and mixes it with the
gases. By this process, only 1 to 10 percent of the aspirated solution ever reaches the
flame. The fraction of the spray introduced into the flame can be increased by indirect
heating of the spray chamber. With the heated chamber, however, the burner head has
a tendency to become clogged and requires frequent cleaning.
Another advantage of the "premix" burner over the total consumption burner is that
small variations in the rate of gas flow have much less effect on the overall nebulization of
the sample. Also, the time the atoms remain in the observed area of the flame will now
depend upon the gas velocity. Since the flame front propagation rate is very high (approx-
imately 1200 cm/s) for an oxygen-acetylene flame in a total consumption burner, the
residence time of the atoms in this flame is very short. On the other hand, the flame
velocity for the air-acetylene or nitrous oxide-acetylene flame is 120 and 180 cm/s,
respectively, thus the decrease in flame velocity for the "premix" burner will permit a
longer residence time for the atoms in the observed area and lead to an increase in
sensitivity. Since the length of the flame can be also increased from 1 to 10 cm again,
an increase in sensitivity is obtained.
The major disadvantage of the "premix" burner is that frequent cleaning of the burner
58 SENSITIVITY, DETECTION UMlT, PRECISION AND ACCURACY [2
is required when aspirating solutions of high salt content. Also, caution is needed
when certain volatile organic solvents with a low flash point are used. Premixed burners
have been used almost exclusively in atomic absorption spectrometry. With the intro-
duction of the nitrous oxide-acetylene flame, this burner also has an excellent potential
for flame emission, especially when applied to the oxide forming elements such as alumi-
nium, barium and rare earth metals.
For maximum sensitivity or detection limits and precision in atomic absorption,
it is essential that the nebulizer-burner produces the largest number of neutral atoms
possible in the flame. Since only atoms in the ground state will absorb the resonance
wavelength emitted by the radiating source, the temperature of the flame should be suf-
ficient to dissociate the molecules, but not high enough to produce ions. Some elements
require a relatively cool flame, e.g., the alkali metals, while those that form refractory
oxides require a high temperature. Table 2. Y gives the average temperature values of
the various oxidant-fuel systems used in atomic absorption and flame emission
spectrometry.
TABLE 2.V
TEMPERATURE OF OXIDANT-FUEL GASES USED IN EMISSION AND ABSORPTION
Oxidant-fuel Temperature, °c
air-methane 1880
air-city gas 1900
air-C 3 H s 1925
air-H 2 2025
air-C 2 H 2 2300
N 20-H2 2600
°rH2 2700
02-C 3H S 2800
N 20-C 2H 2 2950
° rC 2H 2 3100
2.3.2.5 Helium-glow discharge

A new approach in obtaining high absolute sensitivity in emission or absorption is the
use of a helium-glow discharge tube. Yurek and Bowman [22] have developed the
technique whereby picomoles of Na, K, Ga, Mg and Zn are determined in various
tissues. The method requires an aliquot of2 to 10nI which contains 10- 13 to 10- 11 moles
of the analyte to a loop of iridium wire sealed within a quartz tube. After purging the
tube with helium, the wire is heated by means of an R-F field. The analyte is excited
in the helium discharge which lasts from 0.1 to 0.3 s. The light from the discharge is
collected by a collimating lens and transmitted through appropriate light filters to a
photomultiplier. The photocurrent is integrated by an operational amplifier for a timed
interval. The output is then displayed on a mirror-scale taut-band meter. As expected
the analyte in a chloride medium is more volatile. Also, the normal anion interferences
of sulphate and phosphate are encountered. This type of interference can be overcome
by the use of radiation buffers.
2.3.2.6 Furnace
Another method of producing atomic vapor is by means of a high temperature furnace.

L'vov [30] made a tube furnace from graphite and attained a temperature of 2700 °C
with a dc arc for 4 s time intervals. An absolute sensitivity of 5 x 10- 11 g was ob-
tained. The major limitation of this technique was the short duration of the arc and the
cumbersome method of introducing the analyte into the furnace. Woodriff and Ramelow
[31] have used a high-temperature graphite-tube resistance furnace which was capable
of reaching a temperature of 3000 °C. The solution is nebulized into the furnace with
argon gas. The authors reported detection limits that were lower than those obtainable
by chemical flames. The graphite tube was found to have a slight memory effect, especially
at the lower temperatures. As this operation is carried out in an inert atmosphere, this
approach offers great potentialities especially for those elements that form refractory
oxides in a conventional flame.
2.3.3 OPTICS
It is the function of the optical system to collect the radiation from the flame and/or
radiating source, render it monochromatic, and focus it onto the surface of the photo-
detector. In flame emission the most advantageous arrangement for studying and selecting
flame regions is to have the flame slightly out of the perpendicular optical path and to
have the light emitted by the flame focused onto the entrance slit by a concave mirror.
The mirror must be of excellent quality so that any small radiant flux from the flame will
be efficiently focused onto the slit. The height of the flame and of the mirror should
be adjustable so that an optimum height or area of the flame can be selected. To find
the best alignment of the flame and mirror, remove the photodetector from the mono-
chromator and place a source such as a mercury or tungsten lamp at the exit slit. By
reversing the light through the optical system the precise area of the flame under investi-
gation can be selected.
Dean and coworkers [2, 10, 22] used a light guide to focus the inner cone and reaction
zone of hydrocarbon flames on the entrance slit. By this method the line spectra of Sb,
As, Bi, Cd, Co, Hg, Pt, Te, Sn and Zn were investigated. This arrangement provided a
method for increasing the line-to-background ratio (L/B).
The major cause of the lack of sensitivity in flame emission spectrometry is an inade-
quate means of spectral isolation. The function of the monochromator is to provide the
maximum resolution of the spectral line from the flame background. Since the half-
intensity width of the spectral line produced in the flame is about 0.1 A, the resolution
of the monochromator should be of this order for maximum sensitivity. Thus the
sensitivity as well as the accuracy and precision of flame emission can be improved with
the aid of a high-dispersion instrument. This offers the possibility of a large L/B increase
and, therefore, a lower detection limit. For that purpose a monochromator is considered
to have relative high dispersion if it has a dispersion of 16 A per mm of slit width or
better. Rains, Ferguson and Zittel [34] have compared the detection limits of a few
elements using a low-dispersion Beckman DU spectrophotometer with a 0.5 m Ebert
monochromator, as shown in Table 2.VI. The instrumental conditions were the same
except for the two monochromators. Also, the same multiplier phototube was used in
each study. Buell [35] has also made a comparison of spark excitation with high and
TABLE 2.VI
COMPARISON OF LIMITS OF DETECTION OF EBERT 0.5 m MONOCHROMATOR
AND BECKMAN DU FLAME SPECTROMETER
Wavelength Limit of Detection (ILg/ml) *
Element A Ebert I Beckman DU
Ag 3383 0.Q2 0.06
Ba 4554 0.1 0.6
5536 0.01 0.09
Ca 4227 0.0009 0.007
Fe 3720 0.1 0.2
K 4044 0.1 0.3
7665 0.008 0.03
Li 4603 0.7
6708 0.0003 0.0009
Mn 4034 0.008 0.01
Ru 3728 0.07 0.2
Sr 4607 0.001 0.006
*) Detection limit is upper 2a limit of background.
low dispersion flame emission. His high dispersion instrument was a grating spectrograph
with a dispersion of 4 A/mm of slit width. It is interesting to note that in his study a
higher sensitivity ratio was obtained than that observed by Rains et al. Other workers
[36, 27] have made similar observations. Prudnikov [38] was able to determine Li, Na,
and K down to 10- 7 % in a I-gram sample without any preconcentration by using a high-
dispersion monochromator and a sensitive dc amplifier.
The sensitivity of any flame emission system is also a function of the light flux reaching
the multiplier phototube. Light traps (a series of mirrors around the flame) have been
proposed by Gilbert [39]. Also, greater intensities are obtained by increasing the slit
height. This has been observed in studies with a 0.75 m Czemy-Turner scanning
spectrometer with 50 mm curved slits.
For atomic absorption spectrometry it has been suggested that a high-dispersion
monochromator is not necessary. This holds true only if the source is free of any other
emitting lines. In general, it is only necessary to separate the resonance line from any
other spectral line. Any emitted line not resolved by the monochromator, whether
from the filler gas or from an impurity in the metal in the hollow cathode, can produce
a severe loss of sensitivity. The neon filled sodium lamp, which has a strong neon line
at 5883 A, has been found to decrease the sensitivity of sodium unless a relatively high-
dispersion monochromator is used.
The need for a high resolving monochromator can be shown in the case of copper
which has two strong emission lines at 3247.54 and 3273.96 A. While the most intense
copper line is at 3247.54 A, an OH band which cannot be resolved lies under this line.
However, the line at 3273.96 A has been resolved from the OH band head at 3274.21 A
with a high-dispersion monochromator. Under these conditions a detection limit of
0.012 !Lg/ml for copper has been reported by Warren [12].
Complete resolution of the magnesium resonance line at 2852.13 A from a strong

OH band head at 2852.71 A has been achieved with a 0.5 m Ebert monochromator [9].
To obtain complete resolution of the magnesium line it was necessary to use a grating
with 30,000 lines per inch with 25 [Lm slits to measure the second order magnesium line.
Under these operating conditions a detection limit of 0.02 [Lg/ml was obtained.
2.3.4 SELECTION OF WAVELENGTH
Another factor involving sensitivity is the selection of the proper wavelength for flame
emission or atomic absorption. Many authors have pointed out that the resonance line
in which the excited atom returns to the ground state is best suited for absorption mea-
surements. Many commercial manufacturers have produced a listing of the most useful
lines for flame emission and atomic absorption. Unfortunately there is no exact or direct
way of determining which line is the most sensitive. To measure percentage absorption
in atomic absorption one usually scans the spectrum with the monochromator and
examines each line which returns to ground state. Margoshes [40] has proposed a
method for the determination of the relative sensitivities oftwo or more lines ofthe same
element. The lines of the elements he tested were in excellent agreement with the theory.
The fact that lines for a given element have different sensitivities can be of benefit
to the analyst. The sodium line at 5890 A is approximately 200 times more sensitive than
the line at 3303 A. The copper line at 3247 A is 20 times more sensitive than the line
at 2225 A. Therefore, it is possible to extend the range of analysis in atomic absorption.
2.3.5 DETECTION SYSTEM
2.3.5.1 Electric circuit
The limit of detection is directly affected by the choice and quality of components for the
electronic circuit in flame emission or absorption. Kelley, Fisher and Jones [41] have
designed and built a dc system which has provided excellent stability and low detection
limits. Since an ac system is essential for atomic absorption, a newer model has been
produced, using a chopped-light-beam system and the output from the multiplier
phototube amplified by an operational amplifier [42]. The ac signal is rectified and the
output fed to additional amplifiers and to the recorder. A provision was made in the
circuit whereby a signal of low intensity could be integrated for a definite time in-
terval. The integrating circuit yielded additional sensitivity in flame emission, especially
when the signal-to-noise ratio was low.
A new detection system has been designed and assembled at the National Bureau of
Standards using a 0 to 2100 V photomultiplier power supply, a selective amplifier and
synchronous detector, a multiple range recorder and digital readout. This system is used
for flame emission and/or atomic absorption spectrometry. The instrument is capable
of performing differential flame emission for high precision studies and scale expansion
of 40 X in atomic absorption [7].
62 SENSITlVITY, DETECTION LIMIT, PRECISION AND ACCURACY [2
2.3.5.2 Multiplier phototubes
The selection of the proper photomultiplier as the detector is essential for high sen-
sitivity and precision. A variety of phototubes are available commercially to detect photon
radiation or emitted light. Several new tubes have been added in the past year and these
promise even greater sensitivity. A few of these tubes are listed in Table 2.VII. The gain
of any phototube depends upon the power supply, which should provide a very stable
dc supply from 0 to 2000 V. For good control the applied voltage should be capable
of regulation in steps of 1, 10 and 100 V.
TABLE 2.VII
MULTIPLIER PHOTOTUBES USED IN EMISSION AND ABSORPTION
Photomultiplier Spectral Response Range, A
RCA-1P28 S-5 2000-7000

R-106 S-19 1600-6500
RCA-6217 S-10 3000-8000
EMI-6256 S-13 2000-6500
EMI-9558AQ S-20 2000-8800
FW-118 S-l 3200-10000
Editor's Note
RCA = Radio Corporation of America
Electron Tube Division
Harrison, New Jersey
R = Hamamatsee TV Co., Ltd.
Hamamatsee-City, Japan
EMI = E.M.I. Electronics Ltd.
Hayes, Middlesex
England
FW = ITT Industrial Laboratories
A Division of International Telephone and Telegraph Corporation
Fort Wayne, Indiana
At the start of the work period, the slit between the photomultiplier and the flame or
source should be opened for at least 15 minutes. This will stabilize the phototube and thus
minimize any drift of its output. The phototube, when not in use, should be stored in
darkness to prevent the photo-cathode being exposed to light. The photosensitive surface
of some phototubes may become fatigued when exposed to light and require several hours
of darkness to become responsive. If tubes, especially red-sensitive types, are protected
from room light for several hours before use, the initial dark current and noise are reduced
and the stability is greatly increased. Also, the tube noise can be lowered by lowering the
temperature of the tube by an appropriate cooling system [43]. This will lead to an increase
in the signal-to-noise ratio.
2.4 Control of analyte environment
The sensitivity of flame emission and atomic absorption spectrometry can be greatly
2.4] CONTROL OF ANALYTE ENVIRONMENT 63
increased with organic solvents. While this increase in sensitivity cannot be explained
completely by a simple theory, there are several contributing factors which help to account
for this phenomenon. Some of these factors are discussed by Alkemade in Chapter 1
of this book.
In the presence of an organic solvent a slight increase in flame temperature, T, is
observed. However, this alone would not account for the enhancement, and other factors
must be taken into consideration.
The physical properties of the solvent, such as viscosity, surface-tension and volatility
would certainly contribute to the nebulization properties of the system. By using any
solvent which would lower the surface tension and decrease the viscosity of a solution
an enhancement in sensitivity has been observed. Many workers [44,45] have added
surface-active agents for example "Non-Ion-Ox" and "Sterox" to aqueous solutions and
they report a significant enhancement. Gilbert [46] has prepared a very comprehensive
list of organic solvents for the various elements studied in flame emission.
Dean [47] has found that in an organic medium the droplet size is smaller and more
uniform. These characteristics greatly influence the percentage of atoms in the excited
state. Since a greater number of atoms are excited in an organic solvent, the emission
spectrum is stronger. Also, greater absorption is observed in the presence of organic sol-
vents. An increase in flame temperature would result in a reduction of the number
of atoms in the ground state; therefore the smaller droplet size is a major factor leading
to a higher population of ground state atoms as well as excited atoms.
The choice of solvent is also important because it affects the rate of nebulization. If
a miscible organic solvent is added to an aqueous solution, the net increase is usually
less than 10-fold because the solution is inevitably diluted by the addition of the organic
solvent. On the other hand any analytical procedure involving a solvent extraction
step is useful because an advantage is gained not only from the increased concentration
but also from the improved atomization efficiency due to the organic media.
2.4.1 WATER-MISCIBLE SOLVENTS
A vast number of alcohols, ketones and organic acids are used in flame emission and
atomic absorption spectrometry. The enhancement observed ranges from 2 to 4O-fold
depending upon the element, the concentration of organic solvent and the type of
solvent [48]. By the combination of organic solvent and fuel-rich flame a vast number
of elements can be determined. Atomic line spectra of the rare-earth elements from an
ethanol medium have been observed in the interconal zone of a fuel-rich oxyacetylene
flame [49]. Many of the high refractory metals such as Re, Ta, Ti, U, Wand Zr were
found to produce line spectra of analytical importance. These lines are not observed in
an aqueous media, and the best results were obtained by dissolving the salt in absolute
ethanol.
2.4.2 NONAQUEOUS SOLVENTS
Water immiscible, nonaqueous solvents are being used in connection with chelating
agents to separate and preconcentrate many elements. The non-aqueous solvent provides
a more pronounced enhancement (IO to lOOO-fold) over the aqueous miscible solvent
when aspirated directly into the flame. Chemical as well as physical interferences are often
removed and this leads also to higher accuracy. The enhancement achieved with organic
solvents also permits the use of more dilute solutions which helps to overcome the effect
of self absorption. However, the use of organic solvents generally does not improve the
precision of flame emission or atomic absorption methods due to the more turbulent
flame conditions.
2.4.2.1 Elimination of matrix effect
Solvent extraction has been applied to remove the major constituent to leave the trace
impurities relatively free of any matrix effect. By this technique a sample pre-concentration
can be carried out to eliminate interference by any high salt concentration. Cadmium has
been determined in uranium by extraction of the uranium with tributyl phosphate. After
removal of any residual organic solvent, the cadmium in a nitric acid medium is diluted
with methanol, and determined by atomic absorption [50]. This general approach can
be used for many elements in both flame emission and atomic absorption.
2.4.2.2 Direct analysis of organic samples
Trace impurities are determined in lubricating oils by diluting the oil with methyl isobutyl
ketone and measuring the absorption of that particular element. Burrows et al. [51] have
compared the results obtained by atomic absorption and by chemical analysis. The
results are in good agreement considering the problems of sampling and the presence of
heavy sludge in some of the samples. The time required for atomic absorption analysis
was only a fraction of the time required for chemical analysis.
2.4.2.3 Pre-concentration techniques
Many elements are extractable with methyl isobutyl ketone from a halide medium. This
has been found to be an excellent way to pre-concentrate certain elements. The organic
phase is introduced into the flame and the emissivity or absorption measured. An en-
hancement of 10 to 150 fold is observed in emission but to a smaller degree in atomic
absorption. A summary of elements which can be extracted with methyl isobutyl ketone
are given in Table 2.VIII. Similarly the extractions involving metal chelates serve as a
rapid means of pre-concentration and separation.
By choosing a general extractant, several of the minor constituents of a sample can be
removed and then determined by emission or absorption spectrometry. A few of the
reagents which are used extensively in solvent extraction are listed in Table 2.IX. Many
of the organic ligands can be made selective by controlling the acidity, and the by use
of masking agents.
Acetylacetone has been used very successfully in the extraction of iron [74]. The organic
phase is then aspirated into the flame and the emissivity or absorption measured. While
this reagent can be used to extract many elements, its use has been limited because of its
high solubility in aqueous media. An excellent substitute for acetylacetone is 2-thenoyltri-
fluoroacetone. This organic reagent can be used as a general extractant for minor consti-
tuents or as a selective extractant by controlling the acidity.
Ammonium pyrrolidine dithiocarbamate (APDE) and diethylammonium diethyldithio-
carbamate (DDDC) are being used extensively in flame emission and atomic absorption
work. The chelate formed can be readily extracted with a variety of solvents. Of the
2.4] CONTROL OF ANALYTE ENVIRONMENT 65
TABLE 2.VIII
EXTRACTION OF VARIOUS ELEMENTS WITH METHYL ISOBUTYL KETONE

(HEXONE)
Element Oxidation State Aqueous Phase %Extraction Reference
Antimony Sb(V) 6-8 MHCI 100 52

Sb(III) 3MHCI 75 52
Arsenic As(V) 8MHCI 30 52
As(II1) 8MHCI 50 52
Bismuth Bi(lII) 5 drops of Kl,
slightly acid (Spot test) 53
Cerium Ce(IV) 9 MHN0 3 78 54
Chromium Cr(VI) 1 MHCI 100 55,56
Copper Cu(II) 5MHBr 85 57
Cu(I) 2 MNH4Br, 35 57
3MHBr
Germanium Ge(IV) 8MHCI 98 52
Gold Au(III) (CI) Tetrapropylammonium
Nitrate, Aluminium
Nitrate 99.5 58
Indium In(lII) 0.5 M NaI, 1.5 M HCI0 4 99.7 59
Iron Fe(III) 4-8 MHCI 100 60,61
Fe(III) 3.5-6 MHBr 100 57
Lead Pb(II) Excess KI in 5 % HCI 97 62
Manganese Mn(II) High conc. of NH4Br, HBr 14 57
Molybdenum Mo(VI) 7 MHCI 97 63
Mo(VI) 5MHBr 95 63
MO(VI) 6 M He!, 0.4 M HF 99.8 64
N eptunium Np(VI) 6-9 MHN0 3 78 65
N iobium Nb(V) 6.3 M H 2S0 4, 1.6 M HF 99.9 66
Nb(V) 10 M HF, 6 M H 2SO 4,
2.2MNH 4F 96 67
R uthenium - 0.1 MK2Cr20"
70 68
0.2 MHN0 3
2.0 M Al(N03h
Selenium Se(V) 8MHCI 100 52
T antalum Ta(V) 2.2 MHF, 1 MHCI 100 69,70
Ta(V) 10 M HF, 6 M H 2SO 4,
2.2 MNH4F 99.6 12,67
T ellurium Te(IV) 6-8 MHCI 92 52
Thorium Th(IV) 1-3 M HN0 3, Ca, Mg,
or Al Nitrate 90 71
Tin Sn(IV) 8MHCI 99 52
Sn(lV) 5MHBr 98 57
Sn(lI) 3.5 MHBr 98 57
T ungsten W(V) 10 M HF, 6 M H 2SO 4,
2.2MNH 4F 26 67
66 SENSI11VITY, DETECTION UMIT, PRECISION AND ACCURACY [2
Element Oxidation State Aqueous Phase I % Extraction Reference
Uranium U(VI) 0.1 % Tetrapropyl-

ammonium nitrate,
0.26 Aluminium Nitrate 99.9 58
U(VI) 2.5 M Aluminium
Nitrate, HN0 3 99.2 72
U(VI) 9 MHN0 3 95 65
U(VI) 0.25 M HN0 3 , Sat'd.
NH4 N0 3 94 73
Vanadium V(V) 8MHCI 87 52
Zinc Zn(II) 5MHBr 80 57
various solvents used, methyl isobutyl ketone is preferred. Benzene and kerosene are
inferior to methyl isobutyl ketone because they produce a large luminous and smoky
flame. Carbon tetrachloride or chloroform can be used; however, the enhancement is
considerably less than that obtained with methyl isobutyl ketone. Again an improvement
in the extraction characteristics has been obtained by using mixed solvents. By using
3 : 1 mixture of methyl isobutyl ketone-cyclohexane the extraction of cesium with sodium
tetraphenylborate has been improved [89]. Cyclohexane is used to decrease the solubility of
the methyl isobutyl ketone in the aqueous phase without changing the burning charac-
teristics of the ketone.
2.4.3 PHENOMENON OF OVEREXCITATION OR CHEMILUMINESCENCE
The phenomenon of exceptional excitation observed in a fuel-rich flame is called over-

excitation or chemiluminescence. Gaydon [100] has defined the phenomenon as elec-
tronic excitation produced by chemical reaction. By this phenomenon, many of the oxide
forming and high refractor elements are excited and observed in flame emission. Gilbert
[101] has observed a rich line spectrum of tin in the reaction zone when an isopropanol
solution was nebulized into an air-hydrogen flame. Some of the lines were three orders of
magnitude stronger than those observed in the conventional manner. Dean and Carnes
[10,32] have reported similar phenomena for Zn, Cd, Hg, As, Sb, Bi and Pt. Fassel et
al. [102] have reported an enhancement of the line spectra of Ti, Th, Y, Nb, Ta, Mo,
W, D, Re and the rare earths in a fuel-rich oxyacetylene flame with ethanol as the solvent.
The enhancement of the oxide bands of Sc, Y and the rare earths has been studied
by flame emission [78]. Chelates of the different rare-earth metals were formed and ex-
tracted into an organic solvent (methyl isobutyl ketone). The organic extract was intro-
duced into an oxyhydrogen flame and the spectra recorded over the wavelength region of
3500-9000 A. By the use of the organic solvent the enhancement of the lines and bands
due to over-excitation was of the order of 100 times the emissivity obtainable in an
aqueous media. Table 2X is a partial listing of the detection limits for the lines and
bands of Y, Sc and rare earth elements.
Buell [78a] has compared the enhancement for several lines which have excitation
potentials of 2.1 to 8.5 eY, as shown in Tables 2XI and 2XII. While most of these
lines are of little analytical importance, it does clearly indicate the enhancement that can
be achieved with an organic solvent under fuel-rich conditions.
2.4] CONTROL OF ANALYTIl ENVIRONMENT 67
TABLE 2.IX
ORGANIC LIGANDS AND SOLVENTS USED IN FLAME EMISSION AND ATOMIC
ABSORPTION
Organic Ligand Solvent Element Material Reference I
HAA MIBK Be Air sample 75,76
Fe AI, Cu, Ni-base
alloys 74
TTA MIBK Al Minerals, Bronzes,
Zn-base alloys 77
MIBK Fe, Cu, Pb, Bi, 9
MIBK Rare-earths Monazite sand 78
2-octanone Mn 79
MIBK Sn 80
APDC MIBK Co, Cu, Fe, Ni,
Pb,Zn Sea water 21
Cu Fertilizer, plants, soil 82
Zn Fertilizer, plants, soil 83
Pb, Bi, Hg, Ni, Sb Urine 84
Co, Cu, Pb, Cd,
Fe, Mn, Ni KCI 85
Cd, TI, Hg Blood, urine 86
Co Cement 87
n-amyl-methyl
ketone Mo Plants, silicate rocks 88
Na-T0B MIBK Cs Sea water, animal
tissue, minerals 89
Dithizone CHCl 3 Hg 90
Cd 75
Oxine MIBK Mg Natural water, brine
solutions 91
Butanol Mo Nb and Ta 92
CHCl 3 Ca 75
CHCI 3 or AI, Cu, Fe, Ni,
MIBK Sn, Mo, Mn 93
DDC MIBK Te 33
CHCl 3 Cu, Ni, Mn AI alloys 91
Cupferron MIBK Al Mg alloys, limestone 77
CHCl 3 Fe CU,Mn 75
MIBK V 96
Salicylaldoxime Amyl acetate Cu Steel 97
DDDC CHCl 3 Cu, Mn 95
As 75
PAN CHCl 3 Cd, Mn, Ga, Y,
Fe, Hg 98
MIBK Co
TPAC , CHCl 3 Ru 99
HAA - Acetylacetone DDC - SodIUm dlethyldlthlOcarbamate
TTA - 2-thenoyltrifiuoroacetone Cupferron - N-nitrosphenylltydroxylamine
APDC - Ammonium pyrrolidine DDDC - Diethylammonium
dithiocarbamate diethyldithiocarbamate
Na-T0B - Sodium tetraphenylborate PAN - 1-(2-pyridylazo)-2-naphthol
Dithizone - Diphenylthiocarbazone TPAC - Tetraphenylarsonium chloride
Oxine - 8-hydroxyquinoline
TABLE 2.X
DETECTION LIMITS FOR SC, Y AND RARE-EARTH ELEMENTS FROM AN ORGANIC
MEDIUM BY FLAME EMISSION
Element
Wavelength 1/2 Band Width Detection Limit *
nm nm (Lg/ml
Sc 670 10 .01
Y 428 5 .1
598 8 .02
614 8 .02
La 741 10 .1
791 10 .1
Pr 604 5 1
Nd 663 8 .4
700 15 .2
712 8 .4
Sm 614 18 .1
624 10 .1
640 10 .1
652 10 .1
Eu 459 Line .05
H
463 .06
H
466 .2
Gd 464 5 .1
622 20 .03
Tb 535 5 .1
573 5 .1
598 5 .1
Dy 528 5 .1
540 5 .2
549 5 .2
573 10 .1
583 5 .1
Ho 516 8 .1
532 5 .2
566 10 .05
Er 504 12 .1
552 18 .1
Th 482 5 .2
494 10 .1
540 12 .1
Y 399 Line .02
Lu 468 5 .05
517 5 .05
I
*) Detection Limit is upper 2a limit of background
2.5] CRITERIA FOR IMPROVEMENT OF PRECISION AND ACCURACY 69
TABLE 2.xI
SPECTRAL LINES RATED HIGHER THAN 4.0 eV
Wavelength, Height of max. Excitation Enhancing

Element
A
I emission, mm I potential, eV
I factor
Zinc 2801 8 12.5 8.5 0

3345.8" 13 7.8 0
Magnesium 3096.9 13 6.7 0
3336.7 13 6.4 0
Cobalt 3676.6 13 6.2 0
Zinc 4810.5 14 6.7 0
Copper 2618.4 14 6.1 0
Lead 3572.7 14 6.1 0
3740.0 14 6.0 0
Silver 5465.5 14 6.0 0
Magnesium 3838.3 14 5.9 0
Manganese 4451.6 14 5.7 0
Silicon 2881.6 14 5.1 0
Boron 2497" 14 5.0 0
Cobalt 3732b 14 5.2 250
Magnesium 5183.6 15 5.1 12
Manganese 4823.5 15 4.9 80
Aluminium 2575.1 15 4.8 0
Calcium 4454.8 15 4.7 41
Barium 3993.4 15 4.3 200
Cobalt 3745.5 15 4.2 25
Iron 3581.2 16 4.3 8
Magnesium 2852.1 16 4.3 2.5
Strontium 4876.3 17 4.3 2.9
Lead 4057.8 17 4.4 18
8 Double. b Multiple.
Reprinted from Ref. [78al by courtesy of Analytical Chemistry.
2.5 Criteria for improvement of precision and accuracy
The precision and accuracy of flame emission and atomic absorption can be improved
by optimizing the operating conditions, the source of radiation and the electronics. The
work of Cellier and Stace [103] should be considered when optimizing working condi-
tions. They used a statistical approach for the simultaneous determination of several
variables. The normal procedure in emission or absorption spectrometry is to test one
variable at a time by the trial and error technique. This procedure, the authors claim,
is time consuming and presents the problem that one may overlook the effect of inter-
actions. The statistical approach in some cases may offer a quick and precise way of
selecting the best operating conditions; however, it must be recognized that stepwise
optimization of conditions is often more convenient.
TABLE 2.xU
SPECTRAL LINES RATED LOWER THAN 4.0 eV
Wavelength Height of max. Excitation Enhancing

Element
A
I emission, mm potential, eV factor
Titanium 3653.5 14 3.4

Molybdenum 3903.0 14 3.2
Vanadium 3184" 15 3.9
Barium 3501.1 16 3.5 76
Aluminium 3961.5 16 3.1 30
Cobalt 3602.1 17 3.7 12
Sodium 3303 b 18 3.7 7.1
Calcium 3968.5 c 18 3.1 5
Strontium 4215.5 c 18 2.9 3.8
Barium 4934.1 c 18 2.5 -
Cobalt 4092.4 19 4.0 13
Chromium 4351 b 19 3.9 10
Iron 3475.9 19 3.7 6.7
Manganese 4033.1" 19 3.1 2.3
Calcium 4226.7 19 2.9 5.5
Strontium 4607.3 19 2.7 1.9
Barium 5535.6 20 2.2 9
Sodium 5893 b 21 2.1 3.2
Copper 5218.2 20 3.8 18
3247.5 22 3.8 14
"Triple. b Double. C Ion lines.
Reprinted from Ref. [78a] by courtesy of Analytical Chemistry.
2.5.1 INTEGRATION OF THE SIGNAL
Several methods have been used to increase the precision of the measurement. Most of
these are based on some form of integration of the output of the measuring device.
The circuit can be heavily damped but a longer time is required for the measurement
and this increases the consumption of sample volume. The use of a strip chart recorder
allows for visual integration of any slight variable signal; however, the ability to read
a value from a strip chart recorder becomes the limiting factor.
2.5.2 DIFFERENTIAL METHOD
Another approach to high precision measurement is by means of a differential method.

It involves the establishment of optimum parameters and the use of a phase shifter
and attenuator in the electronic circuit to expand the scale of the recorder.
The usual approach in flame emission is to prepare a calibration curve of 0 to 80
per cent emissivity over a concentration range of 0 to X fLgjml. The radiant intensity of
the unknown is measured under similar experimental conditions and the concentration
of the unknown is determined from a calibration curve. By this procedure the best ob-
tainable precision corresponds to a relative standard deviation of about 1.0 per cent. A
100
46
80
l!> 42
l!> z
Z
o«
~ 60
w
a:: li! 38
w
w
<i 40 <i
u
u en 34
en
20
30
__~____~__~__- L__
~~1~1
2.0 4.0 6.0 8.0 10 4.60 4.80 5.00

Li,fL9 /ml Li,fL9 /ml
Fig. 2.2. Fig. 2.3.

Typical lithium calibration curve. Lithium calibration curve - scale expanded.
typical calibration curve is shown in Fig. 2.2. However, by expanding the scale as shown
in Fig. 2.3, the relative standard deviation can be reduced to 0.1 per cent.
To achieve scale expansion in flame emission at the National Bureau of Standards [7],
a phase shifter and attenuator has been designed for an ac synchronous detector. The
schematic diagram of the phase shifter and attenuator is shown in Fig. 2.4. (This type
of phase shifter and attenuator is now available in many of the commercial ac lock-in
amplifiers). This modification in the electronic circuit permits any desired concentration
to be set at zero per cent transmission, and then a finite concentration above this value
is expanded to give full scale deflection. In addition, the recorder was replaced with a
digital readout which circumvented the inherent drag of the pen of the recorder and
eliminated the error of measuring the peak height on the chart paper.
To evaluate this new approach to flame emission spectrometry a synthetic sample of
DY203 glass used for neutron flux measurement was prepared. This contained 350 mg
of Si0 2, 200 mg of DY203, 50 mg of Al 20 3, 300 mg of B20 3, and 124.80 mg of Li 2C0 3.
250kD.
IPHASE ADJUST I
~ IOkD.
U
15kD.
c::
ill
'" IMD.
BUCKING VOLTAGE
50kD.
O.OIBfLF IO-TURN
220kD.
100kD.
1
Fig. 2.4. AC buck-out adaptor for synchronous detector.
72 SENSITIVITY, DETECCTION LIMIT, PRECISION AND ACCURACY [2
The synthetic sample was dissolved with HF and HCl0 4 and then the lithium content
was determined using a typical calibration curve and by the expanded scale technique.
The results are shown in Table 2,XIII. The data show that the expanded scale improved
the precision by a factor of three, compared with the conventional calibration curve.
TABLE 2.XIII
LITHIUM IN SYNTHETIC DY203 GLASS (Li ADDED AS Li 2C0 3 -124.80mg)
Li Found Std. ReI. Std.

Average
mg dev. dev. %
Calibration Curve, 124.6 127.2
2-10 [Lg/ml 125.4 127.2
124.2 123.8 124.9 1.3 1.1
124.2 123.8
123.8 124.7
Expanded Scale 125.11 124.48
124.74 124.16 124.63 0.45 0.37
124.48 124.85
TABLE 2.xIV
DETERMINATION OF LITHIUM IN GLASS BEADS FOR
NEUTRON FLUX MEASUREMENT
No. of Li 20 Std. ReI. std.

Material determinations % dev. dev. %
DY203 Glass -A 6 10.177 .013 .13

6 10.147 .025 .25
-B 6 10.065 .024 .24
-C 6 10.123 .033 .33
3 10.067 .022 .22
-D 6 10.181 .014 .14
6 10.146 .018 .17
5 10.181 .10 1.0
-
44
Av. ofX': 10.139 .052 .51
CoO Glass -A 6 10.Q20 .023 .23
-B 6 10.060 .085 .85
6 9.989 .085 .85
4 9.995 .010 .10
-C 6 10.058 .044 .44
7 10.018 .023 .23
-
35
Av. ofX': 10.040 .058 .57
In203 Glass -A 5 10.008 .022 .22
-B 6 10.075 .028 .28
-C 4 10.174 .035 .35
4 10.070 .019 .19
4 10.131 .035 .35
-
23
Av. ofX' 10.087 .064 .64
This technique was applied to the determination of lithium in three different glass
beads used for neutron flux measurements. To obtain a realistic value of the precision
of the method, the analysis of the samples was performed over a period of two weeks
by two operators. The results are listed in Table 2XIV. From these data and subsequent
work, the major limiting factor of the method was the reproducibility in the preparation
of standards.
2.5.3 THE ROLE OF IONIZATION BUFFERS
The radiation intensity of an analyte can be increased by ionization suppression. It is

well known that when the vapour of two or more alkali metals are introduced into a
flame, the radiant intensity of each is increased to a value which is greater than when
only one metal is present. This phenomenon, which is used for increasing the sensitivity
of cesium and rubidium, is due to the suppression of the ionization of the atom [47].
When the temperature of the flame is high enough, metal atoms are formed as a result
of thermal dissociation of the salts. The metal atoms are partially ionized in accordance
with the following equation.
Me~ Me+ + e- (e- is an electron)
As a result, the partial pressure of the neutral atoms of the metal which is responsible
for the radiation of the resonance line is lowered. By the addition of an easily ionizable
species the partial pressure of the electrons in the flame displaces the ionization equi-
librium, and the radiant intensity of the resonance line is increased. Also, the presence
of negative ions such as OH-, 0- and Cl- is observed to have a marked effect on the
ionization. Free electrons may also be present in the flame gases and this will lower the
ionization of the analyte.
The interference from ionization can be overcome by controlling the flame temper-
ature or by the addition of a large excess of an easily ionizable element. This technique
is often referred to as a radiation buffer. It is useful in compensating for any cation-
enhancement. Lithium has been used as a buffer for sodium and potassium while potas-
sium is an excellent buffer for rubidium and cesium. A similar effect is observed for the
alkaline-earth metals. In any case, caution must be exercised in the use of radiation
buffers. Addition of a high concentration of some element will often change the viscosity
to such an extent that poor nebulization will result. Also, traces of the analyte may be
present in the element added and this may decrease the accuracy.
2.5.4 PROCEDURE FOR STANDARD ADDITION
To increase the precision and accuracy of flame emission or atomic absorption when
chemical interference is suspected, the method of standard addition is often used. Although
there are only two basic methods (single and multiple) of standard addition, the method
has a variety of names such as the standard addition method, mixture method, incremental
addition method, autostandardization method, and method of additions. The multiple
method is generally preferred over the single addition method however, the former
method has some serious disadvantages. The curve must be linear and an appropriate
74 SENSlTIVlTY, DBTECTION LIMIT, PRECISION AND ACCURACY [2
background measurement must be obtained. The mUltiple addition method requires that
three to five test portions of the sample be transferred to volumetric flasks. One of the
flasks is diluted to calibrated volume and various increments of a standard stock solution
ranging from 1 to 4 times the amount of the analyte present are added to the remaining
flasks. The flasks are diluted to calibrated volume and the emission intensity or absorbance
measured. The net intensity or absorbance is plotted against the concentration on linear
graph paper. The concentration is determined by extrapolating a line to the abscissa
by the following equation:
y=a+mx
where the unknown concentration, x, is given by the ratio of y to the slope of the line, m,
when the intercept a = o. The method preferred by these authors is the single addition
method with a standard calibration curve. In the single standard addition method, two
replicate aliquots of the sample are transferred to volumetric flasks, A and B. An aliquot
of a standard from a stock solution is added to B and both solutions are diluted to a
calibrated volume. The concentration of the standard addition added to sample B should
give an emission or absorption value that is approximately 50 to 100 per cent of the
value obtained for sample A. The net emission or absorption of sample A and B is then
measured and the concentration for each sample determined using a calibration curve.
If there is a suppression or enhancement due to the concomitant, the standard addi-
tion will be affected in a similar manner as the analyte. The effect of the concomitant
is determined by subtracting the value obtained in A from B. If the recovery was low or
high, the true concentration can be determined by applying the following equation [47]:
S
X· (Y-X) = C
where X = [lg/ml of analyte in unknown (A) as determined from the calibration curve,
S = amount of standard added, [lg/ml,
Y = [lg/ml of analyte found in unknown (B) containing the standard addition as
determined from the calibration curve,
C = concentration of analyte actually present, [lg/ml.
This method can serve as a duplicate determination and at the same time it gives the
analyst some indication of the accuracy of his method. When the correction factor
S/(Y- X) is less than 0.5 or greater than 1.5, the results have a tendency to be erratic
due to the large correction factor. To overcome this difficulty, the sample and standards
used for the calibration curve should be normalized by the addition of a releasing agent,
a protective chelating agent or by the addition of the major concomitant to the standard.
It is not essential in this procedure to prepare the standards in the same matrix as that
present in the unknown sample.
2.5.5 INTERNAL STANDARDIZATION
The internal-standard method has been reported to give an increase in precision over the
direct reading approach. In this method a fixed quantity of a selected element is added
to the samples and standards. The excitation produced by the test element and internal
standard are measured simultaneously using dual detectors, or by scanning both wave-
REFERENCES 75
length regions for the two emission lines. An error due to viscosity or clogging of the
burner can thus be corrected. The choice of a suitable internal standard becomes a major
problem. The two lines should be close together and have similar ionization potential.
Also, the internal standard should not be present in the sample as an error would result.
Lithium has been widely used as an internal standard in flame spectrometry in the
determination of the alkalies. Foster and Hume [104] investigated the effect of high
temperature flames and the addition of an easily ionized element in the determination
of potassium. Rubidium, cesium, or even a high concentration of sodium, were found
to enhance the emission intensity of potassium more than that of lithium. It was con-
cluded that a small amount of lithium is a poor choice as an internal standard for
potassium when elements with a low ionization potential are present.
However, many workers have reported good success using the internal standard tech-
niques. Table 2.XV lists a few elements for which internal standards are used.
TABLE 2.XV
SOME ELEMENTS USED AS AN INTERNAL STANDARD IN FLAME EMISSION
Internal Standard
Element Wavelength, A Reference
I Element Wavelength, A
Na 5890 Li 6708 105
K 7665 Li 6708 105
Li 6708 K 7665 105
Ba 5536 Li 6708 106
Fe 3720 Co 3873 107
Cn 3248 Ag 3281 108
Ca 4227 Mn 4031 109
Mn 4031 Rb 4204 110
2.6 Conclusion
Progress in flame emission and atomic absorption, as shown by lower detection limits and
greater sensitivity, precision and accuracy, is linked with improvements in instrumen-
tation and better understanding and control of the experimental parameters. In this
chapter the various components and procedures have been described with a view to
attaining optimum results. The tables listing the detection limits and sensitivities illustrate
the best values that have been attained sofar. Further improvements can be expected
as advances in instrumentation and better control of reactions in the flame are developed.
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108. J. A. DEAN, Ibid, 27, 1224 (1955).
109. R. H. HEIDEL, V. A. FASSEL, Ibid, 23, 784 (1951).
110. T. NAKAI, R. ISHIDA, S. HIDAKA, J. Chem. Soc., Japan, Pure Chem. Sect., 73, 19 (1952).
CHAPTER 3
SOME CONSIDERATIONS ON OPTICAL DESIGN AND

SELECTION OF SPECTROSCOPIC INSTRUMENTS
w. Muller-Herget
Briarcliff Manor
New York, U.S.A.
3.1 Introduction
The physics of image formation is a rather involved electromagnetic process, which offers
a definite solution in a few special cases only, and these are of mostly theoretical interest.
Development of an optical system with a prescribed performance is usually accomplished
in a number of steps of increasing complexity, ascending from rough approximations to
the level of accuracy dictated by the degree of perfection desired. All design work begins
with the selection of a promising system layout, then application of geometrical optics,
followed by third-order theory and more advanced methods. Most problems can be
adequately treated this way.
The design procedures are by far too elaborate to be described here in detail, but some
insight into the merits, intricacies or disadvantages of the optical principles involved,
may aid the analytical spectroscopist in choosing the type of instrument he needs for his
work on a particular problem.
The following review of classical and some modern instrument configurations is an
attempt to present the conventional spectroscopic instruments as a family, whose mem-
bers are all considered as derivations of the historically earliest form, the Bunsen spectros-
cope.
When considering the general aspects of the Bunsen-system, one may find that its
principal optical sub-assemblies, which may be identified as collimator, dispersing element
and camera system, have necessarily evolved, with continued technological progress, in
various apparently quite different forms of modern spectroscopic instrumentation.
The first problem in spectroscopy is spatial wavelength separation. Existing instru-
mentation for this purpose employs primarily refraction (prisms) and diffraction (gra-
tings), but a number of other methods and devices, which shall not be discussed here,
are also suitable for extraction of spectral information (filters, Fabry-Perot cavities,
rotation dispersion, derivative spectroscopy, Fourier-analysis [1], interference spectros-
copy [2], etc.).
3.2 The compensation principle
When considering improvements of image quality in any optical system, the first step
80 DESIGN AND SELECTION OF SPECTROSCOPIC INSTRUMENTS [3
will usually be to vary the existing layout, in order to obtain minimum aberration con-
tributions from all the elements, or a better balance of aberrations while retaining certain
beneficial features, such as spherical surfaces, non-exotic materials, etc. Because con-
serving energy is an important requirement in spectroscopic instruments, besides mini-
mising stray light and maximising contrast, one cannot afford to add more surfaces to
the system in order to reduce aberrations. In such cases the compensation principle
may frequently be employed with success, and the number of components in the
system may be reduced drastically.
The basic idea is simply to provide to a (linear) system an input value, which is about
equal, but of opposite sign to the system's output under normal conditions. In an optical
system, this can often be achieved by reversing the direction of light at a point in the
system which is a point of symmetry with respect to the sequence of elements penetrated.
Aberrations produced during the first passage through the system will serve as input for
the second passage in the reversed sequence. The system, producing in the second passage
aberrations of the same type and value, but with opposite sign, may completely cancel
out the disturbing effects in the final result. In practice, one will find however, that the
system is either not linear or not quite symmetrical. Anyway, this principle applies to
many situations and it seems to be especially useful in developing system layouts.
Unfortunately, the compensation sometimes also affects desirable system properties and
a compromise must be found.
If we consider, for example, the Bunsen lens-monochromator with a 60°-prism and equal
focal length for collimator and camera, we shall find that the plane which bisects the prism
is a plane of complete symmetry - at least for minimum deviation and its corresponding
wavelength - and application of the compensation principle results in a new system: the
30°-prism lens-Littrow configuration. Since the system is completely symmetrical and
practically "folded back" onto itself, this special case may be called autocollimation. It
is achieved with a plane mirror surface at the plane of symmetry. The monochromatic
aberrations are cancelled for the central wavelength and nearly compensated for others.
Dispersion, however, is not compensated, but doubled.
The magnification of the system is 1 : 1 as a result of the compensation procedure,
which means that length and shape of the spectral lines are identical to the entrance slit.
The system is stigmatic. The inclination of the spectrum to incident radiation is the same
as in the Bunsen-system.
The symmetrically folded system offers a number of advantages over the original lay-
out: fewer optical components, easier alignment, greater mechanical stability and im-
proved economy, since only half the prism material is required.
Other interesting results can be obtained by extending this principle to mirror-
spectroscopic systems and curved surfaces in place of the flat mirror used above. By
optimizing every single component afterwards according to the requirements, sign-
ificant simplicity can be achieved and a number of well known spectrometric systems
appear to be related to each other (see Table 3.1).
3.2] THE COMPENSATION PRINCIPLE 81
TABLE 3.1
Schematic diagrams of spectroscopic systems
1 PRISM-SYSTEMS
1.1 PRISMS WITH FLAT SURFACES
1
T
Fig. 3.1. Bunsen spectrograph
Fig. 3.2. Czerny-Turner spectrograph
:s~ v --
Fig. 3.3. Littrow spectrograph with 60°-prism
It
--- --- ---
Fig. 3.4. Littrow spectrograph with 30°-prism [3]

1.2 PRISMS WITH CURVED SURFACES
Fig. 3.5. Fery spectrograph
1
T
Fig. 3.6. Callier spectrograph
v
Fig. 3.7. Desvignes monochromator
2 GRATING-SYSTEMS
2.1 PLANE GRATINGS
1
1
R
Fig. 3.S. Bunsen spectrograph [4,5 ]
v ------ ______________ _
Fig. 3.9. Czemy-Tumer spectrograph
v -- ______ _
Fig. 3.10. Littrow spectrograph
~--------------
:?~-------=~-J1:;'
Fig. 3.11. Littrow spectrograph
---- -- --
---
Fig. 3.12. Monk-Gillieson spectrograph [6,7, 8]
Fig. 3.13. Ebert spectrograph
2.2. CONCAVB GRATINGS
Fig. 3.14. Concave grating spectrographs after Rowland (e' = 0), Paschen-Runge (8 = fixed)
[9, 10] and others [11].
Fig. 3.15. Eagle spectrograph [12, 13, 14, IS].
1
T
Fig. 3.16. Grazing incidence monochromators [16,17]. Grazing incidence (e ;;;:;; 45°), Seya-
Namioka (e + e' = 75° 15') and others [18, 19].
1
T
v
Fig. 3.17. Wadsworth spectrograph [20,21,22,23,24].

3.3 The coUimator
3.3.1 GENERAL REMARKS
The collimator in general may be considered as an optical subsystem, consisting of an

aperture of small size in comparison to the collimator's length, located on the optical
axis, and an image forming component, projecting the aperture at a specific image loca-
tion.
Many spectrometric instruments, mostly the well known classical types, requjre the
image to be at infinity, i.e., parallel light output. The entrance aperture, the slit, is then
located at the front focal point. Modem instrumental developments must often conform
to other specifications and therefore deviate from this concept.
The entrance slit is normally rectangular (with the longer dimension perpendicular to
the plane of dispersion), but other shapes may be employed, according to the system
requirements and refinements, e.g., curved slits, multiple slits, various slit heights, use of
slit covers, oscillating slits, or no physical entrance slit at all.
For the single slit of conventional type, the minimum slit width is approximately
determined by the Rayleigh criterion (see Sec. 3.3.5). The resolution of the instrument
will then remain unaffected by the collimator design. A much wider slit will result in
lower resolution, since a spectral line is primarily the image of the entrance slit in the
light of this particular wavelength.
The collimator's image forming component may be a single lens, a curved mirror or
any suitable combination of refracting and reflecting elements. In some special systems
it may seem not to exist at all, because its function is executed by other optical components.
The lens design problem for a collimator objective is, in most cases, fortunately much
simplified when evaluating the requirements carefully. As long as the entrance slit dimen-
sions can be considered to be small, the system will operate with a small field angle and the
off-axis aberrations are of little concern. Astigmatism and distortion may be neglected.
Coma remains, but its influence is primarily in the meridional plane, affecting the length
of spectral lines. In some cases, however, astigmatism of the total instrument is so bad,
that there are significant advantages in incorporating a certain amount of compensating
astigmatism into the collimator's objective.
The most disturbing effects arise from spherical aberration. Depending on the state of
zonal correction, spectral lines may appear in different ways, as ghosts, patchy or with
halos. The image quality can always be improved by reducing the free aperture, but the
relative aperture decreases accordingly. More sophisticated objective systems, consisting
of well balanced components, are, in most cases, open to severe objections.
One prime consideration in the spectroscopy of light sources with low radiance, such
as flames used in trace determinations, is to conserve the available energy and to
minimize stray light. The most interesting spectral region for analytical work is the middle
and short wavelength ultraviolet. Glasses exhibit poor transmission and the designer is
forced to look for the best compromise between few available materials, besides economic
considerations. Curved mirrors frequently offer better solutions.
The variation in focus for a collimator with parallel output is a function which changes
slowly with wavelength. There is no need for elaborate chromatic correction of colli-
mator objectives.
3.3] THE COLLIMATOR 87
The influence of chromatic aberration of focal length is of less importance for longer
focal length values:
a:
J_AR
.~.:::'/ "
L f -I
da:
df
=-
f =FOCAL LENGTH AT AO
~
2.f 2
•CON ST.
III =ENTRANCE PUPIL DIAMETER
Fig. 3.1S. Chromatic aberration of collimator lens.

f = Focal length at Ao,
'" = Entrance pupil diameter,
j = ReI. aperture.
Chromatic correction of the collimator objective has a pronounced bearing on the

shape of the camera system's image surface, where the spectrum is formed, i.e., the
spectrum curvature and inclination to the incident light. Its importance is obvious for
spectrographs and scanning monochromators. The necessary refocussing is at least an
inconvenience in spectroscopes and monochromators. The tilt angle produces wider
spectral lines and requires longer exposures in spectrographs.
Better correction of a collimator's objective lens is always required with increasing
relative aperture, but when considering a layout for a particular application, neither
the relative aperture, nor the quality of the lens should be the decisive factor for the
system's spectral output. The collimator, from a system designer's viewpoint, represents
merely the input portion of the spectrometer, which collects the energy and transforms
it simultaneously into a state (e.g., parallel light) suitable for processing by the following
dispersing and spectrum-forming stages.
3.3.2 LENS COLLIMATORS
The simplest collimator objective, a single bi-convex lens, is usually optimized for spherical
aberration by slight deviation from the symmetrical shape. As a rule of thumb, this
technique is satisfactory for relative apertures of 1 : 10 or higher, depending on the sys-
tem requirements for image quality. In order to achieve larger relative apertures, one must
resort to multi-element lenses, and in the case of short UV light to "exotic" materials,
like Quartz-Fluorite combinations. Spherical aberration of a single lens with spherical
surfaces cannot be entirely eliminated, only minimized. Elimination is possible when
introducing at least one aspherical surface. Grinding aspherical surfaces in a repro-
ducible manner and with the necessary surface quality, still presents some manufactur-
ing problems. For single items "aspherizing" is done as a custom job, which requires
much manual skill as well as care in testing. If parallel light output is required, the
specifications for collimator objectives become similar to those for telephoto lenses and
astronomical telescope objectives used in reverse.
All considerations so far apply to one colour only. Simple collimator lenses are thus
optimized for one certain wavelength, which is usually near the centre of the instru-
ment's dispersive range or the spectral region of prime interest.
Doublets exhibit spherochromatic correction for two wavelengths; apochromats may
have three or more null points. As an interesting new development, superachromats may
be mentioned. They produce surprisingly good chromatic correction over a wide spectral
range. However, all these sophisticated systems are of more interest for the spectroscopic
camera system than for collimator objectives.
Lenses as collimator objectives exhibit various losses of transmitted energy, such as
surface losses (selective reflection, polarization, surface scattering) and material losses
(absorption, vignetting and scattering by inclusions, bubbles, schlieren). Some losses,
which cannot be ignored, are typical for instruments in use for a long time (fingerprints
etched into surface polish, scratches, surface deposits by chemical or biological growth,
oil films, decaying lens cement, etc.).
Surface losses by reflection can be suppressed to about 1/2 %, depending on the
material and on the spectral region, by dielectric coatings in vacuum. These coatings
are also selective and optimized for the desired wavelength. Their efficiency depends
strongly on the angle of incidence.
Reflective surface losses are of considerable interest because of possible multiple reflec-
tions between polished and curved surfaces. They produce multiple images and stray light,
thus decreasing contrast. The result is undesirable background noise, when using photo-
electric sensors, or background blurring and many other troublesome effects on photo-
graphic plates.
3.3.3 MIRROR COLLIMATORS
Reflecting surfaces have found widespread application since it became possible to pro-
duce durable coatings of controlled thickness by vacuum deposition of metals and di-
electrics. Mirrors are mostly of the front-surface coated type, but occasionally mirror-
lens combination components (Mangin mirrors) are also used. Front surface types display
no chromatic aberrations. The only losses are caused by selective reflection and poor sur-
face polish quality. Multiple internal reflections as in lenses are not possible, and defects
in the substrate material are of little consequence, as long as they lie below the surface.
With respect to thermal requirements, there is a much wider choice than for lenses.
Aspherical surfaces become feasible, because all the effort in producing the optically
active area is concentrated into a single surface. Of all the unusual shapes of surfaces
that are considered in modern optical design, the easiest to generate on machines is
perhaps the paraboloid; others can always be reproduced by replication techniques.
The ratio of total effort in producing an instrument mirror of given aperture and image
quality compared to a lens of the same performance and size is approximately 1 : 8.
The reflectivity of mirror coatings today may be as high as 95 %in the visible region.
All coatings exhibit a sharp decrease of reflectivity in the UV region, and more gradual
depressions toward the infrared, depending on the material used, and its protective over-
coating. The short wavelength cutoff-problem, when using mirror optics, is shifted onto
3.3) THE COLLIMATOR 89
other components in the system, e.g., the dispersive element or the absorbing gas
atmosphere along the light path.
Single surface collecting systems are of special interest for similar reasons as mentioned
before for simple collimator lenses. The ideal solution for small entrance slit dimensions
and parallel light output is the paraboloidal mirror. It is completely free of spherical
aberration. Coma is a fixed quantity and independent of the aperture location. Astigma-
tism varies with the aperture position and vanishes at the focus. In this case, the object
surface is a sphere with radius equal to the focal length. This means that the slit should
be curved in the plane, determined by its long dimension and the optical axis. If an
image is formed of a long flat slit, the defects resulting from this aberration alone will
be an image of decreasing off-axis sharpness, similar to and superimposed on the
comatic aberrations. The diameter of the paraboloidal mirror is limited only by diffi-
culties in manufacturing within given tolerances. The advantages, however, vanish
rapidly with increasing slit dimensions or field angle, and for practical purposes a semi-
field angle of one or two degrees may be the limit of usefulness.
When using a slit and curved mirror coaxially, the slit assembly will be located in the
centre of the reflected beam. This can be avoided by tilting the mirror, but the resulting
image formation is equivalent to a large field angle, and it is therefore often open to
objection. The solution is the "off-axis" mirror, which, especially in case of the para-
boloidal surface, is becoming increasingly popular, since significant advancements have
been made in recent years in producing large diameter paraboloids by machines. The
off-axis paraboloid is a circular cut-out from a larger diameter paraboloidal mirror,
eccentric to the axis of symmetry. The reflected beam from the off-axis section may
then pass unobstructed the (small) object at its focal point. The off-axis concept is
occasionally found also in multiple component systems.
In cases where the collimator is not a telecentric system, but has finite conjugates,
the optimum surfaces required for simple objectives may become higher order aspherical
surfaces of rotation or modified telescope systems. Depending on the desired performance,
approximations by spherical shapes may be acceptable.
3.3.4 THE COLLIMATOR PHAROID
All rays transmitted through the collimator fill a volume of particular shape, called the
pharoid. Its geometry is determined by the various apertures, masks and baffles of the
optical system, and its volume is limited by the surface connecting the edges of the en-
trance window and the entrance pupil of the collimator.
A simple example is the Bunsen collimator, which consist of a straight slit with dimen-
sions height (h) and width (w) and an objective lens with circular entrance pupil
(diameter 121). The cross section of the pharoid at any distance (d) from the entrance slit is
-a + -;1)
approximately:
L = Ls +d. ( Ls
a = collimator length (slit to lens),

" = a/l2I, inverse relative aperture of collimator (f-number),
Ls = slit dimension, e.g., h or w.
L is a linear dimension of the pharoid's cross section, which is coplanar with L. and
the optical axis. The area is a rectangle HL x WL with all four comers rounded by the
radius (! = d/2·u.
If the slit width w can be neglected, the term l/u will remain. In this case, the pharoid
becomes identical to the Sturm's Conoid.
The concept of the pharoid is useful in instrument design, because it allows visualization
of best locations for masks and baffles, which do not coincide with pupils and windows,
and thus are not determined directly by the theory of apertures developed by M. v. Rohr
and E. Abbe [26].
If the above dimension d represents the distance of an object from the front of the
slit, the pharoid cross section indicates the object area as "seen" by the collimator,
and the collimator in tum is optimally utilized when the pharoid is uniformly filled with
radiation. This will always be the case if the object, e.g., a flame's aspect area, is larger
than the pharoid's cross section. Small light sources cannot fulfill this condition. When
forming an image of a small light source on the entrance slit, the lens system's exit
pupil acts as a secondary source of a diameter which covers the prescribed dimensions.
However, the pharoid's cross section may deviate significantly from a circular area,
especially when astigmatism is present. If it is desirable to conserve energy, special slit
illuminating systems must be designed using, for instance, optical components with
aspheric surfaces.
Light sources like flames and Raman tubes or cuvettes frequently have rather fixed
dimensions and cannot be shaped easily to suit the pharoid, especially if they exhibit
considerable depth. The extension along the optical axis, and the volume given, can be
described by visualizing oftwo cross sections or diaphragms, one in front of the source
toward the entrance slit, and the other on the far side of the volume. They need not be
of equal size or shape. Such apertures may be considered as separate object windows, and
they impose, either directly or by their projections through image-forming lens systems in
front of the slit, restrictions on the pharoid, thus modifying its shape, even within the
collimator. Some considerations of cuvettes and Raman tubes have been given by Hansen
[27], but they apply just as well to flames.
3.3.5 OPTIMUM SLIT wrom
A spectral line may be considered as the result of the combined effects of geometrical
image formation, aberrations, dispersion and diffraction.
While image shape and dispersion can be attributed to specific components in the
system, diffraction contributions are produced by the boundaries of all components along
the optical path. The treatment in detail, even of simple systems, is fairly mathematically
involved, and one usually resorts to considerations of the standard idealized case, the
existence of a narrow and straight entrance slit and a (thin) positive lens system with
circular aperture, receiving light directly from the slit and forming an image at a finite
distance.
The entrance slit thus causes a Fraunhofer diffraction pattern in the image space, and
the aperture of the following image forming system must be at least equivalent to the
width of the zero-order image. This means, e.g., for a simple lens collimator of length s,
slit width wand lens diameter 0 that the relation must hold:
3.4] THE DISPERSING ELEMENT 91
o ::2:: 2A,"s
- w
The circular aperture of the imaging system in turn produces another diffraction pattern,
which limits the image sharpness, and if we accept the Rayleigh criterion, the slit image
width will be:
, 2A,"S'
W =--
o
o is here the exit pupil diameter of the imaging system or the above diffraction pattern
width, if this is the smaller value. s' is the image focal distance.
When closing a wide slit, the spectral line image of stigmatic instruments closely follows
the geometrical magnification {3':
s' = p'. s,
but in the region of very small slit width, where the linear dimensions become comparable
to low multiples of the wavelength, the diffraction rapidly rises in importance and finally
determines the image independent of actual slit width.
The spectral line's brightness meanwhile decreases from a constant level in the geometri-
cal region abruptly, but almost linearly to zero. The optimum entrance slit width in
general is not precisely defined, because of widely different requirements, depending on
the specific application. It will always be a compromise between image sharpness and
brightness [28,29, 30, 31].
The resulting width of the spectral line image can be expressed as wavelength interval
by the linear dispersion value, and is called "spectral slit width."
The optimum slit width is influenced also by the light's state of coherence and polariza-
tion, but these can be neglected in most cases [32].
Detailed discussions have been given by Van Cittert [32], Stockbarger and Barns [33]
and K. Mielenz [34]. Slit width effects in spectrophotometry have been studied by
Hardy and Young [35], by Eberhardt [36] and by Schuster [37].
3.4 The dispersing element
3.4.1 GENERAL REMARKS
The physical qualities of spectroscopic interest common to prisms and gratings are:
angular dispersion.
free spectral range.
resolving power.
definition.
spectral efficiency.
straylight.
The fundamental relationships determining the properties of prisms and gratings may
be found in numerous books on physics, optics and spectroscopy [38, 39, 40, 31, 41,42, 43,
28], and shall not be repeated here in detail except for some remarks of particular interest.
Angular dispersion is the basic property of interest in prisms and gratings, linear dis-
persion is the function governing the wavelength distribution along the spectral focal
curve. The latter is given primarily by the angular dispersion and instrumental para-
meters, related to the camera's focusing properties. It is therefore a different value for each
particular instrument configuration, for gratings as well as for prism mounts.
Resolving power R is usually stated as the inverse of the limit of resolution in the image
space: R = AjLlA., but other measures are occasionally used also. LlA. denotes a "just
resolved" pair of equally strong spectral lines. The resolving power is directly propor-
tional to the size of the image forming beam.
Resolution is more or less a matter of opinion, depending on the criterion adopted for
its definition (Rayleigh, Sparrow, Half-Intensity Width, etc.). The Rayleigh criterion is
commonly used in visual and photographic instruments, while fractional-intensity criteria
are becoming increasingly popular for spectrophotometry.
There will always be the old question of superiority: prism or grating? The subject
has recently been discussed thoroughly under the aspects of modern grating tech-
nology [44, 45, 46]. The conclusion is that both elements have significant advantages
in their various forms and either one may be the solution for optimum results in a specific
application, which again renders the discussion irrelevant.
3.4.2 THE PRISM
Angular dispersion, produced by refraction, is governed by Snell's law, and was

successfully utilized probably for the first time by Fraunhofer in his discovery of solar
absorption lines.
It is only natural that the prism with flat surfaces and triangular cross section has
dominated the field from the beginning of spectroscopy. There is no simpler optical com-
ponent that would be able to deviate a plane coherent wavefront with complete continu ity
and without distortion.
Later investigations have shown that other shapes can be employed just as well. About
fifteen different prism types are known today.
The application of prisms hinges on the availability of suitable materials, i.e., their
refractive index as a function of wavelength. All materials exhibit characteristic absorption
bands, caused by electron resonances. For most materials of interest in the spectroscopy
of atomic spectra, they are located in the ultraviolet and the refractive index n shows a
typical decrease on both sides of the resonance frequency. The most valuable region to
achieve high dispersion is the area with high values of dn/dA..
The classical prism materials, glass, quartz, fluoride, have been supplemented during the
last few decades by a number of synthetic materials in single crystal configuration, some
transmitting down into the vacuum ultraviolet. Materials like quartz, formerly available
only as natural crystals, are now produced as artificial crystals and as homogeneous
materials as well. The degree of purity exceeds the natural material by far and the optical
designer enjoys more freedom in specifying dimensions. The free spectral range in prism
systems may be limited by mechanical obstructions, the size of the cassette, vignetting or
prism material transmission. A prism produces - besides undesirable surface reflections
- only one spectrum, which contains all the incident energy after reduction by trans-
mission losses.
3.4.2.1 Prisms with flat faces
It may be useful to recall a few facts, which are frequently stated without sufficient
emphasis on the restrictions under which they apply:
A prism with two refracting plane surfaces deviates a ray penetrating both surfaces
by a total deflection angle, which can be made a minimum when changing the angle
of incidence at the first surface.
The angular dispersion also exhibits a minimum when changing the angle of incidence,
but it does not coincide with the minimum for total deviation.
The resolving power of a prism, according to the Rayleigh criterion, becomes a simple
expression only for the minimum deviation position. Its maximum value is never realized
because of aberrations of associated optical components, width of slits and granularity
of photographic materials, etc. The resolving power is approximately proportional to the
effective prism base length, if the prism is the natural aperture stop in the entire system.
Changes caused by vignetting and non-uniform slit illumination have been discussed
extensively by Van Cittert and others [32, 33, 47].
The definition of a prism is influenced by its material homogeneity and surface
quality and to a minor extent by unsymmetric transmission near the transmission limits.
The spectral lines produced in prism instruments are always curved, because of different
refracting conditions outside the plane of dispersion. With plane surface prisms, the lines
are parabolas, which can be approximated by circles. The curvature is more pronounced,
if a long entrance slit is used, if the spectral line length exceeds the length of the entrance
slit or if the principal ray is not co-planar with the principle prism cross section. Line
inclination occurs if the prism is inclined to the optical axis ("vertical" systems).
Every surface introduces reflection losses, scattering and polarization. The prism with
flat surfaces is typically represented by the historical 60 degrees Fraunhofer type as used
in the Bunsen-Kirchoff spectroscope. Its contribution to aberrations is minimized when
used with parallel light incident near the minimum deviation position. The prism con-
tributes to all aberrations and there is usually no effort made to compensate for it, except
occasionally for astigmatism.
Surface losses are minimized when observing polarization angles in selecting refracting
edge angle and prism position.
When double-refracting materials are used, the prism is either cut with the principal
ray of the primary colour parallel to the crystal's optical axis, or assembled from two
component prisms, contributing equal amounts of rotary dispersion with opposing sign
(Cornu).
3.4.2.2 Prisms with curved surfaces
If a dispersing prism is to be used in homocentric but non-parallel light, the surfaces must
be curved in order to maintain constancy of the angie of incidence at all points. This is a
necessary condition for uniform dispersion. The meridional cross section (perpendicular
to the refracting prism edge), which will satisfy this condition, is a logarithmic spiral.
As long as the width of the prism face is small in comparison to the focusing distance,
the spiral can be well approximated by the circle of curvature corresponding to the
principal ray, and the prism face may be shaped spherically. The focusing distance is the
length from the real or virtual source to the prism entrance face, which corresponds to
the distance of the image from the prism exit face.
Thus, a prism surface used with diverging incident light will be concave and with
converging light convex. The optical image produced by the refracting surface is also
located on the same meridional circle. The condition of incidence at the first prism surface
is independent of wavelength, but after refraction and its associated dispersion, the light
is polycentric, and the incidence condition at the next or exit surface can be satisfied
correctly for a single wavelength only. The minimum deviation requirement is usually
fulfilled for this wavelength and spectral definition will consequently suffer for others.
The angle of incidence for glass and quartz is of the order of 50 degrees and, as may
be expected when using any refracting curved surface under such extreme conditions,
aberrations are severe, to say the least. This may be the reason why optical designers
often look sceptically at the idea of curved surface prisms in the first place.
Curved surface prisms have been employed successfully, however. The reason is again
utilization of the compensation principle, and the designer may have been unaware of it.
The aberrations produced by the first surface can be counteracted by reversing the beam
after refraction at the first surface, e.g., by an additional mirror surface, as is the case
in the 30o -Littrow system, where the second prism surface is reflecting. The first surface
becomes exit surface and is used optically exactly in reverse, thus producing aberrations
of opposite sign.
Charles Fery described in 1910 a spectrograph based on this principle (see Appendix
A-I). The instrument's entrance slit serves as the light source in the meridional plane. The
first prism surface is therefore concave toward the incident light; the second prism surface
also is concave and has a reflective coating which acts as the auto-compensating *
mirror. The virtual and dispersed slit image, produced by the first surface, is imaged onto
itself by the mirror surface and refracted a second time and further dispersed when
passing the first surface in reverse. The mirror surface, therefore, replaces collimator
and camera objective in a unique way. Since the prism's front surface is simultaneously
entrance and exit surface, all pupils are almost coincident and there is practically no
vignetting in the system for any wavelength. The entrance slit, the prism front surface,
the virtual intermediate spectrum and the final real spectrum are all located on the front
surface's meridional circle.
Spherical aberration is small, because of the small relative aperture commonly used;
coma is negligible for most applications, astigmatism is very high, but spectral line defini-
tion is at least as good as that obtained with flat-face prisms. The entire optical system
consists of only one single element with two optically active surfaces.Its luminous efficiency
with respect to light losses therefore is very high. A more detailed description is given in
Appendix A.
Other curved surface prisms, similar to the system described above, have occasionally
been published [48, 49], but in general they have found very little application in spite of
their simplicity, ease of mounting and other advantageous features, and despite of
favourable reports of surprised investigators [50].
*) The expression "auto-collimation" is here avoided, since collimation in the correct sense
means parallellight.
3.4.2.3 Liquid prisms
Occasionally it is of advantage to employ liquid components in spectroscopic systems.

Liquids exhibit a number of problems, such as thermal sensitivity with respect to refractive
index and volume, difficulties in handling as optical system components, variable optical
inhomogeneity (schlieren) and static pressure deformation of vessels.
One resorts to their use in the laboratory mainly for two reasons, first, when their
transmission and dispersion characteristics are favourable, and second, when they are
feasible for economic reasons. Liquids are commonly used in 60° flat-faced cuvettes, but
combinations with prisms of other materials (glass, quartz) allow construction of direct-
vision (Rutherford) types, with very large apex angle at the liquid prism, and therefore
high dispersion. The transmission of some liquids extends well down to the short wave-
length ultraviolet (e.g., water), and refractive indices may be as high as 2.7 [51,52].
Duclaux, Jeantet and Ahier described the use of liquids in 600 -cuvettes [53], in a
Zenger-prism cuvette [54] and in a large angle prismatic cuvette between glass prisms
as endplates [55].
G. R. Harrison has described a simple vertically mounted Littrow arrangement for
high speed analysis where the liquid surface itself forms the prism surface [56].
A large, high speed spectrograph for the short UV, using water-prisms in quartz cuvettes
combined with quartz-water lens optics, has been developed by Van Heel [57].
3.4.3 THE DISPERSION GRATING
Although the principle of the grating as a mechanical structure of spatially periodic trans-
mission appears to be a simple concept, lack of technological development has in-
hibited its successful application for almost 100 years. Modern master gratings are pro-
ducts of utmost care, patience and precision.
The basic features of a diffraction grating in general are:
type of grating (master, replica, transmission, reflection),
shape or curvature of its blank,
size of ruled area,
total number of grooves,
groove density,
blaze condition and spectral efficiency,
and further quantities characterizing its performance:
angular dispersion,
resolving power,
free spectral range,
spectral line profile and ghosts,
straylight.
Gratings, in contrast to prisms, produce multiple spectra symmetrically on both sides
of the direct image (zero-order spectrum). Higher orders are increasingly deviated, dis-
persed and overlapping, while the brightness decreases. The incident energy on the grating
has, therefore, a geometrically and physically nonlinear distribution within the entire image
space covered by the diffraction pattern. The spectral distribution is further modified by
the special design features of the grating, such as blank curvature or blaze, as well as by
imperfections in manufacturing. The final performance is governed by many parameters

and therefore every grating may be considered as an individual product.
3.4.3.1 Types of gratings and performance

Gratings are usually categorized as masters or replicas, as transmission or reflecting types,
and labeled according to the shape of the blank or substrate on which they are produced,
and their blaze condition.
It has been shown that plane gratings with curved grooves would be of considerable
practical value [58], but the difficulties involved in producing such grooves are still pro-
hibitive, thus all gratings today are ruled with straight grooves, which are evenly spaced
along the tangent, or, respectively, the chord to the surface.
A recent development of a new type is multi-partite grating. These are ruled with
different parameters in up to 13 sections on the same blank.
The free spectral range of a grating is limited by the overlapping of spectra from sub-
sequent lower and higher orders. The wavelength Am in a spectrum of order m coincides
with wavelength Am+l = Am'm/(m + 1) of the order (m + 1)..
A most valuable design feature is obtained by ruling in soft material (in reflection
gratings usually aluminium) and controlling the groove shape, i.e. the angle of the groove
surface, or the blaze angle. The grating's energy distribution or spectral efficiency
can thus be significantly changed by design. Most reflection gratings available today are
blazed according to their specific application, or vice versa, selected accordingly [59, 60,61].
The blaze condition is usually stated by the manufacturer as facette angle or its corres-
ponding wavelength, for which the angle of incidence equals the angle of diffraction. The
wavelength at which optimum blaze occurs depends also on the angle of incidence. It
may be negligible for the visible and ultraviolet, but must be taken in consideration at
grazing angles of incidence.
The blaze efficiency is defined as the percentage of diffracted light at the wavelength A
with respect to the reflectivity of the surface material, the grating coating (mostly alumi-
nium) at the same wavelength. It is inversely proportional to the amount of scattered
light. Very low scattering is of prime importance in Raman spectroscopy. For a selected
wavelength, efficiency can be made as high as 90 %, but in most cases the emphasis is on
wide spectral range. The peak then may reach only 60 %, with a sharp drop at 2/3 of the
blaze wavelength Ab and a more gradual but irregular descent on the long wavelength
side to about 50 % of peak efficiency at
If the blaze peak occurs at the wavelength Ab in first order, the corresponding wave-
lengths in other orders mare
All these wavelengths appear at the same diffraction angle. The blaze peak efficiency
decreases with higher orders. If a large spectral range with several orders is to be covered
by a single grating, it should preferably be blazed for the longer wavelength limit in
the first order [62,63,2].
Highly efficient gratings have little "land," which is the original blank surface between
grooves, left untouched by the ruling process, and therefore a weak zero-order image may
result, containing only 5 to 10 % of the incident light.
The resolving power of modem gratings can be made as high as 90 % of the theoretical
limit, which is a function of the grating width b (perpendicular to the grooves).
Michelson [64] has shown that Rmax = 2b/A. Gratings have been produced with values
Rmax> 106 •
High resolution is required e.g., for work on hyperfine structure or isotopes; large
gratings are necessary for work with faint sources, e.g., in astronomy.
Very undesirable by-products of gratings are satellites and ghosts. It is known today
that all these features are caused by minute imperfections of the ruling machines and
are therefore more prominent in gratings with a large number of grooves.
Satellites, sometimes called "grass," are observable only under the highest resolution
and disappear for most applications within the spectral line envelope. Ghosts [65, 66, 67],
formerly distinguished as Rowland ghosts (intensity typically about 1 % of the parent
spectral line) and Lyman ghosts ( < 0.1 %), belong to a family of many ghosts, which is
the mark of the ruling machine. These disturbances limit the usefulness of resolution in
higher orders, since they increase rapidly in intensity, approximately with the square of
the order number.
There is a constant effort to suppress ghost formation by improving the ruling techni-
que. Values of 10- 4 % of incident light in first order have been achieved.
In a radical departure from conventional methods, with simple means and great inge-
nuity W. R. Horsfield [68] has ruled some experimental gratings which have been found
to be completely free of ghosts and satellites. Significant advancement of the state of the
art can be expected as soon as his techniques gain entry into the sanctuaries of the
grating ruling laboratories.
A technique of using standing wavefronts of coherent laser light for photographic
production of gratings has been under investigation in several research laboratories.
Another technique, continuous ruling on a rotating cylindrical surface, has been intro-
duced by Merton [70] and is becoming increasingly popular for low cost gratings with
lower groove density. Extremely large areas can be ruled, but application to large sizes
is presently prevented by lack of a suitable mounting procedure.
Since dispersion is produced by diffraction on parallel grooves, the same effect can in
principle be achieved as well with grooves which are parallel in the more general sense
of geometry, maintaining a constant distance from a given curve, e.g., by concentric
circular rulings. Although rulings of this type have been known for a long time [71],
they are still primarily of interest to the decorative and jewel industry. Sakayanagi [72]
has investigated concave spherical gratings with circular grooves as a means for aber-
ration correction.
Every application requires a different type of grating. All the requirements and limita-
tions of a particular problem contribute to the correct choice of grating, which is mostly
accomplished by exclusion. Since there is no grating perfect in every respect and the
list of available items is rather limited, the user must classify his specifications in
order of priority by careful study of all grating properties. It is advisable when
dealing with such highly refined products to discuss all aspects with the grating
manufacturer.
Replica gratings
Originally ruled gratings ("masters") are products of high value and the method of
manufacturing used today is not suitable for production in large quantities.
The best solution available at the present time is replication. This process usually
follows the method described by White and Fraser [73].
The original master is ruled in aluminium, which is vacuum-evaporated on glass or
quartz as substrate. The blank is shaped to a fraction of a wavelength and carefully
polished before coating. Another blank is ground to match the surface closely and also
coated with aluminium. Both blanks are joined by an epoxy resin. Mter hardening, the
layers are split and the second part carries an exact image of the master, with inverted
geometry. Several hundred replicas can be obtained from one master grating. They all
exhibit nearly the same properties. The straylight of the master grating is reproduced just
as well and appears in addition to the replica's own contribution. Most gratings com-
mercially available today are replicas.
Transmission gratings
Transmission gratings are ruled on optically flat and polished plate glass. The plate is
used in straight-through transmission. In old gratings, the grooves, by scattering the
incident light, represented the opaque elements of the grating, while the remaining
polished area acted as transmitting slits. Modern gratings are manufactured differently.
The burnished grooves of replicas in synthetic materials add a blaze to the transmitted
light.
The substrate transmission limits the useful spectral range toward the shorter wave-
lengths. The limit for glass is approximately 300 nm. Rulings on a quartz-epoxy substrate
allow transmission to 200 nm. A typical characteristic of transmission gratings is their
high spectral efficiency and little straylight.
The groove density is limited by internal reflections at the blazed groove face. The
maximum useful blaze angle depends on the refractive index of the ruled medium. As a
rule of thumb for visible light, a groove density of 900 lines/mm is about the limit.
Transmission gratings are of particular interest in applications, where associated
optical components must be very closely spaced.
Photographically produced gratings are limited by the graininess of the photographic
plate. However, some gratings with spacings on the order of one wavelength have been
achieved recently in the laboratory by interference of coherent light [69, 192, 103].
Transmission gratings are frequently replicated on the hypotenuse of a glass prism
in order to obtain a "direct-vision" system with minimum deviation (Fig. 3.19).
GLASS
a = 30°
Fig. 3.19. Transmission grating mounted on prism for direct vision.
Reflection gratings
Most gratings in use today are of the front surface reflecting type. They are replicas of
master gratings. The masters are produced by mechanical ruling of grooves with a dia-
mond stylus in a polished surface of metal or a soft metal coating on glass or quartz as
substrate. As many as 360,000 grooves have been ruled on one surface. A groove den-
sity of 4800 lines/mm has been achieved on areas as large as 350 mm square, while
maintaining a groove position accuracy and total accumulated spacing error on the
order of 1/100,000 mm. A resolving power of about one million has been achieved.
The blank shapes commonly in use are plane and concave spherical with an accuracy
of a fraction of a wavelength. Other surface shapes are of interest for reducing of astigma-
tism (see Sec. 3.6.2) but are more difficult to manufacture in quantity and therefore have
found little application.
Commercially available gratings are usually replicas, vacuum-coated with aluminium
or other metals and occasionally overcoated with MgF z or a similar material for optimum
reflection in a specific region. This extends their usefulness from the vacuum-ultraviolet
to the far-infrared.
The plane grating

The theory of the plane grating and its various applications has been established by
Rowland [74], Wood [42], Meyer [67] and Murty [58]. The plane grating has been con-
sidered primarily with parallel illumination, but its use in nonparallel light has found
increasing interest in recent years. The optical aberrations, produced by the plane grating
in convergent light, have been treated by Hall [75].
Plane gratings are the preferred type for all scanning instruments, since they do not
significantly change the focusing conditions, when rotating about an axis through the
grating centre and parallel to the grooves. Some plane grating mounts are stigmatic
over a wide spectral range, exhibit very little curvature and produce no inclination of the
spectral image surface. The aberrations introduced by the grating do not depend
strongly on grating size and therefore allow larger apertures than concave gratings; they
are more economic and available in a larger variety.
The use of reflecting plane gratings imposes inherently some restrictions on the geo-
metry of the system. Optical components, associated with the light input and output, must
be placed on the same side and therefore cannot be as close to the grating as desirable
in order to avoid vignetting in the camera system when imaging a wide spectral range.
If parallel light is used between two optical components the distance will not be critical,
but - if no field lenses are used - the components must be of increased size in order
to maintain the field of view. This relationship requires the camera system apertures of
plane grating spectrographs to be much larger than the collimator beam diameter, e.g.,
in the Czerny-Turner spectrograph the camera mirror is considerably larger than the
collimator mirror; the Ebert mirror is at least three times larger than the grating width.
The situation is quite different for nonparallel illumination. If the grating is illuminated
by intersecting the converging beam of a real slit image, it will merely add dispersion
to the slit image, and the camera can be entirely omitted. The exit pupil will be located
within the grating surface and the diffraction may be observed in all orders over the entire
field of 180°, as far as the obstruction by the grating illuminating components and the
tolerance on image quality permit [6, 7, 76].
100 DESIGN AND SELECTION OE SPECfROSCOPIC INSTRUMENTS [3
In case of grating illumination in diverging light, the collimator may be omitted and
the entrance pupil is located in the ruling surface. The only image forming assembly will
be the camera system, and, because of the wide angle requirement for spectrographs, the
rapidly diverging beam required for higher light-gathering power and its necessary distance
from the grating, the aperture must be a multiple of the grating size. A system of this
type, called inverted Wadsworth-Mount, has been described by Monfils and Vreux [77].
Oose spacing of components around gratings can be accomplished only when utilizing
the autocompensation principle, which leads, in the case of plane gratings, to the Littrow
system. There are numerous publications about instruments using plane reflection gratings
and only a few of special interest can be mentioned here. An explicit account of the two
most important configurations, the Czerny-Turner and Ebert systems is given in Appen-
dix A.
Kudo [78] has investigated monochromators of the Ebert and Czerny-Turner types
by analytical methods and Yoshinaga, Okazaki and Tatsuoka [79] compared these types
in horizontal and vertical mounts with equivalent prism systems by extensive trigono-
metric tracing.
A high speed plane grating mount, assembled with commercially available lens optics,
has been described by Bass and Kessler [5, 80].
An interesting in-line spectrometer, using a plane grating and prism combination in
converging light, has been described by Barnes and Collyer [81] and Murty [58,82].
Early applications of plane gratings used illumination by parallel light exclusively
[83, 84, 85, 86]. In 1928 Monk described a plane grating mount in converging light [6],
which has been treated again by Gillieson [7], and has found an application as a scanning
monochromator by Schroeder [87]. A special case eliminating astigmatism has been
described by Smyth [76].
Blackwell et a1. described a plane grating as an order-sorter in conjunction with a
concave grating spectrograph [88].
The theory of plane grating spectrographs has been expanded and reviewed by
Keussler [89] and by Mielenz [90] while pointing out the similarities between plane
gratings and Littrow prisms.
The concave grating
Concave gratings have been invented during a period when optical design and manufac-
ture had no better solution to the chromatic problems of collimator and camera systems
than odd-material lenses and doublets. The concave surface, commonly a spherical mirror,
uniquely combines in a single element the imaging property of the collimator and, after
dispersive modification by the rulings, the focusing quality of the camera system. All
functions are performed at practically the same location and, therefore, the entrance
pupil, natural aperture and exit pupil are identical with the ruled area. Vignetting is
not possible at all. The concave grating is thus able to cover an extremely wide angular
dispersion range with nearly uniform imaging quality.
The theory of the concave grating was founded by Rowland [74] and has been de-
veloped further by many other authors [42,91-101]. A complete account, including
aspects of different mounts has been given by Beutler [102] and was extended by Namioka
[103-105]. The special problems involved in systems with grazing incidence have been
reviewed by Samson [106].
Work with concave gratings is always troubled by overlapping of spectra of different
orders, small relative aperture and a large amount of astigmatism.
Overlapping orders can be eliminated by suitable filtering of incident radiation. A large

variety of filters of different types are available for the visible and ultraviolet region.
If a small amount of dispersion is introduced in the incident beam parallel to the slit
length ("crossed dispersion"), the grating spectra of different ofders will be displaced
vertically [107, 108]. Such devices are sometimes called "order-sorters". Practically any
spectroscopic system of a spectrograph type can in principle be used for this purpose by
placing it in front of the entrance slit [109-115]. A system using a direct-vision prism has
been designed by Fastie [116]. Blackwell et al. [88] used a plane grating and its virtual
source images for order separation.
Small relative apertures are necessary in concave gratings in order to suppress aberra-
tions, especially astigmatism, and spherical and comatic deviations when used with large
diffraction angles. The spherical grating is astigmatic for all angles of incidence and for
all directions (wavelengths) of the principal rays in the image space, with few exceptions.
The concave grating possesses inherently the image-forming properties of its blank.
It is therefore obvious that in some special cases, the imaging of the spherical mirror
blank of a spherical grating is of good quality. This is true for illumination in parallel light,
if the angle of incidence is zero and the image is formed at the centre of the Rowland
circle (no astigmatism, no coma, positive spherical aberration only), or when the object
(slit) is placed at the blank's centre of curvature and the spherical surface reflects all
rays back onto themselves, without any geometrical disturbance.
Otherwise, as had been shown already by Rowland, useful imaging of a concave
grating takes place exclusively on a cylindrical surface whose diameter is equal to the
grating's radius of curvature, oriented tangentially to the grating centre, with the
cylinder axis parallel to the grooves. The plane perpendicular to the grooves and going
through the grating centre intersects the image cylinder in the Rowland circle.
The entrance slit must also be located on the Rowland circle. Its astigmatic images are
formed by meridional fans (rays within the Rowland plane) on the Rowland cylinder,
and simultaneously by sagittal fans (rays in a plane containing the principal ray and being
perpendicular to the meridional plane) on the sagittal image surface. The latter is a plane
perpendicular to the grating normal and going through the grating's centre of curvature.
This plane is tangent to the Rowland cylinder and intersects the meridional plane in a
straight line, tangent to the Rowland circle at the centre of curvature of the grating. The
distance between meridional and sagittal images, measured along the principal ray of
any wavelength, is the astigmatic difference. It strongly depends on the wavelength.
This means that full astigmatic correction for spectrographs can be achieved only
by a slit illuminating device, which can provide simultaneously various amounts of com-
pensating astigmatic illumination, depending on wavelength. A device of this type does
not exist at the present time, but a number of approximations of various degrees have
become known. Sirks [118] pointed out as long ago as in 1894, that astigmatism can be
compensated for, if the observations are confined to a narrow region about the grating
normal, if the slit is kept in a fixed location and if it is astigmatically illuminated. If
the vertical illumination is produced by a (real or virtual) source located on the corre-
sponding sagittal image surface of the grating in front of the slit, objects in this loca-
tion will be sharply imaged and the setup can be used for comparison spectra or photo-
metric work. Runge and Mannkopff [119] have described concave mirrors and spherocylin-
dricallenses for astigmatic compensation (see Sec. 3.6).
If a grating is used under high angles of incidence, a number of special problems may
occur that do not appear when the arrangement is used for middle and long wavelength
ranges; the grating efficiency will depend on surface conductivity and coating material, on
groove vignetting and on the precision of blank shape. The slope of the surface may cause
the ruling stylus' heel to dig in the surface, depending on groove shape and blaze angle.
A condensed review of history and techniques in the vacuum-ultraviolet is given by
Tousey [120]. Finally it may be mentioned that most statements about grating imaging
are approximations obtained by discarding all contributions of series expansions beyond
a certain order, or by forced vanishing of a variable. Refinement in theoretical treatment
leads to improvements of existing configurations [121-124].
A concise account of the state of the art has been given by Strong [117].
A listing of modem and more popular concave grating mounts may be found in many
handbooks [125,28, 31, 39, 102, 126, 127, 106].
3.5 The camera system
We shall now consider the general aspects of the spectrometer's image-forming sub-
system, which for simplicity may be called the camera system. The purpose of this part
of the instrument is to transfer the dispersing element's output to the detector area, and to
produce the type of image required for the given instrument class (monochromator,
spectroscope, spectrograph, polychromator, etc.), or for specific applications.
This wide-ranging problem has naturally no universal solution. Each type of instrument
includes inherently a camera system of a different nature and anyone type may appear
with a different optical design of its components, depending on the specific application
for which it is optimized. In general, we can find that the design requirements for camera
systems are mainly dominated by the field angle or the angular extent of the spectral
range specified.
For monochromators, where only one single wavelength at a time is of interest and
all observations of any wavelength take place at the same physical location, at the exit
slit, the field of view is practically zero and imaging conditions are - in reverse - very
similar to those for the collimator system. Aberrations will also be of similar magnitude
and influence since the camera's. aperture is always nearly the same as the collimator's.
For use in conjunction with external detector devices (eye, phototubes, etc.) or other
instrumentation, suitable transfer optics with respect to beam direction, relative aperture,
beam shape and aberrations, must be provided.
In spectroscopes, a certain small portion of the spectrum is observable simultane-
ously and the field of view is not negligible. Spherical aberration and coma must be
removed. Careful chromatic correction is desirable in order to avoid inconvenient refocus-
ing for different wavelengths. The camera systems for this application are of the telescope
type, mostly astronomical inverting telescopes, because they have less components and
therefore less light loss than others. The telescope is adjusted to accommodate the dis-
persing element's output, which is mostly parallel light (flat face prisms; plane gratings).
The most careful considerations need to be given to spectrographs. The performance
requirements, such as high speed, wide angle, high resolution and wide spectral range are
in general contradicting for any lens design. The result will always be a compromise in
favour of one or the other, whereas cost commonly determines the limit.
The size expensive dispersing element is in most cases the aperture determining
factor and the other system components must be tailored to suit the requirements. It is
3.5] THE CAMERA SYSTEM 103
usually possible without too much effort, to find a relation for optimizing collimator
aperture for a given grating or prism aperture. The camera system should be developed
with at least the same resolution as that provided by the dispersive element. Typical
instrumental limitations, e.g., vignetting, must be considered in every case separately. It
is often surprising how fast the luminosity drops in a given instrument, when testing at
other wavelengths slightly off the design center. Such effects can explain the large varia-
tion in performance of low quality instrumentation.
In contrast to collimator design considerations, simple mirror optics for spectrographic
cameras are much more critical than lens objectives, as a comparison of aberrations for
different field angles reveals. The spherical mirror turns out to be superior to the para-
boloidal shape for light of any vergence. Lens systems can provide many more degrees of
freedom to the designer for aberration work. Serious restrictions are imposed by spectral
transmission of conventional materials and by the limited-choice of exotic materials. High
speed and high quality lenses can be produced much easier in short focal lengths, while
wide angle lenses are better made with small relative apertures.
Requirements for monochromatic image quality, which include all applicable aberra-
tions over the entire spectral range, pose tough problems to optical design. In order to
minimize the most inconvenient deficiencies, certain sacrifices must be made. The first
step is to reduce the aperture. This leads to the small relative apertures usually found in
wide range spectrographs. The optimum width or diameter of components in certain
grating instruments can be derived from grating theory, depending on required resolution.
Most spectrographs are designed for use with photographic plates, especially if the
application involves linear mensuration. This requires a flat image, which is here to be
understood as a polychromatic image, as opposed to the flat field requirement in photo-
graphic lens design. The field curvature is caused by the combined effects of all optical
components, primarily by the dispersing element and the camera's chromatic aberration,
but other instrumental parameters can also play an important role. It has been shown for
instance by Mielenz [128], that the distance between the Ebert mirror and the grating
determines the field curvature and thus the useful spectral range. The dimensions would
be entirely different for other applications, e.g., an Ebert monochromator.
The position of the spectrum in relation to incident radiation is in general oblique,
which is a characteristic property of all spectrographs containing lenses. This is tolerable
in spectrographs as long as the angle does not exceed 70-80°. Exposure times become un-
reasonable, and the plate flatness becomes critical. For the all-quartz Bunsen spectro-
graph J. Hartmann [129] has found that the spectrum is located along a spiral with the
prism exit face at its origin and that the photographic plate is inclined to be almost
parallel to the collimator axis.
A very undesirable aberration is astigmatism. It results primarily from optical elements,
used under wide field or off-axis conditions by design. It is an inherent property of grat-
ings. Its appearance and magnitude depend entirely on the method of illuminating the
grating, the angle of incidence and a possible off-plane condition. All spectroscopic sys-
tems exhibit some degree of astigmatism, however, the amount over the spectral range is
small enough in only a few types to justify calling them "stigmatic." Only stigmatic
systems are useful for applications which require discrimination of entrance slit height,
such as spectrophotometric procedures using wedges, Hartmann diaphragms, comparison
prisms or direct imaging of extended sources onto the entrance slit (interference spectro-
scopy, heliospectroscopy, etc.), and some types of slitless spectrographs.
Astigmatism is objectionable in spectroscopes and spectrometers. In astigmatic spectro-
graphs (see table below), only one astigmatic image surface is utilized without any attempt
for correction. Some systems of this type, in spite of all, produce fine spectra with remark-
able resolution over a very wide spectral range. Most systems use the meridional surface
for imaging and therefore always exhibit strong curvature, but fortunately it is mostly
a circular cylindrical surface like the Rowland- or Fery-cylinder.
The following table lists the major systems used in spectroscopy with respect to
astigmatism of their basic spectrometric layout, disregarding any special measures or
auxiliary devices for stigmatic compensation.
TABLE 3.II
ASTIGMATISM IN SPECTROSCOPIC SYSTEMS
(for detailed descriptions, see Appendix A)
Stigmatic types Astigmatic types
Bunsen Fery
Littrow Callier
Czerny-Turner Concave grating mounts after:
Ebert Rowland
Wadsworth Paschen-Runge
Monk-Gillieson Abney
Eagle
Beutler (radius)
Seya-Namioka
Onaka-Johnson
Some systems, e.g., the Monk-Gillieson type, exhibit widely varying astigmatism and
field curvature and do not fit well in either category. A great number of ideas for correction
of astigmatism in spectroscopic instruments have been discussed in the literature. Most
of them involve aspheric surfaces, primarily cylinders. All propositions using lenses are
strongly dependent on wavelength and therefore usually result in pseudo-stigmatic con-
figurations, which are really stigmatic for one certain wavelength only.
The logical application of the compensation principle (Sec. 3.2) to concave grating
instruments results in an astigmatism compensating condenser, consisting of a single
spherical mirror, and used under large off-axis angles, as proposed by C. Runge and
R. Mannkopff [119] and Smyth [76]. Since the amount of astigmatism on the concave
grating is a function of wavelength, compensation can be achieved exactly for one wave-
length only and the system is also pseudo-stigmatic. Other wavelengths necessitate diffe-
rent angles of incidence or different mirror curvature. The sphero-cylindrical lens arrange-
ment, described by the same authors, utilizes the natural dispersion of the refractive com-
ponents and is able to deliver a limited sharp spectral range, still insufficient in com-
parison to the wide range capacity of the concave grating.
Murty [130] has described a cylindrical mirror as an astigmatic correction between
concave grating and spectrum. Similar considerations apply to astigmatic corrections
in Fery-prism instruments.
The astigmatism generated by the concave grating, illuminated by parallel light, can be
sufficiently compensated by a spherical mirror collimator, as has been shown by Beutler
[102] for the Wadsworth system. A paraboloidal collimator would have disadvantages.
These findings verify again the result of Czerny and Turner [25, 131] on two-spherical-
mirror combinations, if the grating spacing between adjoining grooves is made to
approach zero.
The improvement when using a spherical collimator rather than a paraboloidal one is a
typical example of the complexity of optical design. One cannot expect in general to
3.6] ILLUMINATION OF SPECTROSCOPIC INSTRUMENTS 105
obtain an optimum configuration by simply combining optimized sub-assemblies. Careful

balancing of all components involved will always deliver better results. For this reason,
many of the aforementioned general statements should be considered only as giving a rough
picture. The same holds true for evaluation of any given instrument; the entire system
must be considered, because every optical component contributes to the output in its
particular way, which is fully known only to the designer. A more detailed explanation
ofthe influence of astigmatism on luminosity and slit illumination is given in Sec. 3.6.2.
A polychromator may be considered as a separate class of spectroscopic instrumenta-
tion, which is becoming increasingly popular with progress in development of inte-
grated opto-electro-mechanical systems. It may be considered with respect to its applica-
tion as a multiple simultaneous monochromator and the requirements for the single mono-
chromator apply to each channel. Thus, the optical problems involved are entirely different
from those of adjustable or scanning monochromators. The requirements are merely
those of a spectrograph with less demand for spectral line quality, since the output is
"filtered" by exit slits and sensed by opto-electronic devices. A typical example for an
early large scale application is the analytical instrument described by Hasler [132] and
Saunderson et al. [133].
The detectors may range from the familiar selenium cell in instruments of higher relative
aperture to refined solid state photosensitive devices, or from the old fashioned phototube
to sophisticated electro-optical intensifier-scanners. For photoelectric detection and mea-
surement of isolated spectral lines or bands, image quality is usually not important; in
spectra with high resolution, however, intensity measurements become critical. When
astigmatism is present, as in the case of concave gratings, the dispersing element may
receive in different places light from different portions of the source, resulting in system-
atic photometric errors.
Background radiation in polychromators may be rendered negligible if the speed of
the system can be increased sufficiently. A plane-grating polychromator with high angular
dispersion may fill the need for a compact and convenient "multiple channel filter." High
dispersion will allow maximum resolution at short imaging distance, thus resulting in
radiation separation within a minimum volume, and providing sufficient space to accom-
modate the required number of detectors of given physical dimensions.
In view of the requirements on the camera system set by the field angle alone, it seems
obvious that the properties of any spectroscopic system will vary drastically with design
specifications. A layout developed for a monochromator will not be suitable for a poly-
chromator without serious drawbacks, or as an analogy from photography: a telephoto-
lens is not suitable for wide-angle pictures.
3.6 Illumination of spectroscopic instruments. Luminosity and astigmatism
The method of presenting the light source to any spectroscopic instrument must necessarily
be selected to suit the particularities of the system, the source and the application. The
most important performance parameters are optical flux density for photographic work,
and stigmatic coordination. For photo-electric work with integrating detector circuits,
the total flux as the balance against straylight and spectral bandwidth, is of greater
significance. A brief survey of light sources shows that the design requirements
are widely different, and one may expect that there exist at least as many special solutions
as light source types:
point-like sources (stars, small arcs, sparks),
line-sources (Geissler tubes, long sparks, meteor trails, filaments),
area-sources (arcs, hollow cathode tubes, gaseous microwave discharge devices,
fluorescent and phosphorescent areas, surface reflections, apertures
of lenses or mirrors, intermediate instrument images),
volume-sources (flames, Raman-tubes, fluorescent or phosphorescent gases or liquids,
diffused or scattered light, three dimensional intermediate optical
images).
It may also be necessary to give further consideration to spectral energy distribution,
coherence and polarization.
3.6.1 STIGMATIC INSTRUMENTS
When using stigmatic instruments, the problem is usually to fill the entrance pharoid
uniformly with light. This can be achieved in two different ways, by imaging the source
onto the entrance slit or by imaging the source onto the collimator objective.
a. The light source (Q) is imaged on the entrance slit (8) with magnification {J' by use
of a rotation-symmetrical optical system (L). It may be a single element positive lens or
a well corrected lens system and may include centered, on-axis mirror components
(Fig. 3.20).
C
,
--.~~'~ HORIZONTAL
PLANE
I I I
I I I I
I I I I
I I I I
I I I
--~~~
r -- ---
VERTICAL
PLANE
Fig. 3.20. Imaging the light source on the slit.
The horizontal plane is the plane in which the slit width is measured, the vertical plane
is coincident with the slit's height or length. The spectral lines are stigmatic and simultane-
ous images of slit and source-image. It is thus possible to obtain a spectral cross section
through the source along the line, which is equivalent to that portion of the flame which
is imaged within the slit and reproduced in the spectrum. The correct illumination of the
collimator (8-C) depends on the source size and the aperture of the condenser lens (L).
The slit width is usually very small in comparison to the light source image, and the
condition for correct imaging in the horizontal plane is merely to match there1ative aper-
tures of the condenser lens output beam and collimator. The entrance window to the
collimator in the vertical plane, however, is determined by the slit height. This requires
the light source to be of a minimum dimension in vertical direction as may be seen when
following the rays penetrating the condenser lens centre. Simultaneously, the aperture
of the collimator objective must be fully illuminated by the same beam. Thus, the pharoid
geometry and the condenser lens position are determined. A field lens, imaging the con-
denser's aperture onto the collimator aperture, may be added in front of the slit. This
element will contribute to a more uniform illumination of the collimator objective and
require a slightly larger slit, but it is usually omitted because of its additional losses. In
some special spectroscopic systems, which do not contain a collimator objective, the dis-
persive element will be used instead for above considerations. This type of slit illumination
is mostly used and it is suitable for all light sources that can be imaged with sufficient size
and appropriate relative aperture. It is not useful, without further modifications, for point-
like sources which are diffraction-limited (stars, very narrow line sources). For distant
objects oflarge angular extent (aurora,night glow,nebulae) the condenser may be replaced
by telescopes, which combine light gathering power with suitable relative aperture (Casse-
grain- or modified Schmidt-systems). Transfer optics of similar type are available for low
radiance, large area and volume emitters at finite distances. Cuvettes for absorption
spectroscopy with long axial dimensions may also be treated as volume emitters [27].
Special optical systems have been devised for unstable sources (arcs, sparks) [134] and
for spatial and time dependent scanning (angular sweeping, flashes, transient phenomena).
A point of practical value which is frequently neglected may be worth mentioning
here. While it presents no problem in most cases to project a source image on the slit
with the required magnification and relative aperture, success also depends on correct
coaxial alignment of the incident beam and collimator, which is critical, and in addition
sometimes on image rotation, in order to match a tilted or curved slit. Incorrect alignment
results in vignetting, increased straylight and loss of resolution.
b. The source (Q) is imaged by a rotation-symmetrical optical system (L), that is

positioned in front of the slit (S), directly onto the collimator objective (C) or the dis-
persing element (Fig. 3.21).
~1
Q LS~C
---~I --- HORIZONTAL
PLANE
I ; 1 I
I I I I
I I I I
I I I
___
:
~~
:1~1 ___ VERTICAL
- ---- PLANE
-- T----
Fig. 3.21. Imaging the light source on the collimator lens.
The spectral lines are images of the slit, but not the light source as in case 3.6.1.a.
Every point of the slit now transmits light from all points of the source. The condenser
lens acts as a secondary light source with approximately the same luminance as the source
itself, and every slit point transmits light from all points of the source. This setup, thus,
cannot be used for recording a spectral profile of the source. It is, however, most useful
for photometric measurements because of the uniformly illuminated slit.
In order to obtain full coverage of the collimator objective aperture, the source must
be of sufficient size in both planes and the relative aperture of the source, as "seen"
from the center of the slit, must be the same as the collimator's, in contrast to the method
3.6.1.a. The source size or distance will determine the required magnification and thus
the condenser's optical specifications. This method of illumination is obviously more
suitable for applications involving emitters with large area and volume.
In both methods described above the source, and respectively its image, produces
the same luminous flux in the slit aperture, and if the pharoid is correctly filled with
light, there will be basically no difference in throughput. Loss in resolution will occur
if the source is of smaller extent than the pharoid cross section at the source location,
the entrance window.
Lenses, especially those of simpler design, produce chromatic aberration of focal length
and magnification. The imaging conditions for condenser lenses are therefore correctly
fulfilled for one or two wavelengths only, which results in a spectral range limitation for
the entire spectroscopic system. This can be eliminated when using reflective optics for
the condenser system.
c. A further development combining the advantages of the above methods with intensi-
ty control is the triple condenser system, which is frequently preferred for quantitative
analysis when using inhomogeneous light sources (Fig. 3.22).
The lens L1 images the source onto a diaphragm B, which eliminates undesired zones
in the intermediate source image (electrodes, inner cone of flames, etc.) and transmits
the selected radiation to field-lens L 2 • The diaphragm B, acting as a secondary light source
is imaged by lens L3 onto the collimator objective C, while producing uniform illumination
of the entire slit length. Light flux and spectral line illuminance can be controlled if B
represents a variable aperture, e.g., an iris-diaphragm. This system, by suitable modifica-
tions, is adaptable also to astigmatic illumination.
~ - ----
3.6.2 ASTIGMATIC INSTRUMENTS
Similar to the distinction between vertical and horizontal planes used in Section 3.6.1,
one must clearly observe relations in different planes when considering astigmatic sys-
tems.
A luminous point source, as lens theory shows for any astigmatic system, is imaged on
two image shells simultaneously, a meridional surface and a sagittal surface. Consequently
two images of a source will exist along the principal ray in the image space, and they do
not resemble the original object in size or light distribution.
Only the concave grating as a typical representative of astigmatic spectroscopic instru-

ments shall be considered here. In this case, the plane perpendicular to the rulings and con-
taining the grating normal may be regarded as the meridional plane; the plane through
the grating centre and containing the optical axis, while being perpendicular to the
meridional plane, is the sagittal plane. These definitions hold true for the incident and
for the reflected beam separately.
A luminous point-source is imaged by the grating in two short lines, each located in its
corresponding image surface at the intersection with the principal ray. The meridional
image line is parallel to the grating grooves; the sagittal line is parallel to the direction
of dispersion, which is within the meridional plane in all systems with zero off-plane angle.
It may be assumed without restriction in generality that the grating is utilized in the Row-
land circle mount for locating the slit and photographic plate. The meridional image sur-
face then contains the entire Rowland circle.
3.6.2.1 Stigmatic illumination
The slit may be considered as consisting of a chain of many small luminous elements; the
meridional and sagittal slit images will consist of as many line images partially over-
lapping each other lengthwise. The slit images therefore have no point to point corres-
pondence to the slit, which shows the nature of each astigmatic image line. A spectral
source profile can thus not be obtained by an astigmatic system and irradiance along both
image lines is non uniform, at least at the ends of the line.
The concave grating's spectral focal curve is in the meridional shell and spectral lines
are meridional image lines. The intensity profile along the spectral line's long dimension
is nearly trapezoidal in shape, the plateau-width depending on the slit length. A critical
minimum slit length must therefore be retained in order to obtain the maximum irra-
diance corresponding to the plateau, as has been shown by Oldenberg [135].
The stigmatic slit illumination, as described under 3.6.1.a and 3.6.1.b, would result in
image formation with the full amount of astigmatism, as determined by the grating, spread-
ing the available energy over an extended area. The average luminous density at the photo-
graphic plate will be considerably less than in stigmatic instruments of comparable design;
the luminous density in the plateau region will be the same.
Astigmatism can be compensated, at least partially, by modifications of the optical
elements involved, which means in most cases introduction of inconvenient aspheric sur-
faces, or by additional elements. An approach employing anamorphic optics throughout
for increasing luminosity has been used by Eisner [140].
In order to reduce the sagittal extent of the meridional image, additional sagittal con-
verging power is needed in the image beam, or, equivalently, less diverging illumination of
the grating's input. Both ideas have been tried out. A positive cylindrical lens between slit
and grating with the cylinder axis in the meridional plane will reduce astigmatism not
only for one wavelength, but within a limited spectral range, because of the chromatic
variation offocallength. Unfortunately, the associated magnification of slit height cancels
out the possible increase in luminous density [136, 137].
Cylindrical elements between grating and spectrum have been successfully used by
Gehrke [138], Back and Goudsmith [139] and others, thus retaining full dispersion while
decreasing line height. Because of the refractive elements used, the method is also limited
to a certain spectral range. Dispersion can be increased slightly when using negative
optical components, which is useful for high resolution work with gratings, where the
detector is the limiting factor.
A cylindrical mirror arrangement proposed by Murty [130] appears to be useful over
a wider spectral range. Further improvement may be achieved by going to a higher degree
of asphericity, e.g., a conoidal saddle-surface.
The best solution with a single modification, however, is to eliminate the problem at its
roots, e.g., by using a stigmatic dispersing element. In the case of the concave grating,
there are two possibilities of particular interest. First, the correct geometric solution for
imaging an object point obliquely by a mirror is the ellipsoidal surface, and second, the
nearest conventional approach to the ellipsoid in optical technology is a toroidal surface
[141,142]. The theory of the ellipsoidal grating has been treated by Namioka [100, 101]
and Greiner and Schiller [143]. Haber [144] has given a rather complete account of
the grating ruled on a toroidal concave surface. The spectra should appear up to 50 times
brighter than in spherical gratings of comparable dimensions. The technical difficulties
involved in producing such gratings are not beyond the state of the art, since Sch6nheit
[18,145] introduced the toroidal grating in a Seya-Namioka monochromator.
3.6.2.2 Astigmatic illumination
Because of the optical equivalence of object and image, the slit of a concave grating mount
can be visualized as being exchanged with anyone of its meridional images (spectral
lines), if the same wavelength is considered. If a source is imaged in the meridional plane
directly on the slit, and the sagittal component is simultaneously produced by a virtual
source image in the appropriate location within the sagittal plane, the resulting image,
after reflection on the grating, will be a stigmatic image of source and slit. This is in short
the principle of Runge and Mannkopff's [119] method for astigmatic compensation by a
sphero-cylindrical condenser system (Fig. 3.23). The horizontal plane is identical to the
meridional image plane.
L S G P
---~~f ,
,
:
I
I
I
~ HORIZONTAL
I I I PLANE
I I I I
: : I
I I I I
--- ~:-=-=-=--==rl~------\_~
T VERTICAL
PLANE
Fig. 3.23. Astigmatic illumination.
The light source (Q) is imaged by the sphero-cylindrical condenser (L), which is shown
as two separate components for clarity, one spherical lens and a cylindrical lens with its
axis parallel to the slit S. The cylinder lens' refractive power adds to the spherical conden-
ser with respect to the meridional plane, thus forming an image of the horizontal source
dimension at the slit, while in the sagittal plane no refractive power contribution is deli-
vered and the source image for vertical dimensions is formed at the astigmatic element (G).
If G is a concave grating with its own imaging properties - in Fig. 3.23 schematically
indicated by a lens - it can be seen that the source will be stigmatically imaged on the
photographic plate (P). The apertures and spacings of the three elements L, S, G deter-
mine the minimum slit height.
The irradiance of the photographic plate is increased and it is equal to that of a
stigmatic mount of equivalent dimensions. The stigmatic spectral range obtained in such
a way is again restricted, because of the refractive components used, as explained in
Sec. 3.6.2.1.
In general, any astigmatic situation can be compensated by a set of two cylindrical
lenses with axes crossed 90 degrees in place of the spherocylindricallens mentioned above.
Detailed discussions may be found by Harrison, Lord and Loofbourow [31] and
Rosin [146].
3.6.3 SAMPLING AND ABSORPTION CELLS
In contrast to the optics of the condenser, which gives efficient transfer of radiation
from the emitter to the spectrometer, sampling cells are commonly inserted between
emitter or condenser and spectrometer entrance slit. Frequently they must satisfy
simultaneously the matching conditions of the condenser and the collimator, and
meet certain beam geometry requirements in order to assure correct illumination.
The predominant problem in sampling is absorption ofthin solids, liquids, vapours and
gases. Mirror systems are the preferred choice for their simplicity, economy, freedom from
chromatic aberrations and minimum straylight. They are, however, often associated with
partial obscurations or poor accessibility of the sampling area. The optical systems in-
volved may be considered as aperture converters. These can be single lenses or mirrors,
composite objectives with finite object and image distances (Schwarzschild type) or varia-
tions of telescopic systems (Cassegrain type), depending on the specific application. Fig.
3.24 shows, as an example, a possible back-to-back combination of two inverted Casse-
grain systems, which could be employed for probing a large volume with a narrow pencil-
beam of parallel light or for testing a strongly absorbing material of small size when
parallel light is required.
v
r-------,
--- iE---ll=~====:::::;;::::n-----=~
L _______J
Fig. 3.24. The pencil-beam probe.

S = source, SL = slit, V = test volume.
A two-mirror combination, similar to a Czerny-Turner system without dispersing

element may be used for testing a large volume or a large area in parallel light (Fig. 3.25).
Fig. 3.25. Large working volume in parallel light.

S = source, SL = slit, V = test volume. 26;;:;; 5°.
Weak absorbers require long optical path length, but the volume or geometrical length
within the material is frequently limited. It is then necessary to resort to multiple-pass
systems. Double passes can be easily achieved with one or two optical components.
Examples are shown in Fig. 3.26 and Fig. 3.27.
---
Fig. 3.26. Double pass sampling in nonparallel light.
S = source, SL = slit. Off-axis total deviation 26 ~ 5°. V = test volume, C = centre of curva-
ture.
Multiple pass systems with any number of reflections can be made by sending a beam
slightly inclined to an axis of symmetry into a symmetrical system of mirrors. The
emerging beam must be suitably separated from the incident beam with respect to the
linear distance between the points of entering and leaving the system, and with respect
to angular deviation. This may require some additional components and may possibly
result in vignetting of valuable beam portions. Each mirror surface contributes to loss of
energy because of imperfect reflectivity and surface scattering. Aluminized front surface
mirrors for instance, having 90% reflectivity at a given wavelength, will diminish the
signal in 10 reflections by a factor of 0.9 10 or down to 34 %. Straylight and irregular reflec-
tions from mirror surfaces contribute to increased background radiation. Special atten-
tion must be given to sampling cell mirrors in optical design because of possible damage
to exposed surfaces and coatings by chemical corrosion.
\
\ \
\ v I
\ \
\____ --1
~~~~=---------J~~~~~~*:~~
I I _- -~. tF
II __ - -
\..L----- SL
Fig. 3.27. Double pass sampling in parallel light.
S = source, SL = slit, F = focal point. The off-axis paraboloid shown can be substituted by
a spherical mirror if the off-axis angle is e ~ 50.
A serious problem is always presented by the aperture. Most configurations permit a

small relative aperture only. A typical example is the assembly of two parallel plane mir-
rors. If a beam of parallel or nearly parallel light enters the space between the plates, it will
continue going zig-zag from one plate to the other. The larger the distance between the
mirrors and the higher the number of reflections, the smaller is the allowed deviation
from parallel. The mirror surface required for subsequent reflections grows in propor-
tion to their number.
Multiple path systems have been described by Kratz and Mack [147], Smith and
Marshall [148], White [149] and others [150, 191].
The system of Smith and Marshall can be derived from the double plane mirror cell
by a few modifications. Its operation may be described as a recycled autofocusing process.
The first mirror is spherical concave and the source or its condenser image is placed
near the centre of curvature off-axis by a small amount. The source, is thus imaged
on the opposite side of the mirror axis at the same distance from the mirror (first and second
pass). If a small plane mirror is placed perpendicular to the principal ray at the source
image position, the beam will be folded back and the next source image will be super-
imposed on the source (third and forth pass).
Separation of the incident and emerging beam can be achieved by modification of the
plane mirror. It is replaced by an angle-mirror (Fig. 3.28) in such a way that the inter-
mediate focus (F2 ) is brought on to the concave mirror's axis, short of the centre ofcurva-
ture (C), and the beam returns to the concave mirror under a different angle of incidence
(82 > 81 '). After reflection (8/ = 82), the beam will then emerge (fourth pass) on the
opposite side (F3) to the point of entrance (F1 ), without interference with the angle
mirror. The relative aperture will remain unchanged.
If the size of the angle mirror is extended outward from the axis, the exit focus (F3 )
may be intercepted and the cycle repeated, thus adding two more passes through the cell
system.
The number of passes is limited by the mirror reflectivity. Each additional pair of passes
is associated with three more reflections, and limited by the increasing off-axis angles.
-------------, FI_~_
EI __~~~~~
+c
-'
Fig. 3.28. Multiple pass cell by Smith and Marshall.
Other components (mirrors, prisms) may be necessary in order to produce convenient

angular separation of input and output beams. Other folding techniques used with this
type of cell have also been described by Smith and Marshall (loc.cit).
The long path absorption cell by White (Fig. 3.29) consists of three concave spherical
mirrors, located at their conjugated radii position. Higher relative apertures can be covered.
The first and last passes, however, require larger off-axis angles with corresponding loss
of image quality.
r----- -----------,
I
L ________________
=-
~
SL
Fig. 3.29. Multiple pass cell by White.
3.7 Monochromators and double-monochromators
A convenient direction of output versus input is a desirable feature for monochromators.

A favourable configuration is straight throughput, where the monochromator can be used
like a transmission filter. In most cases, however, the output is under some angle to the
input and displaced parallel to it [19]. A 90°-deviation is often acceptable for laboratory
instruments. Additional components, which introduce all their particular disturbances,
must be incorporated in order to achieve certain prescribed angles. Some monochro-
mators employ Newtonian mirrors or prisms in order to achieve angular separation with
3.7] MONOCHROMATORS AND DOUBLE-MONOCHROMATORS 115
'1:tt.=-,-=-=-=-=- - - __ _
--------
,
I
Fig. 3.30. A modified Ebert prism-monochromator using Newtonian mirror-prisms.
minimum off-axis angles. These auxiliary elements produce a central obscuration for
the central beam and oblique vignetting in off-axis beams.
Two monochromators switched in series make a double-monochromator. The main
characteristic of this type is the central slit, which is common to both systems. Both sub-
systems are usually, but not necessarily, of identical design. It is also possible to utilize
one system in a multiple-pass mode [155, 156, 157, 158, 159, 152, 153].
Double-monochromators are employed primarily where high spectral purity or mini-
mum stray light is required. The monochromator portions can be combined principally
in different ways to form a double-monochromator, as aiding or as opposing systems. The
direction of dispersion in an aiding system is the same in the secondary section as in the
primary section, just like combining two 60°-prisms with their apical edges on the same
side in order to increase the total dispersion. The opposing type double-monochromator
is equivalent to the combination, which has the prism bases on opposite sides. There is
principally no advantage of one system over the other with respect to performance. A
distinction can be made only when wide slits are used, i.e., the bandwidth is very large
in comparison to the diffraction limit. One or the other configuration is commonly
selected for reasons of mechanical instrument engineering, e.g., for ease of movement of
interacting components when using Thollon prisms. Correct "tracking" always presents
a major design problem, since the system output depends on correct wavelength coinci-
dence in both sections. This can be accomplished in aiding systems, by choosing identical
optical design for both sections and moving the intermediate slit in the direction of dis-
persion. It results in a minimum number of moving parts. The associated shift in beam
direction causes vignetting and can be eliminated by field lenses.
Such systems, because of their symmetrical layout, lend themselves readily to deviation
compensation by "optical folding." Feasibility of double-monochromators is not limited
to stigmatic systems as has been demonstrated by Leiss [160].
Numerous solutions have become known, using cascaded monochromators of practic-
ally every configuration. Single dispersing elements have been used with as many as four
passes through Littrow- and Fery-prisms (Fig. 3.32 and 3.33) and six passes on gratings.
General surveys on monochromators and double-systems have been published by Vodar
[161, 163], Fortrat [162] and others [154, 151].
116 STRUMENTs
ECTROSCOPIC IN
LE cn ON OF SP [3
DESIGN AND SE
'I'
1,1
~/
-~-
i iss.
mator after C. Le
double-monochro
Fig. 3.31. A Fery
-- -- ------~T-
-
chromator .
pass Littrow mono
Fig. 3.32. A four
--
i
onochrom ator by Vodar.
Fig. 3'.33. Fery-m
3.A-l] rHE FERY SYSTEM 117
APPENDIX A
A-I The Fery system
This system was described first by Charles Fery in two publicatIons in 1910 [164] and
1914 [165]. It consists in principle of three components only, the entrance slit, the
Fery prism and the detector or photographic film (Fig. 3.5). At first glance, its appear-
ance may bear some similarity to the Littrow mount with lens and flat-face prism (Fig.
3.3) and the application of the compensation principle by backfolding can be recognized.
However, by its functional characteristics it may be considered as the closest prism-
counterpart to the concave reflection-grating. The common method of mounting is indeed
identical to the Eagle mount (Fig. 3.15).
The optical principle ofthe Fery prism has been described in Sec. 3.4.2.2. Its advantages
may be summarized as follows:
The entire optical assembly - besides slit and detector - consists of one single element.
Two surfaces only must be ground and finished to optical quality.
The volume required for the prism material is relatively small, thus precious materials
can be used economically.
The two surfaces are used, one in double pass for refraction, the other for internal
reflection. The latter must be reflective coated and can be easily protected against corro-
sion and mechanical damage by additional coatings.
There is practically no vignetting present because of near coincidence of all pupils and
apertures.
An extremely wide spectral range can be imaged simultaneously, long spectra photo-
graphically recorded, and high dispersion can be achieved, especially at the short wave-
length end of the spectrum.
Straylight is negligible for all practical purposes because of the small number of sur-
faces intersecting the optical path, and because internal and surface reflections do not
reach the spectrum location directly.
Entrance slit and spectral lines are straight.
Image degradations by spherical aberration and coma are very small for relative aper-
tures of 1 : 12 or less, and sharp spectral lines are produced.
The luminosity, in comparison with other configurations, is relatively high for spectro-
graphic applications.
The commonly employed mounting method (Eagle) is simple, compact and sturdy.
The prism is relatively insensitive to misalignment and environmental effects.
As disadvantages may be counted:
Astigmatism is very high, the astigmatic difference being of the order of several meters,
and accessories requiring stigmatic imaging cannot be used, unless special condenser
optics are employed.
Entrance slit, prism front face and spectrum are located on a common cylindrical sur-
face, similar to the Rowland cylinder for concave spherical gratings. In mountings of the
in-plane type, the image cylinder intersects the plane of dispersion in the meridional image
circle, sometimes called the Fery circle, which is the equivalent to the Rowland circle on
gratings. When changing the angle of incidence at the prism, all components in the Fery
system must change their positions in exactly analogous ways along the FI~ry circle, thus
requiring the same motions and rotations known for Eagle-mounted gratings. Vodar [161]
and other authors [163, 162] have described mechanisms which allow employment of the
Fery system as a monochromator. A monochromator in double pass has been described
by Leiss [160], but has probably never been constructed. The relative aperture of the Fery
prism cannot be increased sufficiently to compete with other systems with respect to
luminosity. It is therefore not very suitable as a monochromator, in spite of its straight
lines and good resolution. Some manufacturers supply spherocylindricallens systems for
astigmatic slit illumination. The spectrum is strongly curved, depending on the instru-
ments "focal length," thus requiring photographic film rather than plates.
Very few applications have become known in the literature. Fery made some
remarks in his 1914 paper about utilization of a prism without reflecting coating in
straight through transmission, but no applications seem to have evolved as yet.
Table 3.111 shows some typical data for the Fery spectrograph.
TABLE 3.111
THE FERY SPECTROGRAPH
Distance prism to spectrum (mm): 700 1000 3600
Prism height (refracting edge, mm): 30 50
Relative aperture: 1 : 20 1 : 15 ~ 1 :20
Dispersion, avg. (A/mm): 10.0 0.5 1.0
Spectral range (nm): 110-1000 180-2500 200-800
Remarks: 1) 2) 3)
1) Several prism materials used (lithium fluoride, quartz, runt). Vacuum UV.
2) Crystal quartz prism.
3) Commercial, highest dispersion spectrograph [166].
A-2 The Desvignes monochromator
While the Fery prism with its spherical surfaces may be considered as a marginal section
of a large, thick, positive meniscus lens, the prism after Desvignes appears to be of com-
plementary nature, a section of a large negative meniscus lens. Its convex surface is also
coated for internal reflection. There is, however, a fundamental difference in the prin-
ciples involved. The Fery prism is used under a distinct off-axis condition with respect to
its spherical surfaces, while the Desvignes prism is an on-axis device. It belongs, therefore,
in the same category with systems utilizing longitudinal chromatic aberration of refractive
elements for spectral separation [167]. It can be extended to become a completely rotation-
symmetrical component.
The points C1 and Cz are the centres of the refracting or, respectively reflecting sur-
faces. Light emitted by an axial source Q is refracted and dispersed by the first surface,
reflected at the second surface and dispersed again when penetrating the first surface on
its return, thus forming spectral images near C 1 on the optical axis, which is defined by
C1 and C z•
If the location for Q (at a given wavelength A.) is set to:
C1 Q ='1· n;.,
the second surface will reflect in autocompensation and the image will be stigmatic and
3.A-3] THE CZERNY-TURNER SYSTEM 119
·
·· ·
I
• - - tI -
-t
""-..I
Fig. 3.34. The Desvignes prism.
aplanatic. Images corresponding to other wavelengths nearby will exhibit very small aber-
rations (except distortion) and images of longer wavelengths are situated closer to the
prism.
Surface reflections are focused on the optical axis on the long wavelength side in loca-
tions where they can be easily eliminated. Some internal reflections of first and second
order are trapped between the prism surfaces by total reflection and do not contribute
to straylight. Comparatively large relative apertures can be utilized and the system
luminosity is therefore very high.
Desvignes has described different mountings for monochromators and given an ac-
count of the systems' performance. He also pointed out the possibility of employing
liquids as dispersing materials [49]. The following table shows the characteristics of some
monochromators that have been designed according to this principle using flint and
quartz prisms.
TABLE 3.IV
DESVIGNES MONOCHROMATORS
Entrance slit length (mm): 15 20
Spectral range (nm), quartz: 240-450 220-450
flint: 390-1200 380-1200
Solid angle (sterad): 0.053 0.022
Relative aperture: 1 : 3.9 1:6
A-3 The Czemy-Tumer system
When investigating different mirror spectrometer systems, M. Czerny and A. F. Turner

discovered in 1930, that a considerable difference in resolution exists between so called
u- and Z-shaped configurations [25, 131] which is primarily due to coma (Fig. 3.35).
Leo gave a more quantitative explanation [168] and pointed to the importance of beam
width. He concluded that different focal lengths should be used for collimator and camera,
especially when the dispersing element is not used at the condition of symmetry (minimum
deviation of prisms). His considerations have been extended by Shafer [169]. Fastie found
empirically a simple relationship between the angles included by the principal rays before
and after reflection on the mirrors [170], and Rosendahl made extensive calculations on
several spectrographs [171]. Allemand recently gave a more rigorous treatment of the
coma-problem [172], which contains Fastie's relation as a special case.
Two nUll-positions for coma can be established within the spectral range of interest
by careful selection of optical design parameters. These investigations are of particular
interest for the design of flat field photographic spectrographs.
-------- ------
---
--- --- --- --- ---
Fig. 3.35. The Czerny-Turner system.
Short focal length instruments can be made with large relative apertures. The spherical
aberration will be of the same order of magnitude as coma, if the relative aperture is
about 1 : 10.
The conditions with respect to straylight are in principle similar to those outlined for
the Ebert system, but less intensity is experienced, and direct irregular reflections as on
the Ebert mirror are not possible.
Most spectrometers of this type are in-plane meridional mounts, i.e., the centres of
entrance slit, both mirrors, the plane grating and the spectrum are located within the
same plane, and the slit length, the grating grooves and spectral lines are perpendicular
to this plane.
Off-plane or vertical systems are characterized by having all the features mentioned
above, except the spectrum's extension, contained in one common plane, similar to the
vertical Ebert mount (Fig. 3.36).
If a prism is used the refracting edge (apex) will stand in place of the grating grooves
in the above considerations. Prisms can be employed in straight through transmission
(Fig. 3.2) or in double pass in conjunction with Littrow mirrors (Fig. 3.35).
A number of such configurations have been investigated by Kudo [78] by means of
3.A-4] THE EBERT-FASTIE SYSTEMS 121
extensive ray tracing. Those assemblies had been proposed originally for infrared appli-
cations, but the results can be extended as well to other spectral ranges.
As in all plane grating instruments, a straight entrance slit produces curved spectral
lines and vice versa, and the curvature depends on the wavelength. No condition has been
found as yet for design parameters under which the slit shape would be independent of
wavelength.
In order to achieve best spectral purity in monochromators, both slits must be set
exactly at the foci of the mirrors and the exit slit should match the image. Therefore, if one
slit is straight, the other must be curved or both may be curved with a larger radius.
Early publications have employed two-dimensional theory for these systems, but only a
three-dimensional theory can fully evaluate all aspects, as has been shown by application
of the two-mirror system eikonal-theory developed by Kudo [loc.cit.] and Mielenz [90,
128,173].
The nonconcentric Czerny-Turner system is not very suitable as a spectograph in the
vertical configuration, because its image quality is surpassed by the mechanically simpler
vertical Ebert. When comparing the in-plane systems, however, one will find that the
optical performance of the Czerny-Turner system is superior in almost every respect;
mechanically, there are some restrictions and inconveniences (alignment), as can be
expected in a system of higher complexity.
The "Czerny-Turner" is today a familiar sight in every spectroscopic laboratory. With
respect to other spectrometer systems, it may be considered as the basic configuration
for mirror spectrometers, just as most lens-and-prism instruments can be derived in
principle from the Bunsen concept by modification of one or the other optical component
(Sec. 3.2).
The Czerny-Turner is basically a stigmatic system. It appears in the literature and
on the market in numerous variations [152, 153, 174-178]. Relative apertures as high as
1 : 3.5 can be found. The "focal length" ranges from small 200 mm-monochromators to
several meters in large, flat field spectrographs. Flat faced prisms as well as large plane
gratings can be used - the former primarily in the infrared - since the dispersing element
is illuminated by parallel light. An extremely wide spectral range can be covered when
using interchangeable gratings.
Historically, it has triggered the rediscovery of the Ebert system. It provides the designer
with additional degrees of freedom because of its separately adjustable mirrors, and recent
developments have shown that the system is capable of extremely high resolution and
excellent image quality limited by the grating only, which places it in the class of best
quality instruments available to the spectroscopist.
Table 3.V shows some typical data for a variety of Czerny-Turner instruments.
A-4 The Ebert-Fastie systems
When searching for a suitable spectrometer W. G. Fastie [179] found in 1952 a modific-
ation of the Czerny-Turner system, obviously not being aware of a practically long for-
gotten and misjudged system described by H. Ebert in 1889 [180]. The following develop-
ment is reflected in numerous publications. It resulted finally in two different configura-
tions, a considerable improvement of Ebert's original in-plane (or horizontal) layout and
the off-plane (vertical) system modification suggested by Fastie [116, 181, 182].
....
1:'1
TABLE 3.V
CZERNY-TURNER SYSTEMS
t:l
Instrument type Spectrograph Monochromator Double monochromator Spectrograph m
Focal length (mm) 750 300 3000 1000
~
Collimator, type spher. aspher. spher. spher.
rel. aperture 1 : 6.3 1 : 5.3 1 : 18 ~
mirror dia. (mm) 152.4
Slit, type bilat. bilat., straight bilat.
width x height (mm) 0.005-0.4 wide (0.01-0.2) x 20 0.1 x20 0.1 x20
Grating ~
ruled area (mm) 102x 102 50x50 ~
grooves (lin/mm) 1200 1200 1180 1200
blaze 37°
avg. disp. (A/mm) 10 26.5
spectrum; length (mm) 127 (l05)
spectral rante (nm) LlA = 125 105-16000 175-40000 LlA = 300
resolution ( ) approx. 0.4-2.0 0.6 0.035 0.1
Camera, type spher. aspher. spher. spher.
I
e
n
mirror dia. (mm) 254 ~
Remarks: 1) 2) 3) 4)
~
1) Effective rel. aperture given; geometr. rel. apert. 1 : 4.7; plate size 127 x 152 mm; max. A = 500 nm.
2) Incidence at Collimator and Camera: 4°. Entrance and exit beams crossed by 44°. Resolution stated at slit 0.01 x 4.0 mm; half width; first
order. Housing vacuum tight.
I
3) Several gratings. Two horizontal mounts stacked vertically. Common grating shaft. Straylight approx. 1 : 10 10 at 1 nm from parent line.
4) Incidence at Collimator 5° off axis ; at Camera 10° off axis. Coma corrected for two wavelengths. Grating incidence 30°, exit 40° at A = 500 nm.
ow
The system is a special case of the more general two mirror arrangement with separate
elements for collimation and imaging, as represented by the Czerny-Turner configuration.
The centres of curvature are coincident and the mirrors have thus been replaced by one
larger spherical mirror. The entrance slit is located in the focal plane off the mirror axis,
and the light passing the slit is reflected and collimated by the mirror toward the dispersing
element. The latter may be a reflecting flat face prism or a reflecting plane grating, but a
grating is the common choice. After passing this component, the light, still being essentially
parallel, is reflected a second time on the mirror and focused at the spectrum's location
in the focal plane. The image of every point of the slit for the central wavelength is formed
diametrically opposite to the slit with respect to the mirror axis and at the same distance.
The grating is centered on the axis, but not at the focal plane.
The configuration with slit, grating and spectrum positioned in the plane perpendicular
to the grating grooves is the original in-plane Ebert mount (Fig. 3.13). If the elements
are placed in a plane parallel to the grating grooves and containing the mirror axis, the
layout is an off-plane type spectrometer and called the Ebert-Fastie system (Fig. 3.36).
Kaiser, Rosendahl and Mielenz [183] and Krshenovskii [184] have given a two-dimen-
sional theory of the Ebert system, which was subsequently expanded by Vierle [185]. The
eikonal treatment of the system was developed by Kudo [78] and Mielenz [90, 173], with
a later expansion to the three-dimensional theory [128]. It has been found in general
that the in-plane mount is more practical for monochromators and the off-plane mount
for wide range spectrographs.
Fig. 3.36. Ebert-Fastie spectrograph (schematic).
The in-plane system can be developed for very high resolution and for high output.
Following the suggestion of J. Strong [186], Fastie introduced curved slits and tested
their feasibility experimentally [179, 181]. The slits are located at the focal distance from
the mirror and on the Ebert circle, following its curvature. It is thus possible to employ
very long slits and simultaneously increased signal output without sacrifice in resolution.
Circularly curved slits are necessary in order to achieve maximum resolution. Because of
the basic symmetry most aberrations are self-compensated. The grating is employed in
parallel light, which minimizes its aberration contributions. The system's geometry easily
allows adaptation to large grating sizes, which is the prerequisite to obtain high resolving
power.
As may be expected, however, in any system with spherical mirrors used under large
off-axis imaging conditions, the Ebert-Fastie spectrometer still exhibits some residual
aberrations, coma and astigmatism. They are noticeable mainly in the spectrograph at
those locations which deviate significantly from the self-compensating symmetry, e.g., at
the ends of the spectrum. The meridional astigmatic image line is tangential to the Ebert
circle. The total residual image quality depends on slit length and grating angle. Elimina-
tion of coma and astigmatism by variation of the system's geometry is not possible. A
noticeable improvement, however, has been pointed out by Baker [187] and Welford [188]
when replacing the mirror by a paraboloid.
Similar to the Czerny-Turner system, the width of the diffracted beam is, in the Ebert
system, also different from the incident beam. The requirement of Leo [168] for different
focal length cannot be satisfied here.
If a straight entrance slit is employed, the spectral lines, or respectively, the exit
slit will be parabolically shaped and vice versa.
Scanning is usually achieved by simply rotating the grating about an axis in the direction
of the grooves through the center of the ruled area. All other components are kept
stationary.
In place of long slits, the Ebert circle can be divided in small segments, each with its
counterpart of anti-symmetric curvature located diametrically opposite. If small mirrors
inclined at 45° are placed near these positions, linking the output back to the input, mul-
tiple passes through the entire system can be achieved, resulting in extremely high
resolution [189].
Some light passing the entrance slit may reach the exit slit directly after a single reflec-
tion on the Ebert mirror. This is the major source of straylight in this type of instrument.
It can be eliminated by suitably placed masks on the mirror or baffles around the slits.
Irregular reflections are more pronounced at short wavelengths.
The area of best image quality in the in-plane system is just opposite the entrance slit
at the same distance from the mirror axis (Ebert circle). In order to keep the off-axis angles
as small as possible, the distance axis-to-slit is reduced to the amount just permissible
by the grating size. The Ebert circle is reduced also and the spectrum length impaired by
the grating obscuration. This disadvantage for application as a spectrograph is eliminated
when choosing the off-plane Ebert-Fastie arrangement (Fig. 3.36).
The entrance slit in the Ebert-Fastie spectrograph must be straight and perpendicular
to the Ebert circle. It is located in the focal plane, above the axis and grating, while the
spectrum is formed in an equivalent distance below the grating. The spectral lines ~re
straight, and at the centre wavelength, they are also perpendicular to the Ebert circle.
There is no obscuration by the grating and the useful spectrum is approximately twice
as long as in the in-plane mount.
The situation with respect to image quality is different from the in-plane mount. The
major amount of most aberrations is still self-compensating, but the contributions by the
grating are larger and the wide field spectrograph utilizes oblique imaging. The spectral
lines are parallel to the sagittal image lines and astigmatism and coma are increasing with
spectrum length. The entrance slit therefore must be short and the grating location must
be selected as a compromise between image quality and field flatness. Wavelength deter-
mination by linear interpolation must therefore be applied with caution. High tilt angles
at the grating generate inclination of spectral lines, e.g., 8° at 65° tilt, which may be com-
pensated by counter-rotating the slit, but not without some image deterioration.
It may be considered a drawback that the Ebert mirror must be of relatively large size
and only a small area is actually used, especially in a spectrograph for wide wavelength
range, which makes the instrument appear to be bulky, but its many advantages out-
weigh by far this inconvenience:
1. Three reflections only, low loss.
2. "Stigmatic" image of high quality.
3. Flat image field.
4. Radiation perpendicularly incident on plate.
5. Plane grating used, providing large size, high resolving power, brighter spectra, high
dispersion, high orders; higher efficiency and more economic than concave gratings.
6. Wide wavelength range.
7. Low scattered light.
8. Mechanically simple and stable mount [179, 182].
9. Easily adaptable to vacuum operation.
10. Several gratings may be alternately used by means of turrets or Kelvin mounts.
11. Total deviation 180°; all controls in same location.
Both systems, the in-plane monochromator and the off-plane spectrograph, can be
combined in one instrument, while utilizing the same grating [128].
When considering an Ebert system for general or high-order work, the better optical
performance can be expected from instruments of longer focal length. Table 3.VI shows
some characteristic data of instruments that have been assembled for laboratory use
or which 'are offered commercially.
TABLE 3.V!
Instrument type Experimental Spectrograph, Monochro- Spectrograph,
commercial mator, commercial
commercial
Ebert-mirror
focal length (mm) 760 500 580 3500
diameter (mm) 190 R:S 80 R:S 92 R:S350
relat. aperture 1 : 10 1 : 16 1:8 1 : 28
Grating
grooves (lin/mm) 1200 1800 2160
ruled area (mm) 76x63 30x30 128x 102
lin. dispersion (A/mm) 5.0 11.1 1.4
at order number 2 1 1
theoret. resolv. power 54000 276500
Spectrum
spectral range (nm) 200-10000 200-40000 200-30000
spectrum length (mm) 250 1000
resolution (A) 0.05 0.1
Remarks 1) 2) 3)
1) Original experimental setup by Fastie.

2) Spectral range covered by seven interchangeable gratings. Straylight in optimum condition
claimed to be 1 : 10 6 •
3) Available as vacuum system also. One of the largest units on the market.
APPENDIX B
B-1 Instruments for flame photometry
The following list is a summary of commercially offered instruments, reproduced from a
TABLE 3.VII
A. PRISM AND GRATING SPECTROPHOTOMETERS
Radiation Measuring
Manufacturer Model Optical system detector apparatus
American Instrument AMINCO plane grating, photomultiplier amplifier meter

Co., Inc. Flame Czerny-Turner RCA 913 A
8030 Georgia Ave. Emiss. monochromator
Silver Spring Spectrometer
Maryland 20910
USA
Beckman Instruments, B Fery-type glass phototubes,blue amplifier and di-

Inc., prism; range: and red sensiti- rect-reading meter
Fullerton 325-1000 nm ve, or photo-
California 92634 multiplier at-
USA tachment
Beckman Instruments, DU quartz prism 30° phototubes blue amplifier, null in-
Inc. and concave mir- and red sensi- dicator, electric
Fullerton rors in a Littrow- tive or photo- compensation
California 92634 type arrangement; multiplier at-
USA 210-2000 nm tachment
Beckman Instruments, DB similar to D U but photomultiplier amplifier and di-
Inc. with a focal dis- tube rect-readingmeter
Fullerton tance of 30 cm;
California 92634 range: 205-770
USA nm
Beckman Instruments, DK-IA and similar to D U ; photomultiplier amplifier and re-
Inc. DK-2A 185-3500 nm tube and lead corder with va-
Fullerton sulfide cell rious scanning
California 92634, speeds
USA
Cary Instruments, Cary 14 double mono- photomultiplier amplifier and re-

Applied Physics chromator; fused tube and lead recorder with
Corp., 2724 So. silica prism 30° sulfide cell various scanning
Peck Road and grating, con- speeds; repetitive
Monrovia cave mirrors; 186- scan
California 91016 2650 nm
USA
Hilger & Watts, Ltd. Uvispek quartz prism 30° photo tubes blue amplifier, null
98 Pancras Way and concave mir- and red sensiti- indicator, electric
Camden Road ror in a Littrow tive, or photo- compensation; a
London, England type arrangement, multiplier at- recording attach-
focal length 65 tachment ment is available
cm; range: 185-
1000 nm
3.B-l] INSTRUMENTS FOR FLAME PHOTOMETRY 127
publication by R. Mavrodineanu [190]. A few additions have been made in order to

reflect recent changes in the field.
Chemical species
Gas mixture Burner Atomizer determined Remarks
hydrogen-air diffusion direct atom- separate building

ization into blocks
the flame
acetylene or hydro- atomizer-burner unit with elements excitable particularly suit-

gen-air or oxygen direct atomization into the in the particular able for radiation
diffusion flame flame used and ra- measurements in
diating from 325 to the visible
1000 nm
diating from 210 to the ultraviolet
2000 nm
diating from 205 to the ultraviolet
770nm
gen-air or oxygen direct atomization into the in the particular able for recording
diffusion flame flame used and ra- of spectra radiated
diating from 185 to from 185 to 3500
3500 nm nm
acetylene or hydro- Beckman atomizer-burner elements excitable particularly suit-

gen-air or oxygen unit in the particular able for recording
flame used and ra- of spectra; high
diating from 210 to resolving power
2000 nm and low scattered
light over the whole
spectral range 186-
2650 nm
hydrogen-oxygen diffusion; indirect with elements excitable particularly suit-
water-cooled atomization in the H2"02 flame able for spectro-
chamber and within the op- photometry in the
tical range of the range 185-1000 nm
instrument
Radiation Measuring
Instrumentation 153 plane grating, photomultiplier amplifier, solid

Laboratory, Inc. 1200 grooves/mm, state, scale expan-
9 Galen St. 32 x 32mm, Ebert sion, recorder
Watertown monochrom. 330 output, digital
Mass. 02172, USA mm, band pass conc. readout
0.6 A first order,
disp. 25 A/mm,
reI. a pert. 1: 9
Jarrell-Ash Co. 8200 Ebert plane grating dual photomul- direct measure-
26 Farwell St. 15,000 or 30,000 tipliers, ampli- ment and record-
Newtonville, grooves/in., 52 x fier recorder ing; scanning
Massachusetts 02160 52 mm ruled area, speed: 2-500 A/
USA focal length 50 min.
cm; range: 200-
1600 nm, resolu-
tion 0.4-0.2 A in
first order; Ebert
optical arrange-
ment
Jobin-Yvon Maroc quartz prism 60°, phototubes,blue amplifier and
26 Rue Berthollet two concave and and red sensitive direct-reading
Arcueil (Seine) one plane mirror meter
France in 180° constant
deviation, 1/7;
range: 200-1000
nm
Jobin-Yvon Varaf plane grating, two two phototubes amplifier and
26 Rue Berthollet concave mirrors; blue and red direct-reading
Arcueil (Seine) range: 310-900 sensitive meter
France nm
Leres T2 double mono- photomultiplier amplifier and re-
9 Cite Canrobert chromator with tube and lead corder; scanning
Paris, France two 30° quartz sulfide cell speed: 1 min-24
prisms; range: hr
205-2900 nm
Optica CF4 plane grating, photomulti- amplifier, direct

21 Via Gargano 15,000 grooves/ pliers, blue and measurements,
Milano, Italy in., one concave red sensitive; electric compen-
mirror, focal lead sulfide cell sation, manual or
length 80 cm, dia- recording opera-
meter 80 mm; tion
range: 185-1000
nm
Optica CF4NI same as CF4 but photomulti- amplifier, direct
21 Via Gargano equipped with pliers, blue and measurements,
Milano, Italy two interchange- red sensitive; electric compen-
able plane gra- lead sulfide cell sation, manual or
tings, 7500 and recording opera-
15,000 grooves/ tion
in., one concave
mirror; range:
185-1000 nm and
1-4 fLm
Gas mixture Burner Atomizer Chemical species Remarks

acetylene-air or ni- premix, aspir. rate designed for atomic
trous oxide laminar flow, variable absorption, intern-
one slot or 3 al standard, twin
slots, Boling channel readout
type
acetylene or hydro- atomizer-burner unit with elements excitable high resolution and
gen-air or oxyge1, direct atomization into the in the particular high sensitivity
diffusion flame flame used, radia- spectrophotometry ;
ting from 200 to particularly suit-
1600 nm able for flame ra-
diation studies
acetylene-oxygen diffusion
I direct into
the diffusion
flame
elements excitable
in the C 2 H r 0 2
flame and in the
analytical flame
spectrophotometry
from 200 to 1000
range 200-1000 nm nm
acetylene-oxygen diffusion direct into the elements excitable analytical flame

diffusion flame in the C 2 H r 0 2 spectrophotometry
flame and in the from 310 to 900 nm
range 200-1000 nm
acetylene-oxygen not described attachment elements excitable high resolution and
(probably for solid in the C 2 H r 0 2 high sensitivity;
similar to sample flame analysis of samples
Beckman atomization in solution and in
atomizer- through solid state
burner unit) sparking
gen-air direct atomization into the in the particular good sensitivity;
diffusion flame flame used, and particularly suit-
radiating within the able for analytical
range of the instru- work and flame
ment radiation studies
gen-air direct atomization into the in the particular good sensitivity;
diffusion flame flame used, and particularly suit-
radiating within the table for analytical
range of the instru- work and flame
ment radiation studies
Radiation Measuring
Perkin-Elmer Corp. 146 * two glass prisms, phototube amplifier and op-
Norwalk 60°, and two glass tical compensa-
Connecticut 06854 lenses in conven- tion (internal
USA. tional arrange- standard), also
ment direct-reading
U nicam Instruments, SP.900 fused silica prism, photomultiplier direct-reading

Ltd., Asbury Works 60°, two concave tube (mirror galvano-
Cambridge, England mirrors in Czerny meter) and recor-
arrangement; a- ding
perture//4.5 ran-
ge: 250/859 nm
Carl Zeiss PMQII quartz prisms 30°, phototube, amplifier, direct-
7082 Oberkochen/ concave mirror in photomultiplier, reading (mirror
Wiirttemberg Littrow-type ar- lead sulfide cell galvanometer)
W. Germany rangement; ran-
ge: 200 nm-2.5 fLm
B. FILTER SPECTROPHOTOMETERS
Radiation Measuring
Manufacturer Model Filter type detector apparatus
Advanced Advanced three colored three photocells double-beam, in-

Instruments Flame glass filters ternal standard
45 Kenneth St. Photometer compensation
Newton Highlands
Mass. 02161, USA
direct-reading
Baird-Atomic, Inc. KY interference three photometer
33 University Road multiplier tubes
Cambridge
Mass. 02138, USA
Baird-Atomic, Inc. DB-2 interference selenium bar- direct-reading
33 University Road rier-layer pho- meter or internal
Cambridge toceTIs standard compen-
Mass. 02138, USA sation
Baldwin Industrial Flame interference two photo tubes amplifier and in-
Controls Photometer ternal standard
Dartfort operation; attach-
Kent, England ment provision to
a recorder avail-
able
3.B-1] INSTRUMENTS FOR FLAME PHOTOMETRY 131
Chemical species
manufactured gas, premixed indirect with elements excitable discontinued; par-

propane, acetylene- atomization in the particular ticularly suitable
air chamber flame used, and for flame radiation
within the optical studies
range of the instru-
ment
acetylene or propane- Meker type, indirect, with elements excitable high sensitivity;
air premixed, atomization in the particular particularly suit-
electric chamber flame used, and able for analytical
ignition within the optical work
range of the instru-
ment
acetylene or hydro- atomizer-burner similar to elements excitable for measurements
gen-air the Beckman unit in the particular in visible part of
flame used and with- spectrum a mono-
in the optical range chromator with
of the instrument glass optics is avail-
able (M4GII); also
a double mono-
chromator (MMI2)
interchangeable
with former
* A large variety of prism and grating monochromators, detectors, amplifiers, and recorders
are manufactured by the company and can be used as "building blocks" for the assembly of
flame spectrophotometers covering the range 185 mfL - 40 fL with high resolution and high sen-
sitivity.
Chemical species
manufactured Meker type, indirect with Na, K, Li internal standard
gas, natural gas, or premixed atomization Li
propane-air chamber
manufactured Meker type, indirect with Na,K internal standard

gas, natural gas, or premixed atomization Li
propane (butane)-air chamber
manufactured Meker type, indirect with Na, K, Li, Ca

gas, natural gas, or premixed atomization
propane (butane)-air chamber
acetylene-air premixed indirect with Li, Na, K, Ca internal standard

atomization Li
chamber
Radiation Measuring
Establissements Flame interference selenium bar- direct-reading

Beaudouin Photometer rier-Iayer pho- meter
1-3 Rue Rataud to cells
Paris, France
Beckman Instruments 41 light filters phototube amplifier, direct·
Inc. reading meter
Fullerton
California 92634
USA
Coleman Instruments 21 interference phototube amplifier, direct-
Inc. reading meter
Maywood
Ill. 60153, USA
Craftsman Electronic Craftsman,
Corp., Ltd., Flame
Sethna Hall Photometer
Nesbit Road
Bombay, India
Electro-Synthese interference selenium bar- direct-reading
47 Rue Barrault rier-layer pho- meter or compen-
Paris, France tocells sation with in-
ternal standard
Elektronest Schuhknecht various types of phototube or direct-reading
6606 Ottenhausen/ STA58 selective light fil- selenium bar- meter
Saarbriicken ters rier-Iayer pho-
W. Germany tocell
Fearless Camera Universal interference photomultiplier amplifier, integra-
Corp., Scientific Spectro- (wedge) tor, direct-reading
Instrument Div. photometer meter
11801 W. Olympic
Blvd.
Los Angeles
California 90000
USA
Gallenkamp Mark II interference selenium bar- direct-reading
Technico House rier-Iayer cells meter
Sun Street
London, E.C. 2
England
Gelman Instrument Evans light filter selenium bar- direct-reading
Co. rier-layer pho- meter
106 No. Main St. tocells
Chelsea, Michigan
48118, USA
Instrumentation IL-Model 143 three interference three photo- double-beam in-
Laboratory, Inc. Flame filters multipliers ternal standard
9 Galen St. Photometer amplifiers, servo
Watertown Square, amplifiers; motor
Boston digital display
Mass. 02172, USA
3.B-1] INSTRUMENTS FOR FLAME PHOTOMETRY 133
Chemical species
acetylene-air premixed indirect Na, K, Ca
natural and manu- Meker type lindir~ct, .with Na,K

factured gas or pro- atomlzatlOn
pane (butane)-air chamber
city gas or propane atomizer-burner unit with Li, Na, K, Ca, Mg no internal standard
(butane)-oxygen direct atomization into the
diffusion flame
in development sta-
ge, no further infor-
mation available
propane (butane) or premixed indirect, with Na, K, Ca internal standard

city gas-air atomization Li
chamber
acetylene or hydro- specially de- indirect, with Li, Na, K, Ca, Sr, two other models
gen-air or oxygen signed burner atomization Ba, Mg are available:
producing a chamber "Special 5G" and
diffusion or "MED"
premixed flame
city gas-oxygen Weichselbaum-Varney Na, K, Ca, Mg discontinued
atomizer-burner unit
city-gas or propane- premixed indirect Na,K

air
city gas-air premixed flat indirect, with Li, Na, K, Ca

flame atomization
chamber
propane-air diffusion, with direct Na, K internal standard

automatic atomization Li,analog compu-
ignition into the flame ter with digital read-
out directly in con-
centration; micro
sample
134 DESIGN AND SELECfION OF SPECTROSCOPIC INSTRUMENTS [3
Radiation Measuring
Janke Co., Inc. Fox colored glass and selenium bar- direct-reading
38 Railroad Ave. liquid filters rier-Iayer pho- meter or compen-
Hackensack tocells sation with in-
New Jersey 07600 ternal standard
USA
Jobin-Yvon Jouan interference and selenium bar- direct-reading
26 Rue Berthollet colored gelatin rier-Iayer pho- meter
Arcueil (Seine) tocells
France; and Jouan
113 Bd., St. Germain
Paris, France
Keyes Scientific Co. Chaffee-Keyes interference photomultiplier amplifier, auto-
Cambridge matic compensa-
Massachusetts 02138, tion with meter
USA reading, direct-
reading attach-
ment to recorder
is provided
P. J. Kipp and Zonen H45 interference selenium bar- direct-reading

Delft, Holland rier-Iayer pho- meter
tocell
Dr. Bruno Lange 2 and 6 interference selenium bar- direct-reading

14-18 Hermannstrasse rier-Iayer pho- meter
Berlin-Zehlendorf, tocell
Germany
Marius-Instrumenten interference phototubes amplifier, internal
N.V. standard, recor-
Ganzenmarkt 4-8 der
Utrecht, Holland
National Instrument Patwin F-C light filters selenium bar- internal standard
Laboratories, Inc., rier-Iayer cells compensation
828 Evarts Street,N.E.
Washington
D.C. 20002, USA
Netheler Hinz, Eppendorf interference photomultiplier amplifier, direct-
G.m.b.H. Mandl reading meter
Falkrenried 74
2 Hamburg
W. Germany
Gebriider Netzsch Netzsch interference photomultiplier amplifier, direct-
8672Selb, (wedge) reading meter or
W. Germany electric compen-
sation
N orth American Norelco colored glass selenium bar-
direct-reading
Philips Co., Inc. rier-Iayer cells
meter or internal
750 South Fulton com-
standard
Avenue
I
Mount Vernon pensation
N ewYorkl0550,USA
Chemical species
propane or city gas- Meker type, indirect, with Na, K, Li internal standard
air premixed atomization
chamber
city gas or propane premixed indirect, with Na, K, Ca another model is

(butane)-air atomization available for the
chamber determination of
Li, Na, K, Ca and
Ba
hydrogen-oxygen atomizer-burner unit with Na, K, Ca, Mg, etc. for information
direct atomization into the contact R.S. Fish,
diffusion flame; the atomizer 234 Broadway at
is supplied through a motor- Windsor St., Cam-
driven syringe bridge, Mass. and
Aztec Instruments,
Inc., 2 Silverbrook
Rd., Westport,
Conn.
propane-air premixed indirect, with Na, K, Ca another model
atomization using an acetylene-
chamber air flame is avail-
able (H63) an inter-
ference filter for Li
is available (H64)
city gas (gasoline)- premixed indirect, with Li, Na, K, Rb, Cs,
air atomization Ca, Sr, Ba, Mg
chamber
propane-air atomizer-burner Na,K internal standard

Li
propane-air premixed, indirect, with Na, K internal standard

horizontal atomization Li
flask
propane, hydrogen universal, indirect, with Na, K, Ca, Mg interference filter

or acetylene and air premixed, impact wall for the isolation of
or oxygen electric and atom- Li, Rb, Cs, Ba, Sr
ignition ization flask and Mn available
on request
acetylene-air premixed indirect Li, Na, K, Ca
city gas-air Meker type, indirect, with Na,K internal standard

electric atomization Li
ignition flask discontinued
Radiation Measuring
Manufacturer Mode Filter type detector apparatus
Patwin Instruments Barclay light filters selenium bar- direct-reading
41 Brown Street rier-layer pho- meter or compen-
Waterbury toceIls sation with in-
Connecticut 06700 ternal standard
USA
Process and Instru- Hand 1B colored glass selenium bar- internal standard
ments Corp. rier-layer ceIls compensation
15 Stone Avenue
Brooklyn, New York
11200, USA
Sigrist-Photometer,
Ltd.
Zweierstrasse 129
ZUrich,
Switzerland
Technicon Instru- Automatic not described photoceIl-ther- amplifier, simul-

ments Corp. Flame mistor assem- taneous recording
Chauncey Photometer blies ofNa and K
New York, USA
Carl Zeiss PF5 interference photomultiplier amplifier, direct-

7082 Oberkochen reading meter
W. Germany
VEB. Zeiss III interference and selenium bar- direct-reading
Jena, E. Germany colored glass rier·layer ceIl meter and intern-
al standard cor-
rection
Chemical species
propane (natural or Meker type, indirect, with Na,K internal standard

city gas)-air premixed atomization Li
;;hamber
city gas or propane- premixed indirect, with Na, K internal standard

air atomization Li
flask
in development
stage
propane-oxygen atomizer-burner unit with Na, K internal standard

direct atomization into the Li; the sample is
flame supplied to the
atomizer-burner
unit under constant
positive pressure;
constitutes an inte-
grated unit of the
Technicon Auto
Analyzer
acetylene or propane- premixed indirect, with Na, K, Ca Li filter available
air atomization
chamber
city gas, propane or premixed indirect, with Li, Na, K, Rb, Ca, internal standard
acetylene-air impact wall Sr, Ba, Cu, Tl, Mg Li
and atomiza-
tion chamber
APPENDIX B
Manufacturers of instruments for atomic absorption
The technology of atomic absorption and atomic fluorescence is at present stilI in a

rapidly advancing condition, new instruments and improvements being disclosed every
few months.
A listing of instruments offered commercially today would be quickly obsolete. Instead,
a partial listing of manufacturers is given in Table 3.VIII and inquiries about the latest
development should be addressed directly to the manufacturer or their local represen-
tatives.
TABLE 3.VIII
Manufacturer Representative in U.S.A.
Atomic Absorption and Electronics Corp.

50 Broadway
New York, New York 10004, USA
Aztek Instruments, Inc.

2 Silverbrook Road
Westport, Connecticut 06882, USA
Bausch and Lomb, Inc.
84066 Bausch Street
Rochester, New York 14602, USA
Beckman Instruments, Inc.

2500 Harbor Blvd.
Fullerton, California 92634, USA
Bendix
Scientific Instrument Division
3625 Hauck Road
Cincinnati, Ohio 45241, USA
Central Scientific Company of Canada, Ltd. Central Scientific

(CENCO) A Div. of CENCO Instr. Corp.
Toronto, Montreal, Vancouver, Quebec 1700 Irving Ponk Road
Chicago, Ill. 60613, USA
Evans Electroselenium, Ltd. Fisher Scientific

St. Andreas Works, Halstead 711 Forbes Avenue
Essex, England Pittsburgh, Penn. 15219, USA
Heath Company
Division of Daystrom
Benton Harbour, Michigan 49022, USA
Hewlett-Packard Company
1501 Page Mill Road
Palo Alto, California 94304, USA
3.B-2] MANUFACTURERS OF INSTRUMENTS FOR ATOMIC ABSORPTION 139
Manufacturer Representative in U.S.A.

Hilger and Watts, Ltd. Engis Equipment Company
98 Pancras Way, Camden Road 8035 Austin Avenue
London, England Morton Groove, Ill. 60053, USA
Instrumentation Laboratory, Inc.
9 Galen Street, Watertown Square
Boston, Massachusetts 02172, USA
Jarrell-Ash Company
Division of Fisher Scientific Company
590 Lincoln Street at Route 128
Waltham, Mass. 02154, USA
National Instrument Laboratories, Inc.
12300 Parklawn Drive
Rockville, Maryland 20800, USA
Norelco/Philips Electronic Instruments

750 South Fulton Avenue
Mount Vernon, New York 10550, USA
Optica S.p.A. National Instrument Labs.
Via Gargano 21 828 Evarts Street, N.E.
Milano, Italia Washington, D.C. 20002, USA
Perkin-Elmer Corp.
Main Avenue
Norwalk, Conn. 06852, USA
Research and Control Instruments, Inc. Experimental model, not offered
275 Massachusetts Avenue commercially
Cambridge, Mass. 02138, USA
Techtron Pty., Ltd. Cary Scientific Instruments, Applied Physics
South Melbourne, Australia Corp., Subsidiary of Varian Assoc.
2724 South Peck Road
Monrovia, Cal. 91016, USA
Unicam Instruments, Ltd. Philips Electronic Instruments
Part of the Philips Group of Companies 750 South Fulton Avenue
Asbury Works Mount Vernon, New York 10550, USA
York Street
Cambridge, England
Carl Zeiss Carl Zeiss, Inc.
7082 Oberkochen, WUrttemberg 444 Fifth Avenue
West Germany New York, N.Y. 10018, USA
Separate components for atomic absorption technique and instrumentation are offered by the
following manufacturers:
Manufacturer Product
Central Scientific Company of Canada, Ltd. Water cooled hollow cathode tubes
(CENCO)
140 DESIGN AND SELECTION OF SPECI'ROSCOPIC INSTRUMENTS [3
Manufacturer Product
George W. Gates and Company, Inc. Power supplies for hollow cathode tubes
Hempstead Turnpike and Lucille A venue
Franklin Square, New York 11010, USA
Micro-Tek Instruments Corp. Hollow cathode tubes

A Subsidiary of Tracor, Inc.
550 Oak Villa Boulevard
Baton Rouge, Louisiana 70800, USA
North American Philips Co., Inc. Spectral lamps

Lamp Sales Department
100 East 42 Street
New York, New York 10017, USA
Ophthos Instrument Co. Electrodeless microwave discharge lamps,

900 Overlea Drive cavities, generators
Rockville, Maryland 20800, USA
Osram G.m.b.H., K.G.

Berlin and Miinchen, West Germany Spectral lamps
Representative: Macbeth Sales Corp.
Newburgh, New York 12553, USA
Perkin-Elmer Corp. Hollow cathode tubes

Main Avenue
Norwalk, Conn. 06852, USA
Quarzlampen G.m.b.H. Hollow cathode tubes

645 Hanau am Main, West Germany
Representative: Hellma Cells, Inc.
P.O. Box 544
Borough Hall Station
Jamaica, New York 11424, USA
Stuart Skinner, Ltd. Slotted burners for acetylene-air premixed

Malvern, Australia flames
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CHAPTER 4
PRINCIPLES OF ELECTRONIC INSTRUMENTATION
P. G. Cath
Keithley Instruments, Inc. *
Cleveland, Ohio, U.S.A.
4.1 Introduction
This chapter will treat some of the electronic principles used in analytical instrumentation.
The techniques described here are applicable to many types of instrumentation but, wher-
ever possible, special attention is given to spectroscopic applications.
The presentation is intended to familiarize the reader with the principles of electronic
circuits, some of their uses and limitations, and to provide the background needed for access
to and an understanding of the vast electronic literature.
Although there are many ways in which the subject of electronic circuits can be sub-
divided into separate disciplines, this chapter is organized by making a clear distinction
between analog and digital circuit techniques. This subdivision provides a better under-
standing of the process of physical measurements, data taking and data reduction. It
provides a clearer understanding of the applicability of the two circuit techniques to the
different steps of the measuring and automation process.
Most physical quantities that are measured can be classified as analog phenomena.
Examples are light intensities, transmission of a filter element, voltages, currents, meter
deflections, etc. Analog quantities can be defined as quantities to which no discrete levels
can be assigned. Quantities that are of a discrete nature are digital quantities. An analog
quantity whose magnitude has been expressed in the form of a number written as a set
of decimal digits (e.g., 17.3) is said to be recorded in digital form. Quantities can, of course,
also be recorded in analog form such as is often done when plotting a curve.
Some examples may help to clarify the distinction between analog and digital. The ex-
perimenter wants to measure the intensity of a spectral line. If he does not want to count
individual light quanta, the experimenter must consider this intensity an analog quantity.
A photomultiplier can be used to transform the light intensity into an electrical signal, the
output current of the photomultiplier. This output current, again, is an analog quantity
and the photomultiplier acts as a transducer. A transducer is any device which transforms
one physical quantity into another. The output current of the photomultiplier can be
measured with an ammeter on which the magnitude of the current becomes visible as
the deflection of a meter movement. The meter movement is again a transducer and the
amount of deflection is an analog quantity.
The experimenter now "reads" the meter and records the amount of current on a piece
*) Formerly, Philips Laboratories, Briarcliff Manor, New York.

146 PRINCIPLES OF ELECTRONIC INSTRUMENTATION [4
of paper as a number. The measured data is now in digital form and the experimenter
has performed the function of analog-to-digital conversion. The digital form is usually
better suited for performing the necessary calculations even though an analog device,
such as a slide rule, is often used in this process.
Finally, the recording of data on a graph constitutes a digital-to-analog conversion.
This same distinction between analog and digital can be applied to electronic circuits.
Analog circuits are those in which the magnitude of a voltage or current level has signif-
icance. As will be discussed later in this chapter, analog circuit techniques can be used
to perform elementary mathematical operations.
Digital circuits present an entirely different class of circuit. In digital circuits the
magnitude of a voltage at a particular point in the circuit is not of interest, only whether
a voltage is present or not is significant. Instead of operating in a decimal mode like the
experimenter who records a number on paper, digital electronic circuits normally
operate in a binary mode where numbers are expressed in binary form. The use of a
numbering system with radix 2 instead of 10 is not of fundamental significance.
Just as the experimenter can make his calculations more conveniently and with more
accuracy in digital form (using decimal notation), digital circuits are similarly better
suited for performing calculations or other types of data manipulation and storage.
The first part of this chapter will deal with analog circuit techniques. Digital circuit
techniques are discussed in the second part. The chapter will conclude with a discussion
of data handling and a review of present trends in electronic instrumentation, especially
the use of digital computers as an integral part of the experiment.
4.2 Analog circuits
In analog circuits the magnitudes of voltage and current levels are directly related to
some physical quantity of interest. To achieve accuracy in measurements, therefore, major
emphasis in analog circuits is placed on circuit stability. This section will discuss some of
the circuit techniques that are used to achieve this stability.
A second source of inaccuracy is created by electronic noise. Noise is caused by random
fluctuations of the signals in electronic circuits mostly due to thermal effects. Even though
drift in electronic components and instability of flames could be considered as noise, they
are usually treated separately.
This discussion will show that these sources of instability can be minimized by circuit
techniques and by the proper design of the overall measuring system.
4.2.1 AMPLIFICATION
The electronic signals from light sensors, such as photomultipliers, photocells, bolometers,
etc. are usually too weak to drive indicators and require amplification before any further
processing can be done. The principal requirements for amplifiers are gain stability and
low noise.
Because the amplification parameters of active devices such as tubes and transistors
are by no means stable with age or environmental conditions, gain stability can only be
4.2] ANALOG CIRCUITS 147
i, eout
Fig. 4.1. Basic feedback amplifier.
achieved by the use of feedback. With feedback the gain of an amplification stage is
lowered and the loss in gain pays for the stability.
To demonstrate the basic circuit configuration using feedback, an amplifier is shown
in Fig. 4.1. The triangular symbol represents the amplifier, often called an operational
amplifier. Although operational amplifiers using tubes or transistors have been known for
a long time, these elaborate amplifiers have not been in general use in instrumentation
because of economic reasons. The advent of integrated circuits in recent years has drasti-
cally changed this situation.
Operational amplifiers are usually differential amplifiers with two input terminals
marked + and - and one (sometimes two) output terminals. The term differential
indicates that the device amplifies the difference between the voltages at its two input
terminals and that, therefore, the output voltage can be written as
(1)
In the circuit shown in Fig. 4.1 no signal is applied to the + input terminal and there-
fore e2 = O. The value of A, the gain without feedback, or the open-loop gain, is typi-
cally of the order of 50,000.
To analyze the circuit of Fig. 4.1 it will be assumed that the input impedance of the
amplifier is very high and that the current flowing into the (-) input terminal can be
neglected. In that case the currents flowing in resistors Rl and R 2, il and i2 respectively,
must be equal because of Kirchhoff's law. Because
• el - eout (2)
12 = - - -
R2
and eout = -A elo one finds that the gain of the circuit can be written as
(3)
Because of the large value of A, the open-loop gain, this expression becomes
(4)
Neglecting the input current into the amplifier due to its finite input impedance was
fully justified. If Ria is the input impedance of the amplifier, this current (i3) equals
(5)
which is usually much smaller than the currents i1 or i2 and therefore negligible.
The first important result from this discussion is that the gain of the amplifier depends
entirely on the ratio of two resistors, R1 and R 2 , whose values can be extremely stable
with proper selection of components.
The second result concerns the linearity ofthefeedback amplifier. Even if the operational
amplifier itself is not linear, i.e., the gain A depends on the signal level eh the feedback
amplifier of Fig. 4.1 will have good linearity provided, of course, that A is large, because
fluctuations in A do not affect the result of Eq. (4).
The third important consideration in feedback amplifiers concerns signal-to-noise ratio.
Noise which is present in the signal before it enters the amplifier is, of course, amplified
together with the signal. Noise which is internally generated in the amplifier and appears
at its output terminal is reduced by applying feedback by the same amount by which
the gain is reduced. Thus no amount of feedback can improve the signal-to-noise ratio,
neither that of the incoming signal, nor that of the amplifier. Signal-to-noise ratio can,
however, be improved by processing techniques which make use of knowledge about the
signal to distinguish it from the noise which is generally of random behavior. These
techniques will be discussed below.
Where the amplification of dc signals is required, drift in the amplifier can be considered
as a special case of noise. Again, the ratio of drift and signal at the output of the amplifier
cannot be reduced by feedback techniques, unless the feedback technique uses drift-free
amplifiers.
The fourth parameter which is affected by feedback is the frequency response of the
amplifier. Fig. 4.2 shows a plot of gain vs frequency of an amplifier with and without
feedback.
100
t eo
OPEN-LOOP GAIN
Ao
m 60
"~ 40 GAIN WITH FEEDBACK
z Ab
<i
CI 20
OL-__ ~ ____ ~ __ -L~ __ ~ __ ~~ __ ~ __ ~ __

10 102
FREQUENCY IN Hz-
Fig. 4.2. Frequency response of amplifiers with feedback.
Voltage gain (A) is plotted vertically in decibels (dB)

(6)
A = 20log1o ( -eout ) dB
e' ll
Frequency is plotted along the horizontal logarithmic scale so that Fig. 4.2 becomes
a log-log plot.
The bandwidth of an amplifier is usually defined as the frequency at which the gain
has dropped 3 dB below the flat portion of the graph.
As can be seen, feedback has not only lowered the gain of the amplifier from Ao to A b,
but also has increased the bandwidth from Fo to Fb• Because the amplifier response
has a slope of -6 dB/octave, the loss in gain is proportional to frequency, and one finds
that
Ao Fb
---
Ab Fo
or
AoFo = AbFb (7)
Therefore, in general, the gain-bandwidth product of an amplifier is not affected
by feedback. Even though the bandwidth of an amplifier is increased by feedback, one
must realize that the amount of feedback which reduces the open-loop gain diminishes
as the frequency exceeds Fo and approaches Fb • The maximum benefit in gain stability
is, therefore, achieved only at frequencies lower than Fo.
4.2.1.1 Drift-free amplifiers
It is often required to sense and amplify dc signals. An example is the output current of
a photomultiplier tube. The most severe problem in this case is dc drift or, in general,
any unwanted dc signal which contributes to the output voltage of the amplifier. As long
as the unwanted signals are constant they can be removed by subtracting a constant
amount from the amplifier output voltage. In this way, the major portion of the unwanted
dc signals such as photomultiplier dark current and amplifier unbalance, can be removed,
usually with a balancing control. However, random fluctuations in these unwanted signals
are always present. These can, in general, not be removed with balancing techniques and
their magnitude is often considerable.
A drift-free amplifier can be made using a so called chopper. Fig. 4.3 shows the basic
circuit. The dc input voltage is first passed through an RC filter to remove its ac compon-
ents. The resulting (slowly varying) dc voltage is converted into an ac signal using a
chopper contact. This generates a square-wave ac signal which is amplified.
A coupling capacitor removes all dc components from the amplifier output signal.
A second switch which operates in synchronism with the input chopper establishes a
zero reference level at the output during one half of the chopping cycle. The result, then,
is a square wave whose value is zero during one half of the cycle and equal to A . el n
during the remainder.
tI
l,\
'N,
I i:(\ I
\... --- -- --
Fig. 4.3. Chopper amplifier.
- ..:.
The dc component of this square wave equals t . A . el n • The ac components can be

removed by using a second RC filter thus completing the chopper amplifier.
Although all dc drift components caused by the amplifier have been removed, care
must be taken to employ switches which have no inherent offset voltages. Mechanical
choppers have been widely used. Transistors with their inherent voltage drop across the
internal junction are unsuitable. Photoconductors, turned on and off by light (Photo-
choppers), and also field-effect transistors do not have these disadvantages.
Because the bandwidth of chopper amplifiers is always significantly smaller than the
chopping frequency, these amplifiers are not suitable for general-purpose wideband
applications. They are, however, often used for low-frequency applications such as strip-
chart recorders and other measuring instruments.
It is interesting to note that the chopper amplifier is one of the first applications of the
principle of synchronous detection (lock-in amplifiers), which will be discussed later in
this chapter.
4.2.1.2 Chopper-stabilized amplifiers
A narrow-band chopper amplifier like the one described above can be used to stabilize
the operating point and reduce the dc drift of a wideband dc amplifier, as shown in Fig.
4.4. The gain of the wideband amplifier is stabilized to be Al using feedback techniques.
A resistive divider which divides the output signal exactly by the amount Al is connected
to the amplifier output. Any difference between the input signal to the amplifier and the
signal derived from the divider network must be due to dc drift in the amplifier. This
difference signal is amplified in a narrow-band drift-free chopper amplifier and applied
as a correction signal to the wideband amplifier to adjust its dc operating point.
)------t--~ e ou !
A;-
Fig. 4.4. Chopper-stabilized amplifier.
This combination of amplifiers is commonly referred to as a chopper-stabilized ampli-

fier.
4.2.2 MATHEMATICAL OPERATIONS
Elementary mathematical operations such as addition, subtraction, integration and dif-

ferentiation can be performed using wideband dc amplifiers.
The frequency response and phase-shift of amplifiers that are used for these applications
must be carefully controlled to prevent instability and oscillation when large amounts of
4.2] ANALOG CmCUITS 151
feedback are applied to these circuits. Amplifiers that meet these requirements are called
operational amplifiers.
The basic mathematical operations of multiplication and division cannot be performed
with simple circuit configurations. The techniques that must be used to perform these
are more complicated and will not be discussed here.
The basic circuit configuration that is used for addition is shown in Fig. 4.5.
Rf
Fig. 4.5. Circuit for performing addition.
Because the input voltage el of the operational amplifier is very small, it is assumed
to be essentially equal to zero at all times. This was already discussed above (el in Fig.
4.1). Therefore, the current that flows into the input of the amplifier from the input cir-
cuits must equal the current that flows out of this point through the feedback resistor (Rf ).
This is expressed by the equation
(8)
and, therefore,
(9)
where an =R-
f •
Rn
This circuit then performs an addition and an inversion of the input signals.
To perform a subtraction, one of these input signals is inverted as shown in Fig. 4.6.
The output of this circuit is given by the following equation as can be easily verified
(10)
>---+--<>eout
Fig. 4.6. Circuit for performing subtraction.

4.2.2.1 Integration
By replacing resistive elements in the circuits shown above with reactive impedances
such as capacitors and inductors, one obtains integrators and differentiators. Usually
capacitors are preferred over inductors because capacitors whose properties approach
that of the ideal circuit element are more readily available than good inductors.
Fig. 4.7 shows the circuit configuration for obtaining integration.
>-.......--oeoul
Fig. 4.7. Integrator.
Using the same reasoning as before, the voltage at the input terminal of the operational
amplifier will be considered to be at zero potential. Thus, the current (iIJ flowing through
the resistor R must equal the current (ic) flowing through the capacitor C. The voltage
across the capacitor C is the output voltage (eout) and the charge (Q) on the capacitance
is given by the relation
Q = eout C. (11)
The current flowing through the capacitance ie = - ~~.

If iR = ie, then,
_Cdeout. (12)
R dt
Integration of this differential equation, assuming that the initial condition can be
rep resented by eout = 0, gives:
eout = RC -If el n dt.

(13)
Similarly, differentiation can be obtained with the circuit shown in Fig. 4.8.
For this circuit the following equation holds
deln (14)
eout = -RC - - .
dt
';. o---+--lJ{;J--..
R
Fig. 4.8. Differentiator.

4.2.2.2 Signal averaging
In addition to pure integration other functions can be performed with operational ampli-
fiers. One that is widely used is a low-pass filter, which passes a de voltage but which
attenuates ac signals above a given frequency, determined by the time constant of the
circuit. Removing ac components from a signal is useful in obtaining e.g., meter readings
of fluctuating signals.
A basic signal-averaging circuit, not using an operational amplifier, is shown in Fig. 4.9.
R
ein~eout
I
1
Fig. 4.9. Low-pass RC filter.
The frequency response of this circuit for sinusoidal signals can be written as
eON' l/jwC 1 (15)
el ft R + l/jwC 1 + jwRC 1 + jw1'
In this equation w = 2nF (F = frequency) and l' = RC is the circuit time constant.
The magnitUde of the response equals
leoutl 1 / -1-
Iel I =
ft r1+ W 2 1'2
(16)
and the phase shift (q;) between the input and output signals equals
q; = -tan- 1 (wr). (17)
The same averaging function can be performed using an operational amplifier, as shown
in Fig. 4.10. The advantage of this circuit is that it is possible to achieve signal gain as
well as a low output impedance which can be useful for driving other amplifiers or indi-
cating meters.
The frequency response of this circuit equals
eou• -R -R 1 (18)
-;;;: = Rift • 1 + jwRC Rift' 1 + jw1"
The similarity in response with the averaging circuit of Fig. 4.9 is clear.
-A >-+---oeoul
Fig. 4.10. Low-pass filter using an operational amplifier.

Because signals with higher frequencies are attenuated by these circuits, they are said
to have limited bandwidth. By definition, the bandwidth of a circuit equals that frequency
at which the response (eout/etn) equals 1/V2 of its maximum value. From Eq. (16) it can
be seen that this happens for ror = 1 and, therefore, the bandwidth of these circuits (Fo)
equals
1 (19)
Fo = - -
2nr
4.2.2.3 Non-linear junctions
By inserting non-linear elements, i.e., circuit elements that have a non-linear relationship
between current and voltage, in the feedback loop of operational-amplifier circuits,
amplifiers can be obtained whose response is non-linear. Although many different cir-
cuits can be made this way, only one common circuit will be described here: a precision
rectifier.
A precision halfwave rectifier circuit is shown in Fig. 4.11.
0,
Fig. 4.11. Half-wave rectifier.
If an ac signal is applied to the input, a halfwave rectified signal will appear at the
output (eout) as indicated by the waveforms shown in Fig. 4.11.
Whenever etn is negative, the output of the amplifier will be positive and current will
flow through diode Dl and the feedback resistor R f . Diode D2 will not conduct because
it is reverse-biased.
Because the current through Rf has to equal the current through the input resistor RIo
the output voltage eout will equal
Rf (20)
eout = -etn • -
Rl
independent of a possible voltage drop across the diode D 1 •
Alternatively, if the input voltage is positive, no current will flow through resistor R f
because, in this case, diode D2 will conduct. The output voltage eout will then equal the
voltage el at the input terminal of the amplifier, which can be neglected provided that
the voltage gain of the operational amplifier is sufficiently large. Thus, this circuit per-
forms a precision rectification which is unaffected by the transfer characteristics of the
rectifying element.
4.2.3 NOISE
Whenever electronic, or in general any physical measurements are made, a limit to detect-
ability is posed by the presence of noise, i.e., undesired fluctuations in the signal.
When signal averaging was discussed it was mentioned that bandwidth reduction could
remove some of these fluctuations. This is true in general for all random fluctuations.
The most common source of noise in electronic systems is thermal noise which is
generated in every resistor. The average value of the rms voltage across a resistor can be
expressed as
en = V4kT RBW (21)

where k Boltzmann's constant = 1.38 x 10- Joule (deg K)-l
23
T absolute temperature of the resistor in degrees K

R resistance in ohms
BW = bandwidth of the noise signal in Hz.
This thermal noise is a random signal having a Gaussian amplitude distribution. Also,
each unit bandwidth anywhere in the frequency spectrum contains the same noise energy.
Noise signals having this latter property are called white noise.
It is interesting to note that a thermal noise voltage can be reduced by restricting the
bandwidth (BW) of the signal channel. Of course, this also restricts the frequency range
of the signals that can be processed and, thus, the information-handling capability of the
channel.
Not all noise signals are random noise. In many cases noise is introduced into an
electronic system from outside sources, e.g., pickup from power lines and noise caused
by mechanical vibrations. In most cases this type of noise can be eliminated by proper
shielding and other means.
Of course, after white noise has passed through an amplifier of limited bandwidth,
the noise has also become band-limited.
Because the signal bandwidth of the signal channel does not necessarily correspond
to the noise bandwidth (BW in Eq. (21)), the concept of equivalent noise bandwidth is
often used. In the following the equivalent noise bandwidth of the simple RC averaging
circuit will be calculated to illustrate this concept.
o ------,
\
-3
1
III -6
"0
z
gl'!::
Q) Q)
-10.7
L -_ _ _ _ _ _ _~_ _ _--'-_ _ _ _ Fig. 4.12. Signal bandwidth and

fo fn noise bandwidth of a simple low-
LOG F _ pass filter.
Fig. 4.12 shows the frequency response of the simple RC averaging network that was
discussed above (see Fig. 4.9).
A white noise source generating a noise voltage n per unit bandwidth is connected to
the filter. If the rms noise voltage at the output of the filter equals N, then the equivalent
noise bandwidth (BW) of the filter is defined by the following relationship
(22)
The noise bandwidth of the RC filter can be found by a simple integration. Use is
made of the fact that if two random uncorre1ated noise voltages are added, the result
is a noise voltage whose power equals the sum of the noise powers of the two noise
sources.
Thus, to find the noise output of the RC filter, the square of the noise voltage must be
integrated over the range of frequencies of interest. Thus,
(23)
(24)
Thus the equivalent noise bandwidth of the RC circuit is:

1 (25)
BW= - .
4.
Note that this is significantly different from the signal bandwidth which was 10 = 1/2n.
corresponding to the frequency at which the response for sinusoidal signals equals - 3 dB
( = 1- V2). At the frequency In corresponding to B W the network response equals -10.7 dB
as indicated in Fig. 4.12.
4.2.4 SYNCHRONOUS DETECTION
All methods to remove noise from measuring systems are based on narrowing the band-
width of the signal-processing channel. This method can, of course, only be used when
the signal to be measured is itself narrow-band, i.e., is composed of a single frequency
component. This is normally the case in optical instrumentation when light choppers are
used, or for the case of dc signals.
The most obvious way in which the bandwidth of a system can be reduced is by the
use of a narrow-band tuned amplifier. This method has its limitations, because a) it is
difficult to make narrow-band amplifiers at the low frequencies that are generally used
for chopping optical signals, and b) the frequency to which the signal channel is tuned
must coincide with the chopping frequency even when the chopping rate shows slight
deviations and this becomes increasingly more difficult as the bandwidth of the tuned
filter is made narrower.
Synchronous detection (sometimes referred to as lock-in amplifier) offers the possibility
to achieve arbitrarily small bandwidths which are always exactly centered on the chopping
frequency. The exact chopping rate, in this case, is normally derived from a separate
sensor, the reference sensor, attached to the chopping device.
n
LIGHT
S~~ 1--+--'VV'v---t---<> E OUT
REFERENCE
SENSOR REFERENCE
SIGNAL
Fig. 4.13. Basic configuration for synchronous detection.
Fig. 4.13 shows a basic system in which a light emission to be measured by a detector
is chopped by a rotating element. The detector signal will then be an ac signal whose
fundamental frequency equals the chopping rate. A reference signal is derived from the
chopper. The reference sensor is located such that the reference signal it generates is in
phase with the detector output waveform.
The reference signal is used to switch the gain of the channel between the values of
+ 1 and -1. This is equivalent to saying that the signal is multiplied by a square wave-
form ER which has the same fundamental frequency as the signal and which assumes
values of + 1 and -1. Such a reference signal ER can be expanded in a Fourier series.
If the signal voltage Es equals
Es = Esp cos OJ! (26)
and the reference waveform, written as a Fourier expansion, equals
411
ER = -[cos OJt - -cos OJ! + -cos 5 OJt • •• ] (27)
n 3 5
then the voltage EA in Fig. 4.13 will equal
EA = Es·ER • (28)
An RC filter at the output of the circuit removes all ac components from the signal EA ,
leaving only a dc component. Eq. (28) can also be written as
4 1 1
EA = -Esp cos OJt [cos OJ! - -3 cos 3 OJt + -cos 5 OJ! - ••• ]. (29)
n 5
The only term in this multiplication that contains a dc component is
cos OJ! • cos OJt = t + t cos 2 OJt. (30)
Therefore, the dc output voltage will be
2
E out = -Esp. (31)
n
A dc output voltage will not only be obtained for input signals of the form E. = Esp cos OJt,
but also for input signals whose frequency is an odd multiple of the frequency OJ, i.e.,
signals of the form Es = Esp cos n OJ! (n = odd).
In general, the dc output voltage Eout for such signals will equal
2
E out =- Esn (n = odd). (32)
nn
Signals having other frequencies will not give a dc output. However, input signals whose
frequency is close to wo, e.g., Wo ± D, will cause a sinusoidal output signal of frequency D.
The largest frequency D that will appear at the output is determined by the bandwidth
of the RC averaging circuit. In normal operation, of course, the signal will never deviate
from wo, but there may be noise signals with frequency components Wo ± D that may
contribute to the output signal if D is sufficiently small. In this way random noise can
contribute to the output signal (Eout )'
By making the averaging output time constant (RC) large, the noise contribution to
the output voltage can be made arbitrarily small because the bandwidth of the system
is inversely proportional to this time constant.
Therefore, the synchronous detector can be used to detect and measure very small
signal voltages in the presence of large amounts of background noise, provided that this
noise does not occur at the signal frequency Wo or one of its harmonics.
4.2.5 APPLICATIONS TO SPECTROSCOPY
To conclude this section on analog techniques, a discussion will be given here describing
some measuring systems. This discussion will show how, in principle, synchronous
detection techniques can be applied to achieve optimum performance. Some of the
techniques described here have not been used in instrumentation because they are not
always easily realized. However, they have been included in this discussion to provide
a better understanding of the principle of synchronous systems and their potential capa-
bility. It is the author's opinion that these concepts, such as sample modulation, will find
widespread use in future instruments.
4.2.5.1 Emission spectroscopy
A typical system configuration for emission spectroscopy is given in Fig. 4.14. The
optical signal generated by exciting a specimen in a flame is analyzed using a mono-
chromator (prism or grating) and the intensity of the spectral line is sensed with a photo-
sensitive device, such as a photomultiplier. The photo-current is integrated over a fixed
length of time, the exposure time, and this integrated voltage is a measure of the sample
concentration. A major difficulty in this measuring system is posed by dark current. In its
broadest sense dark current is defined as the photocurrent from the photodetector when
no sample, or a clean solution, is introduced in the flame. This dark current is composed
both of true detector dark current and of residual emission ofthe flame without sample.
By making measurements both with and without sample over the same length of time,
corrections can be made for this dark current. Making a measurement in this manner
could be considered as a special case of synchronous detection. Although in normal syn-

chronous detection the level to be measured is continuously compared with a reference
level by chopping techniques, a procedure where the comparison is made only once is
not basically different. This, then, immediately points to a method to eliminate the effect
of dark current from the measurement. This method consists of periodically introducing
the sample into the flame so that the emission detected by the photomultiplier alternates
between signal and dark current. By electronically switching the gain of the channel
before integration between the values of + 1 and -1, a system results which very closely
resembles a synchronous detection system except that sample modulation has been sub-
stituted for light chopping. The system is schematically represented in Fig. 4.15.
Fig. 4.15. The principle of sample modulation.
The reason that a light chopper in the optical path is not sufficient for eliminating the
dark current is that the dark-current component which is caused by the residual emission
from the clean flame is also chopped in this case and treated exactly as the signal.
4.2.5.2 Absorption spectroscopy
In absorption spectroscopy the attenuation, or absorption, of a monochromatic reference

beam is a measure for element concentration in the flame. Because the flame usually also
emits at this characteristic wavelength the measurement must be corrected for this latter
emission. This can, again, be done by making a double measurement or by using modula-
tion techniques. Because it is relatively simple to modulate the monochromatic incident
light beam, generated e.g., by a hollow-cathode lamp, a chopper can be placed in this
beam before it passes through the flame (Fig. 4.16). The chopped beam causes an ac
component in the output of the photodetector. This ac component can be rectified and
integrated over a fixed exposure period. The integrated signal, then, is a measure for
the monochromatic light that is not absorbed by the flame.
MONOCHROMATIC
LIGHT
SOURCE
Fig. 4.16. Basic system for absorption measurement.

The block diagram shown in Fig. 4.16 does not employ a monochromator between
the flame and the photosensor. For this system a monochromator is not an essential
element because the only ac input that is received by the sensor is the chopped light from
the monochromatic source. For practical reasons a monochromator or a filter is often
used to reduce the average light level falling on the sensor to avoid saturation.
Comparison with a signal obtained with a non-absorbing flame and flames with cali-
brated elemental concentrations will then yield the information necessary to determine
the concentration in the unknown sample. As was pointed out above, these stepwise com-
parisons that are used in both emission and absorption spectroscopy are nothing but
special cases of chopping techniques combined with synchronous detection in which
only one single modulation step is used. It is essential that the average flame and sample
conditions be stable during the different steps in these measurements.
To eliminate further inaccuracies resulting from, e.g., instability in flame conditions
between the times that samples are compared to standards and clean flames, the concept
of sample modulation combined with synchronous detection could be extended to com-
prise more than the two comparison levels that are used in the basic chopping method.
Such a hypothetical system suitable for absorption spectroscopy is shown in Fig. 4.17.
A monochromatic source, e.g., a hollow-cathode lamp, is chopped in the normal manner
before it enters the flame. The signal from the photosensor can be rectified as in the
system of Fig. 4.16, or it can be synchronously demodulated. The advantage of the syn-
chronous demodulator is its smaller bandwidth with inherently better noise rejection.
In Fig. 4.17, a synchronous demodulator is used operating at the frequency of the light
chopper.
r----------------,
PHOTO CHOPPER REFERENCE
~ GRATOR
INTE-I ~vSX
MONOCHROMATIC
LIGHT
SOURCE
0-./ INTE- ~ V
GRATOR II ST
Fig. 4.17. Absorption system incorporating multiple-sample modulation.
Simultaneously a second modulation system operating at a lower chopping rate is used

to alternate the sample introduction to the flame between the unknown (SX), the stan-
dard (ST) and no sample (SO). A second switch running in synchronism with the sample
modulator applies the output of the first synchronous demodulator to three integrators.
Both modulation processes, the light chopper and the sample modulator, continue to
operate during a measurement.
The output voltages of the three integrators at the end of the measurement then cor-
respond to:
Vsx unabsorbed signal with unknown sample
VST unabsorbed signal with standard sample
Vso unabsorbed maximum signal.
4.3] DIGITAL CIRCUIT TECHNIQUES 161
If the absorption were linear with sample concentration and if the concentration of the
standard sample were equal to CST, then the concentration of the unknown sample (Cx )
would be equal to
Cx = Vo - Vsx . C (33)
Vo - VST ST·
This calculation could also be performed in the instrument. Although it is technically

feasible to build instruments of the type just described, they tend to become expensive
and too specialized. This is true even more so when nonlinearities in absorption charac-
teristics have to be taken into account and when multiple channels are used for multi-
element analyses. Therefore, when circumstances require this degree of automation and
complexity, it is much more economical to use digital techniques to perform the calcula-
tions needed for data reduction.
4.3 Digital circuit techniques
Analog circuit techniques usually suffice when a measurement does not require more
than the presentation of measured data with a meter movement or a strip-chart recorder,
provided that data reduction is limited to certain simple tasks suitable for analog techni-
ques.
When more sophistication is required, digital techniques must be used. The simplest
measuring system would consist of an analog system in which the indicating meter was
replaced with an analog-to-digital converter possibly provided with a print-out on paper
to achieve a permanent record on a medium such as punched cards or punched paper
tape which can be used to enter the data into an electronic computer for further process-
ing.
A slightly more complex elementary system not only records the data in digital form,
but also performs the timing function to perform the different steps automatically in the
measurement, which can be broken down into a sequence such as, for instance, making
the measurement for a specified length of time, then performing the required analog-to-
digital conversion and finally recording the data in digital form. These automatic sequences
can be generated with digital circuit techniques.
The oldest digital circuit element is the electromechanical relay. The logic or switching
function is performed using the relay contacts which can have two states: open or closed.
Similarly in modem logic circuits only two possible voltage levels are of interest, i.e.,
whether a voltage is present or not. These circuits will be described in this chapter.
Although many variations of logic circuits exist today, only one such group will be des-
cribed here because the principles of all logic circuits are the same.
4.3.1 BASIC CIRCUITS
Several electronic functions are needed in digital control systems. One of the most com-
mon functions is that of electronic counting. Counting circuits are used (a) to count
numbers of events, and thus become integrators, (b) to count clock pulses for timing
functions or for frequency division, and (c) to generate the different parts of automatic
sequences.
The second function that is used is that of control. An example of this function would
be a circuit element whose state, on or off, indicates whether an automatic sequence of
measurements is still in progress or has finished.
Finally,logic circuits are needed to perform the logic function, i.e., to decide when one
part of an automatic sequence has been completed and the next one must be started.
All these functions can be created with four basic building blocks:
a. a memory circuit which has two stable states or positions,
b. a pulse gate which is used to change the state of the memory circuit,
c. two types of logic-gates,
d. a logic-inversion circuit.
These basic building blocks will be described in this section and some examples of
ogic circuits in which they are used will be given.
4.3.1.1 Flip-flop
The memory function in control circuits is performed by a bistable circuit, normally
called a flip-flop or bistable multivibrator. The circuit consists of two active devices,
transistors, which are cross-connected in such a way that only one of the two will conduct
current. The basic circuit diagram is shown in Fig. 4.18. When transistor Ql is conducting,
its collector will be at ground potential. By means of the resistor Rs and R6, the base of
transistor Q2 will then be at a negative potential and transistor Ql will therefore be cut
off and no collector current will flow. The collector of transistor Q2 will then be at a
potential of + 12 volts. This condition will provide a positive bias on the base of tran-
sistor Ql through the resistors R2 and R 3. This will keep transistor Ql in conduction
and maintain the existing state. The other condition in which Q2 conducts current and
Q 1 is in the cut-off condition can be shown to be stable (or self sustaining) also, following
a similar line of reasoning.
OUTPUTS
A A
,.----1--+---.------0+ 12V
,hr0V
L------------+---o-12V
Fig. 4.18. Circuit diagram for a flip-flop.
A flip-flop, therefore, has two stable states which can be called on and off, or they can
be designated with a logic symbol 1 (one) or 0 (zero). Rather arbitrarily we will say that
the circuit is in the "1" state when transistor Ql is conducting and output A, therefore,
OUTPUTS
INPUTS
Fig. 4.19. Symbol for a flip-flop.
is at ground potential. The other output A (not A) will then be at 12 volts. The flip-flop
is said to be in the "0" state when A is at ground potential. The symbol that will be used
for the flip-flop in our further discussions is shown in Fig. 4.19.
To make the flip-flop a useful device, a way must be found to change its state, i.e.,
change conduction from one transistor to the other. This is normally done by applying
a negative pulse to the base of the conducting transistor to drive it into the cut-off con-
dition. The resulting rise in its collector voltage will then cause the other transistor to
conduct, thus changing the state of the flip-flop. To improve the switching action of the
flip-flop during this transition, small capacitors have been connected across resistors R2
and Rs.
The pulse that is used to change the state of the flip-flop is generated in the pulse gate,
which is the next basic circuit that will be discussed.
4.3.1.2 Pulse gate
A pulse gate is shown in Fig. 4.20. It has a control input, a pulse input to which negative
clock pulses are applied, and an output. The clock pulses are continuously present and
their function is to synchronize the actions of the different parts of control circuits~
When the control voltage is positive, e.g., + 12 volts, point A in the pulse gate will also
be at + 12 volts. The clock pulses whose amplitude may be, for instance, 9 volts, are
coupled into point A by means of a capacitor. They will, therefore, cause the voltage at
point A to move from + 12 volts to + 3 volts every time a clock pulse appears. Because
point A is positive at all times, the diode is never allowed to conduct, and no pulses will
appear at the output of the gate. The gate is closed.
When the control input is brought to, or close to, ground potential (0 volts) point A
will also change to this level and the clock pulses then will cause point A to move from
c
OUTPUT
PULSE
INPUT
Fig. 4.20. Circuit diagram for a pulse gate.

o volts to -9 volts. Whenever point A is negative, the diode will conduct and the clock
pulses will therefore appear at the output of the gate. The gate is now open.
Fig. 4.21 shows the symbol that will be used for the pulse gate in the circuit diagrams
that follow. The control input and the output are indicated with arrows; the unmarked
input is the pulse input.
Fig. 4.21. Symbol for a pulse gate.
To show how the pulse gate can be used to control the state of a flip-flop, we shall
interrupt the discussion here to give an example of a manual control function which
combines these two circuits. It is desired to open a shutter upon the momentary closure
of a push-button switch (START) and to close it when a second push-button switch is
closed (STOP). Because only momentary closures are used for the switches, a memory
element, a flip-flop circuit, is needed for this control function. The basic circuit to ac-
complish this function is shown in Fig. 4.22. As long as the switches are open, the inputs
to both pulse gates are at a positive potential and, therefore, the gates are closed and the
state of the flip-flop remains unchanged. Assuming that the flip-flop is initially in the
"0" or OFF condition, its output 2 will be at ground potential and its output 1 at + 12
volts. In this condition no voltage is applied to the shutter solenoid. When the START
button is momentarily depressed, pulse gate No.1 will open and (negative) clock pulses
will be applied to input 2 of the flip-flop. This will bring transistor Q2 in the flip-flop
out of conduction (see Fig. 4.18) and the flip-flop will then be in the "1" or ON state.
Because output 1 is now at ground potential, the shutter solenoid will be activated as
long as the flip-flop remains in this state. Upon operation of the STOP switch, this process
is reversed and the flip-flop is returned to the "0" state and the shutter will again be
deenergized. More than one clock pulse may be applied to the flip-flop inputs upon opera-
tion of the push-button switches, but after the first one of these has cut off the corre-
SHUTTER
SOLENOID
STOP1
START-j
CLOCK
PULSES
Fig. 4.22. Control circuit for operating a shutter.

sponding transistor in the flip-flop, subsequent pulses have no further effect on the state
of this control element.
A difficult problem in digital control systems is always posed by electrical noise. Short
switching transients are almost inevitably present on the wiring inside a control unit.
Some of these are internally generated, others are caused externally, for instance by the
switching of heavy loads connected to the same power line. If such transients are allowed
to change the state of the control elements, the flip-flops, the action of the overall control
system becomes erratic. An important property of the use of pulse gates as shown in
Fig. 4.22, is that they provide noise immunity. It arises from the fact that the voltage at
point A in the pulse gate (Fig. 4.20) cannot instantaneously follow the changes in voltage
on the control input because charge must be removed from the capacitor (C) through the
resistor (R). The time constant of this discharge is determined by the product RC. If this
time constant is chosen to be as large as 10 [LS, then short spikes that are present on
the control inputs will not be able to operate the pulse gates and thus affect the state of
the control elements. Only legitimate control signals being continuously present and
lasting longer than 10 to 30 [LS will be able to effect such changes.
Another useful property of the pulse gates is their high input impedance. The gate
only requires current at the control input when it is either being opened or being closed.
Only the time constant of the charge and discharge is affected by the output impedance
of the circuit that drives the gate. Low-impedance driver circuits, therefore, are not
needed with this type of gate. This fortunate state of affairs is, of course, a consequence
of the fact that the control system for automating a slow measuring process in general
is never required to act very fast.
4.3.1.3 Logic gates
Not all control elements are steered directly by manual switches as was the case in the
example above. During fully automatic operations the state of control elements is changed
internally when certain signals indicate that a particular step of the automatic sequence
has been completed and the next step is to be started. To determine when these conditions
are present, logic gates are used.
In a digital system each wire or signal point can be at only two voltage levels, VI
and V2 • A choice is made and it is said that, by definition, a signal is present at a signal
point when its potential equals VI> and conversely, no signal is present when its potential
equals V2 • To simplify notation, each wire, signal point or control element can be de-
noted by a symbol (e.g., A, B or C, etc.) and the two signal levels are called "1" (ONE)
and "0" (ZERO). The notation A = 1, then, signifies that a signal is present at point A
in the circuit, or, also, that some flip-flop called A is in the "ON" position.
The two voltage levels in the logic system under discussion are 0 and + 12 volts. By
definition, ground potential (0 volts) will be called "1," and +12 volts will be "0." This
choice is compatible with the pulse gates because when the control input to a pulse gate
is ZERO, the gate will be closed whereas a ONE will open the pulse gate.
With these definitions, the two logic gates AND and OR can be described. The AND
function is performed by the diode gate shown in Fig. 4.23. Whenever any of the inputs
A or B or C is at a positive potential (= "0") the diode associated with that input will
conduct, and the output D will then also be positive (i.e., no signal is present). Only
when all three inputs are at ground potential (= "I") will the output be equal to "1."
I NPUTS OUTPUT inputs output

A o----I>t--~--<I
0 ABC D
000 o
B o---C>l---+
001 o
010 o
C o---C>l---+
011 o
100 o
101 o
1 1 0 o
-12V 1 1 1 1
Fig. 4.23. Circuit diagram for the AND gate. The table shows the output D of the gate for all
possible input configurations.
The table in Fig. 4.23 summarizes the "AND" function. It shows the output D for all
possible input configurations for a three-input AND gate. As can be seen the output D
is equal to "1" only when all inputs A "AND" B "AND" C are equal to "1" simultane-
ously.
Symbolically the AND function is written as D = A . B . C and the circuit symbol
for the AND gate is shown in Fig. 4.24.
Fig. 4.24. Symbol for the AND gate.
inputs output
+12V
A B C D
0 0 0 0
0 0 1 1
0 1 0 1
INPUTS OUTPUT
A 0 0 1 1 1
1 0 0 1
B 1 0 1 1
1 I 0 1
c 1 1 1 1
Fig. 4.25. Circuit diagram for the OR gate. The table shows the output D of the gate for all
possible input configurations.
The OR function complements the AND function. The OR diode gate is shown in
Fig. 4.25 together with its input-output table. The output will be at ground potential
("1") whenever any of the inputs is at ground potential. In other words, the output D
equals "1" whenever any of the inputs A "OR" B "OR" C (or more than one of these)
equals "1." The circuit symbol for the OR gate is shown in Fig. 4.26 and the symbolic
notation for the OR function, the logic "equation" is written as D = A + B + c.
~ :=$--D=A+B+C
Fig. 4.26. Symbol for the OR gate.
Two points of interest arise in connection with the logic gates:

1. In formal logic a distinction is made between the inclusive and the exclusive OR
functions. The diode gates shown in Fig. 4.25 perform the inclusive OR. The exclusive
OR requires a more complicated circuit that will be described below in connection with
logic inversion. The distinction between inclusive and exclusive OR is usually not made
when the word "or" is used in languages. The type of OR, then, follows from the con-
text of the sentence. The following sentences will demonstrate these two possible mean-
ings of the word "or":
a. That child always cries or makes noise (inclusive, because he, obviously, could be
doing both at the same time).
b. The book was red or blue (exclusive).
In languages the exclusive nature of "or" is often stressed by the use of the words "either
.. . Of."
2. It is interesting to note that the definition of the ONE and ZERO levels affects the
operation of the gates. If + 12 volts is taken to be the ONE and ground potential taken
to be the ZERO level, then the diode gates of Figs 4.23 and 4.25 perform the OR and
AND function respectively. This can be easily verified by replacing all "1 "'s by "O"'s
and vice versa in the tables of Figs 4.23 and 4.25.
4.3.1.4 Logic inversion
To be able to form all possible logic functions from a set of input variables, a third logic
element is needed in addition to the AND and OR gates. This element must perform the
logic inversion.
The basic circuit is shown in Fig. 4.27. It consists of a single-transistor amplifier stage.
+12V
DUTPUT
+----<>;;F
INPUT Y
Fo--.JV\Iv-~-{r-.
Fig. 4.27. Circuit diagram for performing a logic inversion.
A positive input voltage will cause the transistor to conduct so that its output will then
be at ground potential. In other words, a "0" at the input causes a "1" at the output
and vice versa. In general, when a logic function F is applied to the input, the output will
be NOT F, which is usually written as F. The circuit symbol for the inversion is shown
Fig. 4.28. Symbol for the logic inversion.
in Fig. 4.28. Also, it will be apparent that a signal that is inverted twice remains un-
changed.
To show the use of the inversion in generating logic functions, the circuit arrangement
needed to form the exclusive OR for two inputs A and B will be considered as an example.
The exclusive OR circuit must give an output when A "OR" B "but NOT both" are
present at its inputs. The circuit shown in Fig. 4.29 performs this function. The OR gate
senses the presence of A OR B (inclusive). The input AND gate determines whether A
AND B are present at the same time, a condition that must be excluded. By using a
logic inversion and a second AND gate, the output F of the circuit will be present only
when A AND B are NOT present at the same time, and this is the exclusive OR.
Fig. 4.29. Logic diagram to perform the exclusive OR function.
There may be practical reasons that make the circuit of Fig. 4.29 impossible to build.
For instance, the output of an OR gate may not be able to deliver enough current to
drive the input of an AND gate. In such a case a different circuit arrangement must be
found to create the exclusive OR function. To find such a circuit, use can be made of
Boolean algebra. The variables in Boolean algebra can assume only two values "0" and
"1," and for this reason the algebra uses no coefficients or exponents (A + A = A).
However, the normal commutative and distributive laws of conventional algebra apply.
The circuit that is shown in Fig. 4.29 can be expressed by the following logic equation:
F = (A + B) . (A . B). (34)
In the discussion of the logic gates it was pointed out that an inversion of quantities
changes the OR operation into the AND operation, and vice versa. For this reason the
following identity exists:
(A·B) =A + B. (35)
This is known as De Morgan's rule. Using this identity, the exclusive OR function (34
can be rewritten as:
F = (A + B) • (A + B) (36)
and, as in conventional algebra, this becomes:
F = A .A + A . B + B . A + B· B. (37)
Since a quantity and its own inverse can never be equal to "1" at the same time, the
terms A . A and B . B are equal to ZERO and can be omitted. Thus, the exclusive OR
function becomes:
F=A·B+B·A. (38)
In the case of this simple function, this result could have been found without the use
of Boolean algebra. For more complicated functions, this is not always the case. That
Eq. (38) represents, indeed, the exclusive OR is easy to see. The output F is present only
when A is present while B is NOT present at the same time, OR when B is present AND
A is absent. Fig. 4.30 shows the alternate arrangement for the exclusive OR. Note that in
this circuit the OR gate is not required to drive the input of an AND gate.
Ao---......- l
Bo--__~ F
Fig. 4.30. Alternate arrangement to achieve the exclusive OR function.
4.3.1.5 NOR and NAND gates
It was stated above that all logic functions can be performed using basically the three
elements AND gate, OR gate, and inversion. The discussion will now digress to mention
the existence of another important class of logic circuits in which only a single logical
element is used to perform all logic functions.
The element is based on the observation that inversion of the logic levels changes an
AND gate into an OR gate and vice versa (De Morgan's rule). It is realized by combining
an AND gate with an inversion and it performs the logic function NOT AND and is
called a NAND gate. This gate and its circuit symbol are shown in Fig. 4.31.
Fig. 4.31. NAND logic function and the NAND symbol.
When the logic levels are inverted, the AND gate becomes an OR gate and the NAND
gate then becomes a NOR (NOT OR) gate.
A
()i.B)=A+B
B
Fig. 4.32. The three basic logic functions inversion, AND, and OR as performed with NAND
gates.
Fig. 4.32 shows how the three basic logic functions AND, OR and inversion can be
performed with the NAND gate.
Although it may seem that a logic system using these gates is uneconomical because
more than one gate element is needed to perform the basic logic function AND and OR,
this is not generally true for larger digital systems.
For instance, to realize the very common function AND-OR of four variables A, B,
e and D requires the same number of gates in both systems as is shown in Fig. 4.33. The
logic function performed by these circuits is
F = (A . B) + (e . D). (39)
A
B
F=A.B+C.D
C
o
A
B
F=A.B+C.D
c
o
Fig. 4.33. Comparison of AND-OR gates and NAND gates for performing an AND-OR func-
tion of four logic variables.
4.3.2 COUNTERS
With the basic building blocks that were described above, it is possible to generate all
circuit functions that are needed for digital control circuits. The most widely used function
is that of electronic counting. Counters are used in many control and timing functions.
¥~---4------~
PULSE
INPUT
Fig. 4.34. Basic counter circuit with two states.
The basic counter circuit consists of a combination of flip-flops and pulse gates. One
stage of a counter is shown in Fig. 4.34. With the flip-flop initially in the "0" state,
output 1 will be at +12 volts and output 2 at ground potential. The pulse gates 1 and 2
will then be closed and open respectively. A pulse applied to the pulse input will pass
through pulse gate 2 and change the state of the flip-flop to "1". A second pulse will
change it back to "0", etc. With every other input pulse, when the flip-flop makes the
transition from "1" to "0", the voltage at output 2 will swing from + 12 volts to ground.
This negative-going transition can be used to supply the pulse input signal to an identical
second counting stage.
n A B
0 0 0
1 1 0
2 0 1
3 1 1
4 0 0
A A B B
If
Fig. 4.35. Counting circuit with two flip-flops. The table shows the state of the two flip-flops
after n input pulses.
This is shown in Fig. 4.35 The table shows the states of the two flip-flops A and B after
a sequence of input pulses. Four states are possible and after every fourth input pulse
this system of two flip-flops will return to the same condition. The four possible states
172 PRINCIPLES OF ELECI'RONIC INSTRUMENTATION [4
can be sensed with a decoding network consisting of AND gates as shown in Fig. 4.35.
Use is made here of the fact that each flip-flop provides a logic inversion on its second
output. Because the circuit can be used to determine the number of input pulses that have
occurred after the initial 0-0 state, it can be used for counting.
Just as the system of two flip-flops has four stable states, a counter consisting of n flip-
flops has 2ft stable states. Although such "binary" counters make the most economical
use of flip-flop elements, it is often more convenient to count using a decimal system.
A decimal counter consists of several decades with four flip-flops each. Of the 24 = 16
possible states only ten are used and when the eleventh state is sensed, using a gate
arrangement, the decade is reset to zero and a carry pulse is applied to the next decade.
Such decade counters are widely used.
The AND gates in Fig. 4.35 provide full decoding of all four possible states of the two
flip-flops A and B. In general, to fully decode a counter consisting of n flip-flops, 2ft AND
gates are needed each having n inputs. For the case where a counter is used as a timer to
count a specific number of clock pulses, for instance, a number equal to A, only the state
of the counter corresponding to the number A is of interest. In that case the number A
can be selected by a bank of switches that are connected to the 2n outputs of the flip-
flops. With these switches n of these outputs, one from each flip-flop, are connected to
one AND gate with n input terminals. The AND gate will then give an output only when
the state of the counter corresponds to the number A that was selected by the bank of
switches. This arrangement is symbolically indicated in Fig. 4.36.
2n CONNECTIONS
PULSE INPUT
Fig. 4.36. Symbolic representation for a counter with a switchable sense circuit.
A second function that can be performed by the counter circuits of Fig. 4.35 is that
of frequency division. Each of the AND gates in Fig. 4.35 will have an output once for
every four input pulses applied to the pulse input terminal. Therefore, if the input pulses
are applied at the frequency of 100 Hz, the pulses appearing at the output of the AND
gates will have a frequency of 25 Hz. This type of frequency division is used in control
systems to generate pulse trains whose frequencies are exact multiples of the other. The
use of one accurate crystal-controlled oscillator in combination with a set of frequency-
divider circuits, eliminates the need for a large number of accurate oscillators.
0.2.1 Number representation
The use of decimal notation to represent quantities is well known. In the decimal systems
the base or radix equals 10. Thus the notation, e.g., 932.4 represents 9 X 102 + 3 X 101 +
+ 2 x 10° + 4 X10- 1. By adding more decimal digits, the accuracy of the number can
be improved arbitrarily.
Because it is extremely difficult to make digital circuits with 10 discrete voltage levels,
digital circuits usually employ only two discrete levels, and such circuits were discussed
above. With such circuits a number can now be expressed in a numbering system with
radix 2. In this notation the number 100111.11 for instance, has a value of 1 x2 5 +
+ 1 X22 + 1 X21 + 1 x2° + 1 x2- 1 + 1 x2- 2. This corresponds to the number 39.75
in decimal notation. The process of converting a binary number into a decimal notation
is called binary-to-decimal conversion.
It is also possible to express decimal numbers in binary form using the binary-coded-
decimal (BCD) notation. This code naturally arises when digital counters are used con-
sisting of a number of decades. Each decade consists of 4 flip-flop elements and of the
16 possible positions only 10 are used. Each digit of a decimal number in BCD code is
then represented by its binary equivalent. Thus, to code the sequence of digits 3975 into
BCD the three is represented by 0011, the nine by 1001, etc., and the BCD code for the
decimal number 3975 then becomes
0011-1001-0111-0101.
The hyphens have been added for clarity and do not form part of the notation. The
decimal point presents a special problem because all binary codes are basically suitable
only for integers. To handle this problem the position of the decimal point can be given
as an exponent similar to expressing the number 39.75 as 3975 x 10- 2. This is the floating-
point notation that is widely used to code numbers in binary form in digital computers.
Logic circuits can be designed which perform the binary-to-decimal conversion. The
fact that they tend to be complicated is the reason that counters that have to be inter-
preted by human beings are usually decade counters using the BCD code. However, for
mathematical operations inside a computer, the binary notation is more suitable and
conversion routines to go from one radix to the other are usually part of a computer
program set.
Whenever the radix of a numbering system is a power of 2, the conversion becomes
extremely simple. An often-used system is the hexadecimal system with a radix equal to
16. The sixteen symbols that are normally used are the numbers 0 through 9 and the
letters A through F. Thus the number B7C9 has the value 11 x16 3 + 7x16 2 + 12x161+
+ 9 x 16° = 47049. The binary-coded-hexadecimal notation is 1011-0111-1100-1001 and
this is identical to the binary representation of the number as can be easily verified.
It is not surprising that many different numbering systems and coding schemes are
possible and many of these have been used for special applications because certain binary
circuits such as, for instance, bi-directional counters can be greatly simplified if the proper
coding system is used. To describe these is beyond the scope of this discussion.
4.3.3 ANALOG-TO-DIGITAL CONVERSION
To demonstrate a simple digital system, an analog-to-digital converter will be described.

Because of its nature, this circuit involves both analog and digital circuits. The description
also is intended to show the principles of these circuits, rather than give all the details.
The analog-to-digital converter is shown in Fig. 4.37. The analog voltage to be measured
(Vx ) is compared to a linearly increasing voltage Vb This linear ramp is generated using
an analog integrator. VI is assumed to be equal to zero initially and the time required
Vx COMPARATOR
o----~ AMPLIFIER
COMPLETION SIGNAL
+12V cp
STAR!..i
t
Fig. 4.37. Analog-to-digital conversion.
for VI to reach the value Vx is proportional to Vx as can be seen from the following
equation
VIet) = -
RC
12 J
t
dt = -
12 t
RC
(40)
which is derived from equation (13). This elapsed time is measured using digital techni-
ques.
At the start of the conversion the control flip-flop is in the "0" position. Its output C1
is therefore at + 12 volts and gate G2 is closed and relay A is de-energized (see Fig. 4.22).
Clock pulses generated by an accurate oscillator are applied to the three pulse gates G1>
G2 and G3 •
When the start button is operated gate G 1 opens and the control flip-flop is changed to
the "1" state. Relay A closes and -12 volts is applied to the input of the integrator starting
the linearly increasing ramp voltage VI. Gate G2 is opened and clock pulses are counted
in the counter. As long as Vx > VI the output of the comparator amplifier is positive
and gate G3 is closed. When VI equals Vx • this output voltage becomes zero and gate G3
is opened. The control flip-flop is reset to the "0" condition and gate G2 closes. The num-
ber stored in the counter at this moment is a measure of Vx in digital form. The position
of the control flip-flop can be connected to other digital circuits to be used as a completion
signal to indicate that the conversion process is finished.
In circuits of this kind careful attention must be given to timing problems. If the clock
pulses are assumed to occur at times t1> t 2 • ••• tn. and if the control flip-flop is turned
on at time II. then the relay will close at 11 which will be the start of the conversion
process. However, the first clock pulse that will enter the counter occurs at 12 and this
would result in a one-count error. However, the reverse is true upon completion of the
process. If VI reaches the value Vx at some period in time between clock times I n- 1 and
tn, then the control flip-flop will be reset at In but the In clock pulse will also be counted.
Because of this one-pulse delay both at the start and at the completion of the conversion
process, no error was introduced other than the one-count discrepancy that is always
inherent in this type of converter.
In many cases clock pulses having the same frequency but different phases must be
used to avoid similar timing problems.
4.3.4 DIGITAL-TO-ANALOG CONVERSION
Although digital-to-analog conversion is principally an analog circuit problem it is dis-

cussed here because it involves binary number representation.
Fig. 4.38 shows a basic circuit to convert a binary number consisting of four bits A,
B, C and D into an analog voltage. The quantities A, B, C and D can assume the values 1
or 0 by closing or opening the four switches and the output voltage eout is given by
eout = 12 R f [ - A BCD]
+ -RB + Rc
-- + -RD
RA
(see Eqs. (8) and (9)).
A
>--+----Oeout
B
c
D
-12V
Fig. 4.38. DigitaI-to-analog conversion.
The values of the resistors are chosen as follows:

RD = 12 Rf
RD
Rc=-
2
RD (42)
RB = -
4
With these values eout becomes

eout = 8.A + 4 . B + 2 . C + D. (43)
For the binary number 1011 representing the decimal number 11, the values of the
coefficients A, B, C and D are 1, 0, 1 and 1 respectively and eout equals 11.
This concept can be extended for handling larger binary numbers and other resistance
networks are normally used. It is also possible to make direct conversions from BCD-
coded numbers to analog in this manner.
4.3.5 SEQUENCING CONTROLS
To complete this discussion on digital techniques the principle of sequencing controls

will be described. This type of circuit configuration is used to generate the steps that must
be performed when a measurement process is automated. An example of such a sequence
could be (a) the opening of a shutter to make a fixed-time intensity measurement of a
spectral line, (b) performing the analog-to-digital conversion and (c) printing the measured
quantity on an output device.
A discussion of all the details of such a control circuit is beyond the scope of this
chapter. Fig. 4.39 will serve to illustrate the basic principles involved.
The heart of the control circuit is the sequence generator which is nothing more than
an electronic counter with full decoding, identical to the circuit shown in Fig. 4.35 except
that more flip-flop stages and more AND gates may be needed to generate more than
the four steps possible with this circuit.
TO SHUTTER
CONTROL
ADVANCE
INPUT
SEQUENCE
START
SIGNAL
Fig. 4.39. Principles of sequencing controls.

4.4] ON-LINE COMPUTER CONTROL 177
The m + 1 possible states of this sequence generator will be called So, S10 ••• Sm
where So is the rest position in which the control is not active.
When the sequence generator reaches a certain position, for instance S3, at which point
a certain action must be taken such as a fixed-time measurement, a signal appears on
output S3, which is connected to the control input of the timer circuit.
The signal S3 opens a pulse gate (G 2 ) and allows clock pulses to be counted by a counter
circuit. The counter is provided with a switchable AND gate similar to the arrangement
of Fig. 4.36 which will give an output signal when the correct number of clock pulses
has been accumulated. This signal serves as the completion signal for this part of the
measurement and is applied to an AND gate whose second input is connected to S3.
The output signal from the AND gate passes the OR gate and opens the pulse gate (G 1 )
so that the sequence generator is advanced to the next position S4. The use of the AND
gate in this manner prevents the sequence generator from advancing in case the completion
signal is present during other parts of the automatic sequence where a different completion
signal is logically needed to signal the end of the control step. Also, with the use of the
AND gate, the advance signal for the sequence generator is removed as soon as it moves
out of position S3 even if the completion signal is still present.
To automate a complete measuring sequence the consecutive positions of the sequence
generator are used to initiate the different steps required and the sequence is advanced
when the completion signal for that particular step is received.
4.4 On-line computer control
The design of a measuring system inevitably involves a decision on whether or not to

use digital techniques in addition to analog circuitry. If digital techniques are to be used
it must be decided at which point in the measuring chain the transition from analog to
digital has to be made, and also which part of the measurement should be under digital
control. For this decision-making process all aspects of the measuring problem must be
treated as parts of a single system in its broadest sense. Items to be considered typically
include sample preparation, sample handling, sample identification, the treatment of
standard samples, the selection of measuring parameters which may be different for
different samples, the actual measurement, calibration, data reduction, and the manner
in which the results are presented for further processing, which may involve a certain
amount of purely administrative tasks. The different possible systems configurations must,
of course, always take into account obtainable accuracy and economic feasibility.
These system considerations must be studied for all measuring systems. However,
depending on the application, it may be decided that many of these tasks should not be
automated but rather be performed by human intervention. Even the manual tasks must
be carefully studied as being an integral part of the complete measuring process.
Some of the system considerations were mentioned in the introduction where it was
indicated that making calculations in the data-reduction process is better suited to digital
than to analog techniques in much the same way that the experimenter in the laboratory
uses numbers in decimal notation to reduce his data. Similarly, the experimenter who
controls a measurement by operating a switch, performs a digital control function. Such
digital control functions, as we have seen, are properly handled using digital techniques.
Hence even a simple semi-automatic system without data reduction, but possibly with
digital output capability, will require the use of digital techniques. When digital tech-
niques are used and some amount of data reduction is required, this added function is also
best performed using digital circuits.
A large variety of analytical instrumentation has been built in which analog and digital
techniques are combined automatically to perform the measuring and data-reduction
tasks. In most cases these instruments were designed to perform one well-defined set of
functions. This type of instrumentation tends to become large and expensive very rapidly
and to make even minor modifications often requires extensive redesign and rebuilding.
It is for these reasons that the concept of on-line control by a small digital computer
has found widespread use in recent years. The price of small process-control computers
has dropped sharply during the years 1965 to 1968 and continues to decrease so that their
use becomes more feasible.
Once the size of an instrument system justifies the use of a control computer, the whole
system concept can change radically. However, before some of these implications are
discussed the question must be asked if the use of a computer will reduce the design
effort. The design of logic circuits for control and data-handling functions is very similar
to writing a computer program. Because of this, the realization of a computer-controlled
instrumentation system requires essentially the same amount of design as is needed for
a conventional system using an individually designed logic system. In addition to writing
the computer program, circuitry must be designed and built to convert the measured
quantities which are normally analog signals, into digital form suitable for use in the
computer. The circuitry that performs this function is called the interface which ties the
computer to the measuring instrument. In some cases the interface may resemble the analog
systems that would be used without computer control. However, ifthe computer is used effi-
ciently the interface can be rather simple and some of these possibilities will be discussed
below.
The design eifort, then, is in general not reduced by employing "on-line" computers.
However, the need for constructing a unique digital control system to implement a unique
design disappears. The same computer, using different programs, can be used in a variety
of instruments. Also, as soon as the design effort is completed, the program can be tested
without having to wait for construction to take place.
This approach also has other implications. If the need arises to make modifications
in an existing instrument to match the changing requirements posed on the measuring
system, these modifications can often be achieved by making changes in the computer
program, in contrast to circuit modifications that would have to be made in conventional
digital control systems. Of course, a conventional system would be inoperative while such
changes were made and tested. In the case of a computer-<:ontrolled instrument, however,
the original procedure can be restored by entering the old program into the computer.
In this way the use of an on-line control computer offers a maximum of flexibility to the
system.
Not only does the on-line computer add flexibility, it also opens up entirely new possi-
bilities because of the data-reduction capabilities. The most obvious case occurs when
non-linear calibration curves are involved. Such nonlinearities are very difficult and ex-
pensive to perform using analog circuits. The computational facility of the computer can
replace circuit complexity in the analog portion of the system although it requires more
complexity in the computer program. This concept of replacing and simplifying circuitry
using the computer program is fundamental and a very important one.
The concept can be extended in many ways. For instance, the computer can be used
to be an integral part of the synchronous detection process. The synchronous detection
4.4] ON-LINE COMPUTER CONTROL 179
system consists of chopping the signal and integrating the signal over a large number
of chopping cycles (see Section 4.2). The integration alternates in sign during the two
halves of each chopping cycle. The use of a computer opens up the possibility of integrating
only during one half of the chopping cycle with analog techniques and letting the com-
puter perform the function of subtracting the results during alternate parts of the cycle
and continuing the integration over a selected large number of cycles. One advantage of
such an approach would be that the stability requirements on the analog integrator could
be greatly relaxed, thus again reducing circuit complexity and increasing the accuracy ofthe
measurement. The same is true for a system as is shown in Fig. 4.17 where the computer
would be used in the basic synchronous detection process at the chopping frequency, and
also to handle the sample-modulation process.
In the larger systems where many samples have to be automatically analyzed, the
computer can be used to perform the administrative tasks involved in identifying the
samples, deciding which parameters must be measured for each of these samples, and
finally how the reduced data is to be presented.
Another fundamental task that can be performed by the computer is that of applying
the principle of feedback to the complete measurement. This is possible because the com-
puter can be programmed to make decisions on the basis of the results of a measurement.
Measured parameters can then be used to modify the experimental conditions to suit the
samples being measured in order to achieve a certain statistical accuracy. For example
in spectroscopic measurements, the computer can be used to change the integration time
or the flame conditions. When the concept of sample modulation is used, the computer
can decide, for instance, which standard samples are to be used in this measurement.
With this concept of feedback the accuracy of the measurement can be improved over
that possible with conventional techniques. It is also possible, in principle, to program
the computer to take into account the known systematic errors and thereby greatly
increase the accuracy of the results.
The extension of the role of the computer to become an integral part of the measuring
system requires larger and more complicated programs. The reduction of circuit complexity
in the interface and the additional demands placed on the computer are reflected in the
need for greater computer speed and memory capacity. The proper choice remains one
of economical feasibility where total cost should reflect both the design effort required,
total systems cost and the potential saving in manual labour made possible by the system.
Needless to say this choice can be made only after a careful system study.
Because of the flexibility that is afforded by the use of an on-line computer and because
of the potential benefits that can be obtained in terms of reducing the complexity of
measuring circuits, increasing the accuracy and convenience, the use of computers in
instrumentation has already acquired great importance. The increased use of computers
will undoubtedly continue to develop in the coming years when more experiments will
be reduced to practice using these techniques. As this occurs the scientific laboratory will
at first be provided with a number of small computers each dedicated to one or two
experiments. At a later date, a larger computer can be programmed to time-share the
control of a number of experiments. The experimenter will interact with the system in
a similar manner whether he uses a small individual on-line computer or a time-shared
larger machine. Because the use of the large machine is shared there can be an overall
saving in cost for the combination of automated experiments. By time-sharing the exper-
imenter will benefit from the increase in computational power that would be too expensive
to obtain in small computers.
180 PRINCIPLES OF ELECI'RONIC INSTRUMENTATION [4
References
General
ARGUIMBAU, L. B., R. B. ADLER, Vacuum-tube Circuits and Transistors, 646 pp., J. Wiley & Sons,
Inc., New York (1957).
KLEIN, G., J. J. ZAALBERG VAN ZELST, Precision Electronics, 466 pp., Philips Technical Library
(1967).
ANGELO, E. J., JR., Electronic Circuits, 450 pp., McGraw-Hill, Inc., New York (1958).
TERMAN, F. E., J. M. PETTIT, Electronic Measurements, 707 pp., McGraw-Hill, Inc., New York
(1952).
Re/erence Data for Radio Engineers, 1120 pp., International Telephone and Telegraph Corpo-
ration, New York (1956).
TERMAN, F. E., Radio Engineer's Handbook, 1019 pp., McGraw-Hill, Inc., New York (1943).
Transistors
CoBLENZ, A., H. L. OWENS, Transistors, Theory and Applications, 313 pp., McGraw-Hill, Inc.,
New York (1955).
HURLEY, R. B., Junction Transistor Electronics, 473 pp., J. Wiley & Sons, Inc., New York (1958).
SEVIN, L., JR., Field-effect Transistors, 130 pp., McGraw-Hill, Inc., New York (1965).
WALLMARK, J. T., H. JOHNSON, Field-effect Transistors, 376 pp., Prentice-Hall, Inc., Englewood
Cliffs, N. J. (1966).
Analog and digital computers
SCOTT, N. R., Analog and Digital Computer Technology, 522 pp., McGraw-Hill, Inc., New York
(1960).
KORN, G. A. and T. M. KORN, Electronic Analog Computers, 584 pp., McGraw-Hill, Inc., New
York (1956).
PHISLER, M., JR., Logical Design 0/ Digital Computers, 408 pp., J. Wiley & Sons, Inc., New York
(1963).
LEDLEY, R. S., Digital Computer and Control Engineering, 835 pp., McGraw-Hill, Inc., New York
(1960).
Noise
SCHWARTZ, M., In/ormation Transmission, Modulation and Noise, 454 pp., McGraw-Hill, Inc.,
New York (1959).
VAN DER ZIEL, A., Noise, 450 pp., Prentice Hall, Inc., Englewood Cliffs, N.J. (1954).
Feedback systems
BROWN, R. G., J. W. NILSSON, Introduction to Linear Systems Analysis, 403 pp., J. Wiley & Sons,
Inc., New York (1962).
TRUXAL, J. G., Automatic Feedback Control System Synthesis, 675 pp., McGraw-Hill, Inc., New
York (1955).
CHAPTER 5
NONMETALS
Paul T. Gilbert
Beckman Instruments, Inc.
Palo Alto, California, U.S.A.
5.1 Introduction
This chapter will cover the detection and determination of the elements hydrogen, boron,
carbon, silicon, nitrogen, phosphorus, arsenic, oxygen, sulfur, selenium, tellurium, the
halogens and the noble gases by direct emission flame spectroscopy. The term direct
means that the observed light is emitted by a species containing the analyte; examples
are C, C 2 and CH for carbon, CuCI for chlorine. The term spectroscopy will include
every means of detecting or measuring the light from the flame; after all, every practical
photodetector, including the eye, is spectrally selective. In some recent methods for non-
metals, the photodetector views the flame directly, receiving its whole spectrum.
The discussion will emphasize principles and perspectives. No cookbook procedures
are offered; it is not yet time to select them. The field is at an awkward juncture. Despite
a century-long history, the flame-emission determination of most of the nonmetals is
only now becoming really practical, thanks to the new interest in their determination at
trace concentrations, spurring application of modem instruments to old and forgotten
- or in some cases newly found - phenomena in the flame. For those wanting advice
on practical analysis, I have prepared tables showing, for each element, the basic charac-
teristics (instrument components, sensitivity, interferences, etc.) of every published and
unpublished method that has come to my attention.
Direct emission methods are available - though they have not all been put to use -
for all the nonmetals except the noble gases. I hesitate to say that the noble gases cannot
be determined directly, since such statements have a way of being proved wrong soon
after they have been made. After all, excitations as high as 9 electron volts may be seen
in ordinary flames. But the noble gases can be determined by indirect emission flame
spectroscopy, in which the observed emitting species does not contain the analyte. Indirect
methods are useful for most of the nonmetals, and in this chapter some of the more
interesting examples will be mentioned. General discussions of indirect emission flame
spectrophotometry are found in References [1-6]; [7] covers the years 1960--64.
Some of the direct emission methods have proved exceedingly valuable. For example,
the S2 and HPO emissions in the chilled hydrogen flame offer the best method of deter-
mining sulfur and phosphorus in certain applications of gas chromatography. But other
emissions, e.g., the continuum of arsenic, have not yet been used by anyone, so far as
I know. To help in comparing emission flame spectroscopy with closely competitive
methods that may be more useful in many applications, I shall include a little of the
latest work on atomic absorption and atomic fluorescence spectroscopy and on emission
and absorption spectroscopy employing electric discharges that are flame-like in being
exceptionally stable.
182 NONMETALS [5
Koirtyohann's critical and up-to-date review [8] on atomic absorption and flame emis-
sion compares the two methods without bias; he includes references also on indirect
methods. Christian and Feldman [9] describe a large variety of novel methods of indirect
absorption flame spectrophotometry.
Among discharges, the radiofrequency plasma torch of West and Hume [10] was the
first that combined good stability (about 1 %) with extremely high detection sensitivity
(in the parts-per-billion range for many elements). Although West studied no nonmetals,
similar discharges have more recently been used with high success for the determination
of nonmetals. For current information on methods peripherally related to flame excita-
tion, as well as flame spectrophotometry itself, consult the series of reviews by Margoshes
and Scribner [11].
Detection limits will often be quoted. Although by no means necessarily the most
important characteristic of an analytical method, the detection sensitivity looms large in
spectrochemical analysis simply because this kind of analysis is usually very sensitive and
is often used for that reason. However, the proper method of expressing detection sensitivity
has long been a matter of debate, and the subject is difficult. Winefordner and his associ-
ates have done some of the most helpful recent work on defining detection limits; see their
latest paper [12], which includes references to their other work. Ramirez-Munoz [13]
has clarified the terminology, and I favor his terms percentual and fluctuational detection
limits (concentration limits, in the commoner case in which the least detectable concen-
tration of analyte - as distinguished from the least detectable absolute quantity - is
under consideration). I have not tried to convert published detection limits to a uniform
basis, but have quoted the authors' values. Usually, not enough information is given to
permit recalculating the detection limit.
5.1.1 IMPORTANCE OF THE OLD WORK
In seeking the earlier papers on the flame spectroscopy of the nonmetals, I have been
especially aided by Mavrodineanu's bibliographies [14, 15] and by Kayser's Handbuch
der Spectroscopie. Kayser's labor was immense. In the preface to Vol. VI [16] he said
that he had read 14,000 papers during the 32 years it took him to write the first six
volumes; and he regretted that his memory had grown too poor to permit him to keep
going, except for adding revisions.
Salet's paper [17] on the spectra of the nonmetals has a useful and detailed history
of spectroscopy up to 1873.
Some readers may wonder why emphasis is laid upon the early work. There are several
reasons.
(1) The generation gap has become grievous. Kaiser [18], at the last Colloquium Spectro-
scopicum Internationale, said: "The main problem in spectrochemical analysis ... is a
problem of generations ... The things which have been known for decades or half a
century have been entirely forgotten or not taken up by the young people." This is
peculiarly true of the flame spectroscopy of the nonmetals, which goes back more than
a century. Mavrodineanu, well aware of this problem, says of the older work [14 (p. 663)]:
" ... these often forgotten and truly original contributions will help the scientist avoid
reproducing or rediscovering phenomena known for a long till1e; he will thus be protected
from crashing head first through wide open doors." Fine examples of such crashing
5.1] INTRODUCTION 183
through open doors may be found among the very latest papers on the flame spectro-
photometry of nonmetals.
(2) The excellence 0/ the old work is sometimes very high by modern standards, and
such work has direct application to present-day problems. Salet's work on phosphorus
and sulfur, long forgotten and now being rediscovered and put to use in severallaborato-
ries, is a prime example. In some cases, nothing new has been done except to use a photo-
detector to view Salet's flame. Some of the recently published spectrograms of phosphorus
and sulfur, apparently thought by their authors to be new, are inferior to century-old
spectrograms in both resolution and accuracy. The same can be said ofthe CuCI spectrum;
a paper in Analytical Chemistry offers a recording for CuCI that is on the whole less
useful than Herschel's original hand-drawn intensity trace published in 1823 [19]. Swan
in 1857 [20] measured and mapped what are now called the Swan bands, accurately to
the nearest angstrom, referring them to the Fraunhofer lines; later spectroscopists, after
the wavelengths of the Fraunhofer lines had been measured, converted Swan's data to
wavelengths. The most popular modern spectrophotometers cannot record the Swan
bands with either the resolution or the wavelength accuracy to be found in Swan's work,
and there are recent papers in reputable journals showing recordings of the Swan bands
that are atrocious by Swan's standards. Mitscherlich in 1864 [21] published a long paper
on the flame spectra of many elements; the spectra were mapped with great care against
a fine, precise scale, with the Fraunhofer lines shown for reference.
These are examples of good wavelength accuracy. Modern spectrochemists may feel
proud of the photometric precision of present-day instruments. But there is a paper by
Gouy [22], 90 years ago, that repays close study. Without benefit of either diaphragm
pressure regulators or photoelectric detectors, he built a flame spectrophotometer that
could give readings more reproducible than any but the very best modern instruments.
With his split-field polarizing photometer, he obtained averaged readings with a relative
standard error of about one-half percent, as may be seen in one of his tables of anion
interferences. Yet he was concerned only with the physics of the flame; he had no interest
in spectrochemical analysis, for which his instrument was admirably suited. Most modern
work in flame spectrophotometry is of lower photometric precision than Gouy's.
(3) The beauty of the spectra has been lost. That is a great pity. It is a rare spectro-
chemist who these days ever looks through his instrument; indeed, most instruments do
not permit this. Flame spectroscopy used to have, and ought still to have, a powerful
two-fold motivation that keeps its devotees enthusiastic: the pleasures of flame watching
and the magnificence of the visible spectrum. Flame photometrists can still play with fire;
but they have forgotten the colors of the spectrum.
That loss was poignantly borne in upon me as I read the old literature. Many spectra
are among the most compellingly beautiful visual phenomena that man can behold. Thus,
Salet [17] speaks of the "magnificent channeled spectrum" of CuBr. Weith [23] mentions
the "singularly beautiful spectrum" of boron in the flame. Bottger [24] speaks of the
very rich spectrum of the cyanogen flame and says that copper chloride in the Bunsen
flame gives the most beautiful spectrum of all. Attfield [25], who first established that
the Swan bands are due to carbon, says: "The spectrum of carbon is a very beautiful
one. The lines composing each band oflight regularly diminish in brightness in the direction
of greatest refraction, and appear to retreat from the observer like pillars of a portico seen
in perspective." Draper in 1848 [26], on looking through a spectroscope at the cyanogen
flame, said: "There was a spectrum so beautiful, that it is impossible to describe it by
words or depict it in colors."
184 NONMETALS [5
But many of the early workers did in fact depict their spectra in colors. One runs across
many beautifully printed colored spectra in some of the journals and books. In the oldest
journals, the spectra are individually hand painted, sometimes rather sloppily but often
with loving care. However, Poggendorff, the editor of Annalen der Physik, felt obliged
to offer only black-and-white spectral maps; in two papers [27,28] that I saw, he adds
a footnote regretting that he could not afford to publish the colored spectra submitted
by the authors.
Now, it is a curious fact that modem color photography cannot reproduce the natural
spectrum with satisfactory fidelity. Learning this, we at Beckman Instruments were forced
to paint a picture of the spectrum when we wanted it for an instruction manual [29].
Our artists labored heroically to get the colors as exact as they could be made with pig-
ments on paper and finally turned out the best artificial spectrum I have ever seen. Even
so, the printed version does not do justice to the original painting, much less to the natural
spectrum itself.
(4) Looking at spectra is useful as well as pleasurable. Kirchhoff and Bunsen [30]
pointed out that exact measurement is unnecessary for the experienced spectroscopist in
qualitative analysis; spectra can be recognized by the colors, relative positions and bright-
ness, and shading of the bands and lines. That remark remains valid today. At least in
the visible range, no spectrophotometer can present as much immediate information as
can be gathered by the eye looking through a spectroscope. Visual spectroscopy can be
of great help in many problems. I urge every flame photometrist to keep a direct-vision
spectroscope handy.
The advantages of instrumental spectrophotometry are, of course, greater speed and
relief of eye-strain. It is easier to push buttons and read a meter or a digital printout than
to squint into an eyepiece trying to match the two halves of a field of color by maneuvering
a knob. For example, Stahl [31, 32] as recently as the 1930's recommends a leisurely
procedure in the visual flame-photometric determination of boron. He cautions that the
analyst must not be hasty or fatigued by the day's work. For some reason, such recom-
mendations are hard to find in the instruction manuals of modem analytical instruments.
One feels like asking whether the furious emphasis on speed and bulk of data in these
latter days is worth the loss of half the pleasure of doing a chemical analysis - especially
in flame photometry.
5.1.2 OVEREXCITATION
Many of the most useful applications of flame spectroscopy to the nonmetals depend
on one or another variety of overexcitation. The emissions are brighter than they would
be if all processes were at equilibrium. This phenomenon is often called chemilumines-
cence, but that term should be restricted to cases in which chemical reactions are known
to cause the luminescence.
There has been so much progress in the study of overexcitation in the last few years
that I cannot undertake to review the subject. Instead, a few matters of special interest
for the nonmetals will be mentioned here and, as needed, in the separate sections on the
individual nonmetals.
Gouy [22] was the first to make accurate observations of the overexcitation of certain
metals (Fe, Mn, Co, Bi, Sn, Zn, Cd, Pb, Ag, Os and the chloride bands of Pt) in the
reaction zone of the Bunsen flame. For up-to-date, general surveys, see Alkemade [33]
and Mavrodineanu and Boiteux [14]. For basic and important studies and discussions
(no longer quite up-to-date), see especially Gaydon [34], Bulewicz and Padley [35] and
Sugden [36]. Dissociation energies, needed in many of the calculations on chemilumines-
cence, are tabulated by Gaydon [37] and Wilkinson [38].
There are various kinds of overexcitation. One of the most curious, apparently not yet
understood, is the phenomenon shown especially by tin, which exhibits an abnormally
high population of free atoms in the cooler hydrogen flames. This was first noticed by
Gilbert [39] and was further studied and utilized in emission and absorption by Capacho-
Delgado and Manning [40], Allan [41], Gibsonetal. [42] and Kahn and Schallis [43].
Whether this same effect is at work with arsenic and selenium, which can be determined
by atomic absorption best in cool hydrogen flames [43, 44, 45, 46] is not yet clear.
The special chemiluminescence shown most strongly by sulfur and phosphorus in cool
hydrogen flames has been known for a century, and will be discussed in the sections on
those elements. It has been studied most closely for practical analysis by Dagnall et al.
[47,48]. These overexcitations are due to distinct mechanisms peculiar to each element.
Although Gilbert [49] had found the air-hydrogen flame (cooled by the water spray)
unexpectedly good for certain elements (such as Cd, Ba, Yb, Co, Ag), it remained for
Zacha and Winefordner [50] to go one step further with the "argon-hydrogen" flame in
a sprayer-burner * (that is, argon does the spraying; entrained air serves as oxidant).
For many elements, this flame has unusual virtues. They may be due both to the low tem-
perature of a diffusion flame of hydrogen diluted by argon and water spray, and to the
low quenching cross section of argon. Hooymayers and Alkemade [33, 53, 54, 55] have
found that both argon and water have very low quenching cross sections, far below
those of nitrogen and carbon dioxide. In these flames many elements seem to be overex-
cited or overatomized or both, and the low concentration of good quenchers enhances
the overemission. The extremely low background emission of the cool flames is also a
great help.
A better known variety of overemission occurs in the reaction zone of hydrocarbon
flames. There is a large literature on this. The principal contributions to analytical flame
photometry utilizing this overemission have been made by Buell [56, 57, 58, 59], Carnes
and Dean [60, 61, 62], Dean and Simms [63], Fassel and his associates [64, 65] and
Gilbert [39, 49, 67]. The premixed oxyacetylene sprayer-burner now commonly known
as the Kniseley burner [64] has proved particularly useful for elements not readily deter-
minable by emission in other flames.
More than one chemiluminescent or chemiionization reaction must be at work in these
flames, depending on the element. One reaction that I believe is especially important in
many cases but has not been fully discussed in the literature is the one proposed by
J. C. Sternberg of Beckman Instruments; he suggested it to Dean and Simms, who
mentioned it in their paper [63]. According to Sternberg, CH and 0 undergo a primary
reaction to give H and excited CO in what is now known [68] to be a 3.1 state at 7.6 eV.
*) The name of this device should be settled. It goes by many names, such as "total-consumption
aspirator-burner." It was originally christened "atomizer-burner," but the word "atomizer"
is now frowned upon in this use. The term "atomize" should be restricted to mean convert
to atomic vapor, and it is so used by many atomic absorption spectroscopists (e.g. [51]).
What has heretofore been called an "atomizer" is now called by many a "nebulizer"; but I
can find no reason for preferring "nebulizer" to the shorter word "sprayer". Therefore, both
the inventor and the manufacturer [52] now urge that the device be known as a sprayer-burner.
186 NONMETALS [5
The CO· may directly excite or ionize an atomic element M, or, more commonly, it may
react with an oxide MO to give CO z and an excited or ionized atom of M. I have collected
a good deal of evidence favoring these mechanisms, but cannot present it here. The
hypothesis has been mentioned or discussed in a few further papers [7, 33, 66, 67] and
in Mavrodineanu and Boiteux's book [14 (p. 553)].
One useful byproduct of chemiluminescent flame photometry was establishment of the
radiance of light sources at short wavelengths, down to 2000 A. On the basis of his
studies of tin in air-hydrogen, Gilbert [39] suspected that the oscillator strengths given
in Corliss and Bozman's large table [69], which were based on an extrapolation of the
radiance of a hydrogen lamp, were in error below 2500 A. When Penkin and Slavenas [70]
published their accurate oscillator strengths for tin, the discrepancy was verified and could
be measured quite closely [66]. It has been confirmed by Corliss [71, 72], who has revised
the tables [73]. Since the correction amounts to 2 orders of magnitude for the strongest
lines of arsenic and selenium, it is important in any calculation affecting the flame photo-
metry of these nonmetals.
One of the most interesting of the new flames (new only in application; it was first
burned long ago) is the nitrous oxide-acetylene flame. This is a very pretty flame with a
brilliant red interconal zone, the "red feather." It became popular after Willis [74] first
pointed out its special virtues for atomic absorption, including a slow burning velocity
and an extraordinary ability to atomize and excite difficult elements such as titanium and
tungsten. Amos and Willis [51] extended this work, and further papers on this flame keep
coming out. Burners for the flame are now sold by several manufacturers. Pickett and
Koirtyohann [75, 76] found the nitrous oxide-acetylene flame exceedingly useful for
emission flame spectrophotometry too, and reported unprecedented detection limits for
some elements. I have seen no papers on the mechanism of the apparent overexcitation
occurring in this flame, but Kirkbright et al. [77], as reported by Alkemade [33], thought
that the CN and NH radicals present in the reaction zone might account for the excessive
atomization (dissociation of oxides), and that slow recombination could enable the
abnormal atomic concentrations to persist above the reaction zone.
5.2 Hydrogen
5.2.1 DIRECT FLAME EMISSION
Neither the atomic spectrum of H nor the molecular spectrum of Hz has been observed
in flames, but certain compounds of hydrogen emit strong band spectra. The best known
is OH, whose spectrum was attributed to water in the old days. CH, NH and H 2 0 are
also very commonly seen. The HzO bands in the red and near infrared are due to vibra-
tional, not electronic, transitions. Vibrational bands of water and other molecules are
very intense in the farther infrared, and cause the radiant heat that can be felt close to a
nonluminous flame; but the infrared region beyond about 1 micron has not yet been
used in analytical flame spectroscopy and will not be discussed here.
Tables of wavelengths and intensities and me!iium-resolution recorded spectrograms
of CH, NH, OH and H 2 0, prepared for the practical flame photometrist, are found in
5.2] HYDROGEN 187
Herrmann and Alkemade's book [3]. Similar tables and photographic spectrograms for
the practical molecular spectroscopist are found in Pearse and Gaydon's book [78].
Gaydon [34] gives detailed discussions of CH (Chapter vn of his book), OH and H 2 0
(Chapter V), and he provides helpful tables for these molecules and NH, along with
many interesting spectrograms. Mavrodineanu and Boiteux discuss all these emissions
in Chapter 18 of their book [14] and show densitometric recordings (pp. 570-579). See
also the critical and thoroughly documented French compendium edited by Rosen [79]:
CH on p. 61, NH on p. 209 and OH on p. 230. Wallace [80] provides a valuable summary
of the band spectra of CH, NH and OH. Bass and Broida [81] have published an indis-
pensable spectrophotometric atlas of the OH emission in the oxyhydrogen flame; the
resolution is 0.1 A.
Physicists have often determined concentrations of atomic hydrogen and hydroxyl in
flames by means of the CuH and CuOH emissions; copper is introduced for the purpose.
Hollander discusses this in his thesis [82]. He used a dry carbon monoxide-oxygen flame
to measure the dissociation energies of alkaline-earth oxides. To avoid the formation of
emitting molecules such as CaOH, hydrogen had to be excluded. Hollander studied the
intensity ratio of the green CuOH and the orange CuO bands as a function of water
content, and he noted that the CuH bands appear in the presence of very little water.
The OH bands in particular provide a very sensitive means of detecting traces of water
(or presumably of any hydrogen compound in an oxygen flame). Hollander's data suggest,
however, that the intensities of the CuH and OH emissions are not linear functions of
the hydrogen concentration; the slope is steeper at lower concentrations. Gaydon [34
(p. 102)] discusses the marked effect of water and hydrogen upon the carbon monoxide
flame. The flame may fail to burn at all if it can be made sufficiently free of hydrogen.
Cyanogen is another hydrogen-free fuel. If the gases are not specially dried, the NH
band at 3360 A is strong [3 (p. 578)], and OH and CH will appear [34 (p. 162)]. Water
also suppresses the C 2 and CN emission in oxycyanogen [34 (p. 136)].
Since the wavelengths of the CuH bands are shifted conspicuously when heavy water
is added to the flame [82], an isotopic analysis of hydrogen compounds might be carried
out by means of these bands. Wavelengths for CuH and CuD are given by Rosen [79]
and in the supplement (p. 367) of Pearse and Gaydon [78].
No one seems to have used flame photometry for the practical determination of hydro-
gen, but there is no question that it can be done with good sensitivity and precision. All
that is needed is a hydrogen-free flame and (unless the sample is to be fed to the flame
undiluted) a hydrogen-free solvent. For example, to determine hydrogen in organic com-
pounds, I would suggest spraying the sample, perhaps diluted with carbon tetrachloride,
into a sprayer-burner flame of carbon monoxide or cyanogen with oxygen. The OH peak
at 3067 or 3090 A might be the best one to measure. The Beckman sprayer-burner will
handle these flames if it is equipped with the sheath [39, 49, 84]. However, the carbon
monoxide flame tends to blowout unless the oxygen pressure is kept low. The cyanogen
flame is more practical; it is very stable and does not overheat the burner, but the fuel
is costly.
The method might be extended to the analysis of insoluble samples for hydrogen by the
slurry-spraying technique of Gilbert [49, 85]. The finely ground sample would be quan-
titatively suspended in a hydrogen-free liquid and sprayed into the oxycyanogen flame.
These suggested methods are appealing because of their great speed and potential preci-
sion. Whether their other analytical characteristics would be satisfactory remains to be
discovered.
188 NONMETALS [5
5.2.2 INDIRECT FLAME EMISSION
Goldberg [86] determined hydrogen and oxygen below 50 ppm in sodium, potassium
and NaK by a modification of the Pepkowitz-Judd method (see Section 5.9.2). I have
seen only an abstract of this paper and do not know the details.
5.2.3 ELECTRIC DISCHARGES
Chakrabarti, Magee and Wilson [87] used a Tesla discharge at about 236 kHz and 5-15 kV
in a modified flame spectrophotometer. The sample was confined at reduced pressure in
a tube with a silica window. With ammonia, the bands of NH2 and NH and the Balmer
line of H at 4861 A were emitted. No quantitative work was done.
Much more practical is the microwave electrodeless discharge of McCormack, Tong
and Cooke [88]. Although introduced only four years ago, it has already been put to
use for the very sensitive determination of most of the nonmetals, especially in gas-
chromatographic applications. With a Jarrell-Ash grating spectrophotometer at 3090 A,
the OH emission permits detection of water at a flow rate of 2 [lg/s. At 4861 A, hydro-
gen gas can be detected at 2 ng/s. The OH bands would presumably be emitted by any
hydrogen compound if oxygen were present too.
5.3 Boron
5.3.1 THE FLAME SPECTRUM
Gmelin's Handbuch der anorganischen Chemie summarizes much of the literature on the
flame spectrum of boron through 1949, including the question of the origin of the green
bands [89 (pp. 24, 139), 90 (p. 86)]. Kayser's Handbuch der Spectroscopie also covers the
literature (to 1934), more from the spectroscopic than the chemical point of view [91 (p.
134), 92 (p. 77), 93 (p. 146)].
Herschel [19] was the first to report the spectrum of the green flame of boric acid in
alcohol. Fig. 5.1 is copied from his drawing. It is the visual counterpart of what today
R Y G B v
Fig. 5.1 Flame spectrum of boric acid in alcohol, after Herschel [19].
5.3] BORON 189
would be a spectrophotometric recording. Unfortunately, Herschel left out some bands;

his verbal description shows that the four middle bands must have the wavelengths that
I have marked on the drawing, but there should be more bands in the red and the violet,
and the 494 nm band is too far into the blue.
There is one other pre-spectrochemistry paper on the boron flame spectrum. Miller [94]
published a hand-painted map. He saw the blue bands at 472 and 454 nm and mentioned
an indigo line which, from its position, was probably the sharp CH band at 431 nm.
After Kirchhoff and Bunsen's paper in 1860 [30], there was a series of contributions to
the description of the boron flame spectrum: Simmler [28]; Bottger [95]; Mitscherlich
[21], with a fine drawing; Thah!n [96]; Lecoq de Boisbaudran [97, 98], with the first
actual wavelength measurements and a drawing that Kayser calls beautiful; Salet [17],
who introduced boron chloride and fluoride and boric acid into the hydrogen flame;
Horner [99], using a blowpipe; Smyth [100], with a map showing intensities; Eder and
Valenta [101], who first photographed the ultraviolet bands; Vogel [102], with a map of
visual intensity vs. wavelength that can be quite accurately interpreted, for air-gas and
oxygen-gas flames; and de Gramont [103], in oxyacetylene.
Flames of city gas, natural gas, ethanol, methanol, glycerol, hydrogen and acetylene,
with air or oxygen, have been used for boron by these and other authors. Gaydon [34
(p. 213)] says that the boron bands are sometimes seen in the blue flame of burning coal.
The earlier authors applied Greek-letter designations to the bands, usually in the order
of brightness; but there was no consistency among authors and the system was abandoned
more than 50 years ago.
The boron flame bands are diffuse except at the highest resolution. The wavelengths
of the peaks are not sharply defined and have been variously interpreted. Table 5.I
compares the wavelengths and intensities from several references, both old and new.
From 408 to 639 nm I favor the wavelengths listed under Herrmann and Alkemade, since
these represent the peaks as seen with the most widely used analytical flame spectrophoto-
meters.
Table 5.1I gives data on boron with the Beckman sprayer-burner and DU spectrophoto-
meter. The original data have been converted to absolute radiance J. J b is the background
or blank radiance with pure solvent spraying; Je is the radiance of the boron continuum
underlying the bands and J a is the net band radiance above the adjacent minima, so that
J a + Je is the total boron radiance above the blank at each peak. Since the bands are
diffuse as seen under analytical conditions, the radiance is expressed in units appropriate
for continua, that is, per unit spectral bandwidth. Values are in watts per cm 2 of flame
area (including the light reflected from the concave mirror - usually the greater fraction
of the total), per steradian of solid angle, per nm of bandwidth, per [lg/ml of boron
concentration. J b , of course, does not entail the boron concentration. The data from my
laboratory at Beckman [109] were obtained with an instrument that had been calibrated
with a standardized tungsten lamp. They are probably good within 20 % at least up to
600 nm. Beyond 600 nm the response of the 1P28 photomultiplier falls steeply, so that
the calibration factor is very sensitive to wavelength, and stray light begins to intrude.
The other instruments [108, 111, 113, 115] were not calibrated but were of the same kind.
For them, the radiance calculations were based on the assumption that the analytically
optimized oxyhydrogen flame with water spraying has a radiance of 1.0 x 10- 8 w/cm 2 .sr.nm
at 450 nm (this is usually true within 30%), and on measured backgrounds of the other
flames and solvents relative to oxyhydrogen with water. The first three columns of Table
5.II show the variation that may be found among three different instruments with what
190 NONMETALS [5
TABLE 5.1
THE BORON FLAME BANDS
Wavelengths in nm of the band maxima as seen at moderate dispersion. Intensities, where
available, to right of wavelengths
Salet a Lecoq a Smyth b Vogel b Auerbach a Eder & Valenta a

[17] [98] [100] [102] [106] [104]
- - - - - 376.8 1
- - - - - 389.4 3
- - - - - 402.0 4
- - - - 409 1 409.4 6
- - - - - 419.1 5
- 435.9 w - 437 d It 435 2 433.4 5
454 452.9 - 452 d 2 453 3 452.9 5
470 472.1 - 473t 2t 471 4 470.9 6
- 493 492 4 492.0
:}
491 494.1 5t 6
{ 517.2
520 519.2 522-3 1 520 6 517 3
521.2
- 543.9 - - 546 2 544.0 8
548 548.0 548-9 2 5471- 7 547.7 2 547.8 10
- - - - - 559.4 4
- - - - 570 1 -
580 580.7 581 t 582 5 580 1 579.5 5
603 603.1 - 600 5 - 603.0 3
620 621.0 - 623 4 - 620.8 3
640 639.7 - 644 3 I - 639.8 3
5.3] BORON 191
TABLE 5.1 (continued)
Hagenbach Konen b.d Gramont

Grenat Pearse & Herrmann & IMavrodineanu
& Konen e et al. Gaydon Alkemade e & Boiteux
[91] [103]
[105] [107] [78] [3] [14]
- - - - - - -
- - - - - - -
- - 402 w - - - -
406 - 409 w - - 408 9 407.5 ?
- - 419 w - - 418 6 419 ?
433 438 w d 435 w 434.6 - 437 12 436.5 vvw
452 451 mw 453 453.5 452 453 30 452.9 vw
470 471 m 470.9 471.0 471 471.5 90 471 w
{ 493 165 }
492 493 mw 492 494.0 493 492 w
495 155
519 518 s - 518.0 518 518.0 300 518 m
-
-
548
-
547 s - } 546.2 545
{ 547.;;-350 548
-
ms
- - - - - - -
- - - - - - -
582 581 m - 578.0 580 579 140 580 m
602 603 mw - 602.4 603 603 25 602.5 w

- 621 w - 623.0 620 620 20 620 w
- I
I
654 vw d - 639.4 639 639 20 640 mw
- 674 vw d - 682 - 682 5 681 ?
I 721 - 721 f -
775 - 775 f -
822 - 822 f -
I
Notes:
d = diffuse; s = strong; m = medium; w = weak; v = very.
a) From Kayser [91].
b) Interpreted by Gilbert.
e) Interpreted by Kayser [91].
d) Spectrogram by Konen in Kayser [91 (Plate I)].
C) Compiled by Gilbert from his own work [6, 108, 109, 110] and that of Buell [111], Boycks
[112], Dean and Thompson [113], Schmidt [114] and Watanabe [115].
f) Taken from Grenat et al. [107].
192 NONMETALS [5
TABLE 5.11
RADIANCES OF BORON BANDS, CONTINUUM AND BACKGROUND IN
BECKMAN SPRAYER-BURNER FLAMES
J. = net band radiance and J c = boron continuum radiance in w/cm2.sr.nm.(flg/ml); J b
solvent background radiance in w/cm2.sr.nm
Flame: Oxyhydrogen Oxyhydrogen Oxyhydrogen
I
I
Solvent: Water Water Water
Gilbert Gilbert Watanabe

Source: [108] [109] [115]
Wavelength J. Jc Jb J. Jc Jb J. Jc Jb
1011 1011 1011
X X X 10 8
I X 1011 X 1011 X 10 8 X X 1011 X 10 8
408 1.1 0.85 1.17

418 0.7 1.05 1.13
437 1.25 1.9 1.05 0.6 0.6 1.05
453 3.2 3.4 0.98 2.6 2.9 0.98 1.3 1.3 0.98
471 9 6 0.94 7.5 5.2 1.02 3.3 2.2 0.95
494 17 11 0.93 14 9.5 1.03 6 4 0.89
518 31 13.5 0.96 29 13 1.01 10.5 4.7 0.94
548 37 13 0.84 42 14 1.12 12 4.5 0.79
579 19 11 0.94 27 14 1.4 6 3.5 0.7
603 4 7.5 1.0 19 2.4 1 3 0.8
620 3.5 5 1.2 1 2.5 0.9
639 3 3 1.5
is nominally the same spectrum. The chief sources of variation are the burners, the gas
and mirror adjustments, and the response of the photomultiplier in the red.
Table 5.111 lists practical "intensity" values of the stronger boron bands in various
flames, for the DU spectrophotometer with sprayer-burner and IP28 photomultiplier.
For diffuse bands, the "intensity" is taken as 1000 (J.+ Jc)/Jb • (Radiance and intensity
for lines will be discussed in Section 5.5.4.) Since the root-mean-square noise of the blank
reading, when the instrument is best adjusted, is close to ! % at a time constant of 1 sec,
the detection limit, defined as the concentration giving a net signal equal to 4 times the
r.m.s. noise, may be found by taking 10 times the reciprocal of the "intensity" of Table
5.1I!' Table 5.111 is based on more data than appear in Table 5.11, and so some relatively
small inconsistencies occur. Similar tables of intensities or detection limits have appeared
in [3, 5, 6, 110, 116, 117].
Photographic spectrograms of the boron bands (assigned to B0 2 ; see below) have
appeared in [14, 78, 91 (Plate I), 104, 105, 118, 119]. A densitometric tracing appears in
[14 (p. 475)]. Spectrophotometric recordings can be found in [2, 3, 6, 111, 112, 113, 120,
121, 122]. Many of these, together with the original recordings by Schmidt [114] and
Watanabe [115], have been used in preparing Table 5.1II. One of the recordings is
reproduced in Fig. 5.2.
5.3] BORON 193
TABLE 5.11 (continued)
Oxyhydrogen Air-hydrogen Oxyacetylene Oxyacetylene

1 : I Naphtha- I : 1 Methanol-
Water Water
isopropanol water
Buell Gilbert Gilbert Dean and

[Ill] [109] [109] Thompson [113]
I
J. Jc Jb J. Jc Jb J. Jc Jb J. Jc Jb
X 1011 X 1011 X 10 8 X 1011 X 1011 X 10 8 X 1011 X 1011 X 10 8 X 1011 X 1011 X 10 8
12.5 29
35 31 20
80 63 29 0.16 0.03 0.08 14 14 15 140 95 43
160 105 19 0.25 0.14 0.09 30 22 14 230 150 47
280 140 14 0.6 0.2 0.10 60 29 15 400 200 43
330 120 13.5 1.0 0.27 0.12 80 30 16 500 200 40
155 100 10 0.6 0.28 0.18 50 35 16
25 75 6 0.28 0.32 40 19
25 25 7
Fig. 5.2. Spectrogram of boron in oxyhydrogen flame.

Beckman DU spectrophotometer with sprayer-burner, IP28 photomultiplier, and spectral energy
recording attachment. Aqueous boric acid, 1000 ppm boron. Slit 0.03 mm. The mercury lines
are due to room light. The wavelength scale is also the axis of zero intensity. Reproduced from
[6] by permission of the American Society for Testing and Materials, and from [3] by
permission of John Wiley & Sons.
194 NONMETALS [5
TABLE 5.III
PRACTICAL INTENSITIES OF THE BORON BANDS IN VARIOUS FLAMES PRO-
DUCED BY THE BECKMAN SPRAYER-BURNER
For definition of intensity see text.
Flame: I Air-hydrogen I Oxyhydrogen Oxyhydrogen Oxyacetylene Oxyacetylene
4% Butanol 50 0 Methanol
Solvent: I Water I Water
in water Water 1 In water
Source:
Gilbert Gilbert Schmidt Gilbert I Dean and
[109] [108] [114] [109] Thompson [113]
I I I
Wavelength
453 1 7 I 15 1.2 2.5
471.5 2.5 20 30 2.5 5
494 5 30 50 5 8
518.0 8 50 80 6 15
547.6 11 60 90 15 17
579 7 30 70 10 10
603 2 10 70 7 5
620
I
1.5 7 50 3
I 3
5.3.2 ORIGIN OF THE FLUCTUATION BANDS
The molecule that emits the diffuse bands of the green flame of boron was not identified
until recently. It is B0 2 • The bands had long been called the "fluctuation bands of boric
acid"; "fluctuation" refers to their smooth wavelike appearance under moderate resolution
(cf. Fig. 5.2), earlier thought to be due to the instability of one of the energy levels.
Soulen in 1955 [123, 124] ascribed them to B2 0 3 on the basis of vapor pressure data for
boric oxide and the fact that its hot vapor (at 1400-1700°) emits the fluctuation bands
free from the bands of BO. Grenat et al. [107] reached the same conclusion. Their paper
reviews earlier work on the origin of the bands. They photographed the spectrum of boric
acid in methanol in the Bunsen flame at high dispersion, revealing a very complex rota-
tional structure.
The first to propose that the bands are due to B0 2 were Mal'tsev and Tatevskii [125]
in 1958. They studied the bands in emission and absorption over boric oxide in the visible
and infrared in various atmospheres, employing boron isotopes [126, 127]. Kaskan and
Millikan [128, 129] independently identified the emitter as B0 2 • They studied the emis-
sion and absorption, in a flat flame containing methyl borate, of HOBO (metaboric acid)
in the infrared at 2040 cm- 1 , B0 2 at 547 nm, and OH in the ultraviolet, and interpreted
the results in terms of a rapid reaction OH + HOBO = H 2 0 + B0 2 • The boron is
present largely as HOBO at 1800°; the B0 2 is most abundant near the reaction zone,
where the OH concentration is high. With Mackenzie, they verified the emitter by a
study of the vapors over boric oxide [130]. Rusin and Tatevskii [131] examined the
5.3] BORON 195
combustion of diborane in a bomb and found that only BO z fitted the data on the green
bands.
Johns [132] observed the BO z bands in absorption following flash photolysis of
BCh-Oz mixtures. His paper includes a fine spectrogram showing the rotational structure.
The isotope shift is revealed beautifully. Johns's analysis of the BO z spectrum is very
thorough; Mavrodineanu and Boiteux [14 (p. 476)] list his data on the visible band heads
with their spectral terms and discuss the origin, history and nature of the bands in some
detail. Ramsay [133] also discusses Johns's results.
The isotope shift in the B0 2 bands is so pronounced that it has to be allowed for in
flame-spectrophotometric analysis [109]. The band peaks of B100 Z are shifted 10 to 15 A
toward shorter wavelengths with respect to those of normal boron. Besides, the band
shapes differ somewhat, so that it is impractical to use a standard of normal boron for
the analysis of samples of boron-lO.
5.3.3 THE BANDS OF BORON MONOXIDE
A fairly good spectrograph will show some structure in the flame bands of boron, and
with sufficient resolution bands of BO can be discerned among those of B0 2 • They are
degraded to the red. The spectrogram by Hagenbach and Konen [105] is the first to show
the BO bands in an are, and Kuhne [134] measured them in the following year; it is not
clear from Kayser's discussion whether Kuhne also saw the bands in his oxygen flame.
Eder and Valenta [104] reported weak BO bands in the green among the fluctuation
bands emitted by the oxyhydrogen flame. Kayser and Konen [93 (p.154)] summarized
the data on the BO bands in 1932.
Singh [119] generated a very intense flame spectrum by dripping water on a piece of
asbestos impregnated with boric acid, held above the inner cone of a Bunsen flame. He
saw bands attributed to BllO in the green and yellow fluctuation bands (518, 548 and
579 nm), but Pearse and Gaydon [78 (p. 75)] disagree with his interpretation. Berl eta/.
[135] exploded pentaborane with air and observed only BO z bands, but the nitrogen-
diluted diffusion flame of pentaborane emits mainly the alpha bands of BO with some
BO z ; the flame is blue. According to Gaydon and Wolfhard [136 (p. 341)], the reaction
zone of the diborane-air flame emits the alpha BO bands, the BH band at 4332 A, and
B lines, while the mantle emits very intense BO z bands. They discuss also air-hydro-
carbon flames containing diborane. For summaries and literature on the BO bands, see
[14, 78, 79].
Porter and Dows [137] observed the violet flame of boron burning in air at 800-1000°;
they listed 20 band heads between 4291 and 5050 A and suggested that they might be
due to BzO z . At higher temperature boron burns with a green flame, emitting the BO z
bands.
5.3.4 THE LINE SPECTRUM
The resonance doublet of boron, 2496.8 and 2497.7 A, representing the line spec-
trum, is hard to observe in a flame, mainly because of the very high stability of the boron-
oxygen bond. The dissociation energy of BO is 8.0 eV. As mentioned above [136], the
reaction zone of burning diborane emits the lines. Gilbert was unable to detect the boron
196 NONMETALS [5
lines with aqueous solutions in the oxycyanogen flame [138] or in the fuel-rich oxyace-
tylene flame [39]. But Robinson [139] observed them in oxycyanogen with ethanol as
solvent, and Buell [56, 57, 58] observed them with naphtha-isopropanol and methyl
isobutyl ketone as solvents in the oxyhydrogen flame of a sprayer-burner. The lines were
strongest 14 mm above the burner tip, in a region characterized by overexcitation. Dean
and Adkins [61,140], with boric acid in ethanol in a fuel-rich oxyacetylene sprayer-burner
flame, reported the lines in the reaction zone (very low in the flame), where they were
strong enough to afford a detection limit of 7 fLgjml [61] or 15 fLgjml [140]. In the oxy-
acetylene flame of the Kniseley burner, Fassel and Golightly [65] measured a detection
limit of 30 fLgjml in ethanol solution.
I believe that the most likely reaction accounting for the appearance of the boron lines
in these flames is
CO*(d 3 L1) + BO --+C0 + B*(2S),

2
which, as written, is thermoneutral within the accuracy with which the dissociation energy
of BO is known; see Section 5.1.2.
5.3.5 DETECTION OF BORON BY THE FLAME COLOR OR VISUAL SPECTROSCOPY
In 1732 C. J. Geoffroy discovered the green color imparted by boric acid to the flame of
burning alcohol [143]. Nearly a century later, in 1827, Turner discovered the test that
goes by his name: if a boron-containing sample is heated with calcium fluoride and
potassium bisulfate, the vapors color a flame green [145]. Little use seems to have been
made of these phenomena for chemical analysis before the Bunsen burner was invented.
From about 1870 until two or three decades ago, the alcohol test and Turner's test and
many modifications of them were in common use. The literature is summarized in Table
5.IV, classified according to the compound of boron that forms and enters the flame.
In the presence of acid, alcohol forms ethyl (or methyl) borate and fluorides form boron
fluoride. Rosenbladt [143] first replaced ethanol by methanol, to exploit the greater vola-
tility of methyl borate, which makes the test easier and more selective.
Gmelin's Handbuch [89 (pp. 35, 49), 90 (p. 86)] reviews the literature on flame tests
for boron through 1949. Many textbooks, from 1853 on (e.g., [182, 183]), discussed the
flame tests [186]. Stahl [142] critically summarized earlier recommendations on the
alcohol test. In the course of time many of these discoveries have faded into oblivion;
Geilmann and Bode [141] pointed out in 1949 that the best form of the Turner test had
been forgotten, although Bunsen had placed emphasis on it.
Meanwhile other analytical methods began competing with the flame test. The turmeric
test was widely practiced, and it is curious to read arguments about the relative merits
of turmeric and the flame. In a debate between Velardi [170] and Castellana [171], the
latter emphasized the precautions needed for a sensitive, specific flame test and declared
that turmeric was not better than the flame. The qualitative flame test remains useful
today; research on it has been done as recently as 1949 [141].
The sensitivity of the test, as seen in Table 5.IV, can be as good as 0.1 fLg of boron,
although most investigators have not gone below 1 fLg. The limiting concentration may
be 1 ppm or better, especially with the help of a spectroscope. In the older alcohol test,
TABLE 5.IV
VI
METHODS FOR THE DETECTION OF BORON BY FLAME COLOR OR VISUAL SPECTROSCOPY t..
'-'
Date I Authors Ref. Reagents; Treatment Materials

Flame Interferences
analyzed
A. Boron enters flame as boric acid
1860 Merz
I [146] H 2S0 4 ; hold in flame Bunsen; H2 0.1 !Jog Various elements
1862 Simmler I [28] H 2S04, on Pt loop; spectro- Bunsen 0.2 !Jog Not Li, Na, K, Ca, Sr,
scope Ba or Pb
1873 Bidaud [148] H 2S0 4, (NH4hS04, or tar- Bunsen <IS !Jog Not Na; Cu can be
taric acid on porcelain sup- distinguished
port
1877 I Dieulafait [153, 154] H 2S0 4, on Pt, 4 mm from H2 best; 1 !Jog Minerals,
flame; spectroscope optional Bunsen
I None brines
Also: porous MgO from Bunsen 2 !Jog Brines
MgCl 2 ignited on Pt loop
1881 I Jones & Taylor [158] B2H6-H2 mixture was burn- t!:!
ed in air and the products I
introduced into Bunsen flame
1887 I Kretzschmar [159] Evap. to 1/3, add HCl, evap. Bunsen Milk ~
in crucible
1895 I Villiers & FayoUe [161] None; hold in flame Bunsen Na, K, Ca, Cu, etc. Wine, food
1896 Doherty [162] Evap. with Na2C03 carbon- Bunsen Milk, wine
ize, extract, evap. with HCl,
heat in current of gas
1896 Ludwig [163] No details available Foods
1897 Hartley & Ramage [164] Direct heating OrH 2 Minerals
1909 Arndt [175] None Bunsen 0.3 !Jog
1918 Gramont [103] None, or HCl or H 2SO 4 ; OrC 2H 2 Minerals
spectroscope
B. Boron enters flame as ethyl borate
1732 Geoffroy [143] Boric acid in alcohol EtOH
1785 Macquer-Leonhardi [144] EtOH EtOH I Water diminishes color
1862 Simmler [28] EtOH + H 2SO 4 EtOH 1 !Jog
'-'
1873 Merz & Weith [150] EtOH + H 2SO 4 ; boil in EtOH \0
-..I
flask
Authors Ref. Reagents; Treatment Flame IDe~ec~ion I Interferences Materials 1.0
Date I limIt analyzed 00
-
I I I
1876 Weith [23] Paste ofH 3B0 3 + EtOH + EtOH
3 vols. H 2S0 4 ; boil
1877 Dieulafait [153] EtOH EtOH Cu, Tl, Te, Ba, Mo, P
1878 Gilm [156] H 2S0 4 or HCl + EtOH; Premixed air-
vapors injected into burner EtOH or Bunsen'
1899 Lenher & Wells [165] 5 : 1 EtOH + H 2SO 4 , Bunsen 0.3 mg Not Cu or Ba
warmed in tube
1905 Castellana [169] KEtS0 4, heat near edge of Bunsen 0.1 mg Not Cu or Cl Milk (ashed)
flame
1906 Velardi [170] Castellana's method: says it NH 3-CuCI 2, CuC0 3,
is not free from interferences NaCl, NH 4Cl,
Na3P04, chloral
1906 Castellana [171] 5 parts KEtS0 4 ; only luke- CuCI 2 : blue
warm; reply to Velardi EtCl: bluish
1907 Beckmann [172] H 2S0 4 + EtOH; next to Bunsen
burner inlet
1907 Beckmann [173] H 2SO 4 + EtOH in dish Bunsen
under burner
1908 Mannich & Priess [174] H 2S0 4 + EtOH; see text Bunsen 2 ppm Not Cu or Ba Food
1911 Fellenberg [178] EtOH + H 2S0 4 ; see text Bunsen 0.2% None Preservatives
I
1914 Pieszczek [180] EtOH + >10% MeOH Bunsen Not Na
1921 Partington [182] H 2S0 4 + EtOH in flask Premixed air- Not Cu or Ba
EtOH
1948 Kreshkov & Vil'borg [194] Et4Si0 4, warm in air current Et4Si0 4 0.1 mg
C. Boron enters flame as methyl borate
1887 I Rosenbladt I [143] H 2S0 4 + MeOH in gas cur- Bunsen or H2 Not Cu
rent; spectroscope
1893 I Gilbert [160] H 2S0 4 + MeOH H2 Cu + CI
1895 Villiers & Fayolle [161] Heat with 1 : 3 H 2S0 4 + MeOH 0.1 mg None Wine (ashed)
MeOH
1905 I Mezger [166] Evap. with Na2C03, ash, I H2 (NaCI gives MeCI) Food
reflux with 1 : 9 H 2S0 4 + ,....,
Vl
MeOH; pass H2 over
Date I Authors Ref. Reagents; Treatment Flame 1
De~ec~ion 1 Interferences Materials Y'
limit analyzed ~
I
1905 Spindler [167, 168] Ash + Hel or H 2S0 4 + I Bunsen 20 [Lg I H 20 decreases sensiti- Food;
MeOH; or paste + 1 : 100 I vity sausage
H 2S0 4 + MeOH warmed I
in gas current
1907 Beckmann [172] H 2S0 4 + MeOH; next to Bunsen
burner inlet
1908 Official German test [174] HCI + MeOH in H2 current H2 Food (ashed)
1910 Revised official test [176] 1 : 20 H 2S0 4 + MeOH Meat
1910 Bertrand & Agulhon [177] Distill alk. ash with H 2SO 4 H2 1 [Lg; 0.5 Foods,
+ MeOH into alk. soln., mix [Lg with tissues
with H 2 S0 4 + MeOH on Pt spectro-
loop held in edge of flame scope
1912 Bertrand & Agulhon [179] Same except H 3 P0 4 + H2 Animal
MeOH tissues
1914 Pieszczek [180] See Section B
1919 Jannasch & NolI [181] Warm with H 2 S0 4 + MeOH MeOH (1 [Lg) NaCI
in tube
1923 Bordas & Touplain [184] Evap., distill with 1 : 15 Bunsen 5 [Lg None Mineral
i
H 2S0 4 + MeOH into KOH waters
soln., evap., boil with 1 : 100
H 2 S0 4 + MeOH, inject va-
por intermittently into flame
1926 Krauss [185] H 2S0 4, MeOH Bunsen Ba; see text
1928 Gabriel & Tanner [186] Evap. with alk., heat with Bunsen 30 [Lg
1 : 2 H 2S0 4 + MeOH in
air current
1930 Bottger [188] Apparatus described; have 0.06 [Lg
not seen paper
1930-1 Stahl [31, 189] 1 : 5 H 2S04 + MeOH; see Bunsen 1 [Lg Not Na or Cu
text
1932-3 McHargue & Calfee [190, 191] H 3 P0 4 + MeOH; spectro- MeOH; 10 [Lg; None Plant, anima
scope with KMn04 cuvet; Oz-MeOH 0.3 ppm tissues; wate
see text
19351 Stahl [32, 142] 1 : 5 H 2 S0 4 + MeOH; see Bunsen 0.8 [Lg Sea water,
text etc.
::8
-
Materials tv
Date Authors Ref. Reagents; Treatment Flame I De~ec~ion Interferences
hmlt
I analyzed 8
I
1937 Calfee & McHargue [192] MeOH in gas stream; spec- OrMeOH 1 ppm
trocolorimeter; see text
1938 Weber & Jacobson [193] 1 : 6 H 2S0 4 + MeOH in MeOH jet in (2 fLg) Glass
air current; see text Bunsen
I
D. Boron enters flame as glyceryl borate
1876-7[ lIes [151, 152] Paste with glycerol on Pt wire Bunsen Cu
1899 I Lenher & Wells [165] KHS0 4 bead + glycerol on Glycerol 10.3mg/mlj
! Pt wire
E. Boron enters flame as boron fluoride
1827-81 Turner [145] 2: 9 CaF2 + KHS0 4 Alcohol?
1873 Kammerer 1 [149] Warm with Si0 2, CaF2 & Bunsen None
H 2S0 4 in tube Z
1877 Chapman [145] 2: 9 CaF2 + KHS0 4 Blowpipe
1877 Le Neve Foster I [155] CaF2 + KHS0 4 Bunsen Fumarole
vapors
1;;
1879 Salet [157] Heat with CaF2 + H 2SO 4
in gas current
Bunsen
I
1893 Gilbert [160] CaF2 + H zS04 in Hz cur- Hz 3 fLg Minerals
rent; spectroscope
1899 Lenher & Wells I [165] KF + KHS0 4 on Pt loop Bunsen 3 mg/ml
1922 Adam (in Lunge & Ber!) [183] HF + H z S0 4, warm in H2 Hz 0.003%
current
1930 Kasey [187] 20 : 1 HF + H z S0 4 Bunsen Cu; not Ba or K
1949 Geilmann & Bode [141] CaF z + H z S0 4 on Pt wire; Bunsen 1 fLg See text
see text
Also in a current of H 2 or gas Hz, Bunsen 0.1 fLg See text
F. Boron enters flame as ammonium fluoborate

1862 I Simmler [28] I Heat with NH4F + H zS04 Bunsen Minerals
1870 Stolba I [147] Evap. with Na2C03, ignite Bunsen Not Cu, P or Mo
with t part (NH 4hSiF 6 in
tube U;
5.3] BORON 201
the alcohol burned as a diffusion flame in air and tended to be luminous, so that the boron
colored only the edges of the flame green. Gilm [156] corrected this deficiency in 1878
by premixing the borate-containing alcohol with air and burning the mixture in a small
Bunsen burner. Others have directed a jet of the alcohol vapor into a separate flame or
passed air or fuel gas through or over the reaction mixture before introducing it into a
flame; see Table 5.IV.
The selectivity varies with the details of the test but is often so high that the green color
may be considered specific for boron. In the first careful study of interferences, Simmler
[28] examined all "flame-greening" elements, viz., B, P, Te, Ba, Mo, Cu and Mn. In a
later age he might have added TI, Yb, Re and perhaps a few others. He was using both
Geoffroy's and Turner's tests and also introducing the sample directly into the Bunsen
flame. Both the visual appearance of the flame and the spectroscope permit distinguishing
boron from the other green-flame elements as well as Na, K, Li, Sr, Ca and Pb, whose
flame colors may mask that of boron. For mineral analysis Simmler favored ammonium
fluoride and sulfuric acid, which presumably convert the boron to volatile ammonium
fluoborate (Table 5.IVF), separating it from interferents.
Dieulafait [153], by controlling the test so as to vaporize the boron only, was able to
estimate the boron content of Mediterranean Sea water at 0.2 ppm. Geilmann and Bode
[141] recommended heating the sample with calcium fluoride and sulfuric acid to 150-225°
just outside the edge of a Bunsen flame to avoid interference from alkali metals, alkaline
earths, molybdates and phosphates; the last two cause a green color if the sample is
overheated. Selenium gives a blue color and copper, thallium, rhenium and phosphides
can give an interfering green color. Alternatively, these authors warmed the mixture in a
current of hydrogen or city gas, which was burned at a silica jet. In this method (which is
sensitive to 0.1 [Lg of boron), tungsten, molybdenum, phosphate and selenium do not
interfere, but copper, thallium (I), rhenium and phosphine do; chromate in the presence
of chlorine can also interfere by forming CrOzClz, which imparts a bright streak and red
tip to the flame. In any case, a blank must be run, since boron in the glass is detected.
An interesting case of interference by barium was noted by Krauss [185]. Barium
forms a bisulfate that is appreciably volatile. Its vapors can be carried from a cool mix-
ture of barium sulfate and sulfuric acid into a flame, coloring it green; the color is en-
hanced by methanol.
Perhaps the commonest application of the flame test was for the detection of boron in
foods. Boric acid had been widely used as a preservative for meat during the 19th century,
but this use was made illegal in Germany in 1902 [89 (p. 49)]. Official procedures for meat
inspection were developed subsequently (e.g., [176]). Spindler [168] built a reactor and
burner for testing unashed foods (Table 5.IVC); the apparatus was manufactured by
Auer & Co., Zurich. It could detect 1 mg of boric acid in 10 grams of sausage. Spindler
limited the sensitivity to avoid confusing boron naturally present with boric acid added
deliberately. Mannich and Priess [174] also worked out a method requiring no ashing.
Five grams of sample is ground with 0.25 ml of 20 % sulfuric acid and extracted with
50 ml of 90 % ethanol; 20 ml of the filtered extract is evaporated with 0.5 ml of 15 %
sodium hydroxide to convert the boron to sodium borate. This is ignited and then mixed
with 2 ml of sulfuric acid and 4 ml of methanol in an annular vessel surrounding a Bunsen
burner. If the sample contained boron, vapors of methyl borate rise into the flame and
color it green. In a lO-gram sample, 0.1 mg of boric acid can be detected. Fellenberg [178]
noted that sugar, nitrates or sodium chloride could interfere. He described the following
method of detecting boric acid in preservatives. One gram of sample is dissolved in 2 ml
202 NONMETALS [5
of hot water and treated with 1-2 ml of hydrochloric acid; the alkali salts and boric acid
crystallize out on cooling. Interferents are thus removed. The crystals are boiled with
4-6 ml of ethanol, which is decanted, mixed with sulfuric acid, and subjected to the flame
test.
5.3.6 SEMIQUANTITATIVE VISUAL AND SPECTROSCOPIC METHODS
The duration of the flame color can be used as a measure of the quantity of boron.
Jannasch and Noll [181] (Table 5.IVC) burned the methanol vapors and estimated the
boron by the duration instead of the intensity of the green color: 1 mg of boric acid
gave the color for 10 seconds. With a smaller apparatus they could detect much less.
Weber and Jacobson [193] (Table 5.IVC) blew metered air through the reaction mixture
and into the side of a fishtail Bunsen flame to create a horizontal methanol flame. The
duration of the color was nearly proportional to the quantity of boron: 80 s at 0.02 mg,
360 s at 0.1 mg. The accuracy was within 10% in the analysis of glass containing less
than 1 % of B2 0 3 •
Visual comparison of three flames supplied with a sample and two standards was
employed by Stahl [31, 142, 189] for determining boron (Table 5.IVC). He used Rosen-
bladt's apparatus [143], passing air over each of the methanol-acid mixtures to three
identical Bunsen burners. The standards ranged from 0.0004 to 0.1 molar and differed
by steps of one decidex (antilog 0.1, or a factor of 1.26). The sample was bracketed be-
tween two adjacent standards; accuracy was usually 15 % or better. Stahl studied in detail
the effects of temperature, acid and water concentration, type of alcohol, and rate of
A. POTASSIUM PERMANGANATE CELL E. CONNECTION FOR SAMPLE FLASK

B. OXYGEN INLET F. VAPOR INLET (CAPILLARY)
C. CHIMNEY G. GAS INLET FOR PILOT LIGHT
D. MICROBURNER H. PRESSURE REGULATOR
1. ALCOHOL OVERFLOW
Fig. 5.3. Apparatus tor burning methyl borate in oxygen, by McHargue and Calfee [190].
Reproduced by permission of Analytical Chemistry.
5.3] BORON 203
ester formation; ethyl bisulfate and ether form rather slowly and may interfere. Stahl
also developed [32] a dual-burner micro-apparatus operating on the same principle.
With it he could determine boron in the range 0.01-0.5 mg B2 0 3 with an accuracy of
20% or better. He determined boron in sea water at 1 ppm.
What might be called an "aphanoscope" was built by McHargue and Calfee [190, 191]
(Table 5.IVC). They viewed the flame through a spectroscope and a cuvet into which
potassium permanganate was run until its absorption bands were just dark enough to
obscure the green bands of boron. The methanol was burned with either air or oxygen;
the oxygen burner is shown in Fig. 5.3. Oxygen gives better sensitivity and a less convex
analytical curve. The sample (plant tissue) was ashed with potassium carbonate, acidified
with citric acid, and distilled with methanol into 10 ml of 0.005 N potassium hydroxide;
this was evaporated, taken up in 5 %phosphoric acid in methanol, and run in the aphano-
scope. Phosphoric was preferred to sulfuric acid because it hastens the formation of
methyl borate and better suppresses interferences.
A dual-flame spectrocolorimeter was described later by Calfee and McHargue [192]
(Table 5.IVC). The burner is shown in Fig. 5.4. The flames were fed respectively with
? 'II ,\ ,
OXYGEN
INLET
GAS
IN LET
- - -
SAMP L E
TUBE
~
Fig. 5.4. One of the two oxygen blast burners of the dual-flame spectrocoiorimeter for boron, by
Calfee and McHargue [192].
Reproduced by permission of Analytical Chemistry.
204 NONMETALS [5
standard and sample solutions, and the boron bands, viewed through a spectroscope, were
matched in brightness with a polarizing filter. The sample material was ignited with
sodium carbonate, extracted, and transferred to methanol containing 5 % sulfuric acid.
The best range was 5-35 ppm of boron, but it could be stretched to 600 ppm. Precision
was better than with the aphanoscope.
In appraising these methods, we have to admit that Stahl's is cumbersome and slow,
and those of McHargue and Calfee will hardly be used where there is a spectrophoto-
meter. But these methods are specific, sensitive and accurate enough for many purposes,
and they demand no outlay beyond the most rudimentary equipment. In Latvia in the
1930's, Stahl could perhaps afford nothing more. No doubt most modern laboratories
possess a spectrophotometer, which makes the trace determination of boron far easier.
But some laboratories in the world cannot yet afford such equipment, and it is there
that these less highly instrumented procedures may still be useful. It is not yet time for
them to die a natural death. I vouch for the utility and remarkably good precision of
both of the McHargue-Calfee methods: lacking a photocell, in 1946 I built an aphano-
scope for sodium having a variable-thickness cuvet (which is quicker and more convenient
than a titration cuvet), and also a polarizing colorimeter for the flame-photometric deter-
mination of lithium. This last instrument, assembled from odds and ends, yielded results
with a relative standard error of 0.5 %.
5.3.7 DETERMINATION OF BORON BY FLAME PHOTOMETRY
The first to use photoelectric photometry for boron in the flame was Boon [195]. His flame
photometer comprised an air-acetylene Lundeg,hdh burner, an external sprayer with
spray chamber, a choice of Christiansen or glass filters (or none), a photocell, and a
galvanometer. Boron was tested in methanol solution without filters. The analytical curve
was straight up to 500 [Lgjml, the blank was equal to the net reading on 125 [Lgjml, the
precision was 1-2 % and the detection limit was considered to be about 10 [Lgjml. To
separate boron from interferents, Boon distilled it as methyl borate into sodium hydroxide
(to avoid loss of boron); to absorb the sodium line, he used a praseodymium filter. Hoog-
land [196, 197] later used Boon's flame photometer for boron. He was able to determine
boric acid reliably, but in the isolation of boron from biological samples, the sodium
involved in the methyl borate distillation interfered; he preferred titration.
I have found hardly any later work on the flame photometry of boron. The Lange flame
photometer [198] offered a detection limit of 30 ppm at 548 nm and 70 ppm at 518 nm
in the air-city gas flame. Those are not encouraging sensitivities. Kny and Richter [199]
analyzed drugs flame-photometrically for boric acid by converting it to methyl borate
without separating it; I have no further details.
5.3.8 FLAME SPECTROGRAPHY OF BORON
Lundegardh, with his well known flame spectrograph, was unable to detect the bands of
boron in air-acetylene ata concentration of 0.1 % [200 (Part I, p. 67)]. A later improved
burner emitted the bands; a spectrogram was published [201]. In a still later paper [222]
Lundegardh seems to imply that he detected the resonance lines in the inner cone of air-
5.3] BORON 205
acetylene. Rusin and Tatevskii [202] presumably used a spectrograph for estimating the
concentration of B02 (at 10 micromolesjliter) in exploded mixtures of diborane, oxygen
and other gases. I have seen no papers on analytical applications of flame spectrography
to boron.
5.3.9 FLAME-SPECTROPHOTOMETRIC DETERMINATION OF BORON
Modern analysts are tending to contract the term "spectrophotometry" to "spectro-

metry." This usage is awkward in a paper dealing with old as well as new work, because
for many decades "spectrometer" has meant a (usually visual) instrument for measuring
wavelengths in a spectrum. A spectrophotometer measures intensity at a selected wave-
length. Calling it a spectrometer entails a loss of terminological specificity; but since (true)
spectrometers are now mainly used in teaching, the loss of specificity is probably more
than offset by the saving in syllables. To avoid confusion, however, I shall keep the term
"spectrophotometer" in this chapter.
Unlike filter flame photometry and flame spectrography, flame spectrophotometry has
become popular for boron. During the 20 years since the first commercial flame spectro-
photometers appeared, the output of papers has continued unabated. These are summar-
ized in Table 5.V. Only sprayer-burners, since their introduction in 1951, have been used
for boron, as far as I can tell from the published work. Of special value is the sheathed
sprayer-burner [39,49, 84], which was used for boron by Maeck et al. [221]. Grating
monochromators began to displace quartz prisms after 1960, but their advantage is with
elements other than boron; the greater dispersion of a grating in the visible offers no
advantage with the diffuse bands of boron, and at the short wavelength of the boron
resonance doublet a quartz prism is equal to most gratings.
The boron lines, in the most favorable flame sources yet found [61], are not as intense
as the bands in the more familiar flames. The lines, of course, have the advantage of
being sharp, so that the background can be measured at nearly the same wavelength and
the quoted detection limits are attainable in practical analysis. But the bands are so broad
that the detection limits often quoted for them, which may be valid for pure solutions,
are unrealistic in the presence of unidentified interferents. For example, nickel in oxy-
hydrogen may contribute a continuum of varying intensity that cannot be separated from
the boron continuum unless the nickel is separately determined and accurately com-
pensated. In such cases it is common practice to measure the differences between one or
more boron peaks and the adjoining minima on either side of each peak. But since an
adjacent peak and minimum may be 15 nm apart, there is a good chance for error in
case the background in the sample has a spectral distribution different from that in the
standard. When the shape of the interferent background is in doubt, it helps to take
readings on more than one of the boron peaks. If these do not give the same analytical
result, it may turn out that one of the peaks (perhaps a weaker one) can be shown to be
more reliable than the others.
Among the many interferences on boron that have been studied (especially [113,215,
221, 233 D, that of sodium, in at least two instances, seems curious. In the air-acetylene
flame of Boon [196] and in the oxyhydrogen flame of Pungor and Konkoly Thege's
sprayer-burner [209], in the presence of a constant concentration of sodium the analytical
curve of boron is flattened at the bottom, as if a fixed amount of boron were removed by
206 NONMETALS [5
TABLE 5.V
CONTRIBUTIONS TO THE FLAME-SPECTROPHOTOMETRIC DETERMINATION OF
BORON
Spectro-
Date I Authors Ref., Flame Burner
photometer
Wavelength
1947 Gilbert [108] OAM 10300 DU+PT 518, 548
1950 Gilbert et al. [203] OAM 10300 DU+PT Bands
1951 Gilbert [204] OH,OA BSB DU+PT Bands
1952 Gilbert [205] OH BSB DU + IP28 Bands
1952 Bricker et al. [206] BSB DU + IP28 Bands
1953 Kingsley et al. [207] OH BSB DU + IP28 Bands
1954 Gilbert [109] AH,OH,OA BSB DU + 1P28 Bands
1954 Dippel [208] BSB DU + 1P28 Bands
1955 Boycks [112] OA BSB DU + IP28 Scan
1955 Dean & [113] OA BSB DU + IP28 518, etc.

Thompson
1955 Whisman et al. I [120] OH BSB DU + IP28 Scan
1955 Watanabe I([3]),

[ll5]
OH BSB DU + IP28 Scan
1956-8 Pungor et al. [209] OH BSB, DU+PT Plot

homemade
SB
1957 Burriel-Marti [1] BSB DU Bands
et al.
1957 Bovay & Cossy [210] BSB DU 548
1957 Fornwalt [211, OH BSB DU + IP28 518

212]
1957 Iporter [213] BSB DU 548
1958 DuBois & [214] OH Small-bore· Cary 10-11 Scan

Barieau BSB
1958 Buell [215] OH BSB DU + IP28 Scan

5.3] BORON 207
TABLE 5.Y (continued)
Detection Precision Interferences Materials analyzed and

Solvent limit studied treatment; other remarks
17% PrOH 5 [Lgjml 1% Brine; diluted. Unheated
spray chamber
17~~ PrOH 5 Description of instrument;
heated spray chamber
t% First description of sprayer-
burner; data on boron
t% Data on boron spectrum (cf.
Tables 5.1I and 5.lIn
Me2CO, Dioxan Acids, Na, K, Ba First practical study on detn.
of B with BSB
MeOH, BuOH Comment in discussion:
MeOH enhances B
0.1 1% Na, Ca, F BF 3 ; hydrolyzed. Data on
spectrum (Table 5.I1). Iso-
tope shift
Cl-, Cl0 4 -, N0 3-, Enhancement by organic sol-
P0 4 -3, S04-2 vent
One of first recorded spectro-
grams
50% MeOH 2 2% Many Minerals; acid dissolution.
(EtOH, iPrOH) Thorough study on practical
detn.
(I) Recorded spectrogram, data
on B
0.5 Recorded spectrogram; see
Table 5.I1
EtOH, MeOH HCl, H 2S0 4, HCl0 4, Basic study; solvent effects:
NaOH 10-40% EtOH shows plateau
(p. 309) Agricultural analysis

requires photomultiplier
Fertilizer. Extract with H 20
at pH 4, separate by ion ex-
change
50% MeOH 5 1-2% Ni Plating solutions; diluted
MeOH MeOH in contact with Pyrex

rapidly forms Me3B03
Naphtha Gasoline. Recorded spectro-
gram; effect of height in
I flame
5 t% Na, P0 4 - 3, metals I
208 NONMETALS [5
Date Authors Ref. Flame Burner Spectro-

Wavelength
photometer
I
1958 Buell [111] OH BSB DU + 1P28 518, Scan
1958 La Mont et al. [216] Scan
1959- Gilbert [3,5,6, AH,OH,OA BSB DU + 1P28 Scan

63 110,
116,
117]
1960 Konopicky et al. [121] OH BSB DU + IP28 Scan
1960 Konopicky et al. [217] OH BSB DU + 1P28 Bands
1960 Pungor et al. [220] OH BSB, DU+PT 518

homemade
SB
1961 Zeiss [122] OH Zeiss SB Zeiss RPQ 20A Scan
1961 Waters [227] OH BSB Grating, lP28 Bands
1962 Buell [57] OH BSB DU + IP28 249.7, 518
1963 Maeck et al. [221] OH Sheathed JA + 931A 548

BSB
1963 Lora-Silva et al. [223] OA BSB DU Bands
1963 Buell [58] OH BSB DU + 1P28 249.7, Bands

1963 Yoshizaki [224] OH Hitachi Hitachi EPU-2A 518
H-2
1963-4 Doty & Schrenk [225, OH,OA BSB DU, JA + 1P28 518
226]
1964 Crandall [228] OH BSB B + 1P28; Bands
B &L 33-86-40
+ 6810A
1964 Baum [229] OH BSB DU 518
1964 Ramirez-Munoz [230] Bands

1964 Kniseley [243] OA Kniseley JA 249.7
5.3] BORON 209
TABLE 5.V (continued)
Detection Precision Interferences Materials analyzed and

Solvent limit studied treatment; other remarks
1 : 1 iPrOH- 1-2% Na Organic compounds, gas-

naphtha oline; dilute with oil and sol-
vent
Solutes and corrosion prod-
ucts in nuclear reactor tech-
nology
0.2 Spectrograms, intensities; cf.
Tables 5.11 and 5.I1I
0.1 Recorded spectrogram; gen-

eral study of BuOH solvent
4% BuOH HF enhances B 60 %
+ 3%HF
EtOH, MeOH NaOH, HCl0 4 Probably same as [209]
(1956-8)
0.5 Recorded spectrogram

Industrial process liquids;
monitoring spectrophotom-
eter
N aphtha-iPrO H iBuCOMe also. Emission-
vs-height profiles
iBuCOMe 0.1 2% Many Extract as BU4NBF4 from
H 2 S0 4-HF soln. with
BU4NOH in solvent
50% MeOH Ca Leaves; evap. with Ca(OH}z,
ash, dissolve in H 2 S0 4
Naphtha Emission-vs-height profiles
50% MeOH 1% N Organic compounds; digest
with HN0 3 • Standard-addi-
tion
H 2 0, MeOH, Ca Basic study of interferences
BuOH on and by boron
H 20 1% Reactor coolant; monitoring
spectrophotometer
AI, Cr, etc. Refractories; dissolved in

HF
MeOH Plant tissues; extracted
EtOH 25 Study of detection limits in
premixed OA; integration
210 NONMETALS [5
Date I Authors I Ref. I Flame

I
Burner l Spectro-
photometer Wavelength
1966 Poluektov [231]
1966 Rains & Rush [232] OH BSB JA+EMljUS QB 548

1966 Buell [59] OH BSB 2-m B &L grating 518,249.7
+ IP28
1966 Zacha et al. [50] ArH BSB Aminco 4-8400 Bands
grating + IP28
1966 Dean [61] OAic BSB DU + IP28 249.7
1966 Dean & Adkins [140] OAic BSB DU + IP28 249.7
1967 Agazzi [233] OH BSB DU + IP28 548
1967 Muzzarelli [234] OH BSB DU + IP28 518
1967 Fassel et al. [65] OA Kniseley JA, DU+ 249.7

EMI6255B
Abbreviations: Flames: AH = air-H 2 ; ArH = Ar-diluted diffusion air-H 2 ; OA = OrC2H2

(ic = inner cone); OAM = Ornatural gas with air for spraying; OH = OrH2. Burners:
10300 = early Beckman flame attachment [203]; BSB = Beckman sprayer-burner; SB =
sprayer-burner. Spectrophotometers: DU and B are by Beckman; B &L = Bausch & Lomb;
JA = Jarrell-Ash 82000; photodetector follows + sign; PT = phototube (S-5 response).
the sodium. That is, the boron emits very little light up to a certain concentration, beyond
which its emission rises on a line parallel to the normal analytical curve (without sodium)
but below it. From Boon's figure, 500 ppm of NaOH depresses the boron curve to the
extent of 70 ppm of boron. The corresponding atomic ratio Na : B is 2 : 1. Whether
this is a case of Type Ia solute vaporization interference in Alkemade's classification [235]
cannot be judged without more information; it is surprising that sodium should seem to
form an involatile or undissociable borate.
It has long been realized that the volatility of boric acid in the presence of alcohol is
due to the formation of esters (Table 5.IYA, B). To what extent boric esters formed in
alcoholic solvents affect the emission in the usually hot flames of modern flame spectro-
photometers is in doubt. One would expect an ester to decompose promptly to simple
molecules or atoms on entering the flame, so that the processes by which the B0 2 is
formed and excited should be little affected by the prior state of the boron. Pungor and
Konkoly Thege [209] concluded that ester formation is not important for emission, since
the spectrum is qualitatively the same with alcoholic and aqueous solutions. But Doty
5.3] BORON 211
TABLE S.V (continued)
Solvent
Detection
limit I Precision I Interferences
studied [
Materials analyzed and
treatment; other remarks
Various materials; have not

seen book; first pubJ. 1959
Organic 0.3 Notes on progress
Naphtha 2 1% Study of high-dispersion
Naphtha 200 spectrophotometry
H2O good 1% Study of ArH flame. No
further data on B
EtOH 7 Rich flame; low in flame
EtOH 15 Emission-vs-height profile;
O 2 0.40 x stoich. best
CHCl 3 0.1 2% Many Glass, organic compounds,
etc.; extract with 2-Et-I,3-
hexanediol
H 2 0, MeOH 0.1 mg Uranyl nitrate; separate B
by ion exchange
EtOH 30 Study of detection limits in
premixed OA
[225] reported that the curve of enhancement of boron (in oxyhydrogen at 518 nm) by
increasing concentrations of butanol in water shows a knee at the concentration corres-
ponding to butyl borate, suggesting that ester formation adds to the enhancement norm-
ally due to the physical effects of an alcohol. Being volatile, the boric ester no doubt
enters the gas phase faster and more nearly completely than borate salts do. Doty also
made a good many other interesting and suggestive observations on the various inter-
actions between borate and one, two or three of the concomitants calcium, strontium,
barium, butanol, methanol, ethylene glycol, sucrose and perchloric acid, in oxyhydrogen
and oxyacetylene. The systems are too complex and the data too incomplete to permit
unequivocal interpretation; but in some cases the hydroxy compounds seemed to be
functioning as releasers, competing for the borate and preventing formation of the
alkaline-earth borate.
I shall not further discuss the methods outlined in Table 5.V, since all of the work is
recent and much of it has appeared in journals that are available to almost every analytical
chemist. In particular, the papers that present the most practical flame-spectrophoto-
212 NONMETALS [5
metric methods for boron [111, 113,221,224,233] have all been published in Analytical
Chemistry. Besides, Dean's basic work on boron is summarized in his well-known book
[2 (p. 226)]. It should perhaps be mentioned that the band at 345 nm that he lists, appar-
rently taken from my work [203], is in error; I mistook an OR band at low resolution
for a boron peak. Other reviews on the flame spectrophotometry of boron are found in
[1 (p. 307), 6, 218]. In his review, Buell [219] mentions determination of boron in gasoline
and additives according to unpublished methods by various oil companies.
5.3.10 FLAME-EMISSION MONITORING OF BORON
In recent years several instruments have been built for continuously recording the con-
centration of boron in liquids or air. The first was that of Waters [227], comprising a weir
manifold system for sampling, oxyhydrogen sprayer-burner, grating monochromator,
chopper, photomultiplier, a.c. amplifier and recorder. Sample filters and special gas
regulators kept the flame emission steady. Although designed primarily for sodium at
the parts-per-billion level, the instrument was used also for monitoring boron. Crandall
[228] built a very similar instrument, again mainly for sodium; but he used it also for
monitoring boric acid added to the coolant for controlling the neutron flux in a nuclear
power plant. A fritted stainless-steel sample filter helped avoid stoppage due to sprayer
clogging, one of the main problems in any flame-photometric monitor handling liquid
samples. The instrument was run in a remote-controlled sample room. The boron response
was very reproducible (within 1 %) and linear in the range 100-200 ppm; it held steady
for hours.
A portable borane monitor for air was designed by Braman and Gordon [236, 237,
238]. Intended for detecting toxic pentaborane that escapes during rocket firings, it re-
sponds also to diborane, decaborane and any other volatile boron compound. Ambient
air is pumped through a filter to a small diffusion flame of hydrogen viewed through a
550-nm interference filter by an end-on S-l1 photomultiplier. The monitor responds
linearly up to 1 ppm of pentaborane and detects less than 0.01 ppm. A wide variety of
possible interferents was found to give very little response - from 0.3 % of the penta-
borane reading at equal concentration for carbon disulfide or propyl nitrate to 0.004 %
for chlorine. Dobriner [239] described the Braman-Gordon instrument in use at Edwards
Air Force Base in the Mojave Desert. Braman and Loseke presented a paper [240] on
the same or a similar instrument used presumably for detecting other substances besides
boron; I have no notes on this.
5.3.11 INDIRECT FLAME-EMISSION DETERMINATION
Since the direct emission flame spectroscopy of boron is so successful, there has been
little point to inventing indirect methods. A very few have been described, of which the
most unusual is that of Bovalini et al. [241]. They precipitated the boron as barium
borotartrate, BasB2C16Rs02, dissolved this in hydrochloric acid, and determined the
barium by flame photometry at 873 nm. The method was useful for 4-20 [J.g of boron.
5.3] BORON 213
5.3.12 ATOMIC ABSORPTION SPECTROSCOPY
Some of the nonmetals, boron among them, can be readily determined by atomic absorp-
tion flame spectrophotometry as well as non-flame atomic absorption methods. The latest
unified treatment of the subject is the excellent book by Ramirez-Munoz [242], with a
bibliography of 950 references. The very extensive index gives access to every bit of
information in the book. For current coverage of this swiftly advancing field, the Atomic
Absorption Newsletter, published by the Perkin-Elmer Corporation, is most valuable.
Flame Notes, a periodical published by Beckman Instruments, Inc., covers the latest
results obtained with the unique Hell burner [242 (p. 117)] and related research.
The nitrous oxide-acetylene flame is best for determining boron at 2497 A. In the Hell
burner with heated spray chamber, the percentual concentration limit is 30 to 40 ppm
[242 (p. 244), 244, 245]; the fluctuational concentration limit is 3 ppm at a time
constant of 1 s [245]; the absolute limit is 3 fLg and the relative standard error is 1 %
at 36 %absorption [246]. The latest application of atomic absorption to the determination
of boron is that of Bader and Brandenberger [247], who analyzed biological materials.
The detection limit was about 10 ppm and the analytical curve was linear to 250 ppm.
They review earlier work on the determination of boron in the nitrous oxide-acetylene
flame.
5.3.13 ELECTRIC DISCHARGES AND OTHER SOURCES
Only a few of the non-flame spectrochemical methods that strike me as most interesting
will be mentioned here. The first is a semi-flame method, viz., Straub's spark-in-flame
[248, 249]. A spark was passed between silver electrodes through an oxyhydrogen sprayer-
burner flame fed with a syringe sample pump and viewed by a spectrophotometer. The
detection limit for boron at 2497 A was 0.2-0.3 ppm in aqueous solution. Although some-
what less stable than a pure flame, this source offers unsurpassed sensitivity for boron in
spectrochemical solution analysis at the resonance lines. Unfortunately the instrument
has not been futher developed.
The plasma jet or gas-stabilized arc was used by Vigler and Failoni [250] for deter-
mining boron in gasoline. They diluted the sample with ethanol containing nickel as
internal standard (at 2511 A). The standard error was 8 %, or 0.5 fLg/ml at the lower
concentrations. Collins [251] analyzed oilfield brines diluted with hydrochloric acid
containing lanthanum as internal standard, a Ca-Mg-Na buffer, and propionic acid (40 %).
The method was spectrographic; the detection limit was 2.5 ppm of boron in the brine
and the relative standard error was 4 % at 100 ppm.
The induction-coupled plasma torch was used by Hoare and Mostyn [252] with a
West-Hume sprayer [10] and a multiple sample vessel permitting quick change of samples
without interruption. The frequency was 36 MHz and the carrier gas was argon. The
authors determined boron (2497 A) spectrographically at 0.005-0.07 % in nickel alloys
dissolved in acid. Precision was 4-!- % with nickel as internal standard. Interferences were
negligible.
A focused laser beam has been used to flash-vaporize a tiny sample, the resulting
"plume" or puff of luminous vapor being spectrographed. Stoicheff [253] said that
elemental boron emits its lines and the B0 2 bands. Ferguson et al. [254] reported that
both boron and boron nitride yield bands of BO and BO z.
214 NONMETALS [5
S.4 Carbon
The commonest flames are those fueled by a compound of carbon. Emission spectra
characteristic of carbon occur in all such flames. These spectra have long been studied
and occupy a vast literature. The emissions are often chemiluminescent or non thermal
for one reason or another, and have proved useful for elucidating the nature of com-
bustion. This topic will not be discussed here. The best general book on the flame spectros-
copy of carbon compounds is Gaydon's [34].
A carbonaceous flame is not, however, likely to be useful for detecting or determining
carbon in solutions or gases introduced into the flame. Hydrogen, the commonest non-
carbonaceous fuel, provides the most practical flame for determining carbon or organic
compounds. It is coming into increasing use for this purpose.
The carbon spectra most likely to be useful for analysis will first be considered briefly.
5.4.1 ATOMIC CARBON
The carbon line (not a resonance line) at 2479 A is seen in the reaction zone of many
carbonaceous flames, especially the hotter ones such as oxyacetylene and oxycyanogen.
Flame-spectrophotometric recordings are shown in [3 (Spectrograms 66 and 74)]; cf.
Fig. 5.9. Densitometric tracings in [14 (pp. 576 and 579)] show the line. Since the line
appears in oxyhydrogen flames into which organic solvents are sprayed [58], the pos-
sibility of its analytical application exists. To explain its excitation, which requires 7.7 eV,
Rossikhin and Tsikora [255] suggested a reaction between excited CH(2L') and H to
give Hz and metastable C(2pZ IS), which in turn is excited to 3s IPO, the upper level of
the 2479-A line.
5.4.2 MOLECULAR CARBON, Cz
The Swan bands emitted by C 2 in the visible are the most familiar feature of the spectrum
of the Bunsen flame. They are very pretty in a small spectroscope, with shaded sequences
in the orange, green, bluish-green, blue and violet. The green tint of the inner cone of
an ordinary gas flame, especially when rich, is largely due to these bands.
The bands were first described and measured with great care in 1857 by Swan [20];
they were called "carbohydrogen" bands at that time. Mitscherlich [21] in 1864, who
made flames from a great assortment of fuels and oxidants and observed the flame spec-
trum of every element and compound he could get hold of, prepared excellent drawings
of the Swan bands. Pliicker and Hittorf [256] in the following year published a beautiful
colored drawing of the spectrum of the oxycyanogen flame, including the Swan bands
among others. Attfield [25], who particularly admired these bands, was the first to con-
clude (in 1862) that they are due to carbon and not a carbon-hydrogen molecule.
Regarding the origin of the bands, an enlivening exchange took place in 1875. Piazzi
Smyth [100] published a singularly offensive paper in which he denounced the theory that
the Swan bands are due to carbon; he believed that a hydrocarbon emits them. With
heavy sarcasm he blackened the character of W. M. Watts, who had been so misguided
5.4] CARBON 215
as to agree with Attfield's interpretation. Watts was Physical Science Master in the
Giggleswick Grammar School, whereas Smyth was Astronomer Royal of Scotland. Not
content with demolishing Watts, Smyth next excoriated the Royal Society and its lackeys
for favoring the carbon theory. He finished by calling upon the Society to repent in dust
and ashes.
Watts replied to this obloquy with a restrained and scholarly paper [257]. He described
experiments with cyanogen proving that the Swan bands could not be ascribed to a
carbon-hydrogen compound. He agreed that the bands do look like the spectrum of a
compound rather than an atomic element and concluded that "if ... this spectrum be
caused by a compound, it can only be a compound of carbon with carbon." Attfield's
reply [258] came next. It was a bit less restrained and cogently refuted each of Smyth's
allegations.
There is a long subsequent history, which is summarized in Kayser's Handbuch [91 (pp.
190-234), 92 (pp. 125 if.), 93 (pp. 297 if.)]. Gaydon [34 (consult the index)] covers the
modern work in full detail. Among the older spectrograms, two ofthe best are the drawing
by Lecoq [98] and the photographs by Hagenbach and Konen [105]. An excellent
modern photograph is that in the Vatican City atlas [118]. Wavelength tables and
analyses are given in [14, 34, 78, 79, 80]. Ref. [3] has tables and recorded spectrograms
intended for the practical analyst. Since the bands are strong in hydrogen flames fed with
organic compounds, they are analytically useful.
The molecule C 2 in flames also emits band systems named Mulliken, Fox-Herzberg,
Deslandres-d' Azambuja and Phillips. These are weaker than the Swan bands and seem
less likely to find use in spectrochemical analysis. Descriptions are given in the above
references. The "comet-head" bands of C 3 near 4050 A likewise occur in certain flames.
5.4.3 METHINE, CH
Three band systems of CH appear in flames: a violet band peaking at 4315 A, responsible
for the violet tint of the inner cone of a strongly aerated Bunsen flame; a near-ultraviolet
system with strongest heads at 3872 and 3889 A; and a weaker ultraviolet system near
3144 A. The last is not usually noticed in analytical flame spectroscopy, but the first is
often bright. It is very persistent; it appears, for example, in the oxycyanogen flame
unless the gases are specially dried [34 (p. 162)].
The references listed for C 2 oifer photographic, densitometric and recorded spectro-
grams, wavelength tables and analyses. Of special value is the atlas by Bass and Broida
[259]. In it the entire spectrum of CH, emitted by an oxyacetylene flame under conditions
selected to favor the CH bands, is recorded spectrophotometrically with a resolution
of 0.1 A.
5.4.4 OTHER BANDS
The bands of cyanogen, CN, which are useful for the determination of nitrogen, will be
discussed under that element. The "fourth positive" bands of CO appear in the deep
ultraviolet in certain organic flames (e.g., [3 (Spectrogram 83)]). Strong bands of CO and
CO 2 occur in the infrared. Vaidya's ultraviolet "hydrocarbon flame bands," attributed
216 NONMETALS [5
TABLE 5.VI
DETERMINATION OF CARBON COMPOUNDS BY EMISSION FLAME
PHOTOMETRY
-
Date Authors I Ref. Flame a Emissions Dispersion b Detector
1958 Grant [261] ~-coal gas CH, C z None Se cell

with benzene
1959 Cowan & [262] Air-Hz Incandescence, None Visual
Sugihara C z , etc.
1961 Sternberg [263] Air-Hz CH4315 DU IP28,
& Jones C z 5165 recorder
1963 Gilbert [39] Oz-H z SB C z , CH DU IP28
1963 McCormack [264] OrHz (CH, C z ) JA (IP28)
1966 Braman [265] Air-Hz CH (415 nm) Interference Dumont 6291,
C z (515 nm) filters recorder
1966 Durbin [2661} OrHz CH4315 DU 1P28
C z 5165
1966 Juvet & [267]
Durbin
1966 Zado & [268] Very lean CH 4315 { Spectronic 20 IP28
Juvet OrHz or
Filter >355 nm
1966 Robinson [269] OrHz SB CH, C z DU,DK IP28
& Smith
1966 McCrea (270J} Oz-H 2 , CH 4315 DK-2 IP28
Air-Hz SB C z 5165
1967 McCrea &
Light
[271] I
a) SB = sprayer-burner for liquid samples.
b) DU and DK are Beckman spectrophotometers; JA = Jarrell-Ash 82-000; Spectronic is a
Bausch & Lomb grating spectrophotometer.
C) GC = as a detector for gas-chromatographic effluents.
d) TC = thermal conductivity detector.
e) Arom. > aliph. = response (per C atom) is greater for aromatic than aliphatic compounds
(typically 2-3 times).
to CHO, arise in a cool, lean acetylene flame. These bands are discussed in the references
cited under C z • See particularly the bibliographies in [14 (pp. 356-9), 34, 79].
5.4.5 DETERMINATION BY DIRECf FLAME EMISSION
The practical determination of carbon or its compounds by emission flame spectrophoto-

metry is a very recent development and is gaining momentum, especially in conjunction
with gas chromatography. Grant and Vaughan [260] were the first to suggest this latter
application, but Dippel [208] may have earlier proposed the use of carbon bands for
determining organic compounds in water; I have not seen his thesis.
5.4J CARBON 217
Application C Sensitivity b Linearity Selectivity •
GC; N2 carrier LikeTC; < mg Good Arom. > aliph.
GC; H2 carrier Qualitative By color and height

of flame
GC Like TC Partial; attains max. CHjC 2 rises with
H/C ratio
Alcohol in H 20 .01 % alcohol
GC Good (Replaced by microwave discharge [88])
GC; N 2 carrier 1-2 fLg of compound Curve concave upward Response varies with
compound
GC; He & N z car- Like TC; .1 fLmole Linear .1-500 fLmole Response & CH/C 2
riers. Precision = C 6H 6, .7 fLmole CO 2 vary with compound;
injection reproduci- arom. > aliph.
bility
}
GC 1 fLmole C6H6 Linear Arom. > aliph.
or
.02 fLmole C6H6
Liquid organic com- BuCI > BuOH
pounds
Hydrocarbons in (.001 molar) Linear to I molar Arom. > aliph.
MeOH
Papers on the flame-emission determination of carbon are summarized in Table 5.V!'

In most of them the flame is used to detect organic compounds issuing from a gas chromat-
ograph column. The sensitivity of such a detector is comparable to that of the thermal-
conductivity detector commonly used in gas chromatography. Flame-ionization detectors
and other ionization detectors are much more sensitive for most types of compounds,
but the flame-emission detector can be of very simple design and offers high precision,
usually a wide range of linearity, and corrosion resistance [268]. Although on the whole
nonselective, it offers some degree of selectivity when desired. That is, the response with
different compounds is roughly proportional to the amount of carbon, but the response
factors do vary somewhat with the type of compound, and they differ at the two wave-
lengths (CH 4315 and C 2 5165) commonly monitored. These variations, coupled perhaps
with the response of a flame-ionization detector in parallel with the emission detector
218 NONMETALS [5
(e.g., [265]), afford some selectivity that aids identification. By monitoring the flame at
various wavelengths other than those of CH and C 2 additional selectivity can be achieved,
especially with organic compounds of nitrogen and sulfur [265, 269]. Selection of the
area of the flame observed also helps [267,269,271].
Pieszczek in 1914 [180] (see Table 5.IV) used the boron band emission as a test for
methanol in ethanol. Boric acid in the absence of sulfuric acid gives the green flame with
methanol but not with ethanol; 10% of methanol can be detected in the alcohol.
The enhancement of a metallic emission by an organic solvent added to an aqueous
solution was used by Dippel [208] for determining, e.g., acetone in water. When the
metallic emission is chemiluminescent, the effect can be quite pronounced. For example,
the tin line at 2429 A is undetectable in an aqueous solution sprayed into an air-hydrogen
flame, but if a little alcohol or acetone is added to the solution or a hydrocarbon to the
fuel, the line comes out strongly [39]. Although Gilbert found the enhancement far from
linear with the strictly chemiluminescent lines, leveling off at concentrations not much
over 20% of isopropanol [39 (p. 188)], Gibson et al. [42] found a nearly linear effect
of isopropanol concentration (up to 75 %) on the 2863-A line of tin, which is thermally
excited in a carbon-free air-hydrogen flame.
Sternberg and Jones [263], whose work on the direct flame emission of carbon is listed
in Table 5.VI, also monitored the OH emission at 310 nm. It responds to organic com-
pounds, but, being present and strong in the absence of added organic compounds, the
OH emission is less useful than that of C 2 or CH.
Depression or negative response of a non-carbon emission to a carbon compound
entering the flame has also proved useful. Aue and Gehrke [272] noted that hydrocarbons
depress the sodium emission observed in a Karmen-Giuffrida thermionic alkali flame-
ionization detector. Overfield and Winefordner [273] were the first to exploit this effect
fully for gas chromatography. They called their device a negative flame emission GC
detector. It monitors the OH band emission at 310 nm in a tiny oxyhydrogen flame of
exceptional stability (root-mean-square noise 0.2 %). It responds to many substances;
among carbon compounds, they tried only carbon dioxide, which gave a linear analytical
curve from 0.7 to 5000 Ill. The flow detection limit was 1.4 Ilgjs.
Certain types of stable discharge at atmospheric or moderately reduced pressure have been
used very successfully for detecting carbon compounds, mainly in gas-chromatographic
effluents. Sensitivities can be extremely high. Sternberg and Poulson [274] passed a 50-kV,
3-MHz electrode1ess Tesla discharge through the carrier gas in a capillary (best in argon
at 1 atm) and monitored the C 2 emission with or without spectral isolation. McCormack,
Tong and Cooke [88] passed a 2450-MHz electrodeless discharge through argon carrier
gas and monitored various emissions with a grating spectrophotometer. This instrument
is now being applied to the detection of several elements at very low concentrations in gas
5.5] SIUCON 219
chromatography. For carbon, bands of CN, C z and CH may be used. The CN band at
3883 A is the strongest even though nitrogen is nominally absent; it permits detection
of 0.1 fgjsec of various organic compounds - a sensitivity 1010 times that of Overfield
and Winefordner's detector mentioned above. The Swan bands will detect 0.03 pgjsec.
Braman and Dynako [275], who give an extensive review of emission detectors for gas
chromatography, passed a small direct-current discharge (300-1100 V, 10-15 W) through
argon or helium carrier at 1 atm in a silica capillary. Detection limits for 2-bromopropane
were 50 pg or 3 pg/sec by the C Z 5165-A band, 14 pg or 0.8 pgjsec by the CH 4312-A
band and 6 pg or 0.3 pg/sec by the CN 3871-A band. The C line at 2479 A could be
used too. The response per mole of carbon varied with the compound and in different
ways at different wavelengths. West [276] used 30-MHz and 2450-MHz plasma discharges
in argon and helium carriers. Detection limits were 0.05 to 5 parts per 109 by volume;
I have no details.
5.4.8 LASER EXCITATION
Stoicheff [253] and Ferguson et al. [254], whose work has been mentioned in Section 5.3.13,
focused a laser beam on the solid sample and obtained a spectrogram of the resulting
luminous vapor. Carbon gave bands of Cz and CN and an intense C+ line at 4267 A
5.5 Sllicon
Silicon does emit both bands and lines in certain flames, but under many conditions no
spectrum can be detected. Over the past century there are scattered reports of failure to
find a flame spectrum. Bunsen in 1866 mentioned no flame color for silicon [277]. Huggins
in 1870 said that silica held in an oxyhydrogen flame gives only a continuum [278]. Salet
[17] said that silicon fluoride gives a continuum in air-hydrogen, although the other
halides yield band spectra (see below). Eder and Valenta [104] said that silicates, fluo-
silicates, silane and silicon fluoride give no flame spectrum. Boon [195] found no silicon
spectrum in air-acetylene. Gilbert [39 (p. 187)] found no emission from 2500 mg/l of
silicon in isopropanol in a sprayer-burner air-hydrogen flame. Mavrodineanu and Boiteux
[14 (p. 483)] found no silicon emission, presumably in either the inner cone or the mantle
of air-acetylene or oxyacetylene. Syty and Dean [279,280] observed no useful emission
from silicon between 220 and 400 nm in the rich, shielded air-hydrogen flame.
5.5.2 THE VISmLE FLAME BANDS
There is a band system in the visible, described in 1871 by Salet [17,281,282]. It is emitted
by a hydrogen flame containing silicon chloride and chilled by a surrounding sheath of
flowing air. The spectrum does not appear without the sheath. The core of the flame is
greenish yellow. Silicon bromide and iodide give similar spectra; the iodide gives also the
220 NONMETALS [5
spectrum of iodine (probably 10) in the mantle, the silicon spectrum appearing in the
inner cone. Salet [17] published drawings of the spectra obtained with the chloride and
bromide; they look slightly different. Kayser in 1912 [16] listed Salet's flame bands; Eder
and Valenta [104] mentioned that silicon chloride emits the bands in an oxygen-gas flame,
but they gave no data or spectrograms.
The only observations on these bands besides Salet's appear to be those of Lundstrom
[283] and Hartley [284] published in 1895. Lundstrom had made a study in 1886 of the
flame of the Bessemer converter. He reported that between the "slag period," during
which only a continuum appears, and the "boil," there is an interval of only a few seconds
TABLE 5.VII
THE VISIBLE FLAME BANDS OF SILICON
Wavelengths in nm of the band maxima. Salet's Greek-letter designations identify the brightest
bands, presumably in order; w = weak, vw = very weak. Wavelengths in parentheses are those
verified by Hartley as present but for which he gave no wavelength measurements of his own.
Salet [17,281,282] Lundstrom [283] Hartley [284]
446 w
452 vw
457 w
465 vw 465.5
469
474 vw 474.8
481 480.9
487.5 epsilon 487.1 (487.5)
495 vw
501 gamma (50l)
507
514 w
522 alpha (522)
527 w 526.4
537 w
545 beta 545.1 (545)
551 w
559 w
567 delta 567.8 567.0-.2
578 w
587 w
595
605 w
612 w
622
5.5] sruCON 221
distinguished by a "blue flame." The blue flame emits certain bands that Lundstrom
ascribed to silicon. To verify them, he tried to produce the spectrum in the laboratory
by Salet's method, but failed; he expressed doubt as to the identity of the bands. Hartley,
commenting on Lundstrom's work, verified one of the bands (5270 or 5272 A) in two
Bessemer spectra but could not identify it (except as silicon on the basis of Salet's wave-
lengths). He was inclined to ascribe Lundstrom's other silicon bands to manganese, but
seemed quite uncertain. He suggested that an iron with much silicon and carbon might,
with water, form carbon monoxide and silane, which would burn; he thought that the
"blue flame" might be burning silane.
Table 5.VII lists Salet's and Lundstrom's wavelengths along with Hartley's observa-
tions. These are band centers; the bands are evidently not degraded. What molecule may
be responsible for these bands, I do not know. Modern tables of molecular spectra show
no possible silicon compound having bands in this region. Someone should try to recap-
ture this spectrum and identify it.
5.5.3 THE ULTRAVIOLET BANDS OF SILICON MONOXIDE
The spectrum of SiO between 2200 and 2900 A is well described and documented in the
standard works [78, 79]. However, the only careful study of this spectrum in a flame
source seems to be that of Gramont and Watteville in 1908 [285]. They burned illumina-
ting gas with dry air that had been passed over silicon tetrachloride. The SiO spectrum
appears only in the inner cone; the flame is pinkish violet. Table 5.VIII lists their inten-
sities as estimated spectrographically. The wavelengths are revised to modern values; these
are for the heads of the bands, which are degraded to the red. The data of Gramont and
Watteville appear also in Kayser [16] and Pearse and Gaydon [78].
The only other observations on the flame spectrum of SiO are those of Watanabe in
1955 [115], who sprayed ethyl silicate into an oxyhydrogen sprayer-burner flame; and of
Gilbert [39], who sprayed solutions of silicon in hydrofluoric acid, diluted with water and
methanol, into various sheathed sprayer-burner flames. One of Watanabe's recordings
is shown in Fig. 5.5. Measurements of absolute radiance (cf. Table 5.11) of a few of the
2400 2420 2440 2460 2480 2500

Fig. 5.5. Spectrogram of silicon in oxyhydrogen flame.
Beckman DU with sprayer-burner and IP28 photomultiplier. Slit 0.15 mm. Ethyl silicate in iso-
propanol; concentration not known. Wavelengths of SiO band heads are marked. Wavelength
scale is zero-intensity line, as in all spectrograms in this chapter. Recording by Hideo Watanabe
[115].
222 NONMETALS [5
TABLE 5.VIII
THE ULTRAVIOLET FLAME SPECTRUM OF SiO
Radiance of band and background in

Wavelength Intensity Intensity Beckman sprayer-burner flames
[78] [285] [3] Flame A· Flame B b
J"x 1011 Jbx 10 8 J"x 1011 Jbx 10 8
2215.4 0.25
2236.3 0.5 1
2255.9 1
2277.2 0.5 1
2298.9 2 2
I
2321.4 1
2342.4 4 3
2344.3 4 6 0.030 0.58
2364.5 4 4
2365.7 1
2387.9 3 2
2413.8 8 8 0.031 0.72
2436.3 1
2457.4 2
2459.0 4 2
2481.9 3 2 3.4 44
2486.8 10 8 0.025 1.2 8 44
2509.9 3 2
2557.3 2
2563.8 8 6
2581.2 3
2587.1 8 6
2644.8 4 3
2669.0 8 6
2693.7 7 5
2755.0 6 4
2780.5 6 4
a) Air-oxygen-hydrogen-acetylene flame wit 29 % oxygen m oxidant lIl1Xture. Silicon in a q ueous
hydrofluoric acid.
b) Rich oxyacetylene with trace of hydrogen in sheathed sprayer-burner. Silicon (fluoride) in
80 % methanol.
5.5] SILICON 223
bands and the associated background are included in Table 5.VIII. The relative intensities
that I compiled for [3] are also listed; these are based on all the evidence available,
and are intended for the rich, sheathed oxyacetylene sprayer-burner flame with methanol
as solvent. Detection limits (or their reciprocals) have been published [39, 110, 116, 117];
they are no better than 50 p..g/l. Since the bands are weak in the most favorable flames yet
found, and cannot compete with the silicon line emission (see below), they have never
been used for analysis.
The occurrence of the silicon resonance lines near 251 nm in flames was discovered in
1961 independently by Buell [56] in the oxyhydrogen sprayer-burner flame with naphtha
as solvent and by Gilbert [49] in the rich, sheathed oxyacetylene sprayer-burner flame
with aqueous solutions. Buell also observed the line at 2881.6 A, which has a slightly
higher excitation energy (5.1 eV).
Table 5.IX lists absolute radiances of the silicon lines and solvent background in various
flames, calculated from the original data on which [39] is based. Since the lines are nar-
rower than the bandwidth of a spectrophotometer, J a expresses the total radiance of each
line and does not entail the dimension nm - 1, as in the case of diffuse bands like those of
boron (see the discussion of Table 5.1I).
The practical "intensity" values are also listed in Table 5.IX. As in Table 5.I1I, these
apply to a DU spectrophotometer with 1P28 photomultiplier. Here, however, since the
silicon lines are sharp, a different relation exists between the radiances and the "intensity"
than the one given for diffuse bands in connection with Table 5.IlI. The "intensity" of a
line is taken as 1000 Ja/Jby(Wa + L1 W), where y is the dispersion in nm/cm, W. is the
optimal slit width yielding the lowest detection limit and L1 W is the effective slit widening
due to diffraction, coma, aberrations, curvature mismatch and imperfections. I have long
used a simplified formula to find W.; in terms of radiance, and for the DU spectrophoto-
meter with a photomultiplier of low dark current, it is
W. = 0.015/104 VJ bQ;./Q450,
where Q;. is the product of photocathode sensitivity, geometrical aperture, optical trans-
mittance and dispersion of the spectrophotometer at the wavelength A. L1 W in the DU
may be taken as 0.003 cm; it tends to increase somewhat at shorter wavelengths.
The intensity of a line, thus defined, has the same utility as that defined for a band
(Table 5.IlI); that is, 10 times its reciprocal equals the detection limit. The detection limit
found in this way is virtually equal to that found by the more exact method of Winefordner
(cf. [12]; however, his original formulation for emission spectrophotometry ignored L1 W
and gave poor results with bright sources). In the case of the silicon lines, the r.m.s.
noise, in the flames and at the wavelengths under consideration, is usually nearer 0.5 %
than 0.25 % of the total reading at slit width Wa and at a 1 s time constant; therefore
the detection limits found from Table 5.IX represent the concentrations of silicon in
p..g/ml giving a net line intensity nearer twice than 4 times the standard error of the back-
ground reading.
The causes of the line emission of silicon in flames are of much theoretical interest and
deserve more study. Bulewicz and Padley, in their 1961 paper on overexcitation [35],
examined silicon only to the extent of noting that in nitrogen-diluted oxyacetylene at
TABLE 5.IX N
~
SILICON LINE INTENSITIES AND BACKGROUND IN SPRAYER-BURNER FLAMES
J. = net line radiance in w/cm 2 .sr.([Lg/ml); J b = solvent background radiance in w/cm 2 .sr.nm; Int. = practical intensity (see text).
Sheathed Beckman 4020 sprayer-burner.
Air-oxygen-hydrogen-acetylene Rich, incandescent oxyacetylene. Same, carefully optimized at

Flame:
(29 % oxygen in oxidant mixture) Beam focused It cm above burner 2516 A
Solvent: Dilute aqueous HF Dilute aqueous HF Dilute aqueous HF
[Lg/ml Si
employed: 5000 5000 5000
I I
Wavelength Jax 1011 Jbx 10 8 Int. J a x 1011 JbX 10 8 Int. J.x 1011 J b X 10 8 Int.
I I I I I
2506.9 0.012 1.4 .009 1.6 80 .11 .16
2514.3 1.5 78 .10
2516.1 0.Q38 1.5 .027 4.9 77 .35 7.5 90 .5
2519.2 1.0 77 .07
2524.1 0.009 1.45 .006 1.4 78 .10 .14
2528.5 0.010 1.45 .007 1.7 79 .11 .15
I I
Rich oxyacetylene with trace of Rich oxyacetylene without
Flame: Rich oxyacetylene
hydrogen hydrogen
I I
Solvent: 80 % Methanol 90 % Methanol 96 % Methanol
[Lg/ml Si
employed: 1000 500 190
I I
Wavelength J a x 1011 J b X 10 8 Int. J. x 1011 J b X 10 8 Int. J. x 1011 Jbx 10 8 Int.
I I
2506.9 4.0 51 .37 5.1 64 .4 6 58 .5
2514.3 3.6 52 .33 3.8 63 .3 3.8 59 .3
2516.1 I 13 52 1.2 13.5 63 I 1.1 16.5 59 1.5
2519.2 2.8 52 .26 3.2 64 .25 3.4 59 .3
2524.1 3.5 52 .32 3.8 65 .30 5.5 61 .45
2528.5 3.5 53 .31 4.9 68 .37 6 61 .5
v;
5.5] SILICON 225
2500 K it exhibits no overionization. Following Gilbert's observation of the line emis-

sion, Sternberg [288] proposed that in incandescent oxyacetylene, which is no doubt
saturated with carbon vapor at about 2 ppm, the reaction
SiO + C-+Si + CO
may account for the dissociation. With a dissociation energy of 8.0 eV [38], SiO is one
of the most stable of all diatomic molecules and would not be expected to dissociate
appreciably in the usual analytical flames. The above reaction is exothermic to the extent
of 3.1 eV, not enough to excite the Si atoms without help from the thermal energy of the
flame. Little overexcitation would therefore be expected in the rich oxyacetylene flame
of a sprayer-burner. Measurements of the radiance of the Si lines [39] yielded an exci-
tation temperature of 2500 K, but there were errors in the analysis; the excitation tem-
perature of Si was later corrected to 2700 K [67], equal to the estimated temperature
of the flame.
Both Fassel and Buell have discussed the excitation of silicon, but without offering
any further quantitative data that might be used to test mechanisms. It is likely that in
their flames (which are not incandescent and may not contain much atomic carbon vapor),
the later mechanism of Sternberg involving CO(3L1), described in Section 5.1.2, may
account for the dissociation of SiO as well as the excitation of Si. The reaction
SiO + Coe,1) -+ Si* + CO2
has exactly the energy needed (5.1 eV) to excite the most energetic ofthe Si lines observed
by Buell (2881.6 A). On the other hand, it lacks 3.0 eV of the energy needed to ionize Si.
5.5.5 EMISSION FLAME SPECTROPHOTOMETRY
Contributions to the flame determination of silicon by its line emission have been con-
fined mainly to estimates of the detection limits under various conditions. These are
summarized in Table 5.x. There is no information on linearity or interferences. A
spectrogram is shown in Fig. 5.6, taken from [3]. Buell [58] has published a similar
spectrogram, together with a scan of the line at 2882 A.
Only one (unpublished) analytical application has come to my attention. Johnson [287]
determined silicon in silicones dissolved in dichloromethane or methanol; the Si emission
was 2 or 3 times as great in the methanol as in the dichloromethane. He used a DU
spectrophotometer with Beckman sprayer-burner for oxyacetylene, surrounded by a
sheath, supplied with oxygen, of his own design. The sheath had tapering walls and a
smaller orifice and shorter chimney (flush with the burner tip) than the Beckman burner
sheath.
A good deal of work has been done during the last two years on the absorption flame
spectrophotometric determination of silicon. Its advantage over flame emission is clear
- better sensitivity by one or two orders of magnitude. Trace analyses are therefore
feasible by flame absorption where they are hardly practical by flame emission. But the
N
N
0\
TABLE 5.x
PAPERS CONTRIBUTING TO THE EMISSION FLAME SPECTROPHOTOMETRY OF SILICON
Detection limits represent concentration of silicon giving a net response at 2516 A equal to twice the standard deviation of the back-
ground at a time constant of 1 sec. For abbreviations, see Table 5.Y.
Spectro- Detection Height above

Date Authors Ref. Flame Burner photometer Solvent
limit burner
I I I I
1963 Buell [58] OH BSB DU + 1P28 Naphtha 14mm
1963 Gilbert [39] rich OA sheathed BSB DU + 1P28 MeOH 7 (J.g/ml

Water 20 15
1964 Kniseley [243] OA Kniseley JA (+ 1P28) EtOH 12 8
1966 Buell [59] OH BSB DU + 1P28 Naphtha 30 b

>
2-m B&L 2b
i
!;;
grating + 1P28
1966 Skogerboe, Heybey and [286] OH BSB JA + EMI 6255B EtOH 4 19

Morrison
1967 Fassel and Golightly [65] OA Kniseley DU + EMI6255B EtOH 5 PRZ c

7 IZ
JA + EMI 6255B EtOH 10 PRZ
75 IZ
8) By scanning over line; about 1/10 this with integration.

b) Taken as 1/30 the concentration giving a net line intensity equal to twice background with a slit of 0.05 mm.
C) PRZ = primary reaction zone; IZ = interconal zone.
v;
5.5] SILICON 227
1O
I[)
C\J
(J)
to r<l
<;/"
a:J c:i -'
I[)
(J) to
C\J
a.i
a.i <;/"
<;/" C\J
C\J
0 Q
ZERO
Fig. 5.6. Spectrogram of silicon in fuel-rich, incandescent oxyacetylene flame.

Beckman DU with oxygen-sheathed sprayer-burner and IP28 photomultiplier. Fluorosilicic acid
in 80 % methanol, 1000 [Lg/ml silicon. Slit 0.02 rom. Reproduced from [3] by permission of
John Wiley & Sons.
problem of atomization is the same: special flames are needed to dissociate SiO and
generate a population of Si atoms. For this the nitrous oxide-acetylene flame is out-
standing and has been swiftly adopted for silicon determination.
Willis in his original paper on this flame [74] reported a percentual detection limit
of 5 ppm for silicon at 2516 A; Amos and Willis [51] found 2.5 ppm at 2516 A and they
measured the absorbance also of the other five lines of the group. Slavin et al. [289] and
Cartwright et al. [290] attained fluctuational detection limits of 0.1 ppm, the latter with
a high-brightness Sullivan-Walsh hollow-cathode lamp. With the Hell burner, fluctua-
tionallimits of 0.3 ppm [244], 0.1 ppm [246] and 0.05 ppm [291] have been successively
reported.*
Practical applications of the nitrous oxide flame have been described by McAuliffe
[292, 293], who determined silicon in iron and steel with very good accuracy; Bowman
and Willis [294], who determined silicon in bauxite; and Paralusz [295], who determined
silicon at 1-10 ppm in paper, plastics, elastomers and oils.
No indirect flame emission methods for silicon have proved useful, but there is an
indirect flame absorption method that has yielded the remarkable sensitivity of 0.01 ppm.
In one modification, Kirkbright et al. [296] form silicomolybdic acid and extract it with
butanol. The extract is run through the nitrous oxide-acetylene flame and the molybdenum
is determined at 3133 A. Hurford and Boltz [297] extract the silicomolybdic acid with
ether-pentanol and strip the molybdenum into an aqueous buffer. They reported a relative
standard error of 0.65 % at a silicon concentration of 0.35 ppm in the sample solution,
equivalent to an absolute standard error of only 0.002 ppm.
*) With a similar burner and the nitrous oxide flame, a fluctuational limit of 0.02 ppm was
reported by A. A. Venghiattis, Appl. Optics 7, 1313-6 (1968).
228 NONMETALS [5
Straub's spark-in-flame [248] (see Section 5.3.13) was not nearly as sensitive for silicon as
for boron; the detection limit at 2516 A was 500 ppm. The disk-stabilized arc of Hoffmann
and Holdt [298,299] was used for determining silicon in rocks. At 2516 A, the detection
limit was 1.5 ppm in the sample solution, the relative standard error was 2 % and the
analytical curve was nearly linear over three decades. The induction-coupled plasma
torch was tested for many elements by Wendt and Fassel [300]; for silicon the detection
limit was 3 ppm at 2516 A. None of these sources competes with atomic absorption.
The electrodeless discharge of McCormack, Tong and Cooke [88] (see Section 5.4.7),
although not used directly for silicon, emitted the Si lines when fluorine was present in
the effluent, owing to attack of the glass; the Si lines permitted detection of as little as
0.5 ng of fluorine per second. The discharge would no doubt be very sensitive to silicon
compounds in a gas chromatographic sample.
5.6 Nitrogen
5.6.1 THE BAND SPECTRA
Many flames emit spectra of nitrogen compounds. Probably all flames in which the fuel
is a nitrogen compound, and many in which the oxidant is one, emit such spectra. But
some, such as air-acetylene, that contain nitrogen only as molecular N2 emit weak spectra
of nitrogen compounds; N 2 is the stablest of all nitrogen-containing molecules and reacts
readily only at very high temperatures. The commonest bands are those of CN (violet
and red systems), NH, NH2 and NO (beta and gamma systems). These flame spectra
are discussed in Gaydon's book [34 (pp. 87-9, 214-7) (consult his index)].
The bands of the cyanogen radical, CN, are the best known. The spectrum of burning
cyanogen gas, C 2N 2, was studied as long ago as 1829 by Faraday. Dibbits [301] recounted
the history up to 1864. He examined the spectra of cyanogen burning with nitrous oxide
and with oxygen and published a detailed table of wavelengths for the oxycyanogen flame,
calibrated against the solar spectrum. In the following year PlUcker and Hittorf [256]
published a beautiful colored picture of the spectrum of the oxycyanogen flame, showing
bands of C 2, the CN red system (only a small part of which lies in the visible), and the
CN violet system, including the first three heads of the 3883-A sequence. Although lying
well within what is usually thought of as the ultraviolet region, these three heads are
so intense and sharp that they are often visible to the eye. Gaydon [34 (p. 122)] says that
they used to be known as "the three... The long subsequent history of the CN spectrum is
covered by Kayser and Konen [92 (p. 125),93 (p. 323)]. Excellent photographic spectro-
grams will be found in some of the atlases [105, 118]. For wavelength tables, analyses
and bibliographies, see [14 (p. 347), 78, 79, 80]. Spectrophotometric intensities of the
violet and red CN bands in the oxycyanogen flame are listed in [3 (p. 386)]. A recording
of the oxycyanogen flame spectrum is shown in Fig. 5.7.
Of the nitrogen hydride bands in flames, those of NH (imidogen) peaking at 3360 and
3371 are most commonly noticed. At moderate dispersion they may be mistaken for
atomic lines. In Fig. 5.8 the two peaks (3360 running off scale) are flanked by rotational
lines. The two peaks at about 3283 and 3289 A, visible also in Pearse and Gaydon's
5.6] NITROGEN 229
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Fig. 5.7. Spectrogram of inner cone of oxycyanogen flame.

Premixing platinum-tipped burner. Beckman DU with lP28 and, beyond 600 nm, red-sensitive
phototube (S-l). Slit width changed as needed; height above wavelength scale of adjacent portions
of tracing at breaks shows change of gain due to slit change. Wavelength dispersion changed at
300 and 325 nm. Numbers in parentheses after band head wavelengths are vibrational v', v"
values [78]. Reproduced from [3] by permission of John Wiley & Sons.
230 NONMBJ'ALS [5
;;
"
s
! ;;
"z ::
.
3,.:
~
"z ~
~
3
I !.
i
z
u
\
"s~,·t~"
Fig. 5.8. The NH bands in the oxycyanogen flame.

Tap water pumped to sprayer operating on premixed oxycyanogen. Flame maintained by two
converging jets of premixed oxycyanogen close to base of spray. Total gas flow 200 ml/min.
Beckman DU with IP28. Slit 0.02 mm. Vibrational levels as in Fig. 5.7.
U
<II
,..:
<t
~y (O.!.2) N !iQ Y (0,2)
Pz heod r; °Pt2 head
N
NO Rotational Structure
240 242 244 Z4. 24' 250 mp.
Fig. 5.9. Detail of one of the NO gamma bands and the carbon line 2478 A. in the oxycyanogen
flame.
Apparatus as in Fig. 5.7. Slit 0.02 mm. Reproduced from (3] by permission of John Wiley
& Sons.
5.6] NITROGEN 231
spectrogram [78 (Plate 4)], are of uncertain nature. Even the modem tables [34, 78,
79, 80] disagree on the details of this band system. (It is interesting that the NH bands
in Fig. 5.8 are far stronger than the OH bands, although the flame was filled with a
heavy spray of water.)
The "ammonia alpha" bands, now ascribed to NH 2, are very complex, extensive and
poorly characterized. They cover the green, yellow, red and near infrared. Dibbits [301]
was the first to tabulate them, from the oxy-ammonia flame; he published a colored
drawing. Hofmann in 1872 [302] also pictured the spectrum, from various flames burning
ammonia. Eder photographed the spectrum in 1891. Kayser [91 (p. 835)] critically com-
pared these and other data, which disagreed badly; see also [92 (p. 1327)]. For recent
discussions see [34, 78]. Of special interest is the paper by Sugden, Bulewicz and Demer-
dache [303], who burned mixtures of hydrogen, oxygen and nitrogen, with nitric oxide
added. They observed chemiluminescent NH and thermal NH2 bands and the deep red
band of HNO [78 (p. 172)]. (For a discussion and references on HNO see [322].)
Better characterized are the band systems of nitric oxide, NO, in the ultraviolet [34,78,
79, 80]. Kayser and Konen [92 (p. 1316)] summarized the earlier work. The gamma
system, with strongest heads at 2363, 2471 and 2588 A, is the system most easily excited
in analytical flames. It is visible in Fig. 5.7. In Fig. 5.9, at higher dispersion, the double
double-headed structure is evident, except that the two close heads at 2479 A are obscured
by the carbon line at 2478.6 A. Fig. 5.10 shows the gamma system quite well, in air-
hydrogen fed with isopropanol containing nitric acid.
210 215 220
Fig. 5.10. Spectrogram of nitrogen in air-hydrogen flame.

Mixture of 5 % concentrated nitric acid, 10 % aqueous bismuth solution, and 85 % isopropanol;
NIl mg/ml, Bi 1 mg/ml; Bi lines deleted from spectrogram. Beckman DU with IP28 and sprayer-
burner; slit 0.14 mm above, 0.26 mm below 218 nm. Vibrational levels for NO gamma system as
in Fig. 5.7.
The "nitrogen afterglow" or NO-O continuum is sometimes seen in analytical flames.

It is due to the reaction NO + 0 -- N02 + hv. It accounts for the yellowish-green tint
of a lean oxyhydrogen sprayer-burner flame and for its odor of N0 2. The phenomenon
has been studied especially by Gaydon [34 (p. 70)]; see also Sugden et al. [303]. The
earlier work was summarized in great detail by Kayser and Konen [92 (p. 1289)].
232 NONMETALS [5
5.6.2 DETECTION OF NITROGEN BY FLAME SPECTROSCOPY
The bands discussed above, when observed in flames, have usually been emitted by the
flame gases themselves or by a flame containing an additive introduced for theoretical
studies. There were only a few early attempts to use these flame emissions for spectro-
chemical analysis.
Merz in 1860 [146] found that nitric acid, or nitrates or nitrites acidified with potassium
bisulfate, placed in the Bunsen flame, imparts a bronze-green color with an orange border
to the region surrounding the visible mantle. The test was sensitive to 1/40 mg. Cyanides
and ammonium salts gave the same color, but weaker. In the hydrogen flame, ammonia
gave a weak grey-blue color.
Mitscherlich in 1864 [21] studied many different flames with a great many additives,
including ammonia, ammonium salts, cyanogen and cyanides, and published accurate
drawings of the cyanogen and ammonia flame spectra; but it is hard to say how much
of this is analytical flame spectroscopy and how much is spectroscopic study of novel
flames. For example, having found that various metallic halides introduced into a flame
of hydrogen burning with the corresponding halogen emit spectra characteristic of the
metallic halide itself, Mitscherlich tried the analogous experiment for cyanide: he intro-
duced metallic cyanides into a cyanogen-air flame, hoping to get spectra characteristic
of each metallic cyanide; but he found only the "normal" spectra of the metals (those
emitted in the Bunsen flame).
Hofmann [302] added ammonia to a flame of hydrogen or carbon monoxide burning
with air or oxygen and obtained the NH2 bands. The flames were pale yellow, slightly
greenish; when burned in a separator like Smithells's [34 (p. 6)], both parts of the flame
emitted the bands. However, they were too weak to permit detecting small concentrations
of ammonia.
Watteville in 1909 [304] sprayed solutions of ammonia, ammonium nitrate or nitric
acid into a Bunsen flame and in each case obtained the NH2 bands. I have not seen the
original paper; this information comes via Kayser [91 (p. 836)]. The work was evidently
spectrographic.
S.6.3 FLAME SPECTROPHOTOMETRY OF NITROGEN
Recent studies of the analytical emission flame spectrophotometry of nitrogen are sum-
marized in Table S.xl. The work seems to be gaining momentum, but it is not quite as
far along as the corresponding effort with carbon. The table shows fair progress, especially
within the last five years. Some of the sensitivities are not bad. The high speed and
precision of flame photometry should be kept in mind. Both liquid and gaseous samples
have been analyzed. It is interesting that all of the major flame band spectra of nitrogen
have been applied. Of these, the eN, NH and NO bands are sharp and distinctive, and
the NO bands occupy a region of low background and few spectral interferences. The
NH2 bands, although clearly useful, are troubled by serious interferences.
Table 5.xn gives the absolute radiance of the NO bands, calculated from the spectro-
grams on which the data in [39] were based. The gross radiance at each band head
is listed, even though it may represent the sum of several overlapping bands. The bands
are treated as continua in calculating J a because, although the rotational lines can be
5.6] NITROGEN 233
partly resolved with a quartz-prism instrument (Fig. 5.9), they are not usually seen under
analytical conditions (Fig. 5.10 and [3 (Spectrogram 85)]).
The strongest NO head is the one at 2363 A. In the optimized sprayer-burner flames
studied, regardless of the fuel, oxidant, solvent or sample compound, the radiance of this
band head is close to 2 picowatts per cm 2 per steradian per nm of bandwidth per [Lg/ml of
nitrogen concentration. Only nitric acid and ammonia have been tried as samples. They
emit practically identical NO spectra, but the flame gas adjustments that maximize the
NO emission are different for the two compounds. When the flame is adjusted for maximal
NO emission with ammonia, the background is higher, possibly because ammonia is a
fuel whereas nitric acid is an oxidant.
It is an important point that the nitrogen of the air present in these hydrogen-containing
sprayer-burner flames causes no emission of the NO bands. Consequently, nitrogen can
be determined in nitrogen compounds without interference from the molecular nitrogen
in the flame. However, if the hydrogen is eliminated, the resulting somewhat hotter air-
oxygen-acetylene flame emits distinct NO bands in the background (Fig. 5.23).
Table 5XII also lists practical "intensities," defined as in Table 5.I1I, for the DU with
IP28. As with boron, 10 times the reciprocal of the "intensity" is a good measure of the
fluctuational detection limit. These detection limits are most meaningful for the sharpest
peaks, viz., those at 2149, 2263, 2363, 2471 and 2588 A. The background can be measured
very close to the redward side of each of these peaks. Detection limits or intensities for
some of the NO bands have appeared also in [3,5, 110, 116, 117].
The negative flame-emission GC detector of Overfield and Winefordner (see Section 5.4.6)
was tried with nitrogen and nitrous oxide [273]. Detection limits were 0.6 and 0.7 ,ttl,
respectively, or 0.75 and 1.4 pg/sec. Response was linear to 4000 pI. Ammonia gave a
negative signal (like the others) at low concentrations but a positive signal at high con-
centrations.
A substitution method for amino nitrogen was worked out by Beauchene et al. [2 (p.
265), 308]. They add a cupric phosphate suspension to the sample (e.g., a protein hydro-
lyzate). The amino acids form a complex with copper, which passes into solution in
equivalent amount. After centrifugation the copper is determined by flame spectrophoto-
metry.
In the Beilstein test for halogens, the sample (gas, liquid or solid) is brought into contact
with copper in a flame. The test is successful if the flame is colored green or blue. It happens
that this test responds to certain nitrogen compounds, especially when applied in solid
or liquid form to the copper. Noelting and Trautmann in 1890 [309 (p. 3664)] noticed
that, with copper oxide on a platinum wire in the flame, the green color was given strongly
by 8-hydroxyquinoline and its methyl derivatives with the methyl at the 5, 6 or 7 position,
but not by other derivatives. Milrath in 1909 [310], with a copper oxide bead, obtained
the green flame with ureas, ortho-substituted quinolines, and various related compounds.
Copper cyanide itself colors a flame green, like the halides, and Milrath suspected that
those organic nitrogen compounds that give the Beilstein test form cyanide, which liber-
ates a volatile copper cyanide. Tait [311] used a copper spiral in an alcohol flame for de-
tecting halogen compounds in the air and said that it would detect cyanogen too. Cer-
234 NONMETALS [5
TABLE S.xI
DETERMINATION OF NITROGEN BY DIRECT EMISSION
FLAME SPECTROPHOTOMETRY
(See Table S.V for abbreviations)
Date Authors Ref. Flame Emission Burner Dispersion Detector
1954 Honma & Smith (305) Air-CH. CN 3883. 3590 Smithells + Spectrograph;
sprayer CH 3890 internal standard
1960 Buell (306) Oz-Hz CN 3883. 3871. BSB DU IP28 +

3862 SERA a
CN 3855. 3851
1961 Gilbert (49) Air-0z-Hz-CzHz NO 2363 Sheathed BSB DU IP28 +

I Air-Hz NO 2363 SERA
1962 Buell [57) Oz-Hz CN 3883-3851 BSB DU IP28 +

I SERA
1963 Gilbert (39) Air-02-HZ-C2HZ NO 2263-2596 Sheathed BSB DU IP28 +

(see Table 5.XID SERA
Air-Hz NO 2149-2596
1963 Buell [58) OZ-H 2 CN 3851 BSB DU IP28 +

I SERA
1963 Naval Applied (307) Air-Hz CN3883 Cooled Filter Photomult.

Science Lab. (rich) aluminum
1965 Braman & (238) Air-Hz NHz green Dilfusion Filter DuMont 6291
Gordon (540 run)
1966 Braman (265) Air-Hz NH2 540. 589 Dilfusion Filter DuMont 6291
nm;CN380nm
1966 Buell [59) 02-Hz CN 3883 BSB 2-mB&L IP28

grating
1966 Robinson & (269) 02-H Z CN 417. 387. BSB DU.DK lP28
Smith 358 nm; NH
336nm
a) Spectral energy recording attachment
tain tetraphenyl trimidines (but not all) were found by van Alphen [312] to give the test
on copper oxide.
In applying the Beilstein test to gas chromatography, Gunther, Blinn and Ott [313],
using a copper thimble in a Bunsen flame, noted response to cyanides, thiocyanates and
compounds that form CN in the flame. Eads and Payne [314] used a copper spiral in
burning methane (the carrier gas) and obtained response with organic nitrogen com-
pounds. In these cases, the spectrum is probably the one usually emitted by copper in
conventional flames, most of the green light coming from what is believed to be the CuOH
molecule [3 (p. 548)]. If CuCN survives in the flame, no spectrum attributable to it has
yet been identified.
5.6] NITROGEN 235
TABLE 5.XI (continued)
Height above Solvent Sample Detection limit

Precision Linearity Interferences
burner
I or gas substances forN
Inner cone EtOH MeCN, nitrates, I I mg or G=5% Good but varia- Mg 3832, 3838
nitrites, cyanides 200 Il-g/ml ble, 1-15%
Inner cone Naphtha 120 Il-g/mI (1 %) CH 3872, 3889
I 160 ll-g/ml I
HzO I 14 ppm (1 :Y'> None from air
I iPrOH I 20ll-g/mi I
Inner cone Naphtha MeCN 6OIl-g/ml CH3872
I I
HzO
I NH,
RNO,
14 ppm
25 ppm
1% Good up to 1% I
iPrOH HNO, 20ll-g/ml
I
13mm Naphtha
I I I
Air I Organic N com-I Few Il-g/l I S compounds
I pounds
I
Wholefiame Air MeNOz, PrNO,
NH,
I ppm
10 ppm
Few % I Most vapors, es-
pecially boranes
NOz 10 ppm Linear to 6000
ppm
Wholefiame GCeffiuent Et,N, Me3N , < 0.1 Il-g Variable Most

N2 carrier MeCN, MeNOz. compounds b
PhNOz, iBuCN
Naphtha 10 Il-g/mI 1%
I I I
Controlled by BuOH, BuNHz Concave upward
slit BuCI
I I
b) Favorable case: For Me,N, specificity factor for interference by carbon compounds is > 100 at 515 nm.
Nitrogen is not yet amenable to direct absorption flame analysis, * but two indirect methods
have come to light. Bond and O'Donnell [315] noticed that ammonium salts enhance the
absorption of titanium and zirconium in the nitrous oxide-acetylene flame. Only fluoride
interferes. They used the 3643-A line of titanium at 400 ppm and obtained a precision
of 10% in estimating ammonia. They are continuing work on the method.
*) The bands of NO have been measured with aqueous nitric acid in the long-path absorption
flame spectrophotometer of Rubeska and Moldan [473] (see Section 5.10.9).
236 NONMETALS [5
TABLE 5.XII
RADIANCES AND PRACTICAL INTENSITIES OF NITRIC OXIDE BANDS AND
BACKGROUND IN BECKMAN SPRAYER-BURNER FLAMES
J., J b and intensity defined as in Tables 5.11 and 5.111
Flame: Air-H 2 Air-O r H r C 2 H 2

O 2 in oxidant: 20% 29%
Optimized for: Bismuth Nitric acid
Sample: Nitric acid Nitric acid
Solvent: 85 % Isopropanol Water
Wavelength I J. x 1011 Jbx 10 8 Int. J. x 1011 Jbx 10 8 I Int .
2149.1 .04 .12 .3
2154.9 .03 .12 .25
2239.4 .05 .16 .3
2245.4 .05 .17 .3
2262.8 .13 .24 .5
2269.4 .075 .25 .3
2363.3 .17 .24 .7 .20 .26 .8
2370.2 .09 .25 .35 .10 .28 .35
2440.0 .04 .42 .10 .056 .53 .11
2447.0 .045 .45 .10 .058 .55 .11
2471.1 .11 .44 .25 .13 .50 .25
2478.7 .06 .40 .15 .07 .47 .15
2550.0 .oJ .7 .04
2559.0 .03 .75 .04
2587.5 .06 .57 .10
2595.7 .035 .55 .06
2671.4 (.02) 8
2680.0 (.015)
2713.2 (.02)
2722.2 (.01)
..
8) EstImated for air-hydrogen from relative Illtensltles III oxycyanogen.
Kumamaru et al. [323] determined nitrate via the atomic absorption of copper. They
noticed that nitrate enhances the extraction of cuprous copper together with neocuproine
(2,9-dimethyl-1,10-phenanthroline) from buffered aqueous solution into isobutyl methyl
ketone. The extracted entity is a 1 : 2 : 1 complex of Cu(I)-neocuproine-nitrate. Copper
is determined in the extract at 3247 A. The method was used for samples containing 10
to 100 [Lg of nitrate; it is apparently sensitive to a part per million or so.
5.6] NITROGEN 237
TABLE 5.xn (continued)
29% 28% 28%

Nitric acid Ammonia Ammonia
Ammonia Nitric acid Ammonia
Water Water Water
JaX 1011 Jbx 10 8 Int. Jax 1011 Jbx 10 8 I Int. Jax 1011 Jbx 10 8 Int.
. 12 .7 .18
.07 .65 .11
.12 .26 .45 .065 .60 .11 .20 .56 .35
.06 .28 .2 .034 .64 .05 .10 .62 .16
.028 .61 .045 (.015) 1.7 .01 .03 1.65 .02
.032 .61 .05 (.015) 1.6 .01 .04 1.6 .025
.075 .54 .14 .040 1.3 .03 .14 1.2 .12
.040 .52 .08 .025 1.15 .02 .07 1.15 .06
.06 2.4 .025

(.025) 2.2 .01
5.6.6 FLAME IONIZATION
The Karmen-Giuffrida thermionic flame-ionization detector is extraordinarily sensitive

to phosphorus and sometimes to the halogens. But it can be made rather selectively sen-
sitive to organic nitrogen compounds as well. According to Ives and Giuffrida [316],
Wells [317] was the first to discover this application. He used the detector, sensitized to
238 NONMETALS [5
nitrogen, for analyzing drugs by gas chromatography. The effect was discovered inde-
pendently by Aue, Gehrke, Tindle, Stalling and Ruyle [318,319]. They placed a ceramic
bead loaded with (preferably) rubidium sulfate in the hydrogen flame to obtain selective
response for nitrogen compounds. Phosphorus and chlorine interfered severely.
In 1967 I worked on detectors of this kind, under the auspices of the U.S. Naval
Applied Science Laboratory [320]. The best results were obtained with soap (Lava brand)
as sensitizer upon a nichrome helix in the hydrogen flame. Response was linear up to
10 fLg/1 of organic nitrogen in air; at this concentration the signal was 100 times the
background. The detection limit was judged to be better than 0.01 fLg/l. Specificity factors
(defined in [2 (p. 151)]) were 20,000 for carbon compounds, 400 for sulfur and 5000 for
ammonia, but only about unity for phosphorus and chlorine. However, other sensitizers
(less sensitive to nitrogen) gave specificity factors of 10 or more for phosphorus and
chlorine, so that the prospects for suppressing these interferences are good. The detector
responds in t minute and is precise to 1 %.
Ives and Giuffrida [316] tried many different salts on a platiniridium helix in the flame.
With cesium chloride, the nitrogen response was 150 times that of a normal flame-
ionization detector for carbon and the chlorine response was suppressed; but the detector
was still extremely sensitive to phosphorus (lO,OOO-fold enhancement). Johnson, Rhoades
and Wheeler [321], discussing gas-chromatographic pesticide residue analysis, compared
(for nitrogen) microcoulometric titration, coulometry, microwave emission and thermionic
flame ionization. They pointed out that interfering signals from sulfur, phosphorus and
halogens can be subtracted from the nitrogen signal to correct it.
The Tesla discharge of Chakrabarti et al. [87] (see Section 5.2.3), with ammonia, emits the
"second positive" bands ofN 2, the main bands ofN 2+, the NH bands and the "ammonia
alpha" bands of NH 2. The electrodeless discharge of McCormack et al. [88] (see Sections
5.2.3 and 5.5.7) emits the CN spectrum with great persistence. Nitrogen in argon can
be detected at a flow rate of 0.9 ng/sec by the N2 band at 3371 A and nitrogen dioxide
can be detected at 6 ng/sec.
The direct-current discharge of Braman and Dynako [275] (see Section 5.5.7) and the
radiofrequency torch of West and Hume likewise emit the CN spectrum even in the
nominal absence of nitrogen. The induction torch of Wendt and Fassel [300] shows bands
of N 2, N2 + and NH in the tailflame. These sources have not been tested with nitrogen
compounds despite their probably high sensitivity.
5.7 Phosphorus
Phosphorus in a flame emits three or four kinds of spectra: a greenish-white continuum,

a band system in the green, and bands of the PO molecule in the ultraviolet belonging
to the beta and gamma systems. The line spectrum has also been detected. Much mystery
5.7] PHOSPHORUS 239
has surrounded these emissions. Although the green bands are now known to originate
from the HPO molecule, the nature of the continuum remains unknown.
Wohler in 1841 was the first to report a flame test for phosphorus [324]. He noticed
that phosphine-containing hydrogen bums with a whitish flame, and that if a porcelain
surface is held in the flame, it spreads out into a ring of green light. This green light is a
very interesting phenomenon. It will be described further below. Basically, it appears
whenever hydrogen, containing phosphorus, bums under conditions that keep the flame
rather cool.
Merz in 1860 [146] found that phosphoric acid imparts a greyish yellowish green color
to the mantle of a Bunsen flame, the colored region lying closer to the flame than that
produced by nitrate. Bunsen, however, reported no flame color for phosphorus [277
(p. 290)]. Homer [99] observed the flame spectrum of phosphoric acid, but I have not
seen the paper. Among recent general observations are those of Geilmann and Bode [141] ;
in studying interferences in the flame test for boron, they noted that phosphates and
phosphides color the Bunsen flame green.
5.7.2 THE GREEN FLAME OF HPO
The history of the green flame of phosphorus is a very curious one. It offers an unsur-
passed example of the generation gap deplored by Kaiser [18]. Discovered 127 years ago,
the green flame was well known to chemists concerned with phosphorus - up until the
coming of the gap. During the 1920's oblivion set in. The green flame - a strange and
beautiful phenomenon - is now being discovered all over again. E. C. Haas, for example,
discovered it quite independently during his search for a good way to monitor phosphorus
compounds in air [307]. So useful has it proved - all of a sudden - that applications
of the HPO emission are now appearing monthly. I have noticed over 20 papers within
the last two years. There are patents and a manufacturer of a special burner for phos-
phorus (and sulfur). The analysts and the theorists have not yet joined forces: most of
the authors of the analytical papers seem unaware that the emitting molecule was iden-
tified in 1963. And both groups seem unaware of the long history of their molecule. In
at least three analytical papers, spectrograms are presented as if they were new; unfor-
tunately they are poor spectrograms, less informative than the old hand-drawn ones.
The impact of the generation gap is felt perhaps most sharply on reading either of the
two best modem compendia on molecular spectra [78, 79]. What threw the compilers
off was perhaps Rumpf's 1938 paper [325]. He described a spectrum exactly matching
that of the old green flame, but attributed it to PO, even though Geuter in 1907 [326]
and Ludlam in 1931 and 1935 [327, 328] had offered evidence that the emitter must be
some sort of hydride of phosphorus. R. W. B. Pearse had advised Ludlam on his research,
but ignored his paper in Pearse and Gaydon's book [78]. In his 1957 book, Gaydon
[34 (p. 222)] mentioned Geuter's spectrum but thought it might be due to PO. On the
other hand, L. Huldt in Rosen's book [79 (p. 233)] listed Ludlam's work under PH, but
Rosen himself [79 (p. 235)] placed the very same spectrum (Rumpf's) under PO. (The mole-
cule does, of course, have both PH and PO bonds.) The point I wish to make is that
neither of these handbooks makes it clear that there exists a spectrum - that of phos-
phorus in a chilled hydrogen flame - that is as distinctive, well characterized, and long
familiar as the fluctuation bands of boron. That its emitter was not yet identified is beside
240 NONMETALS [5
the point. In the supplement to their book, however, Pearse and Gaydon [78 (p. 359)]
have now recognized the HPO molecule.
To return to the beginning, after Wohler's observation, Dusart in 1856 [329] found that
if hydrogen was passed over phosphorus or generated (from zinc and acid) in the presence
of phosphorus, phosphoric acid, or phosphorous acid, and burned at a glass jet, it gave
a green flame, but only if the jet was cool or if the flame was directed against porcelain.
He concluded that phosphine was formed in the generator and carried to the flame.
Merz [146] said that phosphorus colors the cool core of a hydrogen flame green. He
noticed also that the smoke from a phosphorus-containing hydrogen flame reduces per-
manganate.
The first to observe the spectrum of this green flame were Christofle and Beilstein in
1863 [330]. They saw two "magnificent green rays" and a third weaker one toward the
yellow. These are the bands whose wavelengths (at the first peak of the R branch) are
now known to be 5097, 5249 and 5597 A. They verified that iron phosphide present in
iron reacting with acid is the source of the phosphorus that makes the resulting hydrogen
burn green. Mulder [331,332] in 1864 reported additional bands, now identified as 5425,
5020 and (probably) 4880 A. He found that a single drop of ether in the hydrogen gener-
ator quenches the green spectrum, and proposed that the phenomenon is the same as the
glow of yellow phosphorus. Mitscherlich [21] in the same year published a careful
drawing of the spectrum.
The most significant early work on the green flame of phosphorus was done by Salet.
He directed a hydrogen flame against a curtain of falling water, to chill the flame and
intensify the phosphorus emission [17,281,333]. Mavrodineanu [334 (p. 399)] offers a
picture of Salet's water curtain. The flame can also be chilled by surrounding it with a
glass tube cooled by a blast of air [281] or with a sheath of cold, flowing air [17]; the
flame stretches out and the green brightens. If the tube warms to red heat, the green fades.
Salet was the first to measure the wavelengths of the HPO spectrum [335]; by 1871 he
could make use of Angstrom's measurements of the Fraunhofer lines. Salet also described
[335] the cold flame formed when hydrogen passes over gently warmed yellow phos-
phorus and emerges (unignited) from a jet. This flame is a greenish yellow cone, not hot
to the hand, showing the three strongest HPO bands and a continuum. Salet summarized
this work in his long paper of 1873 [17], which included an accurate drawing of the
HPO spectrum.
Hofmann [302] also published a drawing. He found that carbon monoxide, wet or
dry, passed over warm phosphorus, would not yield the HPO bands. Lecoq's monograph
of 1874 [98] included a drawing, which Kayser praised. Schuster [336] reviewed the flame
spectrum of phosphorus up to 1880. Lundstrom [283] experimented with the green flame
before 1886; he found that the bands stand out better above the associated continuum
at lower concentrations of phosphorus. In his study of Bessemer flame spectra (see
Section 5.5.2), he recorded bands at 5103, 5264 and 5581-5608 A, which he doubtfully
ascribed to phosphorus.
The first photographs of the HPO spectrum were obtained by Geuter in 1907 [326].
Kayser called this an outstanding piece of work; I have not seen the paper myself. Geuter
elicited the spectrum from hydrogen containing phosphine, chilling the flame simultane-
ously with an air sheath and a vessel of cold water. With a 3-t-hour exposure he was able
to resolve the line structure of the bands. He excited the HPO spectrum also in a Geissler
tube; a green cloud in the wide part of the tube emitted it. There has been a good deal
of speculation about the occurrence of the green flame bands in the luminescence of solid
5.7] PHOSPHORUS 241
phosphorus; recall Mulder's suggestion. But Geuter is the only person who has reported
the BPO bands in the phosphorus luminescence. The phosphorus must be placed in oxy-
gen and water must be present. According to Kayser, Geuter found two regions in the
luminescence spectrum: diffuse headless bands from the ultraviolet to 480 nm, and the
familiar BPO bands at longer wavelengths. The diffuse bands have not been reported in
flames.
Many of the early textbooks and monographs described the green flame of phosphorus.
Formanek's book [337 (p. 183)] discussed the flame and presented a drawing of the
spectrum, showing four bands. Partington [182 (pp. 614-619)] devoted much space to
the luminescence of phosphorus and described the cold green flame obtained by passing
carbon dioxide over warm phosphorus, an experiment that he ascribed to Smithells. This
flame was shown by Rumpf [325] to emit the same spectrum as the chilled hydrogen
flame.
Kayser [16 (pp. 239-255)] summarized the work on phosphorus prior to 1912. Table
5.xIII lists the wavelengths for the green flame reported by him from the early work,
together with Lundstrom's and modem values for comparison. In its larger features the
spectrum has been unambiguously characterized since the beginning. Lecoq listed 3 com-
ponents and Geuter 2 or 4 components in bands that are now considered single. The
central wavelength of Lecoq's triplets and the third component of Geuter's quadruplets
correspond to the maximum of the P branch (cf. Fig. 5.14); Geuter's second component
lies to the violet of the first peak of the R branch. The horizontal alignment in Table
5.xIII correlates roughly equivalent features of the spectrum.
5.7.3 CURRENT WORK ON THE HPO SPECTRUM
After Geuter's paper, aside from the theoretical papers by Ludlam and Rumpf in the
1930's, there was a quiet interlude of more than half a century in the history of the BPO
spectrum. A resurgence commenced abruptly and independently in France, Germany
and the United States in 1961-62, and more recently in England. The spark igniting this
spurt of effort was perhaps the growing importance of detecting trace concentrations of
toxic agents containing phosphorus. Theoretical and practical work on HPO is now
advancing well. The molecule has been found useful in solution analysis, assaying, air
monitoring, and especially the gas-chromatographic analysis of pesticide residues.
The BPO emission is seen to best advantage in the interconal zone of a chilled, rich,
separated air-hydrogen flame, where the background emission is almost undetectable.
This is exploited in a German patent by van der Smissen, assigned to Driigerwerk [342,
343]. It describes a water-jacketed silica burner like a Smithells separator. Excess hydrogen
burns at the bottom in air carrying the sample. A green glow appears just above the reac-
tion zone or primary flame. The green reappears in the inner surface of the secondary
flame burning at the top of the chimney. (The burner is equally useful for sulfur; the
blue glow of S2 appears above the green of BPO.) The chimney can be cooled by air
instead of water, and the flame can be diluted with an inert gas to favor the glow. The
Driigerwerk burner is figured by Mavrodineanu [334 (p. 400)].
Burners of basically similar design but differing in detail, all depending on the chilling
of a hydrogen flame to bring out the BPO emission, have been devised by Baas [307],
Gilbert [341, 349], Brody and Chaney [344, 345], Syty and Dean [279, 280, 346] and
242 NONMETALS [5
TABLE 5.XIII
SPECfRUM OF THE GREEN FLAME OF PHOSPHORUS IN HYDROGEN
Mitscherlich Salet Lecoq Lundstr1>m Geuter
[21] a [17,281, 335] [98] a [283] [326] a,b
- - - - 357 Md l
- - - - 380Md
- - - - 420Md
-
e
- 470 - -
- 478 - - -
- - - - 87 .2}
- 491 489.0 - 489.3
- - 496.0 - 497.3
-
-
500w
-
-
503 w
-
-
502.4
-
-
-
roO)
501.3
503.1
- - - - 504.2
- - -
-
513 s
-
-
511 s
-
1"'0' )
510.6 M
515.0
-
511.0
- 1'"")
509.4
510.8
512.0
- - - -
- fl7.7}
r
- - - 520.4
-
-
525 s
-
-
-
525 MRs
-
-
23 4 M
526.3
.
531.0
}
-
-
525.5
-
rO')
524.5
526.0
527.6
-
-
-
-
-
-
-
-
-
-
-
-
1"'06)
535.6
537.4
- - - - 538.9
- - - - f41.2}
- 547 V 543.6 - 544.1
- - - -
- - - -
1"")
553.1
553 wf 552w 553.8 - 554.1
- - - - 555.2
-
-
-
-
-
559 Ms j"" ]
560.5 M
-
-
559.0
ro0]
558.5
560.9
- - 565.3 - 563.2
- - - - -
- 576 - - -
- 584w - - -
- 590w - - -
- 599MV 603.1 M - -
- 609wd - - -
- - 621.0 M - -
- - - - -
- - 639.7 M - -
- - - - -
- - - - -
- - - - -
- - - - -
Notes:
d = diffuse; m = medium; M = maximum; R = degraded to red; s = strong; v = very;
V = degraded to violet; w = weak.
5.7] PHOSPHORUS 243
TABLE 5.XIII (continued)
Ludlam Rumpf Peyron and Lam Thanh Gilbert

[328] C [325] d [338-340] C [341] •
- - - -
- - - -
- - - -
- - - 464.2 vw
- 477.1 476.65 477.0w
- - 487.95 488.2m}
- 489.2 -
- - 495.70 495.7w
- - -
49'.'~]
- - 501.98 502.4 s
- - -
- 505.3 -
-
509.8
-
-
-
510.8 s
-
509.68
-
m.,w)
- - -
- - -
521.2 519.6 521.01 52L2W}
- - -
525.1
-
-
525.5 vs
524.87
- "'.1 ~ )
526.3 M
- - -
- - -
-
-
-
538.0
536.64
- '''.7W)
- - -
543.5 - 542.52 542.7W}
- 544.3 s -
-
--
-
-
-
553.50 'SO.7W)
553.7m
554.0 -
- - -
- - - '56.6 W
559.9 - 559.73 560.0 s )
- 560.4 s -
- - -
- - 569.84 570.2 vw
- 575.0 - 573.4 vw
- 584.3 s 584.94 585.3 W
- - 592.29 592.7 W
- 600.7 s 599.10 599.4w
- - 610.12 610.3 vw
- - 619.55 -
- - 628.27 -
- - 636.23 -
- 647.2 s 643.64 -
- - 655.70 -
- - 668.23 -
- - 677.46 -
&) From Kayser [16]. b) Wavelengths of heads, degraded to red, except as noted; braces en-
close heads belonging to a single band complex. C) Wavelengths of first peak of R branch.
d) Wavelengths of band centers. e) Wavelengths of central minimum. f) Should perhaps re-
present 559, a much stronger band. B) These first three bands may not occur in flames.
244 NONMETALS [5
EMI95246
PHOTOMULTIPL IER
TUBE
IRROR
SWAGELOK FITTIN G
COLUMN
EFF L UENT (N 2)
Fig. 5.11. Flame-photometric detector for phosphorus and sulfur, by Brody and Chaney [3451.
Reproduced by permission of the Journal of Gas Chromatography.
Johnson [347]. MicroTek Instruments [348] has commercialized the Brody-Chaney de-
sign (Fig. 5.11) for use as a detector of phosphorus and sulfur in gas chromatography.
The performance of these burners as spectrochemical sources will be described later
(Table 5.xVII).
Gilbert made use of two kinds of burners. One (Fig. 5.12) was a sprayer-burner having
a sheath of an improved design furnishing a very smooth flow of sheathing gas. Hydrogen
applied under pressure to the sprayer aspirates sample vapor through the capillary and
' - - Rt910n of flome
CopiHory
\ . . / Air or ni IrOQel'J ....lI h sCiMple
Fig. 5.12. Sheathed burner for nitrogen-cooled hydrogen flame.

5.7] PHOSPHORUS 245
4500 4600 4100 48504900 5000 ~IOO

Fig. 5.13. Spectrum of phosphorus in nitrogen-cooled hydrogen flame.
Sheathed burner of Fig. 5.12. Hydrogen 61/min through sprayer, oxygen O.ll/min through fuel
port, nitrogen l21/min through sheath, nitrogen (with methyl phosphite vapor) about O.ll/min
through capillary. Lowest recording (slit 0.01 mm) is with smaller capillary and air instead of
nitrogen as carrier of sample. Grating DU spectrophotometer, 600 lines/mm blazed for 5000 A,
lP28 photomultiplier, scanning speed 139 A/min, time constant 0.5 sec. Wavelength scale repre-
sents zero on intensity scale in this and the following spectrograms; gain adjusted for convenience.
Mercury lines are from room light. PO bands appear in second order.
5200 5250 5300
P Branch
5220 5230 5240 5250 5260 5270 5280 5290

Fig. 5.14. The HPO band at 5249 A.
Same conditions as for lowest curve of Fig. 5.13, except scanning speed 46 A/min (above) and
14 A/min (below).
246 NONMETALS [5
PYREX CH I MNEY
9 MM . 1.0.
WATER
PYREX JACKET
WATER
STOPPER
TEFLON ADAPTER
1/8" COPPER TUBE

FOR A IR WITH
SAMPLE
E<ll'lllilt--S MM. 1. 0. NUT
PYREX TUBE FOR

HYDROGEN
Fig. 5.15. Water-cooled hydrogen burner for phosphorus and sulfur.
4700
Fig. 5.16. Spectrum of HPO in water-cooled hydrogen flame.

Burner of Fig. 5.15. Hydrogen 10 I/min, air (with ethyl phosphate vapor) 1.0 l/min. Spectro-
photometer as for Fig 5.13. Scanning speed 139 A/min. Wavelengths are those of first peak of R
branch.
5.7] PHOSPHORUS 247
bums in a little oxygen supplied to what is normally the fuel jacket. A rapid flow of
nitrogen through the sheath chills the flame. With phosphorus, the tiny combustion zone
is surmounted by a very stable spindle-shaped green glow. Without chimney or water
jacket, the remoter ultraviolet is easily studied, and the high stability and brightness
permit recording a nearly noise-free spectrogram of HPO in a few minutes (Fig. 5.13).
The higher-dispersion recordings of Fig. 5.14 resemble the densitometric traces published
by Ludlam [328] and Lam Thanh and Peyron [340].
Gilbert's second design (Fig. 5.15) resembled the Driigerwerk burner. It was adjustable
in all of its dimensions to facilitate study of the very complex relationships between
burner design and character of the emission. At low flow rates there is a green shaft of
light along the axis; at higher rates, causing turbulence, a green glow fills the neck of the
chimney. The burner gives an exceptionally pure HPO spectrum, with hardly any back-
ground, as may be seen in Fig. 5.16. Like the Driigerwerk burner, it separates the phos-
phorus and sulfur emissions. (When both elements are present and the gases are adjusted
so as to overheat the glass jet, a pseudospectrum appears: a vertical band of smoothly
merging colors fills the burner - red jet, yellow primary flame, green phosphorus blending
through blue into pure violet sulfur emission at the top. The device would make a lovely
ornament for restaurant tables in place of the usual candle.)
A different flame source of the HPO spectrum is that of Dagnall, Thompson and West
[48], who used the elongated burner of the Unicam SP900A flame spectrophotometer.
Nitrogen operates the sprayer and is then mixed with hydrogen. The aerosol bums as a
diffusion flame in air. The flame temperature ranges from 280 to 850°. When phosphoric
acid is present in the sprayed aqueous sample, the HPO spectrum appears in the cool
heart of the flame. If air is used instead of nitrogen, the HPO emission is 1/5 as bright
and the background is stronger.
5.7.4 ORIGIN OF THE HPO SPECTRUM
I have called the molecule HPO in the above account of its history, burners, flames and
spectrum. The emitter, however, remained unknown until Lam Thanh and Peyron [340]
identified it.
Geuter [326] thought the emitter a hydride and suggested P 2 H 4 • Ludlam [327, 328]
was the first to bring quantum theory to bear upon the question. He passed hydrogen
over white phosphorus and burned it with insufficient air. Spectrographic exposures of
100 hours were needed. (This is nearly 106 times the O.5-second time constant charac-
teristic of the recording of Fig. 5.13.) As seen in Fig. 5.14, each band has a P branch
with hazy lines, an R branch with sharper lines, and a missing line or Q branch between
them. Ludlam's rotational analysis of these lines yielded a moment of inertia and radius
very close to those of PH and convinced him that this was the emitter; but he could not
get a satisfactory vibrational analysis. Rumpf [325] passed a mixture of carbon dioxide
and air over phosphorus at 60° and obtained the cold flame mentioned earlier. He suc-
ceeded in photographing more of the bands, and fitted them into a crude vibrational
scheme. Since the term differences were close to those for PO, he attributed the green
flame bands to that molecule. Ludlam and Rumpf were both right as far as they went:
one had grasped the elephant by its trunk, the other by its tail.
In their first effort with this emitter, Lam Thanh and Peyron [338] in 1961 measured
248 NONMETALS [5
the spectrum of the green chemiluminescence from atomic hydrogen and phosphorus
vapor in argon at reduced pressure. From the rotational analysis they inferred, like
Ludlam, that the emitter must be PH; but although they had measured 23 bands as
against Ludlam's four, they had trouble with the vibrational analysis. In their next paper
[339], based on the same experimental work, they concluded that "the rotational and
vibrational analysis do not seem to confirm the hypothesis of a diatomic molecule."
They tentatively proposed PH 2 • In a note added in proof they said that use of deuterium
had proved that the molecule contains hydrogen but is not PH. In a symposium of the
same year (1962), Peyron [350] suggested that PH 2 is formed from a three-body collision
of the atoms.
In 1963 Lam Thanh and Peyron [340], by a comparison and analysis of the spectra
obtained with hydrogen and with deuterium, established that the molecule is HPO. The
hazy lines of the P branch proved to be doublets; the first few in Fig. 5.14 may be on the
verge of being split into the components. A term diagram was worked out. The funda-
mental vibrational (stretching) frequency is 2308 cm- 1 for P-H and 1179 cm- 1 for P-O,
and the H-P-O bending frequency is 983 cm- 1 • The molecule is bent at an angle of 93°
in the upper and 106° in the lower electronic state. Continuing their work with a brighter
chemiluminescent source (adding a little oxygen to the hydrogen before dissociation into
atoms), these authors [322] in 1964 obtained a spectrogram at very high resolution and
a better rotational analysis. They revised the lower-state angle to 104°44' and reported
an error in the vibrational assignments. A new vibrational analysis was presented in 1966
[351]. This is shown in Table 5.xIV. I have included Lam Thanh and Peyron's unassigned
bands, as well as my own measurements [341]. My data are less accurate, but I have
measured a few bands not observed by Lam Thanh and Peyron. These might help to
complete the vibrational analysis.
5.7.5 MECHANISM OF THE HPO EMISSION
The green glow is obviously not a thermal emission. In the van der Smissen burner, if
sodium is present, the primary flame on the hydrogen jet (Fig. 5.15) bums yellow, but
the green of phosphorus rides above the yellow of sodium. The "cold flame" is hardly
more than warm. Such a "flame" may appear on the top of the burner of Fig. 5.15 when
the hydrogen is burning only at the lower jet; I have put my finger in it; it will not kindle
a match. The importance of cooling the flame gases in some way has been emphasized
since the green flame was first discovered. The green color is weak or absent at the tem-
perature of a normally burning air-hydrogen flame, although it may be seen as a thin layer
lining the reaction zone or inner cone of a premixed, diluted air-hydrogen flame.
In the gas-sheathed burner of Fig. 5.12, I have measured a radiance of 10 picowatts
per cm 2 of glow area, per steradian, per nm of bandwidth at the 526-nm band, per flog/l
of phosphorus concentration in the air carrying the sample. In the water-cooled burner of
Fig. 5.15, the radiance in these units may exceed 100 picowatts. These radiances are
altogether comparable to that of the presumably thermal emission of B0 2 in the air-
hydrogen flame (Table 5.11), when allowance is made for dilution of the analyte by the
flame gases. The flame temperature is 2000 °C in the case of boron [6 (p. 75)] but in
the case of phosphorus only about 300° [48]. Similarly, the background radiation of the
flame gases differs greatly in the two cases. It is about 1 nw/cm 2 .sr.nm in the normal
5.7] PHOSPHORUS 249
TABLE 5.xIV
WAVELENGTHS, WAVENUMBERS, INTENSITIES AND VIBRATIONAL LEVELS OF
THE HPO SPECTRUM
Wavelengths and intensities a Vacuum wavenumbers I Vibrational assignments b
Lam Thanh I Int. I Gilbert Int. Lam Thanh I Gilbert I VI' Vz' V3' VI" Vz" V3"
& Peyron
& Peyron
I
4641 1 21541
4665.8 <1 21426
4766.5 <1 4769 2 20974 20963
4879.5 3 4880.4 7 20488 20484
4957.0 <1 4955.5 20168 20174
4980.9 9 20071
4992.3 3 20025
5019.8 4 5022.5 9 19915 19905 0 0 1 0 0 0
5096.8 5 5097.2 41 19614 19613
5210.1 1 5210.1 18 19188 19188
5248.7 10 5249.4 100 19047 19044 0 0 0 0 0 0
5366.4 2 5365.4 11 18629 18633
5425.2 5 5424 14 18427 18431
5504° 4 18165
5535.0 6 5534.4 20 18062 18064 0 0 0 0 0 1
5563 ° 1 17972
5597.3 8 5597.3 43 17860 17861 0 0 0 0 1 0
5698.4 4 5699.3 (11) 17544 17541 0 0 1 0 2 0
5730.7 10 17445
5849.4 4 5849 6 17091 17092 0 0 0 0 0 2
5922.9 5 5922.5 10 16879 16880 0 0 0 0 1 1
5991.0 6 5990 12 16687 16690 0 0 0 0 2 0
6101.2 4 6099 (11) 16386 16392 0 0 1 0 3 0
6195.5 <1 16136 0 0 0 0 0 3
6282.7 3 15912 0 0 0 0 1 2
6362.3 3 15713 0 0 0 0 2 1
6436.4 3 15532 0 0 0 0 3 0
6577.0 1 15200 0 0 0 0 0 4
6682.3 1 14961 0 0 0 0 1 3
6774.6 1 14757 0 0 0 0 2 2
Notes:
8) Wavelengths are for the first line of the R branch in both columns; compare the somewhat
longer wavelengths of the central minimum listed under Gilbert in Table 5.xIII. Lam Thanh
and Peyron's intensities are spectrographic estimates on a scale of 10. Gilbert's intensities
represent the difference between the central minimum and the peak of the R branch, as meas-
ured with the spectrophotometer of Fig. 5.13, on a scale of 100; this helps to avoid the
effect of overlapping of weak bands by strong ones.
b) The upper levels are v', the lower are v"; the VI levels are those of the P-H stretching vibration,
the Vz levels are those of the P-O stretching vibration, and the V3 levels are those of the
H-P-O bending vibration. From [351].
0) Estimated position; the R peaks were not actually visible.
250 NONMETALS [5
air-hydrogen flame with water spray in the green (Table 5.11); in the gas-sheathed and
water-cooled flames of Figs. 5.12 and 5.15, it is about 0.005 and 0.0025 nwjcm 2.sr.nm,
respectively. These are upper limits, since it is hard to eliminate scattered light coming
from the nearby primary flame.
To account for this nonthermal emission, Lam Thanh and Peyron [322] considered
a few possibilities. Since they could detect no predissociation in HPO, they thought the
reaction H + PO + M -* HPO· + M (M a third body) unlikely. Having observed
beta-system PO bands emitted by phosphorus vapor with oxygen, they contemplated
the reaction H + PO· -* HPO·, but noted that its energy is a good deal (over 3 eV)
higher than that needed to excite the HPO. To be sure, their matrix (atomic hydrogen,
argon, oxygen and phosphorus at low pressure) differs from the chilled hydrogen flame
at atmospheric pressure.
Fenimore and Jones [352] measured the emission of HPO from methyl phosphate in
fuel-rich hydrogen-oxygen-argon flames at 50, 100 and 760 torr and 1000-1380 oK. They
undertook to relate the HPO intensity to the temperature and to the concentrations of
atomic and molecular hydrogen and oxygen, hydroxyl, water and total phosphorus. This
was a laudable and interesting effort, but the results were not exact enough to yield un-
equivocal conclusions. For one thing, they found the emission to be proportional to the
0.4 power of the phosphorus concentration; but all who have used the HPO emission
for practical analysis report linearity over a wide range of concentration. This discrepancy
impairs Fenimore and Jones's main conclusion, viz., that the phosphorus is present
mostly as P 2 in the region of the glow. Their flames were relatively hot, however; the
more practical HPO-emitting flames are probably always cooler. There were two signif-
icant observations: the green glow did not commence until the O 2 was consumed; and
atomic H was the dominant radical in the burnt gas (ranging around 0.03 micromole
per ml).
Syty and Dean [280] were more inclined to favor the reaction H + PO + M-*
HPO· + M. They noticed that when argon replaced the nitrogen of the air-hydrogen
flame, the HPO emission appeared only in the presence of a chimney wall. The air-
hydrogen flame without a chimney emitted the HPO spectrum from the inner cone, but
the corresponding argon-oxygen-hydrogen flame did not. They argued that either nitrogen
or a solid surface may serve as a third body to aid the combination of H + PO; in the
argon flame there is no molecule of sufficiently large cross section to do that.
Organic compounds tend to quench or suppress the HPO emission in hydrogen flames.
Fenimore and Jones added 3% methane in one trial; the HPO intensity decreased 89%
and the H concentration 68 %. Dagnall et al. [48] found that 10% of an organic solvent
added to the aqueous phosphoric acid solution sprayed into their nitrogen-diluted hydro-
gen diffusion flame reduced the HPO emission by 85 %. Syty and Dean [280] reported
that acetylene (less than O.lljmin) premixed with the hydrogen (at 0.2-0.6 ljmin) com-
pletely quenched the HPO emission. (But unlike Dagnall et al., with organic solvents
they found the 3- to 4-fold enhancement usually expected from improved spraying.) It is
known that cool hydrogen flames contain an abnormally high concentration of atomic H,
and that it persists for several milliseconds [34 (p. 194)]; organic flames contain much
less H. If H is needed to form excited HPO, the quenching action of organic compounds
may be due to their removal of H by catalytic recombination to H2 or (with OH) to H 20
via carbon-containing molecules formed in the combustion zone (cf. [303]).
I have suggested [67] that the HPO emission in cool, rich hydrogen flames is a chemi-
luminescence due to the thermoneutral reaction
5.7] PHOSPHORUS 251
PO + Hz + OH -- HPO* + HzO.
There are the following arguments: (1) The reaction has just the right energy to produce
excited HPO; I can think of no other that does. The brightest bands originate in upper
levels at about 2.5 eV. Dissociation energies are 6.2 eV for PO, 4.5 for Hz, 4.4 for OH
and 9.5 for HzO [34, 37, 38]. To estimate that of HPO, consider the series: PO 6.2,
PH 3.3, NO 6.5, NH 3.7, HNO 2.0 (to H+NO) (the last is from [303]*). A reason-
able guess for the dissociation energy of HPO to H + PO is 1.8 eV. (2) The termolecular
collision should be frequent enough. Hz is a major component and hydrogen flame gases
are abnormally rich in OH (and H). (3) The proportionality between HPO emission and
phosphorus concentration indicates a one-phosphorus reacting molecule; PO is the most
stable such molecule and its spectrum can be seen in some of the green flames (Fig. 5.14).
2300 2~SO 2400 2450 2500 2550 2600
Fig. 5.17. Spectrum of PO in water-cooled hydrogen flame.

Lower curve: Same conditions as for upper curves of Fig. 5.13. Slit 0.02 mm. PO bands in second
order; HPO bands in first order. Wavelengths of Q heads of PO bands, marked above curve,
equal Pearse and Gaydon's wavelengths [78] for P heads minus 1.3 A; P heads of PO bands
marked below curve. Upper curve: PO bands in fourth order; slit 0.3 mm.
Fig. 5.17 shows this PO emission more plainly. In these cool flames it must be chemi-
luminescent, and the following reactions nicely account for it:
PO + H + OH--PO* + HzO (5.1 eVavailable)
HPO* (2.5 eV) + H-- PO* + Hz (5.2 eV available)
HPO* (2.5 eV) + OH -- PO* + HzO (5.8 eVavailable).
*) The dissociation energy of HNO is 2.1 eV, according to [486].

252 NONMETALS [5
{4) The reaction accounts for the spatial separation of the HPO from the Sz emission
through the reaction OH + Hz ~ H + HzO, which is slightly exothermic (0.6 eV) and
is driven to the right as the temperature falls. When it shifts far enough the supply of
OH becomes inadequate for generating HPO*. But Sz is excited through termolecular
collision with 2H [34 (p. 220)], and its formation is impeded by the reaction
Sz + OH ~ SH + SO (L1H o = -0.1 eV).
Thus S2* is not formed in abundance until the supply of OH has fallen so low, owing
to the cooling, that it can no longer form much HPO*. However, the flame must be
cooled in the first place to trap the high concentrations of Hand OH needed for the
chemiluminescence. In a hot flame these radicals recombine too quickly. That the
chimney wall can account for much of the HPO excitation (as Syty and Dean surmise)
seems unlikely to me, despite the evidence of their argon experiments. Any such reaction
would amount to a candoluminescence upon the surface itself; the HPO* molecules
cannot get far without being deactivated by emission or collision. But even in configu-
rations in which the green glow hugs the chimney, the glow can be seen to extend some
distance inward from the walls.
5.7.6 THE BANDS OF PHOSPHORUS MONOXIDE
Two band systems of PO occur in flames, called, by (erroneous [78]) analogy with those
of NO, the beta and gamma systems. Only the latter has found analytical application.
Gramont and Watteville [304, 353] sprayed phosphoric acid and ammonium phosphate
solutions into a Bunsen flame and observed the gamma system alone. Gaydon [34
(p. 223)] said he had seen the PO bands (presumably both systems) on adding phosphorus
oxychloride to premixed organic flames. Gilbert [5, 39, 49] obtained the gamma system
on spraying aqueous phosphoric acid into an air-hydrogen sprayer-burner flame, and
much more intensely on addition of acetylene to the hydrogen or isopropanol to the
solution. Enrichment of the air with oxygen, on the other hand, merely raised the back-
ground without much affecting the PO band intensities. Others have more recently
observed the PO bands in various flames and solvents (cf. Table 5XVII).
Even in the absence of carbon compounds the emission seems anomalously strong. In
these flames, as in the HPO-emitting flames, it is probably chemiluminescent, excited by
the recombination of H + OH, which yields just the energy needed to populate the upper
levels of the strongest bands. The additional excitation caused by organic compounds is
probably due to one of the mechanisms mentioned in the section on overexcitation: for
example, excited CO may react with a higher oxide of phosphorus such as POz to give
COz and excited PO.
A recording of the PO spectrum is shown in Fig. 5.18. In Fig. 5.17 the resolution is
somewhat better, and the double double-headed structure is visible on the lower curve.
Wavelength tables and vibrational analyses are found in [78] and [79], and [3 (p. 399)]
has a table of spectrophotometric intensities in the flame. Table 5.XV gives the ra-
diance of the PO gamma bands, calculated from the spectrograms on which the data
in [39] were based. The comments in the text on Table 5Xn apply also to Table 5XV.
Table 5XVI gives the radiance of the strongest PO head in various flame-solvent com-
binations. Notice that in air-hydrogen the radiance of PO varies nearly as the square of
5.7] PHOSPHORUS 253
Fig.S.18. Spectrogram of phosphorus in air-hydrogen flame.

Apparatus as in Fig. 5.2. Slit 0.14 mm. Phosphoric acid in 50% isopropanol, 800 /Lg/mlphosphor-
us. Reproduced from [49] by permission of Beckman Instruments, Inc., and from [3] by
permission of John Wiley & Sons.
isopropanol concentration, whereas the background radiance varies more nearly as the
first power.
The beta system of PO consists of many narrow bands between 322 and 346 nm,
degraded in either direction. The head at 3270 A is the one most commonly noticed. An
arc spectrogram is found in Hagenbach and Konen's atlas [105]. The beta system is not
easily excited in flames, but Hartley [354 (p. 183)] observed six of the bands, all very
faint, when phosphorus pentoxide was vaporized in an oxyhydrogen flame. Phosphorus
and phosphine burning in air or oxygen emit both the gamma and beta systems, according
to Emeleus and Downey [355, 356, 357]. The Will-o'-the-wisp was once thought to be
the flame of phosphine from decaying vegetation in marshes [182 (p. 618)].
We have hot flames, cold flames and cold glows or phosphorescences in the oxidation
of phosphorus and its compounds; it is perhaps pointless to try to distinguish them.
The glow of white phosphorus has been much studied but is still poorly understood.
The older textbooks devoted a good deal of space to it (e.g., [182 (p. 614)]). Centnerszwer
and Petrikaln [358] were the first to observe bands in the spectrum of the phosphorus
glow, which is too feeble, as a rule, to photograph easily. The character of the spectrum
- its intensity distribution and the sharpness of the bands - depends on the way in which
the glow (or cold flame) is produced, but bands of both the beta and gamma systems
always appear, together with a continuum in the visible. These bands have been con-
firmed and further examined by Petrikaln [359, 360, 361] and by Emeleus and colleagues
[355, 356, 357, 362, 363]. Spectrographic exposures as long as 480 hours were needed
to record them. In Rumpf's cold flame [325], a very weak beta band of PO was detected
along with the stronger HPO spectrum.
254 NONMETALS [5
TABLE 5.xV
RADIANCES AND PRACTICAL INTENSITIES OF PHOSPHORUS OXIDE BANDS AND

BACKGROUND IN BECKMAN SPRAYER-BURNER FLAME
J a , J b and Intensity defined as in Tables 5.11 and 5.111. Wavelengths from [78] and [353];
both heads of each doublet are listed. Phosphoric acid in isopropanol-water mixtures in air-
hydrogen flame.
% Isopropanol: I 50 80 90
(Jog/ml P used: 820 330 160

I I
Wavelengths Jax 1011 Jbx 10 8 Int. Jax 1011 Jbx 10 8 Int. I J a x 1011 Jbx 10 8 Int.
2286.8, 2288.2 .11 .15 .75

2293.6, 2294.9 .19 .15 1.3
2300.3, 2301.7 .20 .15 1.3
2305.3, 2306.9 .17 .15 1.2
2312.1, 2313.7 .11 .14 .75
2319.1, 2320.6 .07 .14 .5
I
2366.1, 2367.3 .56 .16 3.5 1.3 .22 6 2.1 .26 8
2373.8, 2375.2 .85 .17 5 2.0 .25 8 3.1 .31 10
2378.4, 2379.9 .75 .17 4.5 1.7 .25 7 2.9 .33 9
2382.2, 2383.5 .8 .17 5 1.9 .25 8 3.0 .32 9
2386.4, 2387.9 .62 .17 3.7 1.3 .25 5 2.3 .32 7
2394.7, 2396.3 .44 .17 2.5 1.1 .24 4.5 1.7 .32 5.5
2453.4, 2454.6 1.0 .30 3.3 2.0 .50 4 3.6 .56 6.5
2462.9, 2464.2 1.9 .30 6 4.1 .48 8.5 6.5 .54 12
2476.5, 2477.9 1.2 .25 5 2.7 .41 6.5 4.2 .47 9
I
2517.4, 2518.7 .55 .27 2.0 1.0 .49 2.1 I 2.1 .57 3.5
2528.0, 2529.4 .75 .30 2.4 1.6 .51 3.2 2.8 .58 5
2539.2, 2540.4 .8 .34 2.3 1.7 .61 2.8 2.6 .8 3.3
2553.8, 2555.0 .47 .37 1.3 .9 .68 1.3 1.5 .95 1.6
I
2595.7
I
.32 .32 1.0
I
.5 .6 .8
I
1.2
.~
5.7] PHOSPHORUS 255
TABLE 5.xVI
RADIANCE AND PRACTICAL INTENSITY OF THE 2463-A PO BAND AND BACK-
GROUND IN VARIOUS FLAMES AND SOLVENTS
Data as in Table 5.XV. All flames on Beckman sprayer-burner

Flame Solvent Jax 1011 Jbx 10 8 Int.
Air-H 2 Water 0.04 0.07 0.6

Air-H2 50 % Isopropanol 1.9 0.30 6
Air-H 2 80 % Isopropanol 4.1 0.48 8.5
Air-H 2 90 % Isopropanol 6.5 0.54 12
Air-H2 96 % Isopropanol 7.5 0.65 12
Air-H 2 99 % Isopropanol 8 0.68 12
Air-H r C2H 2 • Water 0.6 0.5 1.2
Air-H r C 2H 2 b Water 0.52 0.36 1.4
.) Sheathed sprayer-burner, air supplied to sheath to stabilize flame.

b) As in Note '), but flame was viewed by concave mirror only, focused upon best part of flame;
normally, flame is placed directly in entrance beam with concave mirror behind it, the mirror
supplying most of the light.
5.7.7 THE PHOSPHORUS CONTINUUM
Most flames containing phosphorus emit a conspicuous continuum. It looks white with
perhaps a greenish-yellow tint. Starting in 1845, such a continuum has been reported by
Miller [94] in the flame of burning phosphorus; by Simmler [28] with phosphoric acid
in a Bunsen flame; by Mitscherlich [21], Mulder [332], Hofmann [302] and Lundstrom
[283] in a hydrogen flame carrying phosphorus vapor or phosphine (along with the
HPO bands or replacing them at high concentrations); by Hofmann also in the phos-
phorus-oxygen flame, the phosphorus glow and the flame of carbon monoxide carrying
phosphorus vapor; by Hartley [354, 364] in oxyhydrogen charged with phosphorus
pentoxide; and by Emeleus and Downey [355,356] with phosphorus burning or glowing
under various conditions, glowing phosphorous oxide, and phosphine burning in oxygen.
Burriel-Marti and Ramirez-Munoz [1 (p. 42)], Herrmann and Alkemade [3 (p. 79)]
and Mavrodineanu and Boiteux [14 (pp. 62, 486)] comment on the strong continuum
caused by phosphine present as impurity in acetylene. The last authors show a densito-
metric tracing (p. 485) of the phosphine continuum in an air-acetylene flame, the emission
lying mainly in the green and red; and photographic spectrograms (p. 591) in which the
continuum extends through the blue (where the plate is more sensitive). The continuum
is strong in the primary flame of all burners emitting the HPO spectrum. With proper
design, the green glow rides above the whitish flame, and the two emissions can be almost
fully separated (cf. Fig. 5.16). In recent years a good many analysts have exploited the
continuum (see Table 5.XVII, later). There are two recent theses [365, 366] mentioned
256 NONMETALS [5
by Page and Woolley [367], evidently concerned with the phosphorus continuum in
flames, but I have no details.
I have found no published work concerned with explaining the phosphorus continuum.
Of course, the continua in all the assorted flames and glows mentioned above need not
be due to the same cause. Several authors have simply ascribed the continuum to an
incandescent phosphorus oxide aerosol. In my opinion, the continuum is not due to an
aerosol at all, for the following reasons: the emission is proportional to concentration
over a wide range; the spectral distribution is not that of a blackbody, being too high
in the green; the color looks about the same in flames of all temperatures; and the known
oxides and acids of phosphorus are all volatile below red heat. Perhaps the continuum is
analogous to the nitrogen afterglow, i.e., PO + 0 --+ P0 2 + hv.
Until last year, no one had found lines of phosphorus in flames. Both Buell and I repeat-
edly sought the lines near 2535 and 2554 A under conditions favoring overexcitation. If
the dissociation energy of PO is 6.2 eV, Sternberg's mechanism is not quite energetic
enough to dissociate PO and excite the resulting P. I also failed to find the lines 2136
and 2149 A at 5000 ppm in the oxycyanogen flame [138].
However, Skogerboe, Gravatt and Morrison [368] have now elicited the lines 2534.0,
2535.6, 2553.3 and 2554.9 A in the lower part of a slightly fuel-rich oxyacetylene flame
on a sprayer-burner with phosphoric acid in ethanol at low flow rates of sample (below
1 mljmin). At normal flow rates the lines vanish. They believe the emission is mainly
thermal, but the lines have such a high excitation energy (7.2 eV) that some sort of over-
excitation must surely be at work. The authors show a recording of the four lines, which
stand out bright and clear at a phosphorus concentration of 900 [Lg/ml. Their relative
intensities are 15, 70, 30 and 17. The authors give the detection limit as 400 [Lg/ml for
the 2536-A line, but their spectrogram shows this to be much too conservative; the limit
looks like about 50 [Lg/ml. Other solvents (isopropanol, isobutanol and methyl isobutyl
ketone) yield the same emission as ethanol. This work is further outlined in Table 5.xVII
below.
5.7.9 DETECTION OF PHOSPHORUS BY FLAME SPECTROSCOPY
In the case of boron, there were many early papers (Table 5.IV) describing flame test
methods. Despite the great delicacy and specificity of the HPO flame test for phosphorus,
I have found few papers mentioning its use for practical analysis. Many chemists must
have used the test; perhaps they found it so simple and straightforward (which it is)
that it merited no mention.
In Dusart's test [329], if the glass hydrogen jet is V-shaped (bent down and then up),
it can be immersed in mercury up to the orifice to keep it cool and prevent the green
flame from fading. Dusart said that 1 mg of phosphorus in a hydrogen generator deliver-
ing 10 liters per hour is enough to make the flame green for 11- hours. Phosphoric or phos-
phorous acid in the generator also gives the test. The phosphorus in a match can be
5.7] PHOSPHORUS 257
detected; the early matches were a common cause of phosphorus poisoning. An apparatus
for detecting white phosphorus in cases of poisoning, based on Dusart's test, is shown by
Hofmann [369 (p. 231)]. Hydrogen is bubbled through the sample (e.g., stomach con-
tents of the victim) mixed with hot water, and burned at a platinum jet; the green is
enhanced by surrounding the flame with a glass tube or placing a porcelain dish in it.
Salet [335] recommended this procedure (the glass tube, 7-8 mm in diameter, being cooled
by an air blast) in cases of poisoning. Blondlot [370] used the flame test in toxicological
investigations; I have not seen his paper.
The Bunsen flame test was compared with the hydrogen flame test by Merz [146].
He recommended treating the sample with sulfuric acid, to release phosphoric acid. He
claimed that the dull greenish tint in the mantle of the Bunsen flame (presumably the
continuum of phosphorus) will detect 1/8 microgram of phosphoric acid. Boron inter-
feres; in the presence of much borate, Merz recommended heating the sample with fluo-
silicic acid in a hydrogen flame to develop the green color (of HPO) in the core. He said
that the hydrogen test is less sensitive but more selective than the Bunsen flame test.
5.7.10 FLAME SPECTROPHOTOMETRY OF PHOSPHORUS
The new interest in phosphorus has brought with it a great upswing in its flame-emission
determination. Most of the work has been done within the last five years. This work is
surveyed in Table 5XVII, including papers on instruments, basic methods, and routine
applications.
The HPO emission has been mainly applied to gas-chromatographic analysis of pesticide
residues. Most of the newer nonpersistent insecticides contain phosphorus and sulfur.
Bowman and Beroza have done most of this work, using the Brody-Chaney flame photo-
meter (Fig. 5.11), engineered by Melpar and manufactured by MicroTek Instruments
[348]. It can provide simultaneous flame-ionization signals and has recently been fitted
[391] with twin photomultipliers, one on each side of the flame, to receive the phos-
phorus and sulfur emissions at 526 and 394 nm, respectively.
The flame-photometric detector has the following advantages (for phosphorus com-
pounds) over other detectors for gas chromatography: it requires virtually no cleanup
- extracts can be injected directly; response is linear over the full range of use; sensitivity
may be as high as 0.001 ppm or 0.01 ng of pesticide in the original sample; overall accu-
racy, except at the lowest concentrations, is often 1 or 2 %, as seen from the recovery
data in Table 5XVII; specificity factors are extremely high, evidently of the order of a
million for carbon [390], a thousand for sulfur (depending on concentration), and very
high for nitrogen and chlorine; the base-line is very stable, unaffected by column bleed
or temperature; the sensitivity drifts less than 1 %/hr [382] or lO%/day [385]; the de-
tector permits quick elution because extraneous compounds give no appreciable response;
it is easy to operate and maintain and is not contaminated by column bleed or unclean
extracts; it can be kept as hot as need be, for temperature programming; the signal can
be attenuated as much as desired and yet remain reliably quantitative; no stream splitting
is needed - typical flow rates are 160 ml/min for nitrogen carrier, 40 ml/min for oxygen
(which gives a mixture simulating air), and 200 ml/min for hydrogen; and the detector
can be used for carbamate residues by converting them to thiophosphoryl derivatives.
Advantages of the flame-photometric over the electron capture detector include its
258 NONMETALS [5
TABLE 5.xVII
DETERMINATION OF PHOSPHORUS BY DIRECT EMISSION FLAME
SPECTROPHOTOMETRY
Date Authors Ref. Flame Emission Burner Dispersion Detector
1955 Brite [371] OH Con 540 BSB DU IP28
1959 Malinowski [372] I AA Con 535 Zeiss III IF PV

1961 Dinan, Davis [373] OH Con 540 BSB DU IP28
and Tufts
1961 Gilbert [ 49] AH PO 246

(spectrogram)
I BSB DU IP28
I
AHA PO 246 BSB DU IP28
1961 Gilbert [110], AH PO 246, etc. BSB DU 1P28
[116],
[117] AH,AHA I PO 246, etc. I BSB
I DU
I IP28
AH Con 520 BSB DU 1P28
1962 Driigerwerk [342], Rich AH HPO 526 vdS Spectrophotometer
[343]
1963 Buell [58] OH PO 252.9 BSB DU IP28
1963 Gilbert [39] AH,AHA PO 246, etc. BSB DU 1P28

I
1963 Haas [307] Rich AH HPO 526 Al block Wratten 6199
I
1963 Gilbert [341], Dilute OH HPO 526, etc.1 Fig. 5.12 GrDU IP28
[349] I
Rich AH Fig. 5.15 GrDU
IHPO 526, etc. I IP28
1964 Davis et al. [374] OH Con 540 BSB DU IP28
1964 Schmidt [375] AH PO 246, etc. BSB DU 1P28

(spectrogram)
OH I Con 530 BSB DU 1P28

I I I I
5.7] PHOSPHORUS 259
TABLE 5.XVII (continued)
Solvent Detection
IPrecision Interferences,
I
Sample Linearity
or gas
I limit for P etc.
EtOH, Organic phos- 3 !log/ml G=I% Linear ex- Ca ricinoleate,

kerosine phates, phos- cept at high Na benzoate;
phites, phosphon- concn. none from or-
ates, H 3P0 4 , etc. ganic N, CI, S
or I compounds
Kerosine Butyl phosphate (Range 0.4-50 %)
H 2O, alco- Organic P com- G=I% Linear to Metals (sepd. by
hols, dioxan, pounds, P acids, 800 ppm ion exchange);
NH3,Me2CO, phosphates, POCl 3, none from N, S,
Kerosine, etc. PSCI 3, PCI s, etc. CI compounds
iPrOH H 3P0 4 1 !log/ml (1%)

I H P0 I
H 2O 3 4 7 ppm i
H 2O H 3P0 4 20 ppm (1%)
iPrOH, H 2O
I H 3P04 See above
I I
H 2O H 3P0 4 10.3 ppm
Air, etc. Cresyl phosphate, < .01 !log/l S emisison is
POCl 3, etc.; higher up
pesticides I
Naphtha Max. emission
I 14 mm up
iPrOH, H 2O H 3P0 4 See above G=I% Linear to

800 !log/ml
Air Et 3P04 , etc. .01 !log/ml Wide range S compensated

by 460-nm filter
N 2, air Me3P03 .07 !log/l 1% S compounds
Air Et 3P04 <.001 !log/l 0.5% Fig. 5.19 SIP response .002
H 20, EtOH, H 3P0 4 ,Ph 3P0 3,P, 8 ppm G=I%; Linear to Metals (sepd. by
etc. many inorganic and aV.mean 1000 ppm ion exchange)
organic compounds error 0.2 %
CCl4 ,CHCl3, Cresyl phosphate, ca. 5 !Lg/ml Accuracy Linear to None from S or
BuOH, Ph 3P, Pestox III, (in CHCI 3) 1% 2500 !Lg/ml N or mode of
dioxan Malathion, etc. combination ofP
Same Same 1-2 !Lg/ml Same Linear to As above
(in CHCI 3)
I 2500 !Lg/m1
260 NONMETALS [5
TABLE 5.xVII (continued)
~Authors Ref. Flame Emission Burner Dispersion Detector
1965 Brody & [344], Rich AH HPO 526 Fig. 5.11 IF EMI
Chaney [345] 9524B
1966 Beroza & [376] Rich AH HPO 526 Melpar IF EMI

Bowman 9524B
1966 Bowman & [377] Rich AH HPO 526 Melpar IF EMI

Beroza 9524B
1966 Bowman & [378] RichAH HPO 526 Melpar IF EMI

Beroza 9524B
I
1967 Getz [379] Rich AH HPO 526 Melpar IF EMI
9524B
1967 Bowman & [380] RichAH HPO 526 Melpar IF EMI
Beroza 9524B
Bowman & [381] Rich AH HPO 526 Melpar IF EMI

1967 Beroza 9524B
1
1967 Stevens [382] Rich AH I HPO 526 Melpar IF EMI

9524B
I
1967 Bowman &
Beroza
[383] Rich AH I HPO 526 Melpar IF EMI
9524B
I
1967 Bowman & [384] I Rich AH I HPO 526 Melpar IF EMI
Beroza
I 1
9524B
1967 Skogerboe,
Gravatt &
[368] OA I(spectrogram)
P 2536, etc. BSB + pump
(0.4 ml/min
JA EMI
6255B
Morrison sample)
I
AH I PO 246 I (3.7 ml/min) I JA EMI
I 6255B
AH I PO 246 I (3.7 ml/min) I JA EMI
I 6255B
OH I PO 246 I (3.7 ml/min) I JA EMI
I 6255B
OA I PO 246 I (0.4 ml/min) I JA EMI
I 6255B
AH I Con 541 I (1.6 mlfmin) I JA EMI
I 6255B
OH Con 541 (1.2 ml/min) JA EMI
6255B
5.7] PHOSPHORUS 261
TABLE 5 XVII (continued)
Solvent
or gas
Sample
Detection
limit for P IPrecision Linearity Interferences,
etc.
N 2 (GC) Et 3 P0 4 , Parathion, .0004 [Lg/I; Few % Linear over None from or-
Malathion 1 pg/sec 4 decades ganic compounds
of CI, N, 0;
some from S
N 2 (GC) Compound 4072,
Shell SD-8447 in
.002ppm*
in extract
Good I Linear I As above
corn I
N 2 (GC) Insect chemoster-I 0.1 ng* Noise Linear
ilants in insects, ex- 0.6 na 0.1-500 ng*
creta, etc.
N 2 (GC) !midan, Imidoxon I .002 ppm* I Recovery Linear to
Incorn 94-100% 5 ppm*
N 2 (GC) Pesticides in lettuce, Few ng* I None from CI

alfalfa, onion, bees
I
N 2 (GC) NIA-I0242, etc., as .02-.04 Recovery Linear
thiophosphoryl de- ppm* 88-98% .1-100 ng*
riv. in milk and
silage
N 2 (GC) 20 insecticides
milk and silage in I .01 ppm*
I I I
N 2 (GC) Pesticides in citrus 1.02 ppm P a < 4%; I None from CI
oils in 1 mg oil drift
< 1 %/hr
N 2 (GC) Azodrin and Bidrin
in corn
.002 ppm* I
I Recovery Linear to
94-101 % 250 ng*
I pounds
Natural P com-
elute la-
ter
N 2 (GC) Dursban, etc., in
corn and grass
.01 ng*;
.01 ppm*
IRecovery
96-99%
Linear to
250 ng*
I
EtOH H 3 P0 4 400 [Lg/ml Fe (spectral)
etc. (see text)
I
EtOH H 3 P0 4 15 [Lg/ml la = 2-3%/ I Ca, Ba, Ag, Fe
90% EtOH Leaves, liver, bone 1.005 % IAccuracy I I Sepd. by ion ex-
3-20% change
EtOH H 3 P0 4 1400 [Lg/ml I
1 I I
EtOH H 3 P0 4 1900 [Lg/ml
I I I
I I I
I I I I
262 NONMETALS [5
Date I Authors Ref. Flame Emission I Burner DisperSionl Detector
1967 Johnson I [347] AH I HPO 526 FID IF PM

1968 Dagnall, [48] NH HPO 526 7.5-cm SP900A EMI
Thompson Unicam 9601B
& West
Rich AH IHPO 526 I wit~ cooled I SP900A

chImney
EMI
9601B
1968 Bowman &

Beroza
[385] Rich AH HPO 526 I Melpar IF I 9524B EMI
1968 Corley & [386] Rich AH HPO 526 Melpar IF EMI

Beroza 9524B
1968 Bowman & [387] Rich AH HPO 526 Melpar IF EMI

Beroza 9524B
19681 Bowman,
Beroza et at.
[388] I RichAH HPO 526 Melpar IF EMI
9524B
I
1968 Beroza &

Bowman I[389],
[390]
I RichAH HPO 526 Melpar IF I EMI
9524B
1968 Bowman &

Beroza
I [391] I Rich AH HPO 526 Melpar I IF I 9524B
EMI
(twin detectors for simultaneous P and S determination)

1968 Syty and [279], Rich AH I
HPO 526 Modified DU IP28
Dean [280], BSB
[346] 1 - - - - + - - - - - - 1 ( t t)
1__Ar_-O_H__fl_H_P_O_5_26_-!__s_ee_e_x__ :__
D_U_I_I_P_28_
Ar-OH Con 526 Modified BSB\
\ (see text)
DU II IP28
OH IPO 246 I BSB DU IP28
OA I PO 246 BSB DU IP28
OA PO 246 BSB DU IP28
AOA IPO 246 BSB DU IP28
*) Weight or concentration of sample (the pesticide), not of elemental phosphorus.

Abbreviations: AA = air-acetylene BSB = Beckman sprayer-burner
AH = air-hydrogen Con = continuum
AHA = air-hydrogen-acetylene DU = Beckman DU spectrophotometer
AOA = air-oxyacetylene FID = Beckman flame ionization detector
5.7] PHOSPHORUS 263
Solvent Detection Interferences,
Sample Precision Linearity
or gas limit for P etc.
He Pyrolyzed soil I
H2O H 3 P0 4 0.1 ppm Linear Na, Ca, AI, Fe,
0.2-600 ppm Cd, Co, Cu, Pb,
Li, Mg, H 2 SO 4 ,
organic solvents;
see text
H2O H 3 P0 4 > 1 ppm? Similar or worse
N 2 (GC) Ciba C-9491, etc.,

in corn and milk
.003 ppm*
in sample
I
Recovery Linear over
93-96 % 3 decades
Less than in elec-
tron capture
N 2 (GC) Malathion, Diazi- .01 ppm* Recovery
non, etc., in grass, in sample 90-100%
tomato, spinach,
milk, fat
N 2 (GC) Fenthion and .0005-.003 Recovery Extracts fraction-
metabolites in ppm* in 95-100% ated by liquid
corn, grass, milk sample chromatography
N 2 (GC) Coumaphos, etc., .003-.005 I Extracts fraction-
in milk, cow dung ppm* ated by liquid
chromatography
N 2 (GC) Pesticides and me- 0.1 ng*; .01 Linear over Very low
tabolites; carbam- ppm* or less 3 decades
ate derivs.
N 2 (GC) Many pesticides 0.1 ng* Linear to SIP response
250 ng* .0012
H2 O H 3 P0 4 ; see text 6 ppm Linear to See text

I 5000 ppm
H2O
IH 3 P0 4 15 ppm
I I I
H2O H 3 P0 4 I Few ppm
I
iBuMeCO H 3 P0 4 19 fLg/ ml Linear to See text
1
5000 ppm
1
H2O H 3 P0 4 1350 ppm Linear to
5000 ppm
1
iBuMeCO H 3 P0 4 13.3 fLg/ ml Linear to
5000 ppm
1
H2O H 3 P0 4 /46 PPm I Linear
5000 ppm
Gr DU = grating DU (Fig. 5.13) OA = oxyacetylene PM = photomultiplier
GC = gas chromatograph carrier OH = oxyhydrogen PV = photovoltaic cell
IF = interference filter SP900A is a Unicam spectrophotometer
JA = Jarrell-Ash 82000 spectrophotometer vdS = van der Smissen (Dragerwerk)
NH = nitrogen-diluted hydrogen flame
264 NONMETALS [5
stability, linearity, unlimited attenuation, insensitivity to water [376], higher specificity,

longer life, convenience, immunity to contamination, and greater sensitivity [382]. How-
ever, the flame photometric detector can be usefully combined with electron capture, flame
ionization, or alkali thermionic (Karmen-Giuffrida) detectors to help identify compounds.
The two-channel phosphorus-sulfur detector [391] is valuable for the same purpose, since
the phosphorus/sulfur response ratio, although constant to a first approximation (allowing
for the quadratic response to sulfur), does vary somewhat among different phosphorus-
sulfur compounds.
A novel application of the HPO emission is its use for the analysis of simulated extra-
terrestrial soils. Johnson [347] pyrolyzes the sample in helium at about 800° and sends
the gases through a flame ionization detector that can double as a flame photometer,
emitting the HPO and S2 spectra. His main difficulty with phosphorus has been the
inadequacy of other methods used for checking the indications of the flame detector.
Monitoring of air for phosphorus compounds by the HPO emission has been highly
successful, as Table 5.xVII shows. Sensitivity may exceed 1 nanogram of phosphorus
per liter. Testing linearity is a little harder than in the case of gas chromatography or
solution analysis, but one way of doing it is shown in Fig. 5.19. By varying the tem-
perature of the sample tube, the vapor concentration (of ethyl phosphate) was varied from
1 to 500 [Lg/I of phosphorus. The readings agreed with the extrapolated vapor concen-
tration curve within the experimental error. (The Antoine, Miller-Erpenbeck and Cox
extrapolations all gave equally good agreement.) The phosphorus monitor provides, in
fact,'a quick and easy means of measuring very low vapor pressures over any range of
temperature.
Solution analysis with the HPO emission has very recently been investigated by Dagnall,
Thompson and West [48], whose burner was described above, and by Syty and Dean
[279,280,346]. The latter used a sprayer-burner without the capillary, feeding hydrogen
through the central tube and air carrying the sample mist through the outer tube. They
sprayed the sample in a separate chamber and discharged most of the spray to waste
through a branch tube, to permit efficient spraying without overloading the flame. The
burner was surmounted by a chimney to shield and cool the flame. Dagnall's unshielded
nitrogen-hydrogen diffusion flame on the long burner afforded much the lower detection
limit (0.1 as against 6 ppm). As in all other applications of the HPO emission, both papers
reported linearity throughout the range of concentration tested. In Dagnall's flame the
best hydrogen flow was the least that would prevent lift-off; in Syty's, the best emission
was obtained with the least possible oxygen content.
Syty's burner was less subject to interferences. She reported no interference from
10,000 [Lg/ml of arsenic, boron, cadmium, molybdenum, silver, ammonium, nitrate,
acetate, chloride, EDTA, fluoride, oxalate or sulfate. The alkali metals emitted weak
continua and the alkaline earths depressed the HPO emission (from phosphoric acid)
by solute vaporization interference [235]. Organic solvents did not inhibit the HPO emis-
sion, and organo-phosphorus compounds gave 90-100% of the emission of phosphoric
acid at the same phosphorus concentration. However, she found that methyl phosphite
gave no emission at all (not even continuum) and had no effect on the emission of phos-
phoric acid. Since methyl phosphite behaved normally in my burners, I can only suppose
that her methyl phosphite was not what the label said.
Interferences from metals were severe, on the other hand, even at much lower concen-
trations, in Dagnall's flame. Depression occurred with lithium, sodium, magnesium,
calcium, iron, cobalt, cadmium, aluminum and lead; copper interfered spectrally. There
5.7] PHOSPHORUS 265
lro---r~r--.--~-r--~-.--~~--~~--~-'~
e
6
e
~6
o
~4
a:
..,
a:
~2
:e
o
r-
~I
g;e
1=6
hl
3;4
..,
>
~2
..,..J
a:
-30 -20 -10 0 10 20 30

TEMPERATURE, ·C
Fig. 5.19. Linearity of HPO emission.

Dried air saturated with ethyl phosphate vapor at various temperatures fed to burner of Fig. 5.15.
Solid line is theoretical curve of HPO emission vs. temperature of saturation, based on extrapola-
tion of vapor pressure by Antoine equation; circles are observed points.
was no interference from ammonium, chloride, bromide, acetate, nitrate, oxalate, sulfate
or tartrate (as acids). Dagnall's diffusion flame seems incapable of atomizing the metallic
phosphates; in Syty's flame the spray passes through a hot combustion zone -lacking
in Dagnall's - before the gases are cooled. Dagnall obtained some interesting curves of
HPO emission vs. interferent concentration. Sodium and calcium depress the emission
from phosphoric acid linearly up to a 1 : 1 ratio of metal to phosphorus, corresponding
to the compounds NaH 2 P0 4 and CaHP0 4 ; beyond that point the curves fall more gently.
Lithium depresses linearly to 2 : 1 (LhHP0 4 ); next there is a plateau (no change of
depression) out to 3 : 1 (Li 3 P0 4 ); beyond that point the emission falls further. Since
the curve shows no knee at 1 : 1, the authors suggest that LiH 2 P0 4 disproportionates
266 NONMETAL'! [5
to Li 2 HP0 4 and H 3 P0 4 in the flame. These phenomena are instructive to the student
of flames but obstructive to the analyst; the authors recommended removing metals by
ion exchange.
The PO bands and the continuum have also proved useful for analysis, as Table 5.XVII
shows. The PO bands offer good selectivity but the continuum offers none. They both
offer linearity and fairly good sensitivity. In the assay of phosphorus in organophos-
phorus compounds, the continuum has given outstanding accuracy, both because of the
reproducibility of the sprayer-burner flame and because, when diluted with the same
solvent, all inorganic and organic phosphorus compounds and elemental phosphorus
give the same emission per unit of phosphorus concentration. Davis et al. [374] reported
an average difference of only 0.2 % (relative) between the flame-photometric and conven-
tional phosphorus determinations in a wide variety of compounds. In 320 analyses of
pure dimethyl methylphosphone, they found an average phosphorus content of 24.94 %
as compared with a theoretical of 24.96 %.
Most of the work listed in Table 5.XVII has been published in readily available journals,
and the analyst wishing further details will have no trouble obtaining them.
Conventional indirect methods for phosphorus as phosphate have been adequately

covered in the textbooks [1,2,3], in some of the reviews [4,5,6,7, 8], and in Mavro-
dineanu's bibliography [15]. I shall mention just one recent paper from a far country:
Liu [392] determined phosphate with an accuracy of 1 % between 13 and 85 ppm phos-
phorus by its depression of the emission of 200 ppm of calcium.
There is a disputed phenomenon in the thermionic flame detector (see Section 5.7.13):
the liberation by phosphorus of alkali metal from the sensitizer. Karmen [393] said that
phosphorus raises the sodium emission in the hydrogen flame of the detector, but Aue
et al. [394, 395] observed a depression that ranged from 0 to 100%, depending on con-
ditions. It is clearly not a simple effect. This depression can be used for detecting phos-
phorus compounds at flow rates below 1 nanomole per second.
The phosphorus resonance lines at 1775-1788 A are not yet accessible in flames, and the
lower states of the lines above 2000 A are too energetic (1.4 and 2.3 eV) to be usefully
populated in flames. But the conventional indirect flame methods (e.g., depression of
calcium) work equally well in absorption. Of greater interest are the indirect flame ab-
sorption methods of Kirkbright, Smith and West [296] and Hurford and Boltz [297],
described in Section 5.5.6. The former extract the phosphomolybdic acid with isobutyl ace-
tate; the latter extract it from I-M hydrochloric acid with ether and strip it into an
aqueous basic buffer. Precision and sensitivity are as good for phosphorus as for silicon.
Kumamaru, Otani and Yamamoto [396] use the same principle, extracting phosphomo-
lybdic acid with butyl acetate and spraying it into an air-nitrous oxide-acetylene flame
to determine the molybdenum. The reading is linear up to 0.11 ppm of phosphorus in the
5.7] PHOSPHORUS 267
aqueous sample. In their procedure there is no interference from silicon, arsenic or ger-
manium.
The Karmen-Giuffrida detector [393, 397, 398] is now well known to gas chromatog-
raphers and is available commercially. Its main value is its extraordinary sensitivity to
phosphorus, but it can be very useful for chlorine, bromine, iodine and sometimes other
elements (recall the discussion in Section 5.6.6). The detector goes by an unfortunate
variety of names: flame thermionic, thermionic flame, thermionic, thermionic emission,
sodium thermionic, alkali flame, sodium flame or alkali flame ionization detector. More
fully, it is called the alkali thermionic flame ionization detector. One variety is called the
Giuffrida detector and another the Karmen detector. An entirely different detector useful
in gas chromatography, employing a direct-current discharge, is also called the Karmen
detector, adding to the confusion. There has been a proliferation of very sensitive detec-
tors for trace constituents of gas streams, and those utilizing ionization were reviewed in
1966 by Karmen [399]. A rational nomenclature is urgently needed.
The fact that the mechanism of the Karmen-Giuffrida detector is in dispute and may
not be single, does not help the search for good names. The detector entails a flame and
ionization; but the ions may not be thermionic and an alkali metal is not indispensable.
However, there has to be an additive, activator or sensitizer of some sort, if the detector
is to fall into this category. I might suggest "sensitized (or activated or additive) flame
ionization detector." Meanwhile it is perhaps least ambiguous to call the detector by the
names of both inventors.·
Essentially, the detector comprises a small hydrogen flame impinging upon an alkali
salt (the sensitizer) supported between charged electrodes (of which the burner may be
one); a current passes when analyte enters the flame. There may be two flames in tandem;
the first one burns carbon compounds and prevents them from causing an ion current
in the second flame, which responds to phosphorus. For example, Jentzsch et al. [400]
modified Karmen's tandem-flame arrangement by using a porous metal jet impregnated
with potassium hydroxide for the second flame. Abel et al. [401] used a coil coated with
sodium sulfate in the second flame, electrically heated for independent control of the ion
current. Aue et aZ. [394] claimed that in the single-flame (Giuffrida) detector a response
factor or efficiency of unity had been reached - one ion from each atom of phosphorus.
The efficiency is usually only about 10- 4 , which still gives exceedingly high sensitivity.
The latest paper that I have noticed is that of St. John and Lisk [402], who placed upon
the jet of a flame ionization detector a coil of Nichrome holding a wad of steel wool
dipped in saturated potassium sulfate. They used the detector for determining insecticide
metabolites and reported that it remained stable for two months of continuous use.
No convincing theory of the detector has yet been presented. Its properties are too
complex and variegated to be accounted for by a single mechanism valid in all forms of
the detector. Theoretical studies have been limited to conditions that may be quite sub-
*) In writing a later section of this chapter, I attacked the problem of nomenclature once again.
For a more definitive discussion and classification of sensitized flame ionization detectors, see
Section 5.14.6.
268 NONMETALS [5
optimal. The response factor, range of linearity, background current, response time and
degree of interference from other elements or moieties may all vary enormously with
burner design, electrode arrangement, polarity, hydrogen flow, thermal gradients and
especially nature and structure of the sensitizer [320].
Karmen believed that in his oiiginal detector [393] phosphorus raises the rate of
vaporization of alkali metal from the sensitizer into the flame. In his later review [399]
he stressed the probable multiplicity of the mechanism and mentioned the contending
view that phosphorus (or other response-eliciting analyte) does not raise the volatility of
the sensitizer but instead raises the degree of ionization of sensitizer vapor already present
in the flame. This must be the case in the arrangement described by Aue and Gehrke [395],
who fed a constant concentration of alkali metal vapor in helium into the hydrogen flame;
phosphorus (or chlorine) raised the ionization while depressing the alkali emission. At
the same meeting, Saturno and Cooke [403] presented similar evidence and attributed
it to the phenomenon explained by Padley, Page and Sugden [404]: when a halogen X
and an alkali metal M enter a hydrogen flame, the two reactions M + X -- M+ + X-
and X- + H -- HX + e- raise the concentration of electrons above what it would be
from the thermal ionization of M alone, since the concentration of H is abnormally high.
Page and Woolley [367] further discussed this mechanism for the halogens and suggested
that the response to phosphorus may be similarly explained, without, however, showing
just how the phosphorus may react. Baldwin and Malmstadt [405] have also recently
studied the mechanism in the case of halogens, but I have not seen an abstract.
The disk-stabilized arc of Hoffmann and Holdt [299] was used (by W. Steindorf) for
determining phosphine in acetylene at a concentration of 0.04 %. The induction-coupled
plasma torch of Wendt and Fassel [300] detected phosphorus at 1 ppm in solution at
2536 A.
The electrodeless argon discharge of McCormack et al. [88] (see Section 5.4.7) emits the
lines at 2534, 2536, 2553 and 2555 A, the PO beta system, and (in the presence of sulfur)
the blue PS bands; the authors showed spectrograms of each of these emissions. The flow
detection limit at the 2555-A line was 10 pg/sec. Bache and Lisk [406, 407] used the
discharge for the gas-chromatographic determination of organophosphorus insecticide
residues. The response factor varied tenfold or more, depending on the compound; the
best sensitivity (0.6 pg/sec) and specificity factors (1000 for carbon or chlorine) were
found at reduced pressure (200 torr). They used the P lines 2536 and 2553 A and the
PO bands 3246 and 3270 A. Later they tried helium at 5-10 torr and found a limit of
9 pg/sec at 2536 A [408]. Moye [409] got better results in the gas-chromatographic
analysis of pesticide residues with an argon-helium mixture than with either gas alone.
He favored 85 % helium at 25 torr and used the line at 2536 A. The detection limit for
Thimet was 0.1 ng. Although excellent for such purposes, the electrodeless discharge does
not seem as good as the Brody-Chaney flame photometer (Table 5.xVII). It is not
usually as sensitive, it is less specific, its response depends on the compound, and it is
costlier and more complex. West [276] has recently 'discussed electrodeless discharges
as detectors for gas chromatography, but I have no details for phosphorus.
5.8] ARSENIC 269
5.8 Arsenic
Most of the rather meager literature of the flame spectroscopy of arsenic concerns the
ultraviolet line spectrum. It was first photographed sixty years ago by Watteville [304],
who sprayed a solution of arsenic in aqua regia or aqueous arsenous acid into a Bunsen
flame. Eder and Valenta two years later [104] reported the lines 2288.1, 2349.8, 2381.2,
2437.2, 2456.5, 2492.9, 2745.0, 2780.2 and 2860.4 A in a Bunsen flame fed with a spray
of arsenous or arsenic acid. They also said that the lines sometimes appear weakly in the
oxygen-gas flame. Their data were quoted in Kayser's Handbuch [92 (p. 62)]. There
can be little doubt that when the lines were seen, they were emitted in the inner cone.
Lundegardh in his early work [200 (Part I, p. 67)] failed to detect arsenic at 7500 ppm
with the air-acetylene flame, but later [201 (p. 76), 222] he photographed the lines
2288 and 2350 A in the inner cone. A long exposure is required, but the background is
low. A decade later Alekseeva and Mandel'shtam [410] observed the lines in the same
flame.
In the oxycyanogen flame, Gilbert [138] detected weak lines only at 2288 and 2350 A
with an aqueous solution at 1000 ppm; Robinson [139] found no emission with aqueous
or organic solutions.
Analytically useful line emission for arsenic was first reported by Gilbert [5 (p. 349),
39, 49] in an air-hydrogen sprayer-burner flame with isopropanol as solvent, and by
Carnes and Dean [60, 62, 411] in the reaction zone of an oxyacetylene sprayer-burner
flame with methyl isobutyl ketone as solvent. The spectrum in air-hydrogen is shown in
Fig. 5.20; radiances of the lines and background are listed in Table 5.xVIII; the effect
If)
0:>
rt)
.q-
C\J C\J
r0 N
I"- (J'l ¢to
0 r<)C\J
rt)
l"- If) "I
ct ¢
a
i'-'
If)
C\J
~<:OO
OC\J
0:> 0
(J'l If)
If)
1"-- ~II
~
r<)
« C\J
to-
(J'l
C\J + r<) ld
If)
0:> C\J II) (J'le C\J
ai l"- to C\JII)
(J'lC\J 0If)
C\J .f to
C\J
C\J
r<)
C\J
.q-
C\J ~~ «
ai «
r0
C\J
, , , , I I , I I I , , I I I ,I I , , I I I, ,
230 235 240 245 250 255 260
Fig. 5.20. Spectrogram of arsenic in air-hydrogen flame.
Apparatus as in Fig. 5.2. Slit 0.14 mm. Arsenic 500 !J.g/ml in 50% isopropanol. Blank recording
superposed. Wavelengths not otherwise designated are atomic lines of As. Reproduced from [3]
by permission of John Wiley & Sons.
270 NO~TALS [5
E 2
E
"0 c:
.=. ..:
en
..: N·
en E
N· u
E
u "II
"II 0.2 co
Q
x
2 .<>
X •
..f
o 0.0
40 60 80 100
CONCENTRATION OF ISOPROPANOL (%)
Fig. 5.21. Effect of isopropanol concentration on radiance of the two strongest arsenic lines and
background at 2288 and 2350 A in the Beckman air-hydrogen sprayer-burner flame.
TABLE 5.xVIII
RADIANCES AND PRACTICAL INTENSITIES OF THE ARSENIC SPECTRUM AND
BACKGROUND IN THE AIR-HYDROGEN SPRAYER-BURNER FLAME
Data as in earlier tables. Solvent, 50% isopropanol-water. J a calculated from emission at a
concentration of 500 (J.g/ml; in w/cm 2 .sr.«(J.g/ml) for As lines, w/cm 2 .sr.nm.«(J.g/ml) for AsO
bands
Wavelength Jax 1011 Jbx 10 8 Int.
As 2288.1 .39 .15 .9

As 2349.8 .66 .15 1.6
As 2381.2 .035 .16 .08
As 2437.2 .02 .21 .04
AsO 2437.3, 2438.5 .07 .21 .3
As 2456.5 .11 .28 .2
As 2492.9 .10 .24 .2
AsO· .13 .24 .5
AsO 2503.6,2504.7 .20 .24 .8
AsO 2569.7,2570.9 .21 .30 .7
As 2780.2 .06 .56 .07
8) Background band emission at the same wavelength as the 2492.9-A line. Combined intensity
is 0.7.
TABLE S,XIX VI
00
......
CONTRIBUTIONS TO THE DIRECT EMISSION FLAME SPECTROPHOTOMETRY OF ARSENIC
For abbreviations see Table S.Y
Ref. Emission Spectro- Detection

Date Authors Flame Burner Solvent Linearity
photometer limit
1960--61 Gilbert [S], [39], AH Con SOOO BSB DU + IP28 H 2O S ILg/ml

[49, [110]
AH AsO 2S04 BSB DU + IP28 SO% iPrOH 13
AH As 2288 BSB DU + IP28 iPrOH 4 } Linear to
As 23S0 2.5 SOO ILg/ml
1961- Carnes and [60], [62], OAic As 2350 BSB DU + IP28 iBuCOMe 2 Log slope 1.1 to
62 Dean [411] ISO ILg/ml
1964 Kniseley [243] OA I As 2350 Kniseley JA (+ IP28) EtOH 300 I

1966 Juvet and [267] OH Con SOOO BSB DU + IP28 He, N2 (GC) 0.1 ILg Linear to 7S0 ILg
Durbin
1966 Skogerboe et al. [286] OH As 23S0 BSB JA + 62SSB EtOH 2 ILg/ml

OHr 3
1967 Fassel and [6S] OA As 2350 Kniseley JA+ 62SSB EtOH 300
Golightly
DU + 62S5B SO
1968 Dean and Fues II [420] OAic As 23S0 BSB (DU + IP28) C 6 H 6 , etc.
~
-
272 NONMETALS [5
of isopropanol concentration on radiance is shown in Fig. 5.21. Tables of intensities or

detection limits have appeared in [3, 110, 116, 117]. For the meaning of the "inten-
sity" data in Table 5.XVIlI, see Section 5.5.4.
The lines in these flames are highly overexcited and are thought to result from Stern-
berg's mechanism, mentioned earlier, entailing excited CO(d 3L1) [67]: the reaction
AsO + CO· -+ As· + CO 2 has 1.4 eV more energy than is needed to excite the most
energetic of the observed lines. It would be profitable to apply the method of Boiteux
[14 (p. 559)] to find the activation energy in the case of arsenic, employing the radiance
data of Table 5.XVIlI and the revised transition probabilities of Corliss [73].
More recently, Skogerboe, Heybeyand Morrison [286] obtained equally good sensitiv-
ity with the 2350-A line in an oxyhydrogen sprayer-burner flame with ethanol as solvent.
Kniseley [243] and Fassel and Golightly [65] have reported the 2350-A line in the
Kniseley premixing oxyacetylene flame. Details of these studies will be found in Table
5.xIX.
Mavrodineanu and Boiteux [14], observed the lines 2288, 2350, 2456, 2493, 2745,
2780 and 2860 A in the inner cone of air-acetylene. They list the energy levels (p. 487)
and show a term diagram (p. 485). To test the hypothesis that excited N2 might be the
carrier of the energy of overexcitation, they photographed (pp. 554, 603) the spectra of
arsenic and other elements in the inner cone of flames of acetylene with air and with a
20 % oxygen-argon mixture. In the half-tone reproduction of the spectrograms, the lines
2780 and 2860 are clear in the argon flame but scarcely visible in the air flame. This en-
hancement by argon (for every element tested) opposes the hypothesis, and the authors
continue with a discussion of excited CO and other possible carriers of the overexcitation
energy. The enhancement seems to me to be just another case of the phenomenon men-
tioned in the discussion of overexcitation in Section 5.1.2: when argon, with its much
smaller cross section, replaces nitrogen in various flames, there is a marked reduction
of the quenching of overexcitation [39 (p. 197), 33, 50, 53, 54, 55].
Since all of the observed lines of arsenic have excited lower states (1.3-2.3 eV), one
would expect very little self-absorption and hence straight analytical curves. This con-
clusion is supported by the few data available [39 (p. 195), 62]. Whether the logarithmic
slope of 1.1 reported by Dean and Carnes for the 2350-A line differs significantly from
1.0 is a question that calls for further study; such "superlinear" curves are rare in flame
photometry except when ionization occurs.
5.8.2 mE BANDS OF ARSENIC MONOXIDE
The A and B systems of AsO have been seen in flames. The bands are double-headed,
degraded to longer and shorter wavelengths in the two systems, respectively. They are
adequately tabulated and documented in the handbooks [78,79]. In their table of per-
sistent band heads [78 (p. 3)], Pearse and Gaydon list the following expected intensities
in flames: (System B) 2438, 3; 2505, 8; 2571, 9; (System A) 3106, 6; 3171, 9; 3208, 6;
3277, 10. Recently Meyer [412] confirmed and analyzed the A, B and other systems of
AsO.
Hartley [354 (p. 183)] was the first to observe an AsO band in the flame (oxyhydrogen);
he devoted just one sentence to it: "This element gave a faint nebulous line at 168.4 or
A. 3280, which approximates the first line in the P 2 0 S spectrum." He must have seen
5.8] ARSENIC 273
the strongest head of the A system at 3279 A. Hartley and Ramage [413] later published
this spectrogram.
Watteville [304] was the first to observe the B system of AsO - as well as the line
spectrum of As - in the base of a Bunsen flame. His wavelengths closely match those
° ° °
given by Pearse and Gaydon; he listed the double heads of what are now known to be
the (0,1 ii), (0, ii), (0, i) and (1, i) bands. Eder and Valenta [104] reported traces
of bands from arsenic solutions sprayed into a Bunsen flame, but none in the oxygen-
gas flame. Shawhan and Morgan [414] in 1935 observed the A and B systems of AsO
in both emission and absorption in a flame fed with arsenous chloride.
Gilbert obtained a recording (Fig. 5.20) showing the B system along with the line
spectrum in air-hydrogen with isopropanol [3 (pp. 385, 571), 39 (p. 189)]. He could
not detect the A system. The radiances of the B bands are listed in Table 5.xVIII. They
are no stronger than those of NO (Table 5.xII) and much weaker than those of PO
(Table 5.xV). This may simply be due to the lower dissociation energy of AsO (4.9 eV),
permitting development of the atomic spectrum. Detection limits for the bands have
been published [110, 116, 117], but since the lines are stronger, the bands have found no
analytical application.
5.8.3 THE ARSENIC CONTINUUM
Like phosphorus, arsenic emits a continuum in flames that looks bluish or greenish. Merz
in 1860 reported this color for arsenic [146]. Volpicelli [415,416] in 1862 first looked at
the arsenic spectrum in oxyhydrogen and found it continuous. He considered it useless
for spectral analysis. The arsenic continuum was reported also in the chlorine-hydrogen
flame by Mitscherlich [21], in the air-hydrogen flame by K. B. Hofmann [302], K. A.
Hofmann [369 (p. 267)] and Herpertz [417], and in the Bunsen, oxyhydrogen, arsine
and chlorine-arsenic flames by Herpertz. Emeleus (recall his work on the glow of phos-
phorus) studied the flame of burning arsenic [418,419]. Both the cool flame (at 250-360°)
and the normal flame in oxygen give a bluish-white continuum with maximum at 460 nm
but traceable to 320 nm with long exposure; it is free from bands. Gilbert [108] found
the maximum near 500 nm (with quartz dispersion and S-5 photocathode) in the air-
hydrogen sprayer-burner flame. With aqueous solutions the continuum offers a detection
limit of 5 ppm [3 (p. 261)]; its radiance is 2 pw/cm2.sr.nm.(fLg/ml), a good deal weaker
than that of phosphorus. Nevertheless, the continuum has recently been found useful
in gas chromatography by Juvet and Durbin [267] (see below).
5.8.4 FLAME SPECTROPHOTOMETRY OF ARSENIC
Current work on arsenic, summarized in Table 5.xIX, is slightly ahead of that on silicon
(Table 5.x). Detection limits are about the same for the two elements. When higher sen-
sitivity is not needed, the convenience, freedom from spectral interference, linearity and
good precision offered by the short-wavelength arsenic lines make the emission flame
attractive for either occasional or routine determinations of arsenic.
The air-hydrogen, oxyhydrogen and oxyacetylene flames of the normal Beckman
274 NONMETALS [5
sprayer-burner all give similar detection limits (about 2 [Lg/ml) in organic solvents. The
Kniseley oxyacetylene flame [65, 243], despite its utility for other difficult elements, gives
poorer sensitivity for arsenic. However, according to Kniseley [243], about one-tenth the
listed value can be detected with integration. Oxyhydrogen was tried in reversed mode
(hydrogen for spraying, oxygen through the "fuel" jacket) by Skogerboe et al. [286]
(marked OHr in Table 5.xIX). Although it is slightly less sensitive for arsenic, the
reversed flame, floating 4-5 mm above the burner, permits spraying much more con-
centrated solutions without incrustation from evaporation at the sprayer tip. These
authors used a pump to control the sample flow rate. Arsenic emission was best at a
flow of 2.7 ml/min in either the normal or the reversed flame.
In air-hydrogen sprayer-burner flames with organic solvents the "reaction zone" is so
tall that focusing is uncritical. In the hotter flames the arsenic emission is more sharply
localized. Dean, Carnes and Fues [411, 420] used a light guide to define the observed
flame area. They show profiles of emission vs. height [62]; the peak falls at 7 mm above
the burner, in the inner cone of the oxyacetylene flame. In oxyhydrogen with ethanol
the best height is 26 mm in the normal, 23 mm in the reversed flame [286]. In the Kniseley
burner arsenic gives best sensitivity in the primary reaction zone, somewhat lower sen-
sitivity (500 and 60 [Lg/ml for the Jarrell-Ash and Beckman spectrophotometers, respec-
tively) in the interconal zone.
As for the solvents, aside from the data in Fig. 5.21, no comparisons of different sol-
vents in the same flame are available except those by Dean and Fues [420], of whose
paper I have seen only an abstract. They found that benzene, toluene, xylene and chloro-
benzene gave the highest emission; oxygenated solvents gave one-half to one-third as
much. They determined arsenic in organo-arsenic compounds dissolved in the solvent
and sprayed directly into the flame. They determined it also in iron and copper after
extracting the arsenic into benzene from an aqueous solution 9 M in hydrochloric acid
and 0.1-1.0 M in potassium iodide; two 2-minute extractions were needed.
Most of the detection limits in Table 5.xIX can be validly compared. I stress this
statement because others [2 (p. 150), 62, 65, 139] have impugned the validity of
criteria not their own, or have misinterpreted the assorted definitions of detection limits
to be found in the literature. One of my own definitions [39 (p. 191)] is admittedly cum-
bersome but it leads to an unequivocal and conservative result. The debate affects arsenic
in particular. I should therefore like to point out, with regard to Table 5.xIX, that my
detection limit values correspond to 2 or 3 times, and Skogerboe's to 3 times the standard
error of the net reading (i.e., the reading on the lowest concentration minus the back-
ground). Carnes's values, as judged from additional data supplied by Dr. Dean, are
possibly a little more conservative, since the slits were kept narrow. Fassel and Golightly's
limits correspond to twice the root-mean-square fluctuation of the background at a time
constant of 1 second. This is a less conservative criterion, since the standard error of the
net reading is normally greater than the r.m.s. background noise. But their flame bums
in the open air and is focused on the slit by a lens. These conditions do not favor stability,
and the apparent peak-to-peak flicker amounts to several percent. In the case of the
Beckman DU flame attachment, the housing and entrance optics are designed specifically
to minimize flicker; without them the signal is much noisier. It seems likely that with a
suitable housing and optical system the flicker of the Kniseley flame could be reduced
and the detection limits improved.
Interferences have been studied only by Dean, Carnes and Fues. Arsenic suffered no
interference from 500 [Lg/ml of antimony or 1000 [Lg/ml of tin; zinc depressed arsenic
5.8] ARSENIC 275
by 1 % per 100 fLg/ml of zinc present [62]. Nitrate completely suppressed the arsenic
emission; oxalate could be tolerated up to a 6 : 1 ratio and other anions up to at least
24 : 1 [420].
The one gas-chromatographic application, by Juvet and Durbin [267], is of special
interest because it takes advantage of the higher temperature and better excitation that
prevail in an oxyhydrogen sprayer-burner flame that is not cooled by liquid spray. They
passed the effluent through the sprayer capillary. Besides arsenic, they found very good
detection limits for titanium (0.002 fLg), zirconium (2 fLg), rhodium (0.001 fLg) and chro-
mium (0.005 fLg), chromatographed as chelates or chlorides. Their work with carbon
compounds is shown in Table 5.VI. The precision was limited by the reproducibility of
sample injection (1.5 %).
There is one recent indirect method that is worth mentioning. Enriquez-Isava and Posada-
Valencia [421] precipitated arsenate solutions with silver and determined the excess silver
(up to 100 ppm) at 3281 A in an oxyacetylene sprayer-burner flame. Arsenic could be
determined with a sensitivity of 1 ppm or less, up to at least 25 ppm. Sodium did not
interfere. The method was not stoichiometric but it was evidently more sensitive than the
best direct flame emission method.
Arsenic has resonance lines at 1890.4, 1937.6 and 1972.6 A (vacuum wavelengths). These
are no doubt emitted by the flames discussed above, but no one has yet looked for them.
In any case, the lines would be less sensitive in emission than in absorption; absorption
has transcended the sensitivities listed in Table 5.xIX by two orders of magnitude. The
main problems have been achieving adequate source brightness and flame transparency.
Allan [41] was the first to attain a very low detection limit for arsenic (0.04 ppm for
1 % absorption at 1973 A); he used air-hydrogen in a 60-cm Fuwa tube. Menis and Rains
[45, 46] devised an electrodeless microwave discharge lamp with an Evenson cavity as
source. With an argon-hydrogen flame on a sprayer-burner, detection limits were 0.1 ppm
at 1890 and 1938 A, 0.2 ppm at 1973 A. They determined arsenic in selenium and cast
iron. Since organic solvents cause high absorption, the solution must be aqueous. Dagnall,
Thompson and West [44] developed a similar lamp and with a nitrogen-hydrogen flame
on a three-slot burner found a limit of 0.1 ppm at 1890 A. They have used this lamp and
flame also for the detection of arsenic by atomic fluorescence [422].* The Hell burner is
reported to have given a percentual detection limit of 0.19 ppm [423]. Kahn and Schallis
[43] got below 0.05 ppm with an argon-hydrogen flame on a three-slot burner. The
background absorption at 1938 A was 15~1o. With Peterson, they have described the
"sampling boat" [424], which gives extraordinary sensitivity and remarkably good preci-
sion for easily vaporized elements. The sample is placed in a long tantalum boat that is
slowly moved into an air-acetylene flame on a three-slot burner. The sample vaporizes
*) Dagnall and West [4981 reported a limit of 0.2 ppm at 1890 A and 0.15 ppm at 2350 A by
atomic fluorescence in the nitrogen-hydrogen flame. See also Section 5.11.8.
276 NONMETALS [5
quickly and the peak: absorption is recorded. For arsenic the detection limit was 0.02 ppm
in a 1-ml sample of water or methanol solution.
The thermionic alkali flame ionization detector (cf. Sections 5.6.6, 5.7.13, 5.14.13) can be
made to respond to arsenic. Ives and Giuffrida [316] used cesium chloride on a platin-
iridium helix as sensitizer. Triphenyl arsine gave 30 times as great a response in this detec-
tor as in a normal flame ionization detector.
Wendt and Fassel's induction-coupled plasma torch [300] permitted detection of 25 ppm
of arsenic at 2780 A; the solution was ultrasonically sprayed. Fassel and Dickinson [425]
used a similar instrument to determine arsenic directly in molten tin-base solder. The
concentration range tested was 0.006-0.08%; the relative standard error was 6%. The
As 2350 line was compared spectrographically with Sn 2282 as internal standard. The
sensitivity attained in this last application rivals that of atomic absorption, since the
sample would have to be dissolved for conventional absorption flame spectrophotometry.
5.9 Oxygen
5.9.1 DIRECT FLAME EMISSION
It might at first sight seem hopeless to determine oxygen in a sample by means of a flame
supported by oxygen or an oxygen compound. Yet elemental oxygen can be determined in
microgram amounts by the negative flame emission gas chromatographic detector (see
Section 5.4.6, and further Section 5.9.2 below), which employs oxyhydrogen. This
method is nonspecific, but it suggests that a direct method for oxygen in an oxygen-
containing flame may not be as far-fetched as it sounds. Consider that nitrogen can be
determined in a nitrogen-containing flame; admittedly the flame nitrogen is reacting only
slightly with the other gases.
Many kinds of oxygen-free flames are known. Some were tried more than a century ago.
Mitscherlich, for example, observed the spectra of several elements in the chlorine-hydro-
gen flame [21]. The fluorine-hydrogen flame has been reviewed by Mavrodineanu and
Boiteux [14(p. 48)]. Collier [426] operated this flame on a Beckman sprayer-burner and
observed the emission of many elements in it. Whether it could be used for determining
oxygen, I do not know. The nitrogen trifluoride-hydrogen flame was used by Rogers
[427] for brazing; it is easier to handle than fluorine-hydrogen. The noxious products
of these flames (hydrogen chloride or fluoride) require venting or trapping. A less noxious
but even costlier oxygen-free flame is that of fluorine with cyanogen [428], which pre-
5.9] OXYGEN 277
sumably bums to carbon tetrafluoride and nitrogen. These last two flames have not been
studied as spectrochemical sources.
In ordinary flames, oxygen is manifested spectrally as OH, H 2 0, and O 2 (the Schumann-
Runge bands). These radiations are discussed in detail by Gaydon [34 (Chapter 5)]. The
OR bands are normally the most intense and distinctive. In halogen-hydrogen flames, any
introduced oxygen should give rise to OH emission. This emission is so persistent in
flames that are nominally free from hydrogen (recall the remarks under Hydrogen) that
one might expect it to be easily elicited on introduction of oxygen into a hydrogen-con-
taining, oxygen-free matrix. A gas sheath or chimney would probably be needed to keep
air out of the flame.
The utility of a general analytical method for oxygen in any kind of sample would be so
great that it seems surprising that no one has tried to develop a flame-spectrophotometric
one. I would suggest, as easiest to handle, the chlorine-hydrogen flame on a sprayer-
burner. It could be sheathed with a chlorine-nitrogen mixture to exclude air but to keep
the pilot flame burning. Liquid samples could be sprayed directly. Solid samples not sol-
uble in any convenient oxygen-free liquid could be suspended in a light petroleum oil of
suitable viscosity [85].
Two indirect methods for oxygen have come to light. One is the negative flame emission
GC detector of Overfield and Winefordner [273], described earlier. Since the hydrogen
and oxygen flow rates are adjusted to maximize the OH emission, even oxygen in the
effluent decreases the emission. The authors found a detection limit of 0.26 ILl for oxygen
and 0.7 fLl for carbon dioxide and nitrous oxide. The flow detection limits were 0.36, 1.4
and 1.4 fLgjsec for the three gases. These were the only oxygen-containing substances
that they tried. The response was linear up to 4 ml for all gases. Although the detector is
nonspecific, in its intended use the gas chromatograph would separate the constituents of
a sample and permit identification by elution time. The special advantages of the detector
are its generality and its ability to detect fixed gases in very small quantities. (The negative
flame emission detector does not strictly conform to the definition of an indirect method,
when oxygen is the analyte, since the emitter, OR, contains oxygen; but the oxygen in the
OH has little to do with the oxygen in the sample and is certainly not the analyte.)
The other indirect method for oxygen was invented by Pepkowitz and Judd [429, 430].
It is applicable primarily to oxygen in sodium. The sodium is amalgamated; the sodium
oxide, insoluble in mercury, floats and can be separated. Its quantity is determined by
flame photometry of the sodium in the oxide. Thus only the oxygen combined with sodium
is determined; oxygen present as other oxides is ignored. In practice, the sodium is extract-
ed with mercury about ten times. Each time all but a little of the mercury is drawn off, so
as to leave the oxide behind. When the drawn-off mercury finally gives no test for sodium,
as shown by the neutrality of a water rinse, the remaining mercury with the sodium oxide is
washed with water, which is then filtered and run through the flame photometer. At low
concentrations the precision is 0.005 % oxygen in sodium.
A few years later an improved method was published by Pepkowitz, Judd and Downer
[431]. They purified the blanket gas with a NaK bubbler and warmed the extractor. They
determined oxygen in NaK and in lithium. The standard error was 0.002 % of oxygen in
the metal. Champeix, Darras and Duflo [432] increased the sensitivity further. They were
278 NONMETALS [5
able to determine 7 ppm of oxygen in sodium with a reproducibility of 1.5 ppm. Minczew-
ski, Dancewicz and Wasowicz [433,434,435] determined it at 50 ppm with a standard
error of 3 ppm. White, Meyer and Goldberg [436] used the method for determining oxy-
gen in the heavier alkali metals, and Goldberg [86] used it for oxygen and hydrogen below
50 ppm in sodium, potassium and NaK; the abstracts give no details on these two appli-
cations. A different approach is that of Bergstresser, Waterbury and Metz [437], who
determined 1 to 10 ppm of oxygen in sodium. They distilled the metal in vacuum, dis-
solved the residue in acid and analyzed it by flame photometry.
5.9.3 ELECfRIC DISCHARGES
There are good arc methods for oxygen, but I shall name here only Wendt and Fassel's
induction torch [300] and the microwave argon discharge of McCormack, Tong and
Cooke [88], already mentioned under Hydrogen, Carbon, Silicon, Nitrogen, Phosphorus
and Arsenic. The induction torch emits OH bands with aqueous solutions, and the tail
flame, mixing with air, emits O 2 bands. Oxygen was not studied as an analyte. The micro-
wave torch emits OH bands with great persistence; the authors were unable to exclude
them altogether. Water could be detected by the OH band at 3089 A with a sensitivity of
2 (J-g/s. Elemental oxygen was detected indirectly by its depression of the CO+ First
Negative 2897 band or the CO Triplet 6037 band with a sensitivity of 0.1 and 0.004 (J-g!s,
respectively.
5.10 Sulfur
5.10.1 THE FLAME SPECTRA
Flames of burning sulfur or its compounds or flames containing sulfur or its compounds
as additives emit bands of S2, SO, SH and CS, and a continuum. Bands of S02 and S2
are sometimes seen in absorption. The various emissions are highly dependent on the
nature of the flame; conditions must be chosen carefully to bring out one or another
of them. Of these emissions, S2 has proved most useful for spectrochemical analysis, but
CS has potential utility also. In surveying the abundant literature, it is hard to tell where
to draw the line between papers of interest to the spectrochemist and those of concern
mainly to the physicist. Analytical flame spectroscopy has been increasingly characterized
by the utilization of what would earlier have seemed unlikely flames and spectra.
Gaydon in 1957 neatly summarized the spectroscopy of flames containing sulfur [34
(p. 220)]. Wavelengths, intensities and vibrational levels are adequately tabulated in the
handbooks [78, 79] (SH is listed as HS in Rosen's book). Rosen gives a great many ref-
erences, especially for S2, covering the years 1927-1950. I have heeded very few of these,
however; they occupy the spectrophysical gap between the older flame spectroscopy and
the newer flame spectrophotometry, which are of chief concern here.
Although SH and SO have not yet been used for analysis, they should not be ignored.
The recent discovery of strong CS bands in certain sprayer-burner flames was unexpected,
and good analytical sources of the SH or SO spectrum may yet be found. The SH bands,
degraded to the red, with the first 0,0 head at 3237 A, are analogous to OH. They are hard
5.10] SULFUR 279
to excite in flames [78]. Gaydon has seen SH in rich but nonluminous hydrocarbon flames
containing sulfur dioxide and in the inner cone of flames containing hydrogen sulfide
[34, 452]. Durie [454] reported the SH band in the fluorine-hydrogen flame, due to im-
purities. Although not detected in hydrogen flames by Gaydon and Whittingham [452] or
Fenimore and Jones [455], Sugden et al. [303] photographed the spectrum in fuel-rich
nitrogen-diluted oxyhydrogen flames containing 1 % sulfur dioxide. It was strongest in the
reaction zone and was thought to be chemiluminescent; theories of formation and excita-
tion were tested photometrically. A diffuse band was also observed in the red, probably
due to H 2 S. Using flash absorption spectroscopy, Norrish [456] studied the formation
and behavior of SH in photoflash explosions of hydrogen sulfide and oxygen.
The SO spectrum consists of an extensive series of red-degraded bands covering much
of the ultraviolet. SO appears weakly in flames of sulfur, hydrogen sulfide, and oxygen-
carbon disulfide, and very faintly in air-carbon disulfide [438]. It is stronger in the cool
flame of carbon disulfide [34 (p. 221)]. It appears strongly in the inner cone of fully aerated
hydrocarbon or methanol flames containing sulfur dioxide or trioxide or hydrogen sul-
fide [452]; Gaydon and Whittingham published a good photograph. Sugden et af. [303]
interpreted the formation and excitation of SO in their hydrogen flames with sulfur diox-
ide. Like SH, it appears mainly in the reaction zone and is probably chemiluminescent.
Norrish and Oldershaw [456, 457] studied the behavior of SO in the flash photolysis of
hydrogen sulfide-oxygen and sulfur dioxide and trioxide.
5.10.2 THE BANDS OF MOLECULAR SULFUR, S2
Cool hydrogen flames, under the same conditions that give rise to the green light of HPO
with phosphorus, emit a blue-violet light when sulfur is present. The emitter is S2. The
green and the blue emissions differ in nature and mechanism, despite their similar behav-
ior; but because of it, they are closely parallel in history and utilization. The generation
gap is as marked with sulfur as with phosphorus. Long well known, the blue flame was
forgotten by chemists with the rise of modem spectroscopy in the 1920's. Within the last
few years it has been rediscovered repeatedly and chemists are now putting it to use as
eagerly as the green flame of phosphorus. However, they have less excuse for not knowing
that the emitter is S2; the spectrum is well documented. Being simpler, though more
extensive, than the spectrum of HPO, it caused less trouble for the theorists: Fowler
and Vaidya [438] positively identified the emitter as S2 in 1931. There has never been any
real doubt about the character or identity of the spectrum; it has been assigned to elemen-
tal sulfur for the last hundred years. The description of the HPO spectrum is today still
incomplete and relatively inaccurate. By contrast, the wavelengths of the many S2 band
heads have been accurately known for decades.
Herschel in 1823 [19] noticed that burning sulfur emits mostly blue and violet light,
but he drew no spectrum. Merz in 1860 [146] was the first to observe that sulfur or sul-
furic acid imparts a fine blue color to the cool, nonluminous core of a hydrogen flame. He
discovered this while igniting hydrogen in a test tube with a sulfur match; the gas burned
with a blue flame, which he realized was due to the match. As an analytical test, he found
the color sensitive to t [Lg of sulfuric acid or 1 [Lg of sulfate (moistened with hydro-
chloric or fluosilicic acid). He was able to detect the sulfuric acid in rusty laboratory
apparatus. He also noticed that when a hydrogen flame is directed against a surface
of sulfuric acid, the blue glow appears [439].
280 NONMETALS [5
The first to report the spectrum was Mulder in 1864 [331, 332]. The flame of hydrogen
carrying sulfur vapor showed three very broad violet lines and a countless number of
other violet, blue and green lines. Unlike the green of phosphorus, the color was not
quenched by ether. Traces of hydrogen sulfide and carbon disulfide in hydrogen also gave
this spectrum. For example, it appeared when iron sulfide was present in the hydrogen
generator. Shortly after, Mitscherlich [21], interested by the various metal halide spectra
that he had succeeded in producing, tried to get metal sulfide spectra by introducing met-
als into oxygen-carbon disulfide-hydrogen and oxygen-hydrogen sulfide flames; but he
found only the sulfur spectrum or none. His paper included a fine drawing of the spectrum.
A detailed map (from sulfur in a Geissler tube) was published in 1865 by Pliicker and
Hittorf [256], along with a large colored picture of the spectrum. They observed it (as
ill-defined bands) also in the flame of sulfur burning in oxygen.
The prevalence of sulfur led to many interesting observations by Barrett in 1865 [440]. A
hydrogen flame showed the deep blue color on touching various bodies. The color was
strong on vulcanized rubber, alum, sulfides and sulfates (but not sodium sulfate), and
brilliant and continuous on sulfuric acid. Barrett obtained a fleeting blue color from gran-
ite, sometimes ice and water, glass, and even his fingers. He found that any surface with
three days' accumulation of dust gave the test, and realized that it was due to the sulfur
from England's coal fires. A clean surface, e.g., granite that had been heated red hot, did
not give the test; but the blue would return if the surface sat exposed to air for a while.
The blue seen erratically on water was due to sulfur from the inside of the rubber hydrogen
tube. If Barrett touched vulcanized rubber and then rinsed his fingers, the surface of the
rinse water glowed blue under the hydrogen flame. He found the test sensitive to less than
a microgram of sulfur, in agreement with Merz. No blue color, however, could be obtained
with flames of coal gas, town gas, natural gas, alcohol, carbon disulfide (surprisingly),
carbon monoxide, methane, or oxyhydrogen (which is too hot). Similarly, Bunsen [277]
reported no color for sulfur in the Bunsen flame.
Most of the early papers on the sulfur flame spectrum come from Salet, starting in 1869
[441]. He reported that Paris too was full of sulfurous dust, and any dirty surface in the
city glowed blue under the hydrogen flame. Objects in the countryside, however, did not.
He verified Merz's and Barrett's observations, but found that sodium sulfate does give
the test: the blue appears beneath the yellow due to the sodium. He observed the blue glow
also with gypsum, sulfites, hyposulfites and sulfur dioxide, but only with difficulty on
barium sulfate. Barium sulfate is best fused with microcosmic salt (sodium ammonium
hydrogen phosphate) on a platinum loop and then placed in a hydrogen flame chilled in
any manner: the bead emits a blue glow surrounded by a green halo (due to the phospho-
rus). The positive test given by glass, Salet said, was due to dust. He verified Mulder's
spectrum, and gave readings on his spectroscope scale for 20 bands in the blue and green.
Salet's most useful contribution, being exploited in every present-day application, was,
as with phosphorus, his discovery that by sharply chilling the burning hydrogen the blue
emission could be greatly strengthened [333]. Barrett had played the flame on water with-
out recognizing the special advantage of doing that. Salet recommended directing the flame
against a waterfall pouring down a sheet of platinum [333] or glass or marble [17].
Mavrodineanu [334] shows a picture of this arrangement. A platinum tube containing
water [442], an air-cooled tube [281], or a sheath of flowing air [17] has the same effect.
The blue glow fades if the chilling body gets hot. Salet mentioned a detection limit of 2 fLg
and said that sulfur could be detected in hair [17].
In 1871 Salet first measured the wavelengths of the sulfur band spectrum [335,443,444],
5.10] SULFUR 281
based on Angstrom's calibrations. He compared the spectra of sulfur in the hydrogen flame,
in the Geissler tube, and (in absorption) in the vapor of sulfur and found them identi-
cal; he concluded that the spectrum was due to sulfur only. He listed bands from 550
down to 396 nm (actual head at 393.9), the last that he could see. Salet summarized his
work in an extensive review paper [17] and in his later book [282]. Schuster [336] also
reviewed the spectroscopy of sulfur in 1880. Angstrom [445] reviewed it in 1871 and listed
wavelengths, which, however, correlate so badly with modern wavelengths (8alet's corre-
late well) as to mystify a latter-day reader.
There are some scattered later papers of chemical interest. Hartley [364] mentioned the
"beautiful fluted bands" of sulfur. He heated his samples on cyanite in the oxyhydrogen
torch - a rather inefficient way to excite the S2 spectrum. With Ramage [164] he detected
sulfur in minerals, but only as a major constituent. Eder and Valenta [446] mentioned the
hydrogen flame spectrum obtained with sulfur-containing glass, and said it was less com-
plete than the Geissler-tube spectrum, which they photographed and tabulated in great
detail. Schlagdenhauffen and Pagel [447] noticed the violet-blue of a chilled flame of hy-
drogen generated from zinc and sulfuric acid, but they were inclined to ascribe it to traces
of selenium; they offered no spectroscopic evidence. They discovered that if the lower end
of an open glass tube is dipped into the flame, a ball of blue fire climbs the tube to the top,
where it vanishes. If the flame is burned in a 8mithells separator, both cones are blue.
An interesting but apparently short-lived application of the S2 spectrum is Sell's carbon
disulfide lamp [448], used for photography. Nitric oxide is blown across the wick of a
carbon disulfide burner. The flame emits a very fine bluish-white light rich in violet and
ultraviolet. Vogel [449,450] detected 38 bands in the spectrum of Sell's lamp; it extends as
far as the orange and is exceptionally brilliant in the blue.
Kayser's Handbuch [16 (p. 398)] gives a detailed history of the sulfur spectrum up to
1912, with comparative tables. There is an excellent spectrogram (Geissler tube) in Hagen-
bach and Konen's atlas [l05] and an annotated oxygen-gas flame spectrogram in Eder
and Valenta's atlas [104]. Strutt and Fowler [451] measured the bands in the carbon
disulfide flame, and 19 years later Fowler and Vaidya [438] published their definitive
work on the S2 spectrum, carrying the wavelengths down to 2593 A.
5.10.3 MODERN WORK ON THE S2 SPECI'RUM
Besides Fowler and Vaidya, Gaydon and Whittingham [452] and Sugden, Bulewicz and
Demerdache [303] have done important work on 8 2 in flames. The bands of S2 are the
main feature of air flames of sulfur, hydrogen sulfide and carbon disulfide; flames of car-
bon disulfide with oxygen, nitrous oxide or atomic hydrogen; and the cool flame of car-
bon disulfide. The bands appear, but not strongly, in an ethylene or barely nonluminous
Bunsen flame with added sulfur dioxide and, in the inner cone, with hydrogen sulfide
[34 (p. 220)]. The bands are, of course, very persistent in rich hydrogen flames containing
sulfur in any form; they are emitted mainly in the reaction zone and become very weak as
the fuel ratio approaches the stoichiometric. They appear in a flame of oxygen burning in
an atmosphere of hydrogen containing a trace of sulfur [452]. Brinsley and Stephens [453]
detected the S2 spectrum in hydrogen containing t ppm of sulfur. They also observed
a violet-blue reaction zone in flames of coal gas containing 0.2-0.7 mgtl of sulfur, but only
on the fuel-rich side of stoichiometric. The color appeared also when the flame struck cold
metal. Durie [454] reported that carbon disulfide burns with a bright, pale blue flame in
282 NONMETALS [5
fluorine, showing S2' The fluorine-hydrogen flame is greenish-blue with a violet mantle
emitting strong S2 bands, due to impurities.
Sulfur has accompanied phosphorus in the recent spurt of practical spectrochemical
work. Many pesticides contain sulfur. But in addition to the need of determining pesticide
residues, there are problems of air pollution that often call for trace determination of
sulfur (usually the dioxide). The S2 emission in a cool hydrogen flame provides extra-
ordinary sensitivity for these analytical tasks. It is best excited in the same burners as
those described under Phosphorus.
The earliest was the Driigerwerk or van der Smissen burner [342, 343] shown by Mavro-
dineanu [334(P. 4(0)]. The lower flame is 3-5 mm high; the green phosphorus glow is best
developed 1-2 flame lengths above it, and the blue sulfur glow 5-15 flame lengths. Haas
[307] independently discovered the utility of the chilled hydrogen flame for determining
sulfur, and apparently Crider [458,459] did too. Gilbert's work [341,349], based on that
of Haas and van der Smissen, resulted in the burners shown in Figs. 5.12 and 5.15. In
the latter, the sulfur glow, filling the upper part of the chimney, is largely separated from
the phosphorus glow. Fig. 5.22 shows a recording of the S2 spectrum obtained with the
burner of Fig. 5.12. There is also the burner of Brody and Chaney [344, 345] (Fig. 5.11),
resembling Crider'S, and manufactured by MicroTek Instruments [348]. Sytyand Dean
[279, 280, 346] adapted a similar burner to solution analysis.
;;
,Ii
Fig. 5.22. Spectrum of sulfur in nitrogen-cooled hydrogen flame.

Apparatus as for upper curves of Fig. 5.13. Vapors of carbon disulfide diluted with 4 volumes
of isopropanol carried with nitrogen through capillary.
The only other work on solution analysis by the S2 flame emission is that of Dagnall,
Thompson and West [47]. They used the same equipment as in their later work on
phosphorus [48]. The long burner was provided with a special jet in the base to permit
adding a third gas. They tried propane, acetylene and hydrogen as fuels, each with mix-
tures of oxygen and nitrogen or nitrous oxide and nitrogen, as well as diffusion flames of
hydrogen mixed with nitrogen or argon. The inert gas was used for spraying the sample.
The diffusion flames were best for sulfur. The OH bands were only 1/40 and the Na line
1/50 as strong in the hydrogen-nitrogen diffusion flame as in premixed air-hydrogen, while
the S2 emission was much stronger; it was strongest in the core of the flame, at a tempera-
ture of 390°C, Nitrous oxide destroyed the S2 emission. A sprayer-burner flame was
unsatisfactory, being too hot. In the diffusion flame, solutions of sulfur dioxide and hydro-
gen sulfide gave the best emission; other sulfur compounds gave a weaker emission that
varied greatly with the nature of the sample.
To provide a flame source that would give more consistent analytical results for sulfur,
5.10] SULFUR 283
Dagnall and coworkers tried a round propane burner supplied with air (carrying the
spray) and excess hydrogen and topped with an air-cooled Pyrex chimney. This arrange-
ment was more like Syty and Dean's. The S2 emission appeared at the bottom of the
flame. The burner gave as strong an emission with sulfur dioxide as the diffusion flame,
and it gave better emission with sulfates. The analytical characteristics of these and other
flames will be taken up in Section 5.10.7.
Dagnall et al. published a spectrogram of S2, less detailed than Fig. 5.22 but having the
advantage of showing all the bands on a single intensity scale. The relative peak heights,
as seen with the Unicam quartz monochromator (slit 0.02 mm) and an EMI 9601B photo-
multiplier, are as follows: 3369,0.5; 3417, 1; 3469,2; 3500, 3; 3556,4; 3587, 3; 3645,7;
3740,9; 3837, 10; 3939, 10; 4046, 9; 4157,6; 4194, 4; 4274, 4; 4311,3.
5.10.4 THE BANDS OF CARBON MONOSULFIDE
The spectrum of CS consists of clear sequences of double-headed red-degraded bands;

the strongest head is at 2576 A. References and wavelengths will be found in Kayser and
Konen [93 (p. 331)], Pearse and Gaydon [78] and the section by R. F. Barrow in Rosen's
book [79(p. 71)]. The spectrum has been seen in flames at least as early as 1926 (Emeleus)
and 1939 (Kondratjew). According to Gaydon's summary [34 (p. 220)], CS does not emit
in the normal flame of carbon disulfide but it does in the cool flame. The bands are weak
or absent in a fully aerated Bunsen flame containing sulfur dioxide or trioxide, but with
hydrogen sulfide they are stronger. They are strong in a rich but nonluminous flame with
sulfur dioxide or hydrogen sulfide. They appear in the inner cone of rich flames of methane,
ethylene or methanol with sulfur oxides or hydrogen sulfide [452].
In flames of fluorine with carbon compounds, the CS bands are a sensitive indicator
of sulfur impurities [454]. According to Mann, Broida and Squires [460], the same is
true of oxyacetylene containing carbon tetrafluoride. These reports lead to the surmise
that a good analytical flame source of the CS emission for the determination of sulfur
might be found in the form of a more or less conventional flame with a fluorine compound
as additive.
The only report of CS in analytical flames is that of Gilbert [3 (pp. 243, 270, 387, 575);
39, 49, 117]. The spectrum appears with aqueous sulfuric acid in a mixed air-oxygen-
hydrogen-acetylene flame on a sheathed sprayer-burner and much more strongly when the
hydrogen is omitted and the flame is made rich enough to be incandescent. Methanol as
solvent enhances the emission but no more than would be expected from the better spray-
ing. The spectrum is shown in Fig. 5.23. Tables 5.XX and 5.xXI list wavelengths and
radiances.
5.10.5 MECHANISM OF SULFUR EMISSION
The first attempt to find evidence of the nature of the blue flame was made by Salet [442].
A hydrogen flame containing sulfur dioxide or hydrogen sulfide deposited sulfur on a
cooled platinum surface in the region of the blue glow. With stronger cooling, sulfuric
acid condensed. A platinum filament placed in the blue glow became barely red hot, show-
ing the low temperature. If the flame contained sodium too, the blue appeared next to the
cold surface and the yellow at a distance from it. Papish in 1918 [461] also obtained a
deposit of sulfur on a cold object from a Bunsen flame charged with sulfur dioxide.
284 NONMETALS [5
TABLE 5.XX
RADIANCES AND PRACTICAL INTENSITIES OF CS BANDS AND BACKGROUND
IN THE AIR-OXYGEN-ACETYLENE SPRA YER-BURNER-FLAME
Rich, incandescent flame on sheathed Beckman No. 4020 sprayer-burner; oxidant mixture (70%
total oxygen) supplied to sprayer and sheath. Sulfuric acid solutions. J., J b , and Intensity defined
as in Tables 5.11 and 5.111. J. includes J e , which is about 0.1 x 1011 w/cm2.sr.nm.(fLg/ml) at all
wavelengths in both solvents.
Band heads Relative Aqueous 50 % Methanol-

intensities Levels
solution water
I
R Q Ref. Ref.
(Ref. [78]) (Ref. [79]) [78] [79]
Vi
I
v" 10 11 J. 10 8 J b Int. lO 11 J. 10 8 J b I Int.
2507.3 2509.5 4 7 1 0 .38 8.0 .05 .44 9.4 .05
2511.2 3 6 4 .31 8.5 .04 .35 9.7 .035
2523.2 2524.0 7 11 2 1 .42 8.7 .05 .54 10.0 .05
2530.0 2530.6 3 4 7 5 .36 8.7 .04 .43 10.1 .04
2538.7 2539.4 8 10 3 2 .42 9.3 .045 .54 10.8 .05
2549.5 a 8 6 .30 9.8 .03 .33 11.4 .03
2555.8 2556.3 5 9 4 3 .35 9.8 .035 .41 11.5 .035
2572.7 2573.3 5 7 5 4 .31 10.0 .03 .29 12.1 .025
2575.6 2576.8 10 20 0 0 1.4 10.2 .14 2.0 12 .16
2589.6 2592.6 6 20 1 1 .91 10.2 .09 1.2 12 .10
2605.9 2606.8 10 12 2 2 .43 10.4 .04
2621.6 2622.4 7 5 3 3 .24 11.8 .02
2662.6 2664.1 10 20 0 1 .25 13.1 .02
2677.0 2680.1 6 15 1 2 .28 13.6 .02
2693.2 2694.4 8 11 2 3 .27 14.1 .02
a) Measured from the spectrogram of FIg. 5.23.
Miyanisi [462], according to the abstract of his paper, found the band spectrum of
sulfur (presumably 8 2 ) to be enhanced in the region of OH emission in both the stoichio-
metric oxyhydrogen flame and in a discharge tube containing water. He thought excited
OH was involved in the excitation of sulfur. Gaydon and Whittingham [452], whose
observations have been summarized above, analyzed the interconal gases of a Bunsen
flame containing sulfur dioxide. They found that 25 % of the sulfur dioxide was reduced
to hydrogen sulfide and 10% was reduced to sulfur; there was some carbon disulfide and
carbon oxysulfide but no sulfur trioxide. They said that H. G. Crone had suggested the
following chemiluminescent reaction for sulfur:
H + H + 82 -+82 * + H 2 •
The recombination of atomic hydrogen furnishes 4.5 eV of energy for excitation, account-
ing for the fact that only the lower vibrational levels of the upper electronic state of 8 2
are populated in most flames.
Gaydon [34 (p. 221)] pointed out that the presence of 8 2 and absence of C8 in the normal
flame of carbon disulfide suggest that the main reaction is that of C8 2 with oxygen to
5.10] SULFUR 285
, 250 , I .
265
Fig. 5.23. Spectrogram of sulfur in air-oxygen-acetylene flame.

Beckman DU with sheathed sprayer-burner and 1P28 photomultiplier. Fuel-rich, incandescent
flame; air-oxygen mixture, optimized for sulfur, fed to sprayer and sheath. Slit 0.05 mm. Sulfuric
acid in 50 % methanol, 5000 !-lg/ml sulfur. Blank recording superposed. Reproduced from [39]
by permission of Spartan Books and from [3] by permission of John Wiley & Sons.
TABLE 5XXI
RADIANCE AND PRACTICAL INTENSITY OF THE 2576-A CS BAND AND BACK
GROUND IN DIFFERENT FLAMES AND SOLVENTS
Data as in Table 5XX.
Flame Solvent 1011Ja 1011Jc IO B J b Int.

I
Air-Oz-Hz-C 2 H 2 a Water .07 .03 5.1 .014 c
b
Air-Oz-C 2 H 2 Water 1.3 .1 10.2 .14
50% MeOH 1.9 .1 12.3 .16
"
80% MeOH 2.7 10.7 .25
"
90% MeOH 3.2 9.6 .33
"
95% MeOH 3.3 8.7 .37
"
98% MeOH 3.6 8.4 .43
"
99% MeOH 3.5 8.3 .42
"
a Same burner as in Table 5.XX. Oxidant mixture contained 34 % total oxygen. Fuel mixture
optimized for NO emission.
b Same flame as in Table 5.XX
C For net band above continuum (this datum only).
286 NONMETALS [5
form S2 and an oxide of carbon; but the presence of CS in the cool flame shows that its
reactions differ from those of the normal flame.
Sugden, Bulewicz and Demerdache [303] studied the reactions of sulfur in hydrogen
flames. Since the dissociation energies ofH2S (3.9 eV to SH + H), S02 (5.0 eV to SO
+ 0),* SH (3.6 eV), SO (5.4 eV) [457, 463], and S2 (4.4 eV) do not differ greatly, the
behavior of sulfur can be very complex and the distribution among the various species
will vary greatly with the composition and temperature of the flame. Since S2 can partici-
pate, the distribution depends also on the concentration of sulfur. The authors tabulated
the equilibrium distribution of sulfur in various hydrogen flames, listed the possible reac-
tions, and showed how the nonequilibrium concentrations of Hand OH affect the con-
centrations of the sulfur species. The theory was tested by measuring the dependence of
SO, SH and S2 emission intensities on the distance from the reaction zone and (for S2) on
the concentration of total sulfur. In general, agreement was good, supporting the theoreti-
cal calculations and also Crone's excitation reaction. However, the coolest flames em-
ployed in this study were at 1350 °C, about 1000 °C hotter than those used by analysts.
In any case, the theory indicates that in rich hydrogen flames the concentration of S2
should be proportional to the equilibrium constant of 2H 2S + 2H -+ S2 + 3H 2 (which,
since the reaction is exothermic by 3 eV, will rise as the temperature falls), to the square of
the H concentration, and to the square of the total sulfur concentration. Besides, the
chemiluminescent intensity should be proportional to the square of the H concentration.
The emission should therefore vary as the fourth power of the H concentration.
The prediction of a quadratic relationship between the intensity and the sulfur concen-
tration, verified experimentally by Sugden et al., is important for analytical spectrochemis-
try. As will be seen (Table 5.XXII), the Brody-Chaney (Mel par or MicroTek) flame photom-
eter usually gives a quadratic analytical curve for sulfur: the emission varies as the square
of the concentration. Such curves were observed also by Syty and Dean [280], Dagnall
et al. [47] and apparently by Crider [458] (his curve is ambiguous).
However, in the burner developed at the U.S. Naval Applied Science Laboratory [307],
the analytical curve is more or less quadratic only at the lowest concentrations (below
about 10- 6 atm of total sulfur) and linear above that. The same is true of the similar
burner developed by E. Buzza of Beckman Instruments. These burners were optimized
for sulfur and it is likely that in them the formation of S2 is carried to an extreme. If vir-
tually all of the sulfur has become S2 in the downstream portion of the flame being ob-
served, the curve should be linear unless the S2 is slow to form. Such delay would be ex-
pected only at the very lowest concentrations, where the collisions between sulfur-contain-
ing species needed to form S2 become too infrequent for full equilibration within the
available time (roughly 0.1 second).
Even in some of Sugden's flames, concentrations of S2 as high as 50 % of the total sulfur
were calculated (admittedly at high sulfur concentrations). In the much cooler, richer
flames of the analytical burners, any sulfur compound should go to S2' In the primary
combustion, H 2S is the dominant product. In the chilled, burnt gases, the following
reactions will occur:
H 2S + H-+ SH + H 2, L1Ho = -0.6 eV;
SH + H -+ S + H 2, -0.9 eV;
SH + S -+ S2 + H, -0.8 eV.
*) According to a recent review [485], this value should be 5.7 eV.

5.10] SULFUR 287
(These are equivalent to the 2H 2S + 2H reaction mentioned above.) Norrish [456] has
inferred these reactions also in the photoflash-initiated explosion of excess hydrogen sul-
fide with oxygen. Consideration of all other possible reactions leads to the conclusion
that S2 should be the final dominant species in a chilled flame rich in H and H 2. The
gases smell neither of hydrogen sulfide nor of sulfur dioxide; the odor is the same as
that of elemental sulfur, and I suspect that it is the odor of the S2 molecule.
There is, however, an anomaly in the analytical curve not accounted for by the above
considerations. In the Brody-Chaney flame photometer, the curve is duly quadratic at all
concentrations except the lowest, where it is linear. This is exactly opposite to the behavior
of Haas's [307] and Buzza's burners. Most analysts (mainly Bowman and Beroza; see
Table 5.xXII) have used the Brody-Chaney burner in the quadratic range. But Brody and
Chaney's data show that the response is proportional to the square of the concentration
only from about 0.05 or 0.1 [Lg of sulfur per liter of equivalent air (nitrogen carrier plus
added oxygen) up to about 3 [Lgjl (the highest concentration tried); below 0.05 [Lgjl the
curve gradually becomes nearly linear. Bowman and Beroza [380, 466] verify this. In fact,
Maitlen et al. [468] recommend that the analysis be done at the bottom of the concentra-
tion range to take advantage of the linearity there. This curious phenomenon clamors for
interpretation.
The relation between the excitation of HPO and S2 and the concentrations of OH and
H, accounting for the spatial separation of the green and blue glows, was discussed in
Section 5.7.5. Regarding the chemiluminescence of S2, Crone's reaction (H + H) per-
mits excitation of S2 up to the 11 th vibrational level of the upper state. None of the bands
that I have observed (Fig. 5.22) originates at any level above 4.3 eV (v' = 8). However,
Sugden and Demerdache [464] have observed bands of S2 beyond the dissociation limit
(4.4 eV) in the reaction zone of a rich hydrogen flame containing several percent of sulfur
dioxide. They detected v' = 15 (4.65 eV). To account for this they proposed that thechemi-
luminescent reaction
supplying 5.1 eV of excitation energy, also plays a part. But in the analytical flames I
believe that this reaction is of little significance. Peyron [350], in a study of the low-
pressure reaction of sulfur vapor with atomic hydrogen, also concluded that the excita-
tion of S2 was due to Crone's reaction.
In a study paralleling their work on phosphorus [352], Fenimore and Jones [455] exam-
ined with a mass spectrometer the burnt gases of oxyhydrogen flames containing sulfur.
In rich as well as in lean flames they found that added sulfur appeared mostly as sulfur
dioxide owing to the effect of atomic hydrogen in promoting the reaction
This reaction is admittedly exothermic by 2 eV. However, the H 2S and SOz accounted for
only 75 %of the added sulfur in rich flames. They expected S2 on the basis of the SH + S
reaction but could not detect it except by its emission in the reaction zone. Neither could
they detect SH. They believed that the recombination of H + Hand H + OH in rich
flames is catalyzed by S02 via the intermediate molecule HSO z• These conclusions are at
variance with the other work summarized above. They seem quite puzzling. Clearly, more
work is needed to elucidate these interesting flame reactions.
288 NONMETALS [5
5.10.6 THE SULFUR CONTINUUM
A continuous spectrum associated with sulfur in flames has been noticed repeatedly dur-
ing the past century. Mitscherlich [21] saw it in the hydrogen flame, along with the S2
bands. Dibbits [301] saw a continuum, strongest in the blue and very weak at longer wave-
lengths, in the flames of burning sulfur or carbon disulfide; hydrogen sulfide with air,
oxygen, or nitrous oxide; carbon disulfide-hydrogen mixtures with air or oxygen; and
sulfur dioxide-hydrogen mixtures with air or oxygen. He declared that all of these spectra
were "entirely continuous," even with very narrow slits. He could detect none ofthe "lines"
seen by others in the sulfur spectrum. PlUcker and Hittorf [256] saw only a continuum in
the spectrum of sulfur burning in air, but in oxygen they detected diffuse bands too. Salet
[17, 441] verified their observations. Hartley [364] photographed the continuum (and
bands) in oxyhydrogen. A strong continuum under the bands is visible in Ederand Valen-
ta's oxygen-gas flame spectrum [104].
Although all of the earlier work had revealed only the blue continuum in the sulfur-air
flame, Fowler and Vaidya [438] observed the S2 (and SO) bands in it. They found a
strong continuum also in the carbon disulfide flame. Gaydon [34 (p. 221)] mentions the
continuum in the low-pressure flame of carbon disulfide with atomic hydrogen. The con-
tinuum is present under the S2 bands in all modem analytical hydrogen flames. Syty and
Dean [280] mention it, and it is visible in Fig. 5.22. It has been observed in hydrogen by
Charton [465]; I have not seen this book. The spectrograms of hydrogen flames with sul-
fur dioxide published by Sugden et af. [303] show the continuum extending far into the
ultraviolet, to about 260 nm. It is most noticeable in the mantle of near-stoichiometric
flames. Gaydon and Whittingham [452], who observed the continuum in the mantle of a
Bunsen flame containing sulfur dioxide, suggested that it is due to the reaction
S02 + 0-+ S03 + hy.
There is a current review by Thrush [486], including a discussion of the sulfur dioxide
afterglow. He says that this luminescence, first observed in 1934 by Gaydon downstream
from a discharge in flowing sulfur dioxide, is the same as the continuum seen in the com-
bustion of sulfur compounds, and that it is due to the reaction
SO + 0-+ S02 + hy.
5.10.7 FLAME-SPECTROPHOTOMETRIC DETERMINATION OF SULFUR
The recent analytical work on sulfur is summarized in Table 5.XXII. The burners used in
this work have been discussed in Sections 5.7.3, 5.7.10 and 5.10.3. Table 5.xXII should
be compared with Table 5.XVII. Many of the references are the same in both.
Most of these applications utilize the S2 emission. However, this emission is best devel-
oped in flames that are hardly hot enough to decompose every type of sample; the difficul-
ties that result will be mentioned later. The CS emission, on the other hand, is favored by
hotter flames and might prove useful for a wider variety of samples even though it offers
less sensitivity than S2. Besides, CS gives a linear analytical curve, while that of S2 is
mostly quadratic. Now, an emission that is proportional to the square of concentration
offers twice the analytical precision of a linear emission, for a given degree of flame stabil-
ity. That is, a fluctuation of 1 % in the emission corresponds to a variation of only 0.5 %
in concentration. But the interpretation of results is not quite as easy. With a nonlinear
5.10] SULFUR 289
curve there is also the academic difficulty of defining the detection limit, especially when
the logarithmic slope changes at very low concentrations. The detection limit may turn out
to exceed the least difference in concentration detectable at higher concentrations. The
detection limits listed in Table 5.XXII, however, are supposed to represent valid lower
limits of concentration.
Like HPO, the S2 emission has been much used for gas-chromatographic analysis of
pesticide residues. The recent introduction of twin detectors for the simultaneous determi-
nation of sulfur and phosphorus in the same flame [391] has been helpful. In this two-
channel flame photometer, the ratio of phosphorus response to the square root of sulfur
response is nearly proportional to the P/S concentration ratio in the eluted compound; but
it varies a little among compounds, and this variation aids identification. The flame-photo-
metric sulfur detector in gas chromatography has all the advantages listed in Section
5.7.10 except linearity. However, Maitlen, McDonough and Beroza [468] utilized the
linearity occurring at the lowest concentrations. They diluted the sample to bring the
eluted peak into the range 2-10 ng of pesticide.
There is less information on specificity factors for sulfur than for phosphorus, but on
the whole they ought to be at least as high. When the sulfur response is quadratic, the
specificity factors will increase with concentration. With the burner of Fig. 5.15, Gilbert
[349] found a specificity factor of the order of 104 against phosphorus when the sulfur read-
ing was taken as the difference between the peak at 3837 A and the valley at about 3800 A.
The slight phosphorus emission is virtually the same at these two wavelengths. The rel-
atively poor specificity for sulfur reported by Braman [265] was due to the fact that his
flame was not optimized for sulfur but was intended as a general detector for gas
chromatography (see Tables 5.VI and 5.xI). Even so, carbon disulfide gave about 100
times the response of carbon-hydrogen compounds.
The phenomenon discovered by Schlagdenhauffen and Pagel [447] can be used for
completely separating the emissions of sulfur and phosphorus present in the same flame.
The lower end of a long glass tube, held at an angle, is momentarily dipped into the upper
flame ofa burner like that of Fig. 5.15. The piece of fire thus picked oifseparates into two
luminous balls that roll up the tube and vanish as they emerge at the top. The leading ball
is green (HPO) and the trailing ball, separated by a dark space, is blue (S2). No analytical
use has yet been made of this curious effect.
The precision for sulfur in pesticide analysis (there are fewer data) is probably at least
as good as for phosphorus; note the recovery data in Table 5.xVII. An example of the pre-
cision available with the CS emission is shown in Table 5.xXlII. In this example the stan-
dard error of the net reading on the sulfur is less than that of the gross reading or the
blank, because there is a small erratic drift that runs nearly parallel in sample and blank.
This often happens in flame photometry, because flame noise is not white at the lower
frequencies. The standard error of the net reading is equivalent to 10 [log/l of sulfur; the
detection limit estimated from Table 5.xXl, for the same conditions, is 2.5 times this
quantity. The ratio would be a bit larger with an optimal slit, but the slit was kept narrow
to sharpen the band and improve the spectral resolution. The price of better resolution is
greater shot noise - about 2 % (peak-to-peak) in this case.
The S2 emission is being used for other applications than gas chromatography. For the
analysis of simulated extraterrestrial soils, Johnson [347] used the method described in
Section 5.7.10. The burners developed at Dragerwerk by van der Smissen [342,343], at
the u.s. Naval Applied Science Laboratory by E. C. Haas and J. Steinmetz [307] and at
Beckman Instruments by Gilbert and E. Buzza [341, 349] were designed for monitoring
290 NONMETALS [5
TABLE 5.XXII
DETERMINATION OF SULFUR BY DIRECT EMISSION FLAME
SPECTROPHOTOMETRY
Date Authors Ref. Flame Emission Burner Dispersionl Detector

I
1959 Cowan & [262] End of Visual observation
AH S2
Sugihara
I I I I column of height and color
1961 Gilbert [49] AOA CS 257.6 BSB DU IP28
" " " " "
1961 Sternberg & [263] IP28

AH S2 380 FID DU
Jones
I I I
[342]
1962 Dragerwerk RichAH S2 380 vdS Spectrophotometer
[343]
I
:J~bm [39]
I Sheathed IP28
AOA CS 257.6, DU
BSB
etc. ,
(Fig. 5.23)
AOHA
" " "
1963 I Haas [307] RichAH S2 380 Al block Wratten 6199
Grating IP28
1963 Gilbert [341] Dilute OH Fig. 5.12
[349] S2 384, DU
etc.
(Fig. 5.22)
RichAH Fig. 5.15
" "
!
1965 Crider [458]
RichAH S2 375, Icf.Fig.5.11 B &L IP21
[459] etc. grating
S2 402 IF IP21
" "
[344] EMI
1965 Brody & Chaney
[345] RichAH I S2 394 Fig. 5.11 IF 9524B
S2 38O, DuMont
1966 Braman [265] AH Diffusion IF
etc. 6291
Bowman & EMI

1966 [377] RichAH S2 394 Melpar IF
Beroza 9524B
1967 Getz [379]

I " " " " "
1967 IBowman & [466]
Beroza
I " " " " I "
5.10] SULFUR 291
TABLE 5.xn (continued)
Solvent
or gas
Sample Detection
limit for S I Precision Linearity Interferences,
etc.
I I
S recognized by
H2 (GC) CS 2 blue·lavendar
color
H 2O H 2SO 4 70 ppm (l %)
I I I
MeOH H 2SO 4 25 [Lg/ml
I I I I
GC CS 2 LikeTC
I I
S02' Me2S0, I P emission is
Air, etc. thiophene <.01 [Lg/I lower
I I I
Linear to
MeOH,H 2O H 2SO 4 See above a =.4% 5000 [Lg/ml
I
H 2O H 2SO 4 500 ppm a <.4%
Air .03 [Lg/I Linear above

BU2S, S02 Little from P
I 1 [Lg/I
Linear at
N 2, Air I CS 2 I
(.2 [Lg/I) 0.5-2%
high concn.
Air CS 2 «.1 [Lg/I) <1% I Linear above I Very little

1 [Lg/l fromP
Air S02, H 2S .02 [Lg/l Nonlinear Separate H 2SO 4

<10%
I with filter
I (.02 [Lg/l)
I Me2S02, gasoline, .03 ng/sec; I
N2 (GC) Parathion, Mala- Few % Quadratic
thion I .01 [Lg/I
N2 (GC) I CS 2, Et 2 S ca .. 01 [Lg
I
Many
N 2 (GC) I Methiotepa in insects Noise

0.3na
Quadratic
10-500 ng*
I
I Pesticides in lettuce,
alfalfa, bees
I Few ng* Onions
1 ng*;
Mobil MC-A-600 in Quadratic to
grass and milk .01 ppm*
in sample
I 1000ng*
292 NONMETALS [5
1
TABLE S.XXII (continued)
Date Authors Ref. Flame Emission I Burner Disper-

sion Detector
~owman&
Beroza
[380] RichAH S2 394 Melpar IF
EMI
9524B
~r~m& Beroza
I
[467]
" " . . .
1967 Bowman &
Beroza
[381 ] . \
" I " " .
1967 IStevens [382]
" " " " "
7.5-cm EMI
NH,ArH S2 384, SP900A
Unicam 960lB
Dagnall, Thomp- etc.
1967 [47] (spectro-
son & West
gram) Shielded
AH propane " "
1967 Johnson [347] AH S2 FID IF PM

I
[389] EMI
1968 I Bowman
Beroza & RichAH S2 394 Melpar IF
[390]
I 9524B
1968 \ ough
Maiden, McDon- [468]
& Beroza " " " " "
1968 Bowman & [391]
Beroza " " I " I " "
[279] Modified
1968 Syty & Dean [280] RichAH S2 384 BSB DU IP28
[346] (see text)
Abbreviations: See Table S.xVII; also: AOHA = air-oxygen-hydrogen-acetylene; ArH = argon-

diluted hydrogen flame; B & L = Bausch & Lomb.
sulfur compounds in air. Their linear characteristics were discussed earlier. Buzza's burn-
er is probably capable of going below 0.01 fLg/l of sulfur in air. Crider's instrument [458,
459] was intended for monitoring the atmospheres of animal exposure chambers. It too
seems to be exceedingly sensitive, but Crider'S published data are hard to interpret (I have
not seen [459], however). His use of a glass-fiber filter to distinguish sulfur dioxide
from sulfuric acid mist is of special interest. Without the filter, the photometer responds
equally to sulfuric acid.
5.10] SULFUR 293
TABLE S.xXIl (continued)
Solvent Detection In terferences,

Sample Precision Linearity
or gas
I limit for S etc.
Thiophosphoryl
Quadratic
N2 (GC) NIA-I0272 in milk
lO-lOOng*
& silage I I
.OS ppm* Recovery
Imidan in milk
" in sample 95 %
20 pesticides in milk
" and silage
I
Pesticides in citrus
" oils
10 X P I a<4%
I
Quadratic
H 2O 1.6 ppm See text
3-300 ppm
S02, H 2S0 4 , sul-
fates, sulfites, H 2 S, I Quadratic
H 2O etc. 3 ppm I Anions; see text
6-500 ppm
I
He Pyrolyzed soil
I I I I
Pesticides, metabo-
N 2 (GC) lites; carbamate Few ng* Nonlinear
derivatives I I I I
I Temik & metabolites 2 ng*;
Linear None after
in fruit, beets, .01 ppm*
" 2-10 ng* cleanup
potatoes in sample I
Quadratic
"
I Many pesticides Few ng*
25-100 ng*
PIS response .05
I I
15 ppm [280]
H 2O Various Quadratic CoS bond
5 ppm [346]
* Weight or concentration of pesticide, not of elemental sulfur.
Two troublesome problems in atmosphere monitoring are sample feeding and calibra-
tion. At the very low concentrations that have to be handled, the analyte is readily ad-
sorbed upon and may be absorbed into any surface it meets before reaching the flame. The
air should reach the flame through an orifice that is as short, straight and wide as possible.
Crider used an upstream pump (between the air to be sampled and the burner), but the
analyte can be lost or delayed in such a pump. Faster and more reliable results are obtain-
ed with a downstream pump (suction feed). Buzza used a Venturi device beyond the flame
294 NONMETALS [5
TABLE 5.xXIII
ANALYTICAL PRECISION OF THE CS EMISSION
Repeated readings on the band at 2576 A emitted by the flame and burner of Table 5.xX with a
sulfuric acid solution in methanol containing 100 ILg/ml of sulfur, obtained with a Beckman DU
spectrophotometer with spectral energy recording attachment and strip-chart recorder. Slit
0.05 mm, time constant 0.8 s. Sample and blank readings were taken alternately.
Sample Blank Net Reading
36.2 35.0 1.2
36.5 35.1 1.4
36.5 35.0 1.5
37.0 35.4 1.6
36.4 34.8 1.6
36.7 35.3 1.4
36.6 35.0 1.6
37.0 35.6 1.4
Average: 36.61 35.15 1.46
Standard error: 0.28 0.26 0.14
and Gilbert [320] used a vacuum pump to create a large and stable pressure drop through
a capillary to suck the burned gases from the burner. The suction produced merely by the
burning jet of hydrogen may also be adequate in the absence of breezes.
For calibration of a monitor, various methods have been used. I prefer the method of
quantitatively diluting the saturated vapor of a suitable liquid sample of low volatility
with the incoming air [320]. A carrier gas passes slowly through a tube containing the
liquid. It emerges, saturated with vapor, through a needle placed close to the burner en-
trance, where it mixes with the air being drawn into the burner. By varying the flow and
with an assortment of liquids, a wide range of concentration can be covered. The method
is precise and quick. Recall also the method described in connection with Fig. 5.19.
Among other methods, gravimetrically calibrated permeation tubes inserted in a diluent
gas stream have been used by Stevens et al. [472] to calibrate a flame-photometric sulfur
detector for gas chromatography of sulfur dioxide, carbon disulfide, hydrogen sulfide
and methyl mercaptan.
Solution analysis for sulfur has been tried only by Gilbert [39], Dagnall, Thompson and
West [47], and Syty and Dean [280]. Various aspects of these studies have been described
above and under Phosphorus, and Table 5.xXII gives further details. Syty sprayed the
sample in a separate chamber, discarding 90% of the spray and conducting the rest to the
rich air-hydrogen flame, which was shielded by a glass chimney. She reported that each
sulfur compound gave a different response, that organic solvents did not significantly
strengthen the signal, and that thioacetamide and o-thiocresol gave no S2 emission. The
C-S bond is evidently too stable to be disrupted by the cool flame. This very stability, on
the other hand, permits use of the CS emission in the hotter, carbon-rich flame of Gilbert
[39]. The beneficial effect of methanol as solvent in this flame is shown in Table 5.xXI and
Fig. 5.24.
The study by Dagnall et at. [47] was much more thorough. Of the various flames that
they tried (described in Section 5.10.3 at the bottom of p. 282), the shielded air-hydrogen
flame, resembling Syty and Dean's, gave the best compromise between adequate decompo-
5.10] SULFUR 295
:: tOI_ _~~~QM
'"z
...!!:
III
III
~ 10
....or
III
D:
~LO----~---6~O----L----.~O----~---'O~07%~-J
CONCENTRATION OF METHANOL
Fig. 5.24. Effect of methanol concentration on emission of sulfur (CS 2576 A) and on background
in air-oxygen-acetylene flame. Reproduced from [39] by permission of Spartan Books.
sition of the sample (requiring heat) and adequate formation and excitation of S2 (inhib-
ited by heat). Even so, the relative responses (for equal sulfur concentrations) were as
follows: sulfur dioxide 100, sulfuric acid 4.5, ammonium sulfate 5, sodium sulfate 2.5,
potassium sulfate 2.5. The ratios were much more extreme in the diffusion flames (e.g.,
600:1 for sulfur dioxide and ammonium sulfate). The detection limit of 3 ppm given in
Table 5.xXII refers to sulfuric acid. For practical analysis, the authors recommended
converting sulfates to sulfuric acid by ion exchange. For concentrations above 100 ppm,
the nitrogen-hydrogen diffusion flame is sensitive enough for sulfuric acid and is easier to
use. No interference on the emission of sulfuric acid at 0.005 M in the shielded air-hydro-
gen flame was found with boric, acetic, oxalic, hydrobromic, nitric or phosphoric acid
at 0.05 M, or hydrochloric or perchloric acid or hydrogen peroxide up to 0.2 M. But
phosphoric, nitric and hydrobromic acids above 0.05 M depressed the emission and ace-
tic and oxalic acids above 0.05 M enhanced it, probably through physical effects (viscosity
and surface tension).
Indirect methods for sulfur as sulfate are reviewed in the references listed in Section
5.7.11. First utilized by Lundegardh [200 (Vol. I, p. 145; Vol. II, p. 66)], these methods
all depend on the reaction of sulfate with an alkaline-earth metal, usually barium but
sometimes strontium; strontium sulfate is less insoluble but strontium emits (and
absorbs) more strongly in the flame than barium. Of special interest are the methods of
Cullum and Thomas. They precipitated barium sulfate and suspended it in a starch
solution. The suspension was sprayed into a flame photometer for determination of the
barium [469]. Later they dissolved the barium sulfate in ammonium EDTA [470].
Among the more usual methods, in which the excess barium is determined by flame
emission after precipitation of sulfate, that of Alt [471] is the latest that I have noticed.
296 NONMETALS [5
The resonance lines of sulfur (1807, 1820, 1826 A) are of inconveniently short wavelength
and have not yet been observed in flames. However, certain sulfur-containing molecules
can be seen in absorption in flames. The only such observation reported for a practical
analytical apparatus is that of Rubeska and Moldan [473]. They used a 45-cm Fuwa tube
of alumina with an air-hydrogen sprayer-burner. Sulfuric acid showed the absorption
spectrum of S02, but no data were given.
The indirect methods mentioned above work equally well when the alkaline-earth metal
is determined by atomic absorption. Koirtyohann's review [8] mentions one or two such
applications. The paper by Christian and Feldman [9] describes several approaches to the
indirect determination of sulfate or sulfide by atomic absorption, but these have not yet
been tested in detail as analytical methods.
The electrodeless argon discharge of McCormack et al. [88] (see Section 5.4.7) emits the
bands of CS and PS. The CS band at 2576 A permits detecting as little as 1 ng/sec of sulfur
present as carbon disulfide. Bache and Lisk [408], using helium at 5-10 torr instead of
argon, detected sulfur at 0.05 ng/sec by its line at 5453.8 A. West [276] has discussed the
use of electrodeless discharges in helium or argon for the very sensitive determination of
sulfur in gas-chromatographic effluents.
5.11 Selenium
5.11.1 TIIE FLAME BAND SPECTRA
Selenium, of all the elements determinable by emission flame photometry, has been the
most neglected. Probably very few flame photometrists know anything about its band
spectrum. Only within the last few years has its line spectrum been seen in flames. Never,
except for the detection of selenium as a major constituent of minerals with the oxy-
hydrogen blowpipe by Hartley and Ramage [164], had anyone used the flame to do a
practical analysis for selenium - until the advent of atomic absorption. Remarkably high
sensitivity is now routinely achieved by atomic absorption, and atomic fluorescence bids
fair to rival it. In view of that, a discussion of the emission flame spectra of selenium might
seem an academic exercise.
The success of the chemiluminescent S2 emission, however, suggests that something
similar might turn up with selenium. If Se2 luminesces in hydrogen flames, the emission is
certainly dimmer than that of S2. The highest excitation observed with Se2 in flames cor-
responds to v' = 10, at 3.5 eV, where predissociation sets in. The H + Hand H + OH
recombination reactions are therefore too energetic to excite this molecule efficiently.
Conceivably some weaker flame reaction, yielding 3.5 eV or less, could make Se2 lumi-
nesce.
SeO, on the other hand, has the right excitation energy to chemiluminesce in a hydrogen
flame. Perhaps the right conditions are merely awaiting discovery. SeH is unknown, but
CSe is fairly stable and its excitation energy is about 0.5 eV below that of CS. Although no
5.11] SELENIUM 297
one has yet seen the CSe spectrum in a flame, quite possibly a rich, hot, carbonaceous
flame would be a good place to look for it.
The flame color of selenium is blue- a pure cornflower blue in the Bunsen flame, accord-
ing to Bunsen himself [277]. Scblagdenhauffen and Pagel [447] considered the sele-
nium color more violet than that of sulfur and they thought that, as with sulfur, a chilled
or separated hydrogen flame will burn blue with selenium. They ascribed the color of
burning hydrogen generated from zinc and sulfuric acid to selenium, not sulfur; and they
reported that if ferrous selenide is added to an iron-sulfuric acid hydrogen generator, the
liberated hydrogen selenide imparts an intense violet-blue color to the burning hydrogen.
But they offered no spectroscopic evidence. Sulfur too may show a beautiful violet color,
and sulfur must have been present in their experiments. It would have needed very little
sulfur to account for the color.
Lenard in 1902 [474] placed selenium in a Bunsen flame and observed a streak of color,
which could be deflected by an electric field. Papish [461] passed selenium dioxide vapor
into a Bunsen flame and observed an intense blue color. Cold porcelain held in the flame
became coated with red selenium. Geilmann and Bode [141], in studying the Turner
test (see Section 5.3.5), noted that selenium colors the flame blue under the test conditions.
Selenium itself bums with a blue flame. When warmed in ozone, it gives a weak glow,
according to Strutt [475], but he obtained no spectrogram.
Observations on the flame spectrum of selenium go back over a century. Bottger [24,
476] in 1860 saw a series of many evenly spaced "dark lines," from the extreme violet to
the yellow, when selenium was placed in the edge of a Bunsen flame. Simmler [28], how-
ever, saw only a blue continuum with selenium or its dioxide. Werther [477] observed
many uniformly spaced "lines" in the green and blue, on a strong continuum.
Mulder [331,332] also commented on the continuum and on the even spacing of the
"countless lines" in the green and blue (weaker in the violet). He obtained the spectrum
by heating selenium in a current of hydrogen and burning the gas; the core of the flame
was greenish-blue, unlike the blue core produced by sulfur. Mitscherlich [21] in the same
year, 1864, obtained the selenium spectrum in the same way. Selenium dioxide and selenic
acid gave the same spectrum. His data and those of Salet and Hartley will be considered
below, in connection with Se2.
The absorption flame spectrum was observed by Lockyer and Roberts [478] in 1875.
They placed selenium in a lime tube, directed a rich oxyhydrogen flame upon the sample
so as to fill the tube with (reducing) flame and vapor, and, with expendable glass plates
to close the ends of the tube, passed the light of an arc lamp through it. Selenium gave a
channeled spectrum, but no data were published.
There are a few negative reports. Lundegardh [200 (Vol. I, p. 68)] sprayed selenium
at 8000 ppm into his air-acetylene flame but found no emission. Gilbert in 1948 [108,
203] sprayed selenium at 10,000 ppm through a heated spray chamber into an air-oxygen-
natural gas flame but found only a very weak, continuous ultraviolet emission. Syty [279]
found no useful selenium emission (2200-4000 A) in the rich, shielded air-hydrogen flame
that proved useful for sulfur and phosphorus [280]. Claus [479] could not detect the CSe
bands in an air-hydrogen sprayer-burner flame with ethanol as solvent.
5.11.2 TIlE' SPECTRUM OF SELENIUM MONOXIDE
On surveying the published work on the flame spectrum of selenium, I felt at first that it
298 NONMETALS [5
was hopeless to correlate the data. But when it is reviewed alongside the data on discharge
and absorption spectra, it begins to fall into a pattern. Whenever a flame is charged with
a very high concentration of selenium, as by placing the element directly in it - or when
selenium burns -, a complex, confusing spectrum of many bands appears in the blue and
green, probably due mainly to Se2. But at lower concentration, selenium in certain flames
emits a spectrum of sharp, well-spaced, red-degraded, double-headed bands in the near
ultraviolet, and the visible bands are weak or absent. The ultraviolet bands are ascribed to
SeQ. Although the Se2 spectrum takes historical precedence, the SeQ spectrum is neater
and easier to cope with, and will be taken up first.
The only spectrophotometric recording of the SeQ spectrum that I have seen is the one
presented here as Fig. 5.25. This was obtained in 1965 by Richard W. Claus [479]. The
air-hydrogen flame with aqueous solution seems to favor this spectrum. The continuum
radiance J c of the selenium (cf. Table 5.11) is 5 x 1O-13w/cm2.sr.nm.ppm at 340-380 nm,
falling to 3 x 10- 13 at 400 nm; the net radiance J a of the unresolved band is 4x 10- 13
w/cm 2.sr.nm.ppm at 370 and 381 nm, and 3 x 10- 13 at 358 and 394 nm. The flame back-
ground (blank) radiance J b is 5 X 10- 10 w/cm 2.sr.nm at 360-400 nm. The detection limit
based on the net band height above the continuum is about 13 ppm. The analytical
curve for SeQ is linear between 100 and 5000 ppm.
~ ;
~
m
~ 0
0",
'0"
:g
~
.
~
, , I , ! , , , t, t •, , ! !, ! , ! , ! , !, !
340 350 360 370 380 390 400 420 440 460 480 !500
Fig. 5.25. Band spectrum of selenium in air-hydrogen flame.

Selenium 5000 ppm in aqueous 0.5% nitric acid. Beckman DU with sprayer-burner and IP28;
slit 0.05 mm. Recordings by R. W. Claus [479].
The wavelengths of the SeQ spectrum are summarized in Table 5.xXIV. I have listed
only wavelengths above 3100 A, since no bands of shorter wavelength ascribed to SeQ
have yet been seen in flames. Asundi, Jan-Khan and Samuel [480,481] were the first to
describe the spectrum. After trying various other means of exciting it, they sprayed aqueous
5.11] SELENIUM 299
selenious acid into a Bunsen flame and obtained bands in the region 3200-4500 A. Of
these, the ultraviolet bands were due to SeO; a vibrational analysis was worked out.
In an oxygen-coal gas flame, some weak red-degraded bands of shorter wavelength also
appeared. Calculated from the wavenumbers, the wavelengths in air are: 2501.0,2531.0,
2558.4, 2591.6, 2615.1, 2653.1, 2683.6, 2718.3. 2795.2, 2944.8. No one else has observed
these bands. The authors ascribed them to Se02, of which they listed the absorption
spectrum. They stated that the above flame bands are "identical" with Se02 bands, but
inspection of their tables shows that the match is very bad, even if errors of 10-15 cm- 1
are allowed. Neither do the bands match Choong's absorption or emission wavelengths
for Se02. In my opinion, the selenium flame bands at 2500-3000 A have not been identified.
The most comprehensive work is that of Choong [482]. He used no flames, but his
wavelength tables are indispensable. See the notes to Table 5.xXIV for details. The in-
tensities were visual estimates from the photographic spectrograms. Choong believed that
several of the bands in this wavelength region, and most of those at shorter wavelengths,
are due to Se02. Above 3100 A, he listed 3150.0,3156.1 and 3156.7 (all intensity 4), and
3165.6 and 3210.4 (weak) as due to Se02, and 3331.0 and 3336.4 (weak) as possibly due
to Se02. The last two seem to be present in Fig. 5.25.
Davis [483] studied the emission spectrum of SeO using separated isotopes, but his
work was never published. Barrow and Deutsch [484,485] published a rotational analysis
and measured isotope shifts (see the notes to Table 5.xXIV). The wavelengths calculated
from their vacuum wavenumbers agree well with Choong's except for the 2.5 A and the
0,9 A bands. The latter seems quite strange; Choong himself was puzzled by it. The earlier
band-head wavelengths of Asundi et aI., in the last column of the table, run a little high,
since their resolution was inferior. Allowing for that, however, their value for the 0.9 A
band supports Barrow and Deutsch's value rather than Choong's.
5.11.3 THE SPEcmUM OF MOLECULAR SELENIUM, Se2
Five systems are listed for Se2 by Barrow in Rosen's compendium [79 (p. 269)], but Pearse
and Gaydon [78] accept only two. The "main" system extends down to 3200 A in absorp-
tion, but in emission the bands lie between 3700 and 5800 A. (In the list of Asundi and
Parti's wavelengths in [78], 4596.3 should be 4586.3.)
From 3700 to 4100 A the spectrum consists of closely packed but distinct, red-degraded
bands. This part of the spectrum is presented in Table 5.XXV. Most of the wavelengths are
reliably established. Messerschmitt's Geissler-tube wavelengths of over 60 years ago
[487] agree satisfactorily with Nevin's absorption data [490]. The bands observed in flames
by Messerschmitt and later by Miyanisi [462] are mostly identifiable, but Miyanisi's
3988.8 and 4026.9 are rather far from the nearest wavelengths in other columns of the
table. I have not had access to his paper and cannot list all his wavelengths. His 4049.0
agrees with a discharge band given by Asundi and Parti [491] but may not be the same as
Nevin's 4052.2. These discrepancies may be due to the fact, mentioned by Messerschmitt,
that the bands are less distinct in the flame than in the discharge, and lie upon a continuum.
Even Hartley's old data on the flame spectrum of selenium [354, 364] - he was the first to
observe it in the ultraviolet - agree well enough with modem wavelengths. The exact
identity of some of his bands, in view of the complexity of the spectrum, may be in doubt.
Note that although the Sez spectrum overlaps the SeO spectrum, the flames of
Table 5.XXV do not emit the SeO bands.
300 NONMETALS [5
TABLE 5XXIV
NEAR-ULTRAVIOLET SPECTRUM OF SeO
v" a I Choong [482] Barrow [485] Asundi [481]

I
V'
Discharge b Int.
Discharge C Flame d
I !
1 3 B 3133.1 2
1 3 A 3139.8 5
2 4 B 3170.2 3
2 4 A 3175.5 3
0 3 B 3184.2 1
0 3 A 3191.9 2
1 4 B 3222.0 5
1 4 A 3229.0 6 3231
2 5 B 3260.0 1 (3260.1) I
2 5 A 3265.1 1 (3267.3)
0 4 B 3275.7 2
0 4 A 3283.9 4 3285
1 5 B 3314.7 5 (3314.9) 3317
1 5 A 3322.2 5 (3322.6) 3324
0 5 B 3372.1 5 3372.4
0 5 A 3380.5 6 3380.8 3382
1 6 B 3412.1 2 3412.2 3415
1 6 A 3420.2 4 3420.5 3421
0 6 B 3473.1 6 3473.2 3476
0 6 A 3481.8 9 3482.2 3484
1 7 B 3514.4 e 3514.4
1 7 A 3523.1 2 3523.2
0 7 B 3578.9 f 7 3579.1 3582
0 7 A 3588.3 9 (3588.7) 3590
1 8 B (3621.6)
1 8 A 3630.7 1 (3631.1)
2 9 B 3665.0
2 9 A (3674.4)
0 8 B 3690.2 a 7 3690.4
0 8 A 3700.3 9 3700.7 J 3701
1 9 B (3734.4)
1 9 A (3744.5)
2 10 B 3779.2
2 10 A (3789.1)
0 9 B 3807.3 8 3807.5 k
0 9 A 3815.6 h 10 (3818.6) k 3821
0 10 B 3930.7 8 (3930.9)
0 10 A 3942.9 10 (3942.7) 3945
.) Adjusted according to Barrow and Deutsch [485]. The A and B subsystems, so called by
Choong [482], are called F z and FI by Barrow and Deutsch. Pearse and Gaydon [78] think
they may be the Rand Q heads of the same band.
b) Geissler discharge in selenium dioxide. Wavelengths and intensities are Choong's data from
5.11] SELENIUM 301
TABLE 5.xXIV (continued)

his grating spectrogram, accurate within 0.1 A. His wavelengths obtained with a quartz
prism agree within a few tenths of an angstrom. Only bands above 3100 A are listed in this
table.
C) Electrodeless radiofrequency discharge in oxygen passed over hot selenium. Wavelengths are
calculated from Barrow and Deutsch's listed vacuum wavenumbers for the band origin of
the 80SeO isotope.
d) Selenium dioxide solution sprayed into oxygen-coal gas flame. Wavelengths calculated from
the listed vacuum wavenumbers, stated by the authors to be accurate only to 1 A.
e) From quartz prism spectrogram; not measured with grating.
f) For the 80SeO isotope. Choong listed also 3577.6, intensity 1, and 3580.6, intensity 4, ascribed
tentatively to 82SeO and 78SeO, respectively. From Barrow and Deutsch, 3580.8 is calculated
for 78SeO.
K) For 80SeO. Choong listed also 3688.6, intensity 2, and 3691.8, intensity 4, ascribed tentatively
to 82SeO and 78SeO. From Barrow and Deutsch, 3692.4 is calculated for 78SeO.
h) Choong marked this with a ?; it seems too low. The quartz prism gave 3816.6, which still
seems too low. Barrow and Deutsch's value is probably better.
i) Wavelengths in parentheses are calculated from wavenumbers deduced by combining wave-
numbers listed by Barrow and Deutsch, or, in a few cases, estimated by close analogy.
J) For 78SeO, 3702.8 is calculated from Barrow and Deutsch's data.
k) For 78SeO, 3809.8 and 3820.9 are calculated from their data.
Reference should be made also to Rosen's paper [492]. He remeasured the spectrum
of Se2 from an electrode1ess discharge and stated that the wavelengths agreed completely
with Nevin's, but he did not list them. He said that the Se2 emission spectrum in every
source is accompanied by a continuum from 3700 A through much of the visible. He
studied the isotope shift and interpreted all available data on the Se2 spectrum in great
detail. Some additional, later references on Se2 are given in Rosen's book [79].
5.11.4 THE VISIBLE FLAME SPECTRUM
Above 4100 A the flame spectrum of selenium gets more confused. The various listings
for flames, discharges and absorption correlate poorly. The bands are so numerous that
in parts of the visible almost any spectrum can be more or less matched to any other, if a
few angstroms of leeway are admitted. The visible flame bands may be due to Se2 and
Se02 but identifications are not yet definite. Table 5.xXVI summarizes these bands. It
overlaps Table 5.XXV, to accommodate the violet ends of the spectra of Eder and Valenta
[104] and Emeleus and Riley [489]. Only flame spectra are included. The discharge and
absorption spectra, with their scores of ill-matching wavelengths, shed little light upon
the nature of the flame spectrum above 4100 A.
The diffusion flame of hydrogen, of special interest because of its performance with
sulfur and phosphorus, is not represented in Table 5.XXVI. Of real value, therefore, is
Mitscherlich's 104-year-old drawing of the spectrum of selenium in this flame [21]. We
wish to know whether it matches the spectra in the hotter flames of Table 5.XXVI.
302 NONMETALS [5
TABLE 5.XXV
SPECTRUM OF Se2, 3700---4100 A
Hartley Messerschmitt Miyanisi Asundi, Parti Nevin Vibrational

[354] [487] b [462] [491 ] [490] levels f
Flame a Fl. Dis. Flame C Disch. d Absorp. e v' v"
3707 3707.3 4 3706.4 3707.7 4 10 4

3718.2 2 8 3
3728.0 2
3735 3733.3 2 6 2
3740.3 2 3739.5 4 9 4
3749 3751.9 3
3760.7 2 6 3760.1 3760.5 4 10 5
3772.5 1 2 3771.9 2 8 4
3782.0 2
3796 3794.2 3 5 3793.4 3794.2 4 9 5
3807.5 3 3806.2 2 7 4
3815.5 4 7 3815.3 3815.5 3 3815.4 4 10 6
3827 3828.1 4 6 3828.1 2 3828.4 2 8 5
3838.5 1
3843.1 2 3843.0 2 6 4
3851 3850.1 5 7 3849.8 3849.9 5 3849.9 3 9 6
3863.1 2 7 5
3871.7 5 3871.4 3872.0 2 3871.2 3 10 7
3879.7 2 5 4
3883 3885.0 6 7 3885.9 4 3885.0 4 8 6
3900.3 3 4 3900.4 2 6 5
3907.2 4 6 3906.6 3907.2 6 3906.9 4 9 7
3921.5 • 3920.6 5 7 3921.3 3d 3920.3 4 7 6
3929.1 3930.3 1 10 8
3938.6 2 3938.5 2 5 5
3941.5 3943.1 6 7 3943.5 7 3942.9 4 8 7
3953.7 2 3953.5 3
3959.3 4 5 3959.8 1 3959.3 b 3 6 6
3976.5
3965.9
3976.2 2
4 3965.7 3965.8 3 9 I 8
3980.4 6 8 3980.7 8 3980.1 3 7 7
3988.8 3991.1 2 10 9
3998.2 2 3998.6 1 5 6
4002.0 6 5 4002.9 5d 4002.7 1 8 8
4014.1 3 4 4014.8 2 4013.8 1 11 10
4020.3 6 6 4019.8 2 4019.9 1 6 7
4026.9 4024.6 1 9 9
4032.9 2d 12 11
4041 4041.3 7 7 4041.7 4 4041.0 1 7 8
4049.0 4049.0 3 4052.2 1 10 10
4060.2 2
4064.4 5 4064.4 2 4064.0 1 8 9
4074.7 3 4074.4 1
4082.4 7 4082.9 2 4082.3 1 6 8
4089.2 4088.3 2 9 10
4093 i 4093.6 2 4093.1 1 12 12
4104.5 5 4103.9 4 4102.6 1 7 9
a) Solid selenium placed in oxyhydrogen flame. Short-wavelength edges of the bands.
b) Intensities for selenium in a blowtorch (Fl.) and Geissler tube (Dis.). From Kayser [16].
C) Oxyhydrogen flame. Data from Rosen [79] and Pearse and Gaydon [78], listing strongest
heads only.
5.11] SELENIUM 303
TABLE 5.xXV (continued)

d) Discharge through selenium vapor in argon. Wavelengths claimed accurate to 0.2 A (0.5 A
for diffuse bands); d = diffuse.
e) Absorption spectrum of selenium vapor.
f) From Nevin and Asundi and Parti.
I) Not consistent with Hartley's micrometer measurement; if the latter is right, the wavelength
is closer to 3920.
b) Misprinted as 3953.9 in Rosen [79 (p. 269)].
i) Not consistent with Hartley's micrometer measurement. Either the wavelength should be
4091 or the micrometer should be 92.89 instead of 92.99. But 4091 would agree better with
Miyanisi's 4089 and with Asundi's 9, 10 band, which is more likely in a flame than the 12, 12
band.
Mitscherlich's paper seems to be the only one bearing on this question. Now, he worked
before the days of Angstrom. But his spectra can be calibrated by the Fraunhofer lines
marked on them and by the known flame lines. Unfortunately the calibration graph comes
out a bit lumpy, so that the wavelengths are uncertain by about 5 A in the blue and 10 A
in the green. In the selenium drawing, the pencil work looks very careful. But the spectrum
was complex, diffuse, and obscured by a continuum. Twenty bands can be made out between
409 and 586 nm; the continuum fades out near 670 nm. These bands come close enough,
in spacing and wavelength, to those listed in Table 5.xXVI to convince me that the cool
hydrogen flame emits essentially the same selenium spectrum as the hotter flames. Eme-
leus and Riley [489] produced the spectrum in the same way and reported an intense
blue color with visible bands, but did not separately list the wavelengths.
Salet [17, 444] reported only the spectrum of burning selenium. It seems to be the
same as the other visible flame spectra. He did not list the bands between 410 and 461 nm,
which were numerous and indistinct. Formanek in 1905 [337] listed the flame bands of
selenium and said that they appeared in a chilled hydrogen flame; but I have not seen this
book lately and cannot criticize the wavelengths.
Messerschmitt's discharge wavelengths [487] agree with Nevin's absorption spectrum
[490] only up to 4082 A. Beyond that, Messerschmitt listed 150 bands out to 5880 A that
hardly match the selenium bands observed by others. Of these, only the trio near 4700
was reported by him in the flame. Asundi and Parti [491] also listed 150 bands between
4100 and 5880 A in their discharge, but I cannot reconcile them with Messerschmitt's.
Eder and Valenta's data [104] can be compared with their photographic spectrogram of
selenium in the oxygen-gas flame and with Fig. 5.25. Their flame clearly did not emit the
SeQ bands.Their spectrum fades out with the band at 3940, which is certainly not the
(double) SeO band of nearly the same wavelength. There are numerous diffuse bands
in the violet, not separately listed. But the strong head at 4080 A stands out. Such a
head appears also in Fig. 5.25. I would have ascribed it to SeO, but since Eder and
Valenta's spectrogram shows it and yet lacks the 3931-3943 SeQ band, and especially
since it is not listed in any of the other six flame spectra of Table 5.xXVI, the origin of the
4080 band remains doubtful. The rest of Eder and Valenta's spectrogram is not inconsis-
tent with Fig. 5.25. However, except for the rather sharp band near 4230, the bumps in
the blue region of Fig. 5.25 cannot be adequately matched with listed wavelengths. The
spectrum is altogether too vague.
304 NONMETALS [5
TABLE 5.XXVI
THE VISIBLE FLAME BANDS OF SELENIUM
Salet Hartley Messerschmitt Eder & V. Emeleus & Riley Miyanisi

[444] a [354] b [487] C [104] d [489] e [462] r
3941.5 3943.1 6 3940 w

3959.3 4 3965 3965.7
3976.5 3980.4 6 3988.8
4002.0 6 4000 p 4000
4014.1 3
4020.3 6 4030 4030 4026.9
4041 4041.3 7 4038 w, d 4060 4060 4049.0
4080 s
4093 g 4093 w 4089.2
4100 h 4100 mw 4100 4095 q
4124 4124 m 4130 4125 4112.4
4134 m
4151 w, d 4153.4
4170.5 4170 w, d 4165 4160 4177.0
4200 r 4190
4222 4223 m 4240 4225 4217.3
4270 4260
4299 4310 4295
4339 4340
4375
4400 I 4407.5 4410 } 4405
4420 m,d
4450 m,d 4435
4491.5 to 4493 m
4569.5 j 4550 d
4570 d
4610 4599 to 4618 mw 4600 s (4600) n
4643
4670 4676 to 4683.7 5 4685 (4685)
4720 4689.2 5
4750 4746 to 4713.3 5 4700 w k 4750 (4750)
4804
4840 m 4816to 4850 (4850)
4890
4950 4930 (4930)
5050 5025 (5025)
5160 5140 t (5140)
5270 5245 (5245)
5370 5370 (5370)
5410
5500 5530
5650 5620
Notes: Horizontal alignment of wavelengths in different columns does not necessarily mean that I
believe these to represent the same band.
a) Selenium burning in air. Band centers. Wavelengths precise only to 10 A.
b) Selenium in oxyhydrogen. Violet band edges. Cf. overlapping portion of Table 5.XXV.
C) Band heads in blowtorch flame, from Kayser [16]; cf. Table 5.XXV.
5.11] SELENIUM 305
TABLE 5.xXVI (continued)

d) Selenium in oxygen-gas flame. Band heads or violet edges. Intensities are my estimates from
the spectrogram, above the continuum; w = weak, m = medium, s = strong, d = diffuse.
e) Left-hand column: flame of alcohol burning in selenium dioxide vapor; right-hand column:
selenium burning in oxygen. Wavelengths precise only to 5 A; violet edges or heads.
f) Oxyhydrogen; from [78] and [79], listing strongest heads; cf. Table 5.XXV.
I) See Note I), Table 5.XXV.
h) This is the last of a series of indistinct bands occupying the blue below 4610 A.
I) Listed by Salet for the Geissler discharge.
J) In this and the next 4 bands, the violet edge is the stronger, the red edge the weaker.
k) This is the last band visible on the spectrogram; both the continuum (strong through the blue)
and the bands fade out towards longer wavelengths, partly owing to loss of plate sensitivity.
m) Salet listed this and the following bands also in the Geissler spectrum.
n) Wavelengths in parentheses were stated to be the same as in the alcohol-Se02 spectrum (pre-
ceding column) but were not separately measured.
P) From 4000 to 4435, heads of relatively sharp bands. In addition, a series of closely spaced,
very diffuse bands appear at 3800-4100, weaker down to 3600. Much continuum in blue and
green.
q) Up to 4295, these bands are sharper and brighter than those in the alcohol-Se02 flame, and
not identical in wavelength.
r) The continuum (strongest at 4400-4600) almost obscures these bands up to 4435.
8) This and the following bands are broad; violet edges are given.
t) This and the remaining bands are very diffuse, 50-70 A wide; violet edges.
TABLE 5.XXVII
RADIANCES AND DETECTION LIMITS FOR THE 2040-A SELENIUM LINE IN
VARIOUS FLAMES AND SOLVENTS
J a and J b as in Table 5.IX. Beckman sprayer-burner. Data calculated from observations by
Claus [479].
tLg/ml Se Detection
Flame Solvent employed
Jax 1011 Jbx 108 limit, tLg/ml
Air-hydrogen Water 5000 0.0004 0.022 (4000)

Air-hydrogen 80% Ethanol 1000 0.4 0.35 (30)
Air-hydrogen Ethanol 10-100 1.0 0.23 4.7
Air-hydrogen Ethanol e 10-100 1.0 0.37 6
Oxyhydrogen Water 5000 Invisible
Normal
oxyacetylene Water 5000 Invisible
Rich oxy-
acetylene a Water 100 1.3 6 23
Rich oxy-
acetylene a Ethanol 10-100 7 25
Rich oxy-
acetylene b Ethanol 10 9 6 3.7
8) Very large, incandescent flame.

b) Slightly less rich.
e) Later set of observations.
306 NONMETALS [5
Next we have Emeleus and Riley's comparison [489] of the flame of methanol (and
other organic compounds) burning in selenium dioxide vapor with the flame of selenium
in oxygen; see the notes in Table 5.xXVI. Their spectra showed three regions: closely
spaced, diffuse bands below 4100 A; sharper, red-degraded bands up to 4450 A; broad
bands from 4600 to 5620 A. The continuum was strongest at 4400-4600 A. The middle
group of bands was sharper, brighter, and of shorter wavelength in the selenium-oxygen
flame than in the Se02 flame. The authors thought that the bands of the third region were
due to Se2 and those of the second to Se02, but they were uncertain. For comparison, they
listed the absorption spectrum (3930-4470 A) of selenium dioxide vapor at 3500 measured
by Evans and Antonoff [488] in 1911 ; it agrees pretty well with the flame bands.
In summary, the visible spectra of selenium emitted by the various flames that have
been studied (hydrogen diffusion, air-hydrogen, oxyhydrogen, air-gas, oxygen-gas, air-
selenium, oxygen-selenium, and selenium dioxide-alcohol) are all ill-defined but similar
in general character and distribution of bands. However, there seem to be some verifiable
differences of detail. It is likely that more than one emitting molecule is at work, and
that the relative excitation of these emitters varies with the flame. More work is needed to
characterize these spectra. Besides, a search might show how to enhance one of them to
the point of analytical utility.
The resonance triplet of selenium is 1960.26 (air), 2039.85 and 2062.79 A. Thermal energy
alone would hardly excite these lines usefully in ordinary flames. But chemiluminescent
flames should excite them [39]. Earlier work on anomalous line-reversal in flames, re-
viewed by Bulewicz and Padley [35], mentions selenium only to the extent of pointing out
that it shows no overionization in a rich nitrogen-diluted oxyacetylene flame, which over-
ionizes elements of intermediate ionization potentials. The expected overexcitation of the
2040-A line has now, however, been observed by R. W. Claus [67,479] and by Skogerboe,
Heybey and Morrison [286]. This is the shortest-wavelength line yet found useful in
emission flame spectrophotometry. For the experimental conditions of Skogerboe et ai.,
see Table 5.xIX and the text accompanying it. They reported a detection limit of 3 fLg/ml
in ethanol solution pumped at 2.7 ml/min into the normal oxyhydrogen sprayer-burner
flame.
Claus's work on the 2040-A selenium line was more detailed. Two of his recordings are
shown in Fig. 5.26. The scans stopped just short of the 2063-A line. Radiances in various
sprayer-burner flames are listed in Table 5.xXVII, calculated from Claus's data. The de-
tection limits, calculated for a DU spectrophotometer, are the concentrations giving a net
response equal to 1 % of the background at the optimal slit width. The analytical curve
in rich oxyacetylene with water has a logarithmic slope of 0.8 between 100 and 5000 ppm
(the only two concentrations tested). In air-hydrogen with alcohol the curve is linear up to
100 fLg/ml; between 100 fLg/ml (in 98% alcohol) and 1000 fLg/ml (in 80% alcohol) the
logarithmic slope is 0.7: it would be higher for constant alcohol concentration. Self-ab-
sorption in these flames is evidently not severe. The line is obviously greatly overexcited in
the presence of either alcohol or excess acetylene.
As for detection limits, they are much alike for ethanol solutions in air-hydrogen and
oxyacetylene (Claus) and oxyhydrogen (Skogerboe). Although one or two orders of mag-
nitude poorer than those attainable by atomic absorption, these detection limits (3 to
5.11] SELENIUM 307
CD
(1)
rri o
oc
..
2
II)
·0
ID~
0"
NE
OD
UU
..,
ID
'<i
o
N
oU
Zero
I i
205 206
Fig. 5.26. The selenium line in the air-hydrogen flame.

Beckman DU with 1P28 and sprayer-burner. Upper spectrum: Se 100 ILg/ml in 98% ethanol;
slit 0.5 mm; blank tracing superposed. Lower spectrum: Se 1000 ILg/ml in 80% ethanol; slit
0.1 mm. Same gain and same zero for both spectra. Reproduced from recordings by R. W.
Claus [479].
5 (Jog/mI) may be good enough for some applications. The selenium line is highly specific.
No spectral interferences are likely.
5.11.6 INDIRECI' FLAME EMISSION
There are several papers by Malinowski and coworkers, listed in [3] and [7], which
propose the determination of selenite, among other anions, by its quenching effect on the
emission of calcium or strontium in the flame. The method does not seem to have been
put to practical use.
308 NONMETALS [5
Selenium can now be routinely determined at trace concentrations by atomic absorption.

The true resonance line, 1961 A, is the most strongly absorbed. However, the lower states
ofthe other two members of the triplet, 2040 and 2063 A, lie at 0.25 and 0.31 eV, respec-
tively, and these states are appreciably populated in flames. The intercombination lines at
2075 and 2164 A are too weakly absorbed to be useful [493]. The main problems in the
use of the 1961-A line, as with arsenic, are flame transparency and source intensity.
The first to attain a really high detection sensitivity for selenium was Allan [41]. He
reported a limit of 0.015 ppm at 1961 A with a sprayer-burner air-hydrogen flame in a
long-path Fuwa tube. With such sensitivity he could determine selenium in soil. This is an
important application, because the gap is not wide between a toxic excess of selenium and
a harmful lack. Rann and Hambly [493,494] made a comprehensive study of the atomic
absorption spectroscopy of selenium. The sensitivity was 1 ppm at 1961 A in air-acetylene
or air-propane, the latter with a silica T-tube over the flame to raise the path length. They
determined selenium in wheat and galena with excellent precision [493].
In the Beckman atomic absorption spectrophotometer with the Hell burner, the detec-
tion limit for selenium has been reported as 0.2 ppm in air-acetylene [242, 495]. In the
Perkin-Elmer instrument, highly transparent flames have recently been used for the short-
est wavelengths [43]. With the argon-diluted hydrogen diffusion flame, less than 0.1 ppm
of selenium can be detected, Addition of oxygen raises this limit. The sensitivity is consid-
ered anomalously high. A limit of 0.1 ppm was reported also by Dagnall et al. [44] with
a nitrogen-diluted hydrogen diffusion flame and a microwave-excited electrodeless dis-
charge lamp (see Section 5.8.6). Kahn [496] has described a method of compensating back-
ground absorption at short wavelengths by means of a deuterium lamp, useful for sele-
nium. With Peterson and Schallis [424], he applied the "sampling boat" (see Section 5.8.6)
to selenium, attaining the remarkable detection limit of 0.01 ppm in a 1-ml sample.
5.11.8 ATOMIC FLUORESCENCE SPECTROSCOPY
With their electrodeless lamps, Dagnall, Thompson and West [497, 498] achieved a
detection limit of 0.25 ppm for selenium by atomic fluorescence at 2040 A in an air-pro-
pane flame. The 1961-A line gave a limit of 0.15 ppm, but the 2040-A line was considered
more practical. The analytical curve was linear up to 125 ppm. There were no interferences
from 100-fold excesses of many cations. The same flame, source and spectrophotometer
(a Unicam SP900A), operating by atomic absorption, yielded a detection limit of 1 ppm.
Employing electrodeless lamps of their own design, Zacha, Bratzel, Winefordner and
Mansfield [499] have reported a detection limit of 0.4 ppm for selenium in fluorescence
at 1961 A in the argon-hydrogen flame on a Zeiss sprayer-burner.
5.12 Tellurium
5.12.1 THE FLAME BAND SPECTRUM
The band spectra of tellurium that have been reported in flames are more consistent than
5.12] TELLURIUM 309
those of selenium. They all seem to be the same spectrum - that of TeO. Of the known
molecular spectra involving tellurium, only those of Te2 and TeO have been seen in
emission sources. TeH and eTe are unknown. I have found no evidence that Te2 occurs
in flames, although it would be expected there. Thus TeO is the only tellurium-containing
molecule known to have a flame spectrum.
Among qualitative observations, Simmler's was the first [28]. He reported that tellu-
rium or its dioxide on a platinum loop held in the Bunsen flame yields a blue-green color
showing only a continuous spectrum. Werther [477] also saw the continuum, with faint
traces of bands; impure tellurium showed only the flame spectra of thallium and lead.
Bunsen [277 (p. 274)] said that tellurium colors the inner cone of the flame pale blue and
the mantle green. Lenard [474] studied the effect of an electric field on the streak of color
imparted to a Bunsen flame by tellurium. Papish [461] passed tellurium dioxide vapor into
a Bunsen burner; the flame was slightly greenish blue, green at the tip, and it precipitated
a mirror of tellurium on porcelain. Partington [182 (p. 532)] mentioned that tellurium
bums with a blue flame.
Hartley and Ramage [164] seem to have been the only early workers to use the flame
for detecting tellurium. They identified it in minerals, but only as a major constituent.
Lundegardh [200 (Vol. I, p. 68)] could not detect tellurium at 1.3 % in water sprayed into
his air-acetylene flame. Syty [279] found no useful ultraviolet emission from tellurium
in a chilled, rich hydrogen flame, a rather surprising result in view of the observations of
Mitscherlich and Salet discussed below.
Spectroscopic data on the tellurium bands of interest for flame photometry are collected
in Tables 5.XXVIII, 5.XXIX and 5.XXX. These should be compared with Fig. 5.27,
which is the best available spectrophotometric recording of the flame bands, although the
resolution is only moderate. As with selenium, the red-degraded bands of TeO are clear-
est in the near ultraviolet. They continue through the visible into the orange, becoming
more confused. The bands are always accompanied by a relatively strong continuum, well
shown in Fig. 5.27.
;
~
~
N +
:;;
.+
N.
m ~ ~ ~
:':
~ ~
m
~
+
*
:':
Fig. 5.27. Spectrogram of tellurium in air-hydrogen flame.

Tellurium 4000 ppm in dilute aqueous nitric acid. Beckman DU with sprayer-burner and IP28;
slit 0.05 rnrn. Mercury lines are due to room light. All wavelengths marked on upper spectrogram
are TeO band heads. Wavelength scale is zero-intensity line, as in all preceding spectrograms.
310 NONMETALS [5
TABLE 5.XXVIII
ULTRAVIOLET SPECTRUM OF TeO
Choong b Migeotte C Purbrick d Haranath C
[482] [500] [501] [502]
Sys. v' Vi' a Disch. I Int. Disch. Disch. Int. Arc Int.
B 6 0 3194.2 2
B 5 0 3226.3 2 3226.3 0
B 4 0 3259.1 3 3259.1 0
B 6 1 3276.8 0
B 3 0 3294.7 3 3293.8 0 3294.7 1
B 5 1 3310.5 2 3310.5 1
B 2 0 3332.2 2 3331.5 0 3332.2 1
B 4 1 3345.6 6 3344.4 5 3345.6 1
B 1 0 3371.9 0 3370.0 4 3371.9 J 1
B 3 1 3382.9 6 3382.0 3382.6 5 3382.9 1
B 7 3 3405.0
B 0 0 3414.2 00 3412.3 2
B 2 1 3422.2 7 3422.2 3422.5 6 3422.3 1
B 1 1 3463.8 7 3464.3 3463.6 7 3464.0 II 2
B 3 2 3473.6
B 5 3 3490.0
B 0 1 3507.5 5 3509.0 3507.6 7 3508.0 2
B
A
B
2
2
4
2
0
3
} 3517.2 6 3516.3
3529.4
3516.9 8 3516.4 2
B 1 2 3560.6 8 3561.5 3560.3 9 3560.8 3

B 5 4 3588.4
B 0 2 3607.0 8 3607.8 3606.6 9 3607.0 4
A 2 1 3616.9 1
B 4 4 3630.0
- - - 3657.8 -
B 1 3 3661.3 8 3661.2 10 3661.7 5
A 3 2 3664.5 1
A 1 1 3668.5 2
B 3 4 3672.7
B 0 3 3710.0 10 3712.3 3710.7 10 3710.8 4
3714.4 f
B 2 4 3717.6 10 3718.7 3
A 0 1 3723.2 2
3764.4 f
B 1 4 3767.7 5 3769.2 a 3766.6 8 3767.9 3
A 1 2 3776.9 3
B 0 4 3818.8 10 3819.5 7 3819.8 4
B 2 5 3823.7 f 3824.4 10
A 2 3 3831.9 3
A 0 2 3835.6 b 10 3834.7 3
B 1 5 3879.0 5 3876.2 7 3879.0 5
B
A
3
1
6
3
3881.5 f I 3883.0 10
3890.7 I I 10 3890.6 4
8) System designation and vibrational levels according to Haranath et al. [502].

Haranath's B = Choong's system = Migeotte's I(A - X) = Purbrick's I.
Haranath's A = Purbrick's II. These authors' vibrational levels all agree (except as noted),
but Migeotte's v" has been increased by 1 unit to bring it into agreement with the others. In
one of his tables, Haranath inadvertently interchanged v' and v" for B.
b) Discharge in tellurium with oxygen; visible also in absorption in Te02 vapor above 1000°C;
original wavelengths given to 0.01 A.
5.12] TELLURIUM 311
C) Strongest bands quoted by Rosen [79 (p. 307)] from the unpublished thesis of Migeotte. Ob-
served in discharge and absorption.
d) Electrodeless discharge in tellurium with oxygen and argon. Grating spectrogram.
C) High-current 2000 V arc. Prism spectrogram. Accuracy claimed to be only 2 cm -1 (0.2 A).
f) Choong thought that these bands b",longed either to Te2 or TeO.
8) Listed as 3796.2 by Rosen; this must be a misprint, since the band is assigned to B 0,4) (in
Haranath's notation).
b) Purbrick gives v' = 2.
I) Purbrick assigns this to B (5, 7).
J) No levels assigned by Haranath; Choong and Purbrick give 0, 0).
TABLE 5.XXIX
ULTRAVIOLET FLAME BANDS OF TELLURIUM
Hartley [354] 8 Gilbert [108] b Haranath [502] C
3348 2 3345t
3386 6 3383
3425 d 2 3422 1
3465 d 3 3464 2
3515 e 3 3508 2
3525 4 3516t 2
3560 3565 6 3561 3
3604 3610 9 3607 4
3630 r 2 (3617 1)
3661 3668 11 3662 5
3677 8 2 3668t 2
3708t 3715 12 3711 4
3719 3
3725- 2 { 3723 2
3769 3775 b
3768 3
11 { 3777 3
3830 13 3820 4
3832 3
(3840 - 2) { 3835 3
3880 3879 5
3890 b 14 { 4
3890t
8) Tellurium in oxyhydrogen blowpipe. Darker (short-wavelength) edges. All bands fainter

than the visible bands, 3560 being faintest. Accuracy within 1 A for sharp features.
b) Air-hydrogen; conditions of Fig. 5.27. Band peaks as seen on the recording are given, not
the heads; accuracy ±2 to 3 A. Relative intensities above continuum as measured on Fig. 5.27.
C) Arc wavelengths (band heads) for TeO from Table 5.XXVIII, for reference and identifica-
tion; these are the most accurate wavelengths.
d) On an OH band, partly obscured.
C) Shoulder.
f) Possibly Migeotte's 3630 (Table 5.XXVIII), or a noise bump.
8) On slope of preceding band; intensity above the latter.
b) Peak looks wider than the sharp, single peaks, but is not resolved.
312 NONMETALS 5]
TABLE 5.XXX
VISIBLE FLAME BANDS OF TELLURIUM
Mitscher- Salet [17, 444 ] Hartley d Eder e Gilbert d Haranath d

lich a [21] FI. b Dis. C [354] [104] [108] [502]
3934 3
!.
3945 r 10
3937 3940 3940t 5
3955 14 3948 4
3953 3952 6
!.
3995t 2
3999 4002 4000 r 12
4003 6
4006t 3
4010 16
!.
4012 4010 0 7
4061 h 4065 2 4059t 6
4069t 5
4072t J 4074 4085 1 14
4075t 8
4080 w
4127 w (4130 r 8) 4125 7
4131 2
415 4130t 4136 4140 14 4136 9
415It 1 4151 k
4190 2 4184t 1
4194 2
420 4201 s 4211 4210 13 4205 10
425 4250 f 3 4247t 2
4258 1
426t--428 428 4261 ms 4270 • 4270 13 4268 9
430 -432 433 p 433 4308 nw 4320 4 4318 2
4325 1
433 -435 435 s 435 4335 s 4343 4355 15 4343 10
436t-437t 4379 4395 r 6 4382t 3
438 -444 440 440 4397 4412 4415 11 4407t 8
4426 4435w
4465 3 4459t 4
4468w
4475 3
446 -451 447 447 4495 4490s 4500 16 4487t 9
451 4532 4535 vw 4545 r 4 4527 2
4544t 4
453 -456t 456 4580 4560 4565 1 10 4555t 7
4593 4585 VW
459 460 p 460 4600mw
5.12] TELLURIUM 313
TABLE 5 XXX (continued)
I
I
Mitscher- Salet [17, 444] Hartley d Eder e Gilbert d Haranath d
lich a [21] FI. b Dis. C [354] [104] [l08] [502]
4620t 4620 row 4625 I 1 4616 3

4625 4
462t-466 4648 4648 ro 4655 11 4640 7
4668t 4669 q w
467 -4701- 467 467 4702t 4705 f 7 4698t 5
4705 5
473 -475 472 473 4720 11 4711 6
4760 4760 row
477 476 477 (4774 q w) 4780 2 4774 3
4784 3
478t-480 482 4818 w 4820 4815 4 4802 4
4825 r 2
4852t 1
484 -488 487 4880 9 4862t 4
49Qt-495 492 p 492 4955 6 4941 4
4981--499t 496 4990 2 4975 3
500t 5025 2 5006 2
5023 2
503 -505 501 502 5055 5 5035 3
507 507 5125 4 5118 2
509 -519
515 516 5155 r 3 5139 2
519t-524 522 522 5235 3
524t-528t 527 528 5315 4 5280 3
531t-535 534 534 5380 r 2 5350t 3
537 -54It
542 t 541
542t-548 5431 1
547 547
550 -555 5515 3 5504 4
556 -563 556 556
564 -569 565 566 (5640 1) 5668 3
57371- 2
571 -577 574 573 5750 1 5746 4
578 -585 5818 1
585 u 584
587 -592t 5908t 3
593 -601 594 594 5925 5
601t-608 605 605 6007 3
610 -615 615 615 6094 2
v
625 625 6203 3
I
314 NONMETALS [5
TABLE 5.XXX (continued)

8) Flame of hydrogen containing tellurium vapor. Band boundaries estimated from drawing.
b) Flame of hydrogen containing tellurium vapor. Band heads.
C) Tellurium in Geissler tube, for comparison.
d) See notes, Table 5.xXIX, of which these listings are a continuation.
C) Tellurium in oxygen-gas; band heads.
f) Shoulder.
I) Double head clearly visible in spectrogram.
h) Not listed by Eder and Valenta but visible in spectrogram; close to Pb 4058 (impurity).
I) Peak looks wide but is not resolved.
J) Head ofa band extending to 4120, with markings at 4085, 4098 and 4107 A.
k) Listed by Eder and Valenta but not visible in their spectrogram.
1) Head of a band with markings at 4163 and 4179 A.
m) Hartley has 4211, but this is inconsistent with his micrometer reading, which yields 4261.
Moreover, it is one of the "stronger" bands, lying between the stronger 4201 and the dark
4335, so that it must correspond to Haranath's 4268.
D) Again, Hartley's wavelength (4325) does not match his micrometer cc'/lding (79.5), which
yields 4308. Besides, his wavenumber agrees with 4308.
0) Misprinted 4009.0 in Pearse and Gaydon [78]; should be 4009.9.
P) Diffuse; listed only in [17].
q) Not listed by Eder and Valenta but visible in their spectrogram.
r) On slope of preceding band.
S) Partly obscured by C 2 bands.
t) 542 in [444]; 541 in [17].
U) 585 in [444]; 587 in [17].
Y) Three more vague bands are discernible beyond the 610-615 band; the spectrum fades out
at about 650 nm.
Note: w = weak, m= medium, s = strong, v = very.
The question of the presence of Te2 in the flame spectrum, particularly in the blue,
where its strongest bands are, may be examined in the light of several of the listed spectra.
Te2 would be expected at high concentrations of tellurium or perhaps in cool hydrogen
flames. Mitscherlich [21] produced the tellurium spectrum in a diffusion flame of hydro-
gen carrying tellurium vapor, and I have evaluated his drawing in the manner described
in Section 5.11.4. The results appear in Table 5.XXX. It must be emphasized that his
drawing shows the bands to be quite vague and obscured by the continuum. Salet [17,444]
produced the spectrum in the same way. The core of the flame was greenish and favored
the longer-wavelength bands, while the combustion zone was blue and emitted the violet
and blue bands more strongly. This color difference, which seems to be reversed in the
Bunsen flame, suggests that both TeO and Tel may be emitting. The air-hydrogen sprayer-
burner flame of Fig. 5.27, on the other hand, is of a lovely indigo blue, with no greenish
core.
With these circumstances in mind, we look for significant differences between the TeO
arc spectrum of Haranath et al. [502] and the flame bands listed for Mitscherlich, Salet,
Hartley, Eder and Valenta, and Gilbert. Besides, Eder and Valenta's spectrogram [104]
can be compared directly with Fig. 5.27. Through the ultraviolet and up to 4500 A the
bands all match Haranath's TeO wavelengths with little or no ambiguity. If some of the
matches seem poorer than the precision of measurement (e.g., Hartley's 4201, Eder's 4211
5.12] TELLURIUM 315
and Haranath's 4205), it should be remembered that the heads may not be sharp, there
are isotope shifts, and the continuum is troublesome. Above 4500 A there are some un-
resolved inconsistencies. However, the bands that match Haranath's TeO wavelengths
poorly show no correlation with the published data on Te2 [78,79].
Haranath's arc wavelengths agree well in the ultraviolet with those of Choong [482],
Migeotte [500] (quoted by Rosen in [79]) and Purbrick [501], all obtained under
more spark-like conditions. But in the visible the discrepancies become severe between
Purbrick and Haranath, the only two to have measured the visible wavelengths with accu-
racy. Besides, their vibrational analyses disagree in the visible. A critical comparison of
the visible flame spectra (Table 5.xXX) with those of Haranath and of Purbrick shows
unquestionably better agreement with Haranath's. His arc evidently produced a more
flame-like TeO spectrum than Purbrick's electrodeless discharge. I recommend adoption
of Haranath's wavelengths for the identifiable visible flame bands of TeO. These wave-
lengths are used in Fig. 5.27. But since even in the ultraviolet (Table 5.xXVIII) the deci-
mal is not certain, I have rounded Haranath's data in Tables 5.xXIX and 5.xXX.
Several current reference works [3, 5, 110, 116, 117] list the flame bands of tellurium.
These were based on a blend of Haranath's and Purbrick's wavelengths and should be
superseded by those shown in Fig. 5.27 or Table 5.xXXI. The wavelengths published in
the first edition of [110] are earlier spectrophotometric measurements, obtained in
1952 with a DU spectrophotometer with a slit of 0.1 mm. They agree well enough with
the peaks listed in Tables 5.xXIX and 5.xXX; however, the "bands" at 340.6, 361.0
and 363.6 nm are palladium lines (361.0 only in part) due to attack ofthe palladium cap-
illary of the sprayer-burner by the diluted aqua regia used to dissolve the tellurium.
Unfortunately the spurious wavelength 363.6 crept into [1 (pp. 147, 167)] and [205].
Hartley [354, 364] listed four lines (3248, 3273, 3281, 3383) that he evidently did not rec-
ognize as being due to copper and silver.
The intensities of the principal bands, as seen under the moderate resolution of Fig.
5.27, are converted to absolute radiance in Table 5.xXXI. The older measurements (1952)
in air-hydrogen, mentioned above, agree closely with those of Table 5.xXXI. There are
some other measurements available for aqueous tellurium in oxyhydrogen and oxy-
acetylene sprayer-burner flames [108]; the practical intensities have been published in
[110], [116] and [117]. In oxyhydrogen, which is colored blue by tellurium, the
radiances of the bands and continuum are all about 1.7-1.8 times those in air-hydrogen.
But the 20-fold greater background emission of oxyhydrogen makes it less useful. In oxy-
acetylene the bands disappear. Only a continuum is emitted, having 4 times the radiance
of the tellurium continuum in air-hydrogen. The continua in the three flames have similar
spectral distributions, but the wavelength of greatest radiance appears to diminish slightly
in the order air-hydrogen, oxyhydrogen, oxyacetylene.
In 1952 I sought the strongest lines of tellurium in the oxyacetylene sprayer-burner flame
but could not detect any of them at 10,000 ppm in aqueous solution [l08]. In 1960, how-
ever, I observed the lines at 2383.2 and 2385.8A [39,49] (also [3,5, 110, 116,117]). In the
air-hydrogen sprayer-burner flame they were very weak with aqueous solution at 4000 ppm
of tellurium, but addition of isopropanol enhanced them enormously. This overexcitation
316 NONMETALS [5
TABLE 5.xXXI
RADIANCES AND PRACTICAL INTENSITIES OF THE PRINCIPAL TELLURIUM
OXIDE BANDS, CONTINUUM AND BACKGROUND IN THE AIR-HYDROGEN
SPRAYER-BURNER FLAME
Conditions of Fig. 5.27. J a, J b and J c defined as in Tables 5.11 and 5.111. Gross "intensity" =
1000 (Ja + Jc)/Jb ; net "intensity" = 1000 Ja/Jb •
Band heads Practical Intensity

J a x 1011 J c X 1011 J b X 10 8
(Haranath) Gross I Net
3508 + 3516
3561
.022
.033
.11
.115
.09
.06
1.5
2.5
I .25
.5
3607 .047 .115 .055 3 .9
3662 .052 .125 .05 3.5 1.0
3711 .061 .13 .05 4 1.2
3768 + 3777 .054 .135 .05 4 1.1
3820 .059 .135 .05 4 1.2
3879 + 3891 .061 .135 .05 4 1.2
3948 + 3952 .052 .13 .05 3.5 1.0
4003 +4010 .060 .125 .055 3.5 1.1
4070 + 4075 .049 .125 .055 3 .9
4136 .047 .125 .055 3 .9
4205 .044 .12 .055 3 .8
4268 .043 .12 .05 3 .8
4343 .047 .115 .05 3 .9
4408 .033 .11 .05 3 .6
4487 .047 .11 .05 3 .9
4556 .028 .105 .05 2.7 .5
4640 .028 .105 .05 2.7 .5
4711 .031 .105 .05 2.7 .6
4863 .026 .10 .05 2.5 .5
may be due to one of Sternberg's mechanisms, mentioned in Section 5.1.2 and in [63],
involving excited CO. Its reaction with TeO is energetic enough to produce even
ionized tellurium; but according to Bulewicz and Padley [35], tellurium, like selenium,
shows no overionization in a rich nitrogen-diluted oxyacetylene flame at 2500 K. Whether
tellurium is ionized in the chemiluminescent air-hydrogen flame is not known.
In 1963 Dean and Simms discovered the line spectrum in the reaction zone of the oxy-
acetylene sprayer-burner flame and utilized it for the determination of tellurium [63]. The
lines were detectable with aqueous solutions but were more intense by two orders of mag-
nitude with organic solvents. The resonance lines 2142.75 and 2259.04 A gave equal read-
ings in the DU spectrophotometer, although the former has the higher radiance and ab-
sorbance; 2383.25 and 2385.76, with excitation energy of 5.8 eV (not resonance lines),
were stronger, 2386 being 1.83 times as intense as 2383; and 2081.03, requiring 7.3 eV,
5.12] TELLURIUM 317
was barely detectable at 1000 fLg/ml. I estimate that the radiance of the tellurium lines
in the reaction zone of oxyacetylene with methyl isobutyl ketone as solvent is of the order
of 10- 9 w/cm 2 .sr.(fLg/ml); the radiances of 2259 and 2383 should be about the same, and
those of 2143 and 2386 about twice as great.
Skogerboe, Heybey and Morrison [286] reported the 2143-A line in the oxyhydrogen
sprayer-burner flame. The detection limit was 0.6 fLg/ml in ethanol solution pumped at
3.9 ml/min. At this flow rate it was ten times as good as at 1.5 ml/min (a more usual flow
rate). Fassel and Golightly [65] reported the 2383 and 2386-A lines in the Kniseley pre-
mixing oxyacetylene flame with ethanol solutions. Further details on these studies are
given in Table 5.xXXII below.
5.12.3 FLAME SPECTROPHOTOMETRY OF TELLURIUM
The few contributions to the emission flame-spectrophotometric determination of tellu-

rium are gathered in Table 5.XXXII. Regarding detection limits, refer to the discussion
of Table 5.xIX in Section 5.8.4. In Table 5.XXXII the limits represent the concentration
giving a net signal equal to 3 times the root-mean-square fluctuation of the blank at a
time constant of 1 second. In the case of the band spectrum in the air-hydrogen flame, I
have allowed for the fact that this flame on the Beckman sprayer-burner tends to flicker
a little more than the oxyhydrogen and oxyacetylene flames. If the continuum is included,
the detection limits for the bands are about one-third as great, as low as 3 ppm; but this
sensitivity cannot be utilized unless the tellurium is freed from all continuum-generating
concomitants.
Skogerboe's detection limit corresponds to 3 times the standard error ofthe net reading,
not of the blank. This value, 0.6 fLg/ml, is by far the best yet reported, and should prove to
be of real utility. Inspection of Fassel and Golightly's data suggests that the limit in
Skogerboe's flame would be still lower, perhaps 0.2 fLg/ml, if a DU spectrophotometer
were employed instead of the grating monochromator, which is not at its best at 2143 A.
(However, Fassel and Golightly's values for the two lines of the 2383-2386-A doublet
seem anomalous in view of the greater intensity of 2386.) Inspection of Dean and Simms's
data suggests, further, that at 2386 A (and with a DU) Skogerboe's flame ought to yield
a detection limit of 0.1 fLg/ml. It should be emphasized that Skogerboe's excellent result
was obtained by forced feeding of the sample at about 3 times its free aspiration rate,
and by use of a small, lean flame (3 l/min oxygen, 4.5 l/min hydrogen). The ethanol con-
stitutes over half the fuel in this flame.
The only analytical study is that of Dean and Simms [63]. They show profiles of inten-
sity vs. height for the 2143, 2259 and 2386-A lines; the curves are similar, and they peak
higher than the 2478-A line of carbon, just above the inner cone. The fuel flow is critical;
an oxygen/acetylene flow ratio of 2.4 is best. The relative tellurium emission given by
different solvents under free aspiration is as follows: water, 1; methyl isobutyl ketone, 190;
cyclohexane, 100; carbon tetrachloride, 65; acetone, 240; 80% acetone, 35. Although ace-
tone gives a higher signal than methyl isobutyl ketone, the flame is steadier and the sample
consumption lower (2.2 ml/min) with the latter. The analytical curve shows self-absorption
for the resonance line (2143) but it is linear for the 2386-A line up to 4000 fLg/ml. Above
that there is some convexity. The noise data show that peak-to-peak flicker was a little
over 1 % at a time constant of 1 sec.
Interferents tested by Dean and Simms include arsenic, antimony, cadmium, chromium,
TABLE 5.XXXII. PAPERS CONTRIBUTING TO THE EMISSION FLAME SPECTROPHOTOMETRY OF TELLURIUM w
00
Height
Date Authors Ref. Flame Emission I Solvent
Detection
above Linearity C
-
Burner I p~~:~~~;er limit b
burner
1952 Gilbert [108,205, BSB DU + IP28 AH 372 8 H2O 10 High 1.0 (10,000)
6,110, 401 10
116,117] 450 13
OH 372 8 H2O 80 Normal
383 100
389 100
401 100
414 110
OA Con. 450 H 2O 400 I Normal
1960 Gilbert [5, 110, BSB DU + IP28 AH Bands; H 2O 8
49,39] 5.xXXI
AH 238.3-.6 H 2O 1000
iPrOH ca. 10
1963 Dean & [63] BSB DU + IP28; OAic 214.3 MeCOiBu 14 6mm 0.93 (10-125)
Simms light pipe 0.78 (125-1000) i
225.9 14 6mm
238.3 8
238.6 4 6mm 0.98 (10-4000)
I 238.6 H2O 800
I OHic 238.6 (MeCOiBu) Less good I 5-8mm

1966 I Skogerboe, [286] BSB I JA 82000 OH 214.3 EtOH 0.6 26mm
I Heybey & + pump + EMI 6255B
Morrison I I
1967 Fassel & [65] Kniseley DU+6255B OA 238.3 EtOH 300 PRZ
Golightly 238.6 900
I
JA 82000 OA 238.3 EtOH 3000 PRZ
+ 6255B 238.6 2200
--- -------- ----------- ------- ------- I t
8) Selection of strongest bands. b) [Lg/ml equivalent to 3 times r.m.s. background noise; for bands, the net band height, exclusive of
continuum, is taken. C) Logarithmic slope of analytical curve over concentration range ([Lg/ml) given in parentheses. 'v;
Abbreviations: See Table 5.Y; Con. = continuum; PRZ = primary reaction zone.
5.12] TELLURIUM 319
cobalt, copper, iron, lead, manganese and nickel. At 5000 (lg/ml, only chromiumdepres-
ses the signal from 125 (lg/ml of tellurium by as much as 5 %. To avoid interferences from
the very high interferent/tellurium ratios encountered in most samples, the authors
extract the tellurium from the aqueous phase at pH 4, containing EDTA, with sodium
diethyldithiocarbamate in carbon tetrachloride. The solvent is evaporated and the residue
is dissolved in methyl isobutyl ketone and sprayed into the flame. Simulated steel samples
containing 0.05 %tellurium, analyzed by Dean and Simms's procedure, gave results within
2 % of the amount of tellurium present.
The papers by Malinowski et al. listed in [3] and [7] (cf. Section 5.11.6) propose the de-
termination of tellurate by its quenching effect on the emission of calcium or strontium
in the flame.
Tellurium is a little more easily determined than selenium by atomic absorption, since its
best resonance line, 2143 A, is of longer wavelength than the 1960 of selenium. Absorp-
tion by the flame gases is less troublesome. Although the 2386-A line is about as strong in
emission as 2143, it is much weaker in absorption since its lower level lies at 0.59 eV. In
the air-hydrogen sprayer-burner flame, 2386 is 0.005 and 2259 is 0.10 as strong as 2143
[505]. In air-acetylene these ratios are about 0.05 and 0.16, respectively [507].
Good detection sensitivity has been reported, for example, in the analytical procedure
of Chakrabarti [505]. He passed the beam three and five times through triple sprayer-
burner flames (air-hydrogen) or a lO-cm air-hydrogen or air-acetylene flame. Solvents
were water and methyl isobutyl ketone. Detection limits were below 0.1 (lg/ml. He extract-
ed telluriunl as iodotellurite or diethyldithiocarbamate, and by coprecipitation with arse-
nic to concentrate the tellurium he could reach 1 part in 109 • Roth, BoW and Sellers
[506] also reported a limit of 0.1 (lg/ml in methyl isobutyl ketone with air-acetylene.
By extracting the tellurium from strong hydrochloric acid solution into the ketone they
determined it in bismuth down to 0.1 ppm in the metal. Wu, Droll and Lott [507]
extracted tellurium with ammonium 1-pyrrolidinecarbodithioate into 2,4-pentanedione
to separate it from most interferents. They sprayed the extract into an air-acetylene flame.
• Rains and Rush [232] listed a detection limit of 0.02 (lg/ml (twice the standard devia-
tion ofthe background) at 2143 A using a quartz tube; no details were given. Rubeska and
Moldan [473], using an air-hydrogen sprayer-burner in a 45-cm alumina tube, r<:ached
0.025 (lg/ml. Ramirez-Munoz [242 (p. 247)] has attained a fluctuational detection limit of
0.015 ppm with the Beckman atomic absorption spectrophotometer. Hell et al. [503] re-
ported 0.11 ppm in air-acetylene with the burner designed by him. With the Perkin-Elmer
Model 303, an Intensitron tellurium lamp, and a three-slot burner, Schallis and Kahn
[504] found limits of 0.03 (lg/ml in air-hydrogen and 0.1 (lg/ml in air-acetylene. With
Peterson [424], they applied the "sampling boat" (see Section 5.8.6) to tellurium, attain-
ing a limit of O.ot flg/ml in a 1-ml sample.
320 NONMETALS [5
5.12.6 ATOMIC FLUORESCENCE SPECTROSCOPY
The work of Dagnall, Thompson and West [497, 498] and ofZacha, Bratzel, Winefordner
and Mansfield [499] was mentioned in Section 5.11.8. At 2143 A detection limits for
tellurium were reported by these authors, respectively, as 0.05 ppm in premixed air-
propane, and 0.5 ppm in air-hydrogen or argon-hydrogen on a sprayer-burner. The 2383
and 2386-A lines fluoresce strongly too. The analytical curve was linear up to 125 ppm
[497]. No interferences were noted with lOO-fold excesses of many cations.
5.13 Fluorine
5.13.1 FLAME SPECTRA
The first attempt to identify a distinctive flame emission from fluorine was made by Bott-
ger in 1860 [476]. He placed calcium fluoride in a Bunsen flame and observed, besides
the green calcium band, a bright blue line close to the Fraunhofer b line. Cryolite and
potassium fluoride did not emit this line. Bottger described these experiments again in
1862 in a paper [24] to which O. L. Erdmann added a postscript pointing out that Bottger
must have been mistaken about the position of the blue line, which was that of calcium
at 423 nm. Kayser [91] confirmed this opinion.
The first genuine flame spectra of fluorine were obtained by Mitscherlich in 1862 [27,
508]. He supplied the flame with mixtures of ammonium fluoride and barium or calcium
fluoride and observed the band spectra of what are now known to be BaF and CaF. Later
[21] he mapped the flame spectra of CaF, SrF, BaF and CuF, the last obtained from a
mixture of cupric and ammonium fluorides in oxyhydrogen or oxygen-gas. Diacon in
1865 [509] also described the spectra of CaF, SrF and BaF, which he said require a hotter
flame than the other halides. He could not get spectra from copper or bismuth fluoride.
He considered that calcium gives the most distinctive fluoride flame band, viz., the green
band at 529 nm, and he recommended it as a test for fluorine.
Subsequent observations on the spectra of the fluorides of calcium, strontium and bar-
ium were summarized by Kayser in 1910 [91] and by Kayser and Konen in 1932 [93
(p. 378)] and 1934 [92 (p. 99)]; the CuF spectrum was also summarized [93 (p. 652)]. Some
of the best work on CaF, SrF and BaF (in an arc) was that by Fabry [510]. Posch [511],
in particular, studied the flame spectrum of SrF. Ritschl's work [512] on the absorption
spectra of the copper halides, including CuF, was very thorough. The modern compendia
[78, 79] tabulate the fluoride spectra well enough; a further discussion hardly seems
warranted here. Brief tables of flame emission intensities of MgF, CaF, SrF, BaF and CuF
appear in [3 (p. 385)]. A more recent detailed work on the spectrum of SrF (in a
discharge) is that of Novikov and Gurvich [513].
The strongest bands of the alkaline-earth fluorides, as emitted in flames, are the follow-
ing: for MgF, the double violet-degraded band at 3594 A is over 10 times as strong as the
next-strongest bands at 3503 and 3586 A; for CaF, the double red-degraded band at 5291
Ais 50 times as intense as the one at 5145 A; for SrF, the closely-spaced set of red-degraded
bands of the 0,0 sequence at 5772-5785 A is probably best suited for the commonly used
photomultipliers, but there are also strong violet-degraded heads of sequences at 6512 and
6633 A; for BaF, the red-degraded sequence head at 5001 A is a little stronger than that at
5.13] FLUORINE 321
4951 A. All of these emissions consist of close sequences, not resolved by the commonly
used flame spectrophotometers.
The use of metallic fluoride spectra for the flame-emission detection or determination of
fluorine is an inelegant approach in that an appropriate metal has to be added (in rather
massive amounts) to bring out the spectrum. More appealing would be the use of a fluo-
rine-containing molecule generated in the flame gases themselves without help from an
additive. Such a molecule is CF. It has been observed by Mann, Broida and Squires [460] in
an oxyacetylene flame to which carbon tetrafluoride was added. The A-X system (234-
256 nm) was emitted. The spectrum can hardly have been bright, since it was obscured in
part by strong CS and CCI bands, due to impurities. Whether the CF bands could be elicit-
ed with useful intensity from a carbonaceous flame on introduction of inorganic fluorides
is not known. Carbon tetrafluoride in an oxyhydrogen flame shows no CF; only impurity
spectra were seen - CuD, CuCI and CuF, all fairly intense [460]; the copper came from
the brass burner. For wavelengths of CF, see Pearse and Gaydon [78], Gaydon [34 (p.
236)], and the references quoted by them. The strongest bands lie at 2403 A (intensity 9),
2479 (10) and 2559 (7).
The CF bands are emitted also by flames supported by fluorine or chlorine trifluoride
as oxidant. Such flames will hardly be useful for determining fluorine, but they are certainly
of interest in analytical flame spectroscopy for other reasons. For a discussion see Gaydon
[34 (pp. 162, 218-220)]; and recall the remarks on oxygen-free flames in Section 5.9.1.
Perchloryl fluoride, CI0 3 F, is a promising oxidant generating very hot flames and usable
in a Beckman sprayer-burner. It has been studied by Collier [426] and Schmauch and
Serfass [514,515,516]; and see [14 (p. 47)]. It emits strong band spectra of MgF, CaF,
SrF, BaF and CuF when solutions of the metals are sprayed into the flame.
5.13.2 FLAME SPECTROPHOTOMETRY OF FLUORINE
All of the published emission flame analytical methods utilize the fluoride bands of calcium,
strontium and barium. Most of the following information comes indirectly through
[1,2,3,4] and Chemical Abstracts; I have seen few of the original papers.
Mitchell [517] used the CaF bands at 5291 and 5145 A in the spark, arc or flame, as
well as those of SrF and BaF, for the determination of fluorine; he was mainly concerned
with the analysis of agricultural materials. Sherman [518] mentioned the use of the green
CaF bands for the flame-photometric determination of fluoride, the sample being mixed
with lime. Yoshihei [519] observed the CaF spectrum, presumably in acetylene and pro-
pane flames with the Beckman and Perkin-Elmer flame spectrophotometers. Fuwa [520]
used a visual spectroscopic method for the determination of fluorine by the CaF bands in
hot-spring sediments and soils at fluorine concentrations of 0.001-0.05 %; I am not sure a
flame was used, but the paper is referred to in [1,2,4] as though it were a flame-photo-
metric application. In a later work [521] he employed the BaF bands at 4951 and 5001 A,
and possibly also the SrF bands; this paper is listed in [1, 2, 3, 4, 15].
Ishida [522, 523] utilized the CaF band at 5291 A in oxyacetylene, in which it reached
greatest brightness at the rather low temperature of 2400 K; in the hotter parts of the
flame the CaF was evidently dissociated. However, the band was not found in air-acetylene
or in flames of propane or hydrogen with air or oxygen. Ishida sprayed into the flame a
322 NONMETALS [5
solution of 20 g of calcium chloride per 100 mI, mixed with the sample, and determined
fluoride by a semiquantitative spectrographic method. The detection limit was 300 ppm
fluoride. If more than 10 % phosphate was present, the fluorine had to be separated by
distillation.
Burrows and Horwood [524] built a flame spectrograph for monitoring the fluorine
content of air. The air to be sampled was blown at 100 l/min into a chamber where it
mixed with a mist of concentrated aqueous calcium or strontium nitrate (40 % in the case
of strontium) generated by a sprayer consuming moistened air (from a separate supply)
at 161/min. The aerosol was next helically mixed with an oxyhydrogen or oxyacetylene
flame from a welding torch. The CaF (5291) and SrF (5772,5780) bands were emitted low
in the flame. Oxyacetylene, as lean as possible, was much better than oxyhydrogen, and
strontium was better than calcium; the 5780-A band was brightest. Exposure was 5 min,
and the microphotometer reading varied as the cube root of the difference between the
fluorine concentration and a constant. A signal/background ratio of 0.3 was attained
at 47 [J.g of fluorine per liter of air sample. The authors tested air containing dichloro-
difluoromethane at fluorine concentrations of 21 to 186 [J.g/l.
The Beilstein test (Section 5.14.7) may give a weak response to fluorine compounds.
Recall the earlier remarks on CuF. Eads and Payne [314] used methane as carrier gas in a
gas chromatograph and burned it on emergence in contact with copper. Trifluoroacetic
acid and other fluorine compounds gave a subtle green flame. Recently Herman, Levy
and Leng [525] compared the flame-photometric detection of fluorine compounds with
other methods of detection employed in gas chromatography, but the abstract of the
paper provides no details.
5.13.3 INDIRECT FLAME SPECTROPHOTOMETRY
Menis and House [4] refer to a data sheet mentioning the determination of fluoride by
precipitation with calcium and measurement of the excess calcium by emission flame
spectrophotometry.
Several indirect atomic-absorption methods have been described by Bond and O'Don-
nell [315]. In one, fluorine depresses the magnesium line at 2852 A in the air-coal gas
flame. By proper choice of the magnesium concentration, a range of 0.2 to 200 ppm of
fluorine can be covered, with linearity up to an atomic Mg : F ratio of 1 : 2. Precision
is 2 %. Phosphate, sulfate, oxalate, acetate, aluminum and lanthanum interfere; sodium,
potassium, ammonium, cobalt, nickel, mercury, cadmium, lead, nitrate and other halides
do not.
In another method, fluorine enhances the absorbance of zirconium at 3601 A in a rich
nitrous oxide-acetylene flame. The zirconium concentration may be 500 to 2000 ppm,
and fluorine can be determined in the range 5 to 200 ppm, with linearity up to a Zr : F
ratio of 1 : 1. Sensitivity and precision are not as good as in the magnesium method,
but there are no interferences except from phosphate. Sodium chloride (500 ppm) is
added as deionizer, and an ammonium salt may be added to saturate the enhancement
of zirconium by ammonium (see Section 5.6.5). Hafnium can replace zirconium.
A third method involves the enhancement of titanium (400 ppm) at 3643 A in hydro-
chloric acid solution in the same flame. Reproducibility is 10 % in the range 20--200 ppm
fluorine. The advantage of titanium is its freedom from phosphate interference.
5.14] CHLORINE 323
The microwave electrodeless discharge of McCormack, Tong and Cooke [88] emits the
silicon spectrum (from the silica tube) when a fluorine compound is present in the argon
carrier; the detection limit is 0.5 ng/sec of fluorine. An unidentified emission at 5166 A
also appears, offering the very low limit of 3 pg/sec. Besides, fluorine greatly depresses
the very sensitive CN emission and the 3360-A band of NH. Bache and Lisk [408], how-
ever, could not detect fluorine with their low-pressure helium discharge. Braman and Dy-
nako [275] were able to detect fluorine at 6902.5 and 6856.0 A with their d.c. noble-gas
discharge (see Section 5.4.7).
5.14 Chlorine
From the point of view of flame spectroscopy, chlorine, bromine and iodine are the
"typical" halogens. Much of the work cited in this section applies equally to these three
elements. Two applications calling for trace chlorine analysis are the detection of leaks in
refrigerating systems and the detection of chlorinated pesticide residues. The sensitive
flame methods developed for these purposes will not, unfortunately, detect traces of
fluorine compounds. Fluorine differs markedly from the other halogens. For better or
for worse, the need for a good fluorine detector created by experimentation with chemical
warfare agents has not been met, as far as I know. But there is much unexplored territory
in the realm offlame spectroscopy; more sensitive and selective detectors for the individual
halogens will surely be found.
Astatine is a halogen and a nonmetal. Its resonance line must lie in the accessible ultra-
violet, and it should be detectable with extremely high sensitivity in an electrodeless
discharge like that of McCormack et af. [88]. But its stablest isotope has a half life of only
8 hours. Flame spectroscopists will perhaps never be concerned with this element.
5.14.1 FLAME COLORS
The early spectroscopists tried chlorine and its compounds in flames. Merz [146], intro-
ducing hydrogen chloride into a Bunsen flame, found only a very weak greenish-blue color
in the mantle. Bottger [24] found that chloroform in burning illuminating gas turned the
inner cone green, and he described its spectrum. It evidently consisted only of the en-
hanced C 2 and CH bands. Salet [17] found no bands in the flame of hydrogen burning
with chlorine or with chlorine plus oxygen, and he saw only the CH and C 2 bands when
organic chlorine compounds entered a Bunsen flame. Castellana [171] mentioned that
ethyl chloride in the Bunsen flame imparts at most a bluish color.
Recently Cowan and Sugihara [262] introduced various compounds into the hydrogen
flame of a demonstration gas chromatograph; carbon tetrachloride, chloroform and
1,I-dichloroethane all turned the flame blue at first and then yellow from excess carbon.
The blue color is probably mainly due to C 2 • Sternberg [263] has noticed anomalously in-
tense C 2 emission in a hydrogen diffusion flame containing carbon tetrachloride. When
carbon tetrachloride is sprayed into an air-hydrogen sprayer-burner flame, the C2 bands
324 NONMETALS [5
are stronger than when alcohol is sprayed, but the CH bands are about the same [l08]. Ac-
cording to a patent to Griese [556], a refrigerator may be tested for leaks by running it for
a time in a gas-tight, heated chamber. An air-acetylene flame, normally yellow, turns
blue-green when a Freon is present in the chamber. Nothing is said of the spectral nature
of this emission.
None of the above tests has much analytical utility; the emitting molecules contain no
chlorine and their emission is not strong.
5.14.2 NONMETALLIC FLAME SPECTRA OF CHLORINE
All of the practical flame-spectroscopic methods for chlorine utilize line or band spectra
of metals. The necessary metal has to be introduced into the flame in some way. A specific
chlorine emission needing no extraneous additive would have advantages. Several such
emissions are known in flames.
Faint, diffuse bands of CIO were first noticed by Urey and Bates [526, 527] in an oxy-
hydrogen flame containing chlorine. The bands were measured and analyzed by Panne-
tier and Gaydon [528], who obtained them from chlorine fed to an oxygen-methyl chlo-
ride or an oxyhydrogen flame; oxygen-carbon monoxide was a poorer source. The bands
lie between 3500 and 4500 A; absorption bands of CIO (in flash photolysis) have been ob-
served at shorter wavelengths, below 3000 A. Wavelengths and intensities are listed in
[34, 78, 79].
The bands of CCI are more distinctive and might be useful in flames. They lie at 2700-
2900 A; the strongest heads, degraded to shorter wavelengths, are at 2778 and 2788 A.
For data and literature, see [34, 78, 79]. The bands appear in the inner cone of flames
containing chloroform, methyl chloride or carbon tetrachloride. They are strong in flames
supported by chlorine trifluoride [34 (p. 162)]. The observation by Mann, Broida and
Squires [460] is suggestive: they recorded prominent bands of CCI (2778-2790 A) in an
oxyacetylene flame fed with carbon tetrafluoride; the chlorine was present only as an
impurity.
An infrared emission band of HCI, peaking at 3.68 [lm, is strong in chlorine-hydrogen
flames [34 (p. 177)]. This flame also emits the visible bands of C1 2 , 5590-6500 A [34 (pp.
219, 239)]. A diffuse ultraviolet band of Clz at 2580 A appears in the inner cone of
organic flames containing chlorine [34 (pp. 218, 239)]. Ref. [79] summarizes the literature
(up to 1951) of the Ci 2 emission and absorption spectra.
In addition to these bands, chlorine yields two kinds of continua in flames [34(P. 218),
526, 527, 529, 530]. Lean hydrogen flames favor a continuum due to an association
reaction such as
CJ(2Pt) + CJ(2Plt)-+Clze~) + hv;
the emission lies in the visible. Rich hydrogen flames emit a continuum due to H + CI-+
HCI + hv, occupying the visible and near ultraviolet down to 3000 A.
5.14.3 THE BANDS OF CUPROUS CHLORIDE
The molecule CuCI is preeminent in the analytical flame spectroscopy of chlorine. When
5.14] CHLORINE 325
copper and chlorine are present together in a flame, bands of CuCI are usually conspicuous.
Most of the reported flame tests for chlorine depend on copper. These tests are often all
loosely referred to as the "Beilstein test." However, they take many forms. In most of
them the CuCI spectrum is not pure, being accompanied by other copper emissions, in-
cluding Cu, CuH, CuO and CuOH. Indeed, in some of the most practical forms of the
Beilstein test, only these latter emissions appear; the CuCI bands are absent. No line can
be drawn between those cases in which CuCI appears and those in which it does not; in
other words, the direct emission flame spectroscopy of chlorine merges with the indirect.
Hence the various practical embodiments of the Beilstein test will be covered in a later
section; here only the CuCI spectrum will be discussed.
One hundred and forty-five years ago Herschel [19] drew an intensity trace (cf. Fig. 5.1)
of the spectrum produced by the blue flame of alcohol containing cupric chloride. It
portrays the CuCI bands about as well as some recent spectrophotometric recordings do.
Herschel distinguished this spectrum from that of the green flame of alcohol containing
cupric nitrate, characterized by bands long afterwards ascribed to CuOH. In 1845 Miller
[94] published a water-color plate of the spectrum of copper chloride in alcohol. These
alcohol flames, it should be remembered, were produced by a lamp with a wick, and the
material whose spectrum was to be studied was dissolved in the alcohol.
After Bunsen invented his burner and inaugurated the science of spectrochemistry,
many people examined the flame spectrum of CuCI. Bottger [24] obtained it by placing
cupric chloride on a bit of copper foil in the edge of the flame. He thought the spectrum
supremely beautiful. Simmler [28] said that copper chloride turns the flame azure blue
with an emerald green interior and purple-red streaks at the edge, while oxygen salts of
copper give only the green. Mitscherlich [27, 508] mapped the spectrum obtained by
feeding a solution of cupric chloride and ammonium acetate from a chicken-feeder tube
through a wick of platinum wires into the flame [14 (p. 86)]. The acetate enhanced the
spectrum and kept the wick clear. He mapped the ordinary green copper spectrum as well,
which he ascribed to the oxide. In his later paper [21] he mapped the pure (blue) spectrum
of CuCI obtained by introducing copper chloride into a chlorine-hydrogen flame. Diacon
[509,531] did the same; he called the spectrum "magnificent." He also mapped the spec-
trum produced by cupric chloride in the coal-gas flame and recognized its mixed character,
ascribing the bands to chloride and oxide.
Lecoq de Boisbaudran included in his monograph [98] a map of the copper chloride
spectrum in the Bunsen flame. He said that a bead of cupric chloride placed in the flame
gives first a yellow color with a reddish fringe, followed by a bright blue halo around the
yellow with green beyond the blue; the yellow fades fast, the blue next, and the green last.
Vogel [102] published drawings of the spectra of copper chloride and oxide in the oxygen-
gas flame; he ascribed the blue and violet bands to the chloride.
Smithells in 1895 surveyed the history of the copper halide flame spectra [532]. He
used Gouy's sprayer [14 (pp. 6, 99)] to introduce solutions into a separated flame. Copper
chloride gave the green copper "oxide" spectrum in the upper cone with only faint CuCI
bands; but if hydrogen chloride was introduced into the upper cone or added to the fuel
gas, the green changed to a vivid blue, showing greatly intensified CuCI bands with faint
"oxide" bands. (Smithells was doubtful about the ascription to CuO.) Addition of chloro-
form suppressed all but the CuC] bands. Smithells presented detailed maps of both spectra
as seen by himself and by his predecessors. Agreement was good. He mentioned the reddish
fringe of a flame heavily charged with cupric chloride, noted also by Simmler and Lecoq;
he thought it was due to the CuCl 2 molecule. (Andrade [551] later found the spectrum of
326 NONMETALS [5
this red emission to be continuous.) Smithells confirmed that a bead of solid cupric chlo-
ride placed in the flame gives the CuCI bands at first, which fade and are replaced by the
green "oxide" spectrum. He tested the nature of the emitters by placing water-cooled
porcelain in the flame from such a bead: the initial yellow flame deposited metallic copper;
the blue deposited cuprous chloride; the green, cupric oxide. Smithells obtained the pure
blue CuCI spectrum from cupric chloride in a flame of carbon monoxide or carbon di-
sulfide; but in a hydrogen flame the green spectrum predominated. If hydrogen or water
was injected into a carbon monoxide flame colored blue by CuCI, a light green color
appeared at the point of injection.
Friedlander [533] obtained the CuCI spectrum by introducing ammonium chloride into
a Bunsen flame with copper oxide placed in the edge of the flame. Kien in 1908 [534],
whose paper I have not seen, made a definitive study of the flame spectrum of CuCI.
Two photographs and the wavelength tables from this work were included in Kayser's
Handbuch [91 (p. 415)], which fully covers the extensive literature on CuCI up to 1910.
Later volumes [92 (p. 361), 93 (p. 652)] carry the survey up to 1934. Eder and Valenta's
atlas [104] includes spectrograms and wavelength tables for copper chloride and copper
in the Bunsen flame.
I have not tried to survey the modern (non-flame) literature on CuCI, but Ritschl's
work [512] deserves notice; his principal data, obtained in absorption, are quoted in
Pearse and Gaydon [78]. Ritschl's tables were very detailed, and he compared his results
critically with those of his more recent predecessors. Sinha in 1948 measured new bands of
the E system of CuCI in the flame and compiled a new table [535]. The condensed wave-
length tables in the compendia [78, 79] are adequate for analytical flame spectroscopy.
They list also the principal recent papers. Brief wavelength tables with intensities in the
flame are found in [3 (p. 290), 34 (p. 240)]; the intensity scale in [34] is not sufficiently
expanded. Most of the bands listed in [3] are visible in the spectrophotometric
recording of Fig. 5.28.
5.14.4 CuCI AS AN IMPURITY SPECTRUM
The extraordinary persistence of the CuCI flame spectrum that makes it valuable for de-
tecting chlorine gives rise to several curious phenomena. Bands of CuCI may appear,
sometimes quite strongly, in flames to which no copper or chlorine has been knowingly
added.
One of these phenomena was described by Smith [536] in 1879, although it must have
been noticed by our earliest fire-watching ancestors. Most people are (or used to be) fa-
miliar with the clear blue color imparted to the flame of a coal or charcoal fire when salt
(sodium chloride) is tossed upon it. The blue flame emits a spectrum of red-degraded
bands that Smith thought was due to HCI. That they are the bands of CuCI was recognized
by Salet [537, 538]. He demonstrated the presence of copper in the ashes of coke and
observed that hydrochloric acid placed on glowing coke also gives the blue CuCI bands.
Gaydon [83] found the CuCI bands very persistent in the cool flame of nitrous oxide-
carbon monoxide (in a furnace at 600 °C). The copper came from the steel reaction vessel
and the chlorine was present in the nitrous oxide. Gaydon's paper includes photographs
of the clean CuCI spectrum in this flame and in the cool oxygen-carbon monoxide flame, as
well as the spectrum of copper chloride in the Bunsen flame, comprising CuCI and CuOH.
5.14] CHLORINE 327
'"
N
'"
a
~
<D
0
o" ui
on
'"
~
1~~~ '"'"
xXJ:
OJ
10
o
10
000
:;J::!I:::I
u UO
Z"
:x:
'5
u
I
'"
'"'"z"
",po.
",,,,
~~
55~~==~~~~--------------__
Zero
Fig. 5.28. Spectra of copper in oxyacetylene flame, showing CuCl bands.

Beckman DU with sprayer-burner and IP28. Slit 0.1 mrn. Lower spectrum: Aqueous copper sul-
fate, about 0.1 % Cu. Upper spectrum: Same solution with concentrated hydrochloric acid added.
Bands of the B, D and E systems of CuCl are so marked. Recordings by Hideo Watanabe [115].
The intensity distributions differ in these flames: the nitrous oxide flame is green, owing to
dominance of the A, Band C systems of CuCI, while the oxygen flame is blue from the
stronger D and E systems. Gaydon suggested that the CuCI acts as a catalyst in the oxida-
tion, being excited thereby, and that this effect is at work in a salted coal fire. That such a
fire is not yellow, as one might expect, is due not to its coolness (as stated by Salet) but to
suppression of the sodium line by the CuCl. The line is strong in the absence of CuCl.
These effects are mentioned also in Gaydon's book [34 (p. 92)]. He says that the CuCI
bands may appear in coal fires even in the absence of added salt and that they have been
seen in gun flashes.
328 NONMETALS [5
Hollander [82] studied the CuCI spectrum in air-carbon monoxide and air-propane
flames. He suggests that CuCI is brighter in the (dry) carbon monoxide flame because
hydrogen ties the chlorine up as HCI. Recall Smithells's observations on this point. Durie
[454] noticed that the fluorine-carbon monoxide flame is very sensitive to CuCI as an
impurity spectrum.
This behavior of CuCI in carbon monoxide (and perhaps carbon disulfide and other)
flames suggests that the Beilstein test has not been fully exploited. Avoidance of hydrogen
might not only greatly enhance its sensitivity but would also suppress the CuOH and
CuH bands that mask the halide bands and spoil the selectivity for the individual halogens.
5.14.5 FLAME SPECTRA OF OTHER METALUC CHLORIDES
Any element whose halides can emit optical spectra might in principle be used as an addi-
tive for the detection of the halogens. Flame spectToscopists have long been interested in
the alkaline-earth halides and a few others. Mitscherlich [21,27,508] mapped the Bun-
sen flame spectra of CaCI, SrCI and BaCl, using his chicken-feeder and platinum wick,
aided by ammonium acetate. He did not know the formulas of the emitting molecules but
felt sure that they were chlorides. If hydrochloric acid was fed to the flame above a bar-
ium acetate sample, the ordinary barium flame spectrum (cf. [3 (p. 502)]) was re-
placed by that of BaCt The BaCl spectrum resulted also from barium and ammonium
chlorides in hydrochloric acid. Mitscherlich found that bismuth yields distinctive halide
spectra too.
Diacon [509] refined Mitscherlich's work on the halide spectra, obtaining them in pure
form in the chlorine-hydrogen flame. He studied them also in the Bunsen flame, catching
the fugitive halide spectrum that flares up briefly after a metal halide is placed in the flame.
He confirmed that copper, calcium, strontium, barium and bismuth give the best halide
spectra. Friedlander in 1900 [533] made a detailed study of the Bunsen flame spectra of all
the halides of calcium, strontium and barium. He introduced the ammonium halide into
the flame and placed the metal oxide in its edge. Barium gave the most distinctive spectra.
Some of these spectra have been reviewed by Kayser and Konen; see particularly
[92 (p. 172)] and [93 (p. 378)] on CaCl and [92 (p. 99)] on BaCt For modern wavelengths
and references on any of the metallic halide spectra, see [78] and [79], especially the data
on MgCl, CaCl, SrCl and BaCl in the Addendum of [79 (p. 332)]. Short tables of wave-
lengths and flame intensities for MgCl, CaCl, SrCI and BaCl appear in [3 (p. 385)]. Good
photographic spectrograms of the flame spectra of CaCI, SrCl and BaCI will be found in
[104] and [105]. The SrCI spectrum shown in Formanek's old book [337] is also helpful.
Like the fluorides, the alkaline-earth chlorides emit close sequences of bands, some of
which will not be resolved by the usual flame spectrophotometers. The most conspicuous
flame bands are the following: MgCl, a multiple violet-degraded band at 3776 A with
weaker bands at 3711 and 3845 A; CaCI, multiple red-degraded bands at 3828 and 3882
A, weaker ones at 3775 and 3728 A, and two much stronger systems in the orange (5934
and 5810 A, red-degraded) and red (6212 and 6185 A, violet-degraded); SrCl, a red-degraded
system in the far violet (3894-4009 A) and a stronger violet-degraded system in the red
(6359 and 6614 A, brightest; 6362 and 6745 A, half as bright); BaCl, a group of sequences
in the green, with rather indefinite heads, viz., 5240-5244, 5138 and 5321 A, in order of
decreasing brightness.
5.14] CHLORINE 329
Of interest to flame photometrists are the observations on MgCI, CaCI and SrCI in the
perchloryl fluoride-hydrogen flame [426, 514, 515, 516] (BaCI was not detected). These
spectra were used, to be sure, for the determination not of chlorine but of the metals. Of
interest also is the recent study by Zhitkevich et al. [540] of the effect of halogens on the
emission of the alkaline-earth metals in the air-acetylene flame. They fed carbon tetra-
chloride into the flame at rates up to 270 mg/min. With rising CI concentration, the in-
tensity of MgCI rises steadily while that of CaCI, SrCI or BaCI reaches a maximum; the
other emissions of the metals diminish, except that the ion lines of Sr and Ba pass through
a maximum. All the halide bands are very weak in this flame unless the halogen feed is
copious.
Very recently one other metallic chloride spectrum - that of indium, InCI - has
proved exceptionally useful for the flame-spectrophotometric determination of chlorine
[539]. Since this spectrum had not previously been observed in flames, it will be described
later in connection with the "indium burner."
5.14.6 SENsmZED FLAME DETECTORS
We come next to the practical methods of detecting and determining chlorine by emission
flame spectroscopy and related techniques. There is a surprising variety of such methods.
They may seem disparate, yet most of them have an underlying strand of relationship. The
attempt to reveal this relationship confronts us with a task of classification and nomen-
clature.
The category in need of a name includes the Beilstein test, the Karmen-Oiuffrida detec-
tor, and all related methods or devices in which emission or ionization is measured.
What characterizes them is the chemical interaction of the analyte with a substance
placed in the flame, resulting in a change in a physical property of the flame. In
Section 5.7.13, I had offered the term sensitized flame ionization detector for all such
devices in which ionization is the property measured; and I had called the reacting
substance the sensitizer. Since writing that, I have read the paper by Nowak and Malm-
stadt [544]. They recommend the term sensitized flame detector for the sodium therm-
ionic detector utilizing either emission or ionization. The term was suggested by
Baldwin [545], a student of Malmstadt's (cf. [405]). I welcome this suggestion and
urge its adoption.
We have, then, sensitized flame emission detectors and sensitized flame ionization de-
tectors, in which the analyte reacts with the sensitizer to cause a change in emission or
ionization. These are the only two properties thus far employed in sensitized flame detec-
tors; but any other property of the flame, e.g., atomic absorption, that is altered by the
analyte-sensitizer reaction, might be used.
A more rigorous definition of sensitized flame detector is elusive. By gradual steps we
can eliminate the flame as an essential component and arrive at the concept of sensitized
detector. In a sensitized detector the analyte reacts with the (heated) sensitizer yielding a
gaseous product one of whose properties varies with the amount of analyte. But this def-
inition may be uncomfortably loose. For example, liquid water can be detected by allow-
ing it to touch a stone that has long lain in the desert sun; a distinctive odor - the "smell
of rain" - is at once evident. I suppose this is a sensitized olfactory detector.
Less far afield, all of flame spectroscopy can by easy steps be swept into the compass of
the term sensitized flame detector. Thus, we start with the Beilstein test, the prototype.
330 NONMETALS [5
Closely related is the method of Honma [573] in which a copper salt is added to a solution
to be analyzed for chlorine by flame spectrophotometry. But Honma and Smith had
noticed [305] that CuCI bands may result from the copper in the brass burner that they
used. This copper was not added intentionally. Similarly, the sensitized flame ionization
detector for nitrogen [320] works without a deliberately incorporated sensitizer, if the
burner happens to be made of copper. There are many other examples of sensitized detec-
tors in which the active ingredient of the sensitizer is an impurity, often unavoidable,
such as sodium-containing dirt. Hence the idea of deliberateness in the introduction of a
sensitizer becomes empty.
With this point in mind, consider next that the sensitizer may be gaseous. Without
altering the principle of operation, Aue and Gehrke [395] and Saturno and Cooke [403]
(see Section 5.7.13) replaced the solid sensitizer with a gaseous one (sodium vapor). And
so, if the sensitizer may be gaseous and present unintentionally, then a flame photometer
used for determining boron is a sensitized flame emission detector: the boron reacts with
the oxygen in the flame to produce the emitting molecule B0 2 • The same argument applies
to any other molecular emission.
The concept can be stretched in another direction. If a copper salt added to the sample
solution may be called a sensitizer for chlorine, then alcohol is a sensitizer for tin in a
hydrogen flame; reaction of the tin with substances formed from the alcohol causes the
chemiluminescence by which the tin is determined. Instead of alcohol in the sample,
acetylene in the hydrogen fuel has the same effect [39]; another example of this is seen
in Table 5.xI (Nitrogen). We can next eliminate the original fuel (hydrogen) and let the
acetylene, present in excess, serve as both fuel and "sensitizer"; this works with silicon
(Table 5.IX), arsenic (Table 5.xIX), beryllium, etc. It enhances the resonance line of
magnesium, too [39 (p. 172)]. But this line is emitted also in a normal acetylene flame, by
thermal excitation. By insensible degrees we have allowed the sensitizer to fade away alto-
gether.
If we cannot rigorously state what a sensitized flame detector is not, we shall have to
decide what it is, by listing specimens. The following characteristics are useful for classi-
fication:
1. The property measured: ionization; emission.

2. If emission, the nature of the source: flame; arc; spark.
3. If a flame, the state of the fuel: solid; liquid; gas.
4. If emission, the presence of the analyte in the emitter: direct (e.g., CuCI for CI);
indirect (e.g., Na for Cl).
5. The direction of response: positive (measured quantity increasing with analyte con-
centration); negative (decreasing).
6. The state of the sensitizer: solid; liquid; aerosol; vapor.
7. The method of heating the sensitizer: by the analytical flame; by a preliminary flame;
by electric resistance; by an electric discharge.
S. The state of the sample: solid; liquid; solution; suspension; aerosol; vapor; gas.
9. The method of introducing the sample: on the sensitizer; mixed with the sensitizer;
as vapor or aerosol in the fuel, in the oxidant, or in a separate carrier gas.
10. The duration of sample feed: rapid, complete consumption of entire sample; as an
eluting peak; continuously and uniformly but briefly; continuously, as in monitoring.
Examples of each of the above cases may be found in the literature of sensitized detectors.
5.14] CHLORINE 331
However, not every combination of cases is known. The above list, which by no means
exhausts the possibilities, generates about 18,000 combinations or kinds of sensitized detec-
tors. The following linear classification, with examples, covers most of the varieties of
interest for chlorine:
I. Sensitized flame detectors.

A. Sensitized flame emission detectors.
1. With a stationary solid or liquid sensitizer.
a. With sensitizer supported in and heated by a single flame.
(1). Solid or liquid sample introduced in, on, or near the sensitizer: the
Beilstein test and other methods of Table 5.xXXIII A.
(2). Gaseous or vaporized sample entering the flame: various leak detectors
and gas chromatographic detectors as in Table 5.xXXIII B and most
of 5.XXXIII C.
(3). Sample solution sprayed into the flame: Honma and Smith's observa-
tions on chlorine [305].
b. With sensitizer between two flames, heated by the lower: the van der Smis-
sen burner [564]; Karmen's arrangement [393] (Table 5.XXXIII C); the
indium burner (Table 5.xXXIII F).
c. With sensitizer heated electrically: Nowak and Malmstadt [544] (Table
5.xXXIII C); Dragerwerk burner [563].
2. With sensitizer solution sprayed into the flame.
a. Sample dissolved in sensitizer solution: the methods of Honma [573] and
others, to be discussed later.
b. Sample vapor entering flame: Burrows and Horwood's detector for fluorine
[524]; Zhitkevich's observations (discussed in Section 5.14.5 and in Table
5.xXXIII D).
3. With sensitizer vapor continuously fed to flame: Aue and Gehrke's experiments
[395] (Table 5.xXXIII C); also Saturno and Cooke [403].
B. Sensitized flame ionization detectors.
1. With a stationary solid sensitizer.
a. With sensitizer supported in and heated by a single flame: most of the devices
mentioned in Sections 5.6.6 and 5.7.13, typified by the Giuffrida alkali
thermionic flame ionization detector.
b. With sensitizer between two flames, heated by the lower: the detectors of
Karmen [393] and Jentzsch [400] (Section 5.7.13).
c. With sensitizer heated electrically: the detector of Abel et al. [401] (Sec-
tion 5.7.13); also Nowak and Malmstadt [544].
2. With sensitizer solution sprayed into the flame: the experiments of Page and
Woolley [367] with cesium as sensitizer for phosphorus.
3. With sensitizer vapor continuously fed to flame: see Category I.A.3 (emission
and ionization were both used).
II. Sensitized electrical detectors.
A. Sensitized discharge emission detectors.
1. Sensitized arc emission detector: in the Davis halide meter [547], a copper arc
emits CuCI bands in the presence of chlorine.
2. Sensitized spark emission detector: Midgley [548] used a copper spark in the
same way.
332 NONMETALS [5
3. Sensitized Geissler discharge emission detector: Snyder [576] used a low-

pressure discharge between nickel electrodes to detect halogen compounds,
which turned it green.
B. Sensitized electrical ionization detectors: typified by the General Electric halogen
leak detector [577], based on the patent by Rice [546]; an electrically heated ceram-
ic element emits ions when air containing a halogen compound flows past it.
Not all of the ten classes of characteristics listed earlier are displayed in the above
table. Some interesting cases of special characteristics are the following:
3. State of the fuel: The salted coal fire (Section 5.14.4) may be thought of as a sensitized
flame emission detector with a solid fuel containing the sensitizer (copper) for chlorine.
Liquid fuels have been used by Tait, Gaugler, Nolcken and Mitchell (Table 5.xXXIIIB).
4. The emissions are more often indirect than direct, but, except in the case of alkali
metals (Table 5.XXXIIl C), both kinds are commonly present together or consecu-
tively. The most distinctive direct emission is that of lnCl (Table 5.XXXIII F).
5. Negative emission response (with sodium as sensitizer) has been reported by Aue et al.
[394, 395], Saturno and Cooke [403] and Nowak and Malmstadt [544]. Negative
ionization response is less common [320].
6. The sensitizer is liquid in the indium burner (Table 5.XXXIIl F) and perhaps in a
few other cases. A liquid sensitizer should last longer and drift less than a solid one.
9. Methods of introducing the sample are listed in Table 5.XXXIII. A novel method is
that of Gutsche, Herrmann and RUdiger [570], who place a few microliters of sample
solution in a capillary tube, where it is suddenly heated and vaporized in a stream
of nitrogen that sweeps it into the burner.
The above listings should suffice to delimit the concept of sensitized detector in a com-
mon-sense way, at least for the case of chlorine. Table 5.xXXIIl lists an assortment of
sensitized flame emission methods for chlorine. It excludes, however, Category I.A.2.a,
which comprises several useful published methods that seem less closely related to the
other sensitized flame emission methods.
5.14.7 THE BEILSTEIN TEST
Any means of detecting chlorine (or bromine or iodine) by its enhancing effect on the
emission of copper in a flame (whether Cu, CuH, CuO, CuOH or CuC!) may be called
a Beilstein test. For perspective the reader should be acquainted with the spectrum of
copper in the usual analytical flames. Ref. [3 (pp. 547-8)] has a good spectrogram, and
another is shown in Fig. 5.28, with and without added chlorine. The photographic flame
spectrograms of copper in the atlases [104, 105] are excellent. The green color of the
copper flame results mainly from the diffuse bands identified by Padley [541] as due to
CuOH.
Beilstein did not discover the test, but his paper [542] in 1872 focused the attention of
analysts upon it. He says it was based on Berzelius's test for chlorine, bromine or iodine
in minerals, employing cupric oxide and microcosmic salt. Beilstein developed the test
specifically for organic substances, but his name has become associated with every other
form of the test. He put cupric oxide in a platinum loop, ignited it, dipped it into the
sample or sprinkled sample upon it, and placed it in the lower inner edge of a Bunsen
5.14] CHLORINE 333
flame. After the organic compound burns off, a green or blue color ensues; its duration
indicates the amount of halogen. The test works even with volatile samples. The copper
oxide bead may be purified by ignition with acetic acid. The Beilstein test has been used
virtually unchanged for nearly a century. A recent textbook [543 (p. 64)], for example,
recommends dipping a loop of copper wire into the organic compound and placing it in
the edge of a Bunsen flame. Very volatile samples, however, may evaporate from the wire
before showing the characteristic color.
In the Beilstein test, halogens induce volatilization of copper. Copper placed in an air-
gas flame as solid metal or oxide is not very volatile, and scarcely colors the flame. But
when chlorine, bromine or iodine, as element or compound, comes into contact with the
hot copper (or oxide), the volatile halide of copper is formed. As long as the halogen is
present, the rate of escape of copper into the flame is greatly increased.
Sternberg and Jones [263] have studied the process. Typically, chloride forms on the
copper faster than it can evaporate, so that copper continues to escape into the flame, at a
diminishing rate, after the sample is no longer present. While the sample vapor is present,
the chlorine concentration in the adjacent region of the flame is often high enough to keep
much of the volatilizing copper chloride from decomposing. At lower chlorine concentra-
tions, however, the escaping chloride reacts with the flame gases to give the other species
that are observed - CuO, CuOH, CuH and Cu. The conspicuous azure blue of CuCI
support
II-_-Copper tube
Flam. shield and
Chimney
l.l-'H---Bollam of flame
..
II:I-_--Bu'n
l->-lI""""I. Sample air

inl.,
Fuel ;0.
inlet
Fig. 5.29. NoIcken's halogen-detecting lamp.

334 NONMETALS [5
TABLE 5.XXXIII
METHODS OF DETECTING CHLORINE BY SENSITIZED FLAME EMISSION
Authors Ref. Method of

Date Type of sample applying sample Sensitizer
A. Copper as Sensitizer; Solid or Liquid Sample
1860 Merz [146] Solid CuCl2
1862 Simmler [28] Aqueous HCI Dip Brass wire
Solid or liquid Dip NaNH4HP04

Diacon [509]
1865
+ CuObead
Mitscherlich [549] Solid Mix 1/2 part (NH4hS04
1865
+ 1/10 part CuO
Ag halide ppt. Mix 2 parts CUO
1872 Beilstein [542] Org. compds. Dip or sprinkle CuO in Pt loop
1890 Salet [538] Procedure as with Beilstein
1890
N oelting and
Trautmann I [309] Procedure as with BeUstein
1900 Friedlander [533] NH4 salts Held in flame I CuO

1909 Milrath [310] Procedure as with Beilstein
Erlenmeyer and [550] Procedure as with Beilstein

1910 Hilgendorfi'
Gilman and [552] Procedure as with Beilstein

1929 Kirby
1933 van Alphen [312] Procedure as with Beilstein
Shriner, Fuson [543] Org. compds. Dip Cu wire loop

1964 and Curtin
B. Copper as Sensitizer; Gaseous Sample
In dish under Cu
1907 Beckmann air inlet
5.14] CHLORINE 335
TABLE 5.XXXIII (continued)
Probable Means of Detection Interferences,

Flame detection limit for CI etc.
emission •
Bunsen CuCI Visual 0.15 fLg
Bunsen CuCI Spectroscope 0.3 mgCu
CI distinguished
Bunsen CuCI,CuOH Spectroscope
from Br and I
H2 passed over CI distinguished

CuCI Spectroscope 0.2% easily
heated mixture from Br and I
CuCI appears be-

Same CuCI Spectroscope 0.1 % in Ag ppt.
fore CuBr or CuI
Visual Duration shows

Bunsen CuCI, CuOH amount
No intf. from Na,

I CuCI Visual
I I Ba
8-Hydroxyquinoline
CuOH and 5-, 6-, or 7-Me
I derivs.
Bunsen Br, I intf.
I I
Cu(CNh, urea,
CuOH
I quinoline derivs.
Cinnamic acid,
CuOH
I CUC0 3
CuOH Benzoic acid, etc.
.1 2_1, 3,4, 6-tetra-

CuOH phenyltrimidine, etc.
Bunsen CuCl, CuOH Visual
Bunsen I Visual
336 NONMETALS [5
Date Authors Ref. Type of sample Method of

applying sample Sensitizer
1913 Andrade [551] I CHCl 3 In air supply I Cu wire

I
1919 Air (ships, battle- Entrained by
Tait [311 ] Cu helix, etc.
I fields) lamp
1935 Dasher [553] Refrig. leaks Air sucked

by Venturi Cu cone
1938 Hull [554] Refrig. leaks Suction probe Slotted Cu cone
1938 [555] Entrained by

Gaugler Refrig. leaks Cu ring
Venturi
I
1940 Tuel [557] Refrig. leaks, etc. Entrained Perforated Cu disk
1943 Schmidt [558] Freon for leak: test-

ing
Entrained
through probe I Cu plate
1952 [559] Entrained Cu cylinder at

No1cken Freon leaks, etc. 1000 °C
through probe
Entrained
1957 Anthes [560] Refrig. leaks, etc. through probe 13 % Si-Cu ring
1957 I Mitchell [561 ] Refrig. leaks Entrained

through probe
Cu ring
[562]
Dragerwerk; [563] Any gas or vapor Introduced with Cu foil cylinder
1959 primary air between flames
van der Smissen [564] 1
Dubois and Through hypo-
1961
Monkman [565] I GC effluent dermic needle
Cu helix
~Onbnan"'d
DubOIs
[566] GC effluent Mixed with gas Cuhelix
H.M. Factory [567] Org. halides in air Enters flame

1961 Cu wire
Inspectorate
Sternberg and GC effluent in He Enters flame

1961 [263] carrier Cu tube
Jones
1962
Gunther, Blinn
and Ott
[313] GCeffluent Enters flame I Cu thimble
I
5.14] CHLORINE 337
Probable Means of Detection Interferences.

Flame emission a detection limit for Cl etc.
Bunsen CuCl,CuOH Spectroscope

I
Alcohol CuOH Visual Cyanogen
,
Meker-type
CuCl, CuOH Visual
burner
Blowtorch; air-
C 2H 2, etc.
CuOH I Visual \10 fLg/sec
Gasoline in
Meker burner
CuOH I Visual
Bunsen with
\ CuOH Visual 100 ppm
C 2H 2, etc.
I
Bunsen with
C 2H 2, etc.
CuOH; CuCI
(high concn.) IVisual 0.1 fLl/sec
I
Bunsen (Fig. I
5.29); inverted I CuOH Visual
gasoline torch
I I
Bunsen with
C 2H 2, etc. CuCl, CuOH Visual 100 ppm
(Fig. 5.30)
I
Gasoline torch
with pilot flame I CuOH I Visual
\
Sepd. H2 CuOH Photocell 0.1 fLg/1 Linear response

II
I
Natural gas CuOH I Visual; I fLg Br, I intf.
photocell
I
Natural gas in Intf. filter 520
Lange flame CuOH nm + Lange fl. Nearly linear
photometer photometer I
EtOH CuOH Visual
I
Hydrogen
CuCl, CuOH DU + IP28; 0.05 fLg extrap- Nearly linear
flame detector 436nm olated
526nm SF: 30 for S;

25 for C
I
Bunsen CuOH IVisual j 0.2 fLg/sec
j
Br, I, CN, SCN
338 NONMETALS [5
Date Authors I Ref. I Type of sample

Method of
applying sample Sensitizer
19631 Anonymous 1 [568]1 Halogen leaks
1964/ Eads and Payne [314] GC effluent in CH 4

carrier Present in fuel I Cu helix
1964 _/ Karmen [393] CHCl 3 in air Entrained I Cu screen between
flames
C. Alkali Metal as Sensitizer
[569] Entrained
1954 Bendt Refrig. leaks, etc. NaClon wire
through probe
[560] Entrained N a in stainless

1957/ Anthes Refrig. leaks, etc. through probe steel, etc.
/ I
Sternberg and [263] GC effluent in He Enters flame Na in dirt on
1961 burner jet
Jones carrier
I
1964 Karmen [393] GC effluent Enters flame I Na salt on grid
between flames
1966 Aue et al. [394] GC effluent Enters flame Na salt
1966 IAue and Gehrke [395] GC effluent Enters flame

Alkali salt on sup-
port; alkali metal
vapor in He
Saturno and Enters flame Na salt
1966 [403]1 GC effluent
Cooke
I
Baldwin and [405] Enters flame
1968 GC effluent
Malmstadt [545]
Nowak and GC effluent in He Electrically heated

1968 [544] Enters flame
Malmstadt carrier Na2S04 on Pt helix
D. Alkaline Earth as Sensitizer
Oxide, especially
1900 Friedlander [533] NH4 salts Held in flame
BaO
1919 ITait [311]

Air (ships, battle-
fields)
I
Entrained by
lamp
CaO, SrO, etc.
I salts
Mg, Ca, Sr, Ba
sprayed into
1963 Zhitkevich et al. [540] CCl 4 vapor Enters with air
flame
5.14] CHWRINE 339

Flame
I emission • detection limit for CI etc.
No details
Blowtorch available
CH 4 burns at CI color is
glass tip I CuOH Visual
distinctive
I
Tandem Bun-
CuOH Visual
sen burners
Gas Na Visual
C 2H 2, etc. 10 ppm
(Fig. 5.30) Na Visual
I
Hydrogen
flame detector INa DU + IP28
Tandem H2
flames Na Visual
I
H2 (Giuffrida) Na Neg. response
I
H2 Na Photo detector <0.1 [Lg/sec (1) Neg. response
H2 Na Neg. response
H2 Na
I
Hz Na I Intf.
IP28
filter + 0.1 ng; Pos. or neg. response;
Br, I intf.
0.01 [Lg/I
I
CI distinguished
Bunsen BaCI Spectroscope 13 [Lg
1 from Br and I
EtOH, etc. Visual No details

I
Air-C 2H 2 M+ '
I
MX MOH M Spectrograph,
"spectrophotom- Poor See text
eter .
340 NONMETALS [5
Date Authors Ref. Type of sample I applymg

M~thodsample
of Sensitizer
E. Nickel, etc., as Sensitizer
1913 Andrade [551] CHCl 3 vapor Enters with air

Ni wire
I Co salt on Pt wire
I
I Fe wire
1938 Hull [554] Cf. Section B Nickel (mentioned
only)
I Nickel (mentioned
1940 Tuel I [557] Cf. Section B only)
F. Indium as Sensitizer
[539] o-Chloroaniline, Introduced with Indium on support

1966 Gilbert CHCl 3 vapors primary air between flames
Gutsche, Herr- Vaporized in Indium on Be-Cu

[570] Insecticides in petro cylinder between
1968 mann and ether capillary in N 2
RUdiger stream flames
Gutsche and [571] Insecticides in
1968 MeCN as above as above
Herrmann
1968 I Herrmann [572] GC effluent as above as above
Notes:·) CuOH denotes the normal flame spectrum of copper salts, as distinguished from
the CuCI spectrum.
Abbreviations as in Chemical Abstracts. Also GC = gas chromatograph; intf. =
interference, interferes; refrig. = refrigerant; SF = specificity factor.
may appear, therefore, only at first contact of the sample with the copper; as the chlorine
concentration drops, the blue is replaced by the green of CuOH. The CuCI is best ob-
served at 435-436 nm and the CuOH at about 537 nm (Fig. 5.28). In gas chromatography
(Table 5.xXXIII B), the 435-nm emission will therefore give a sharp peak corresponding
to the eluting compound; the 537-nm emission will show considerable tailing. On the
other hand, because the strength of the CuCI emission depends on both the rate of volatil-
5.14] CHLORINE 341

Flame emission a detection limit for CI etc.
Green edge
(continuum) ; I Spectroscope
Bunsen
pink cone and
mantle (bands)
Red edge
(continuum) ;
lavendar mantle
(contin., bands)
Yellow
(contin., bands)
Should be highly
Sepd. H2
(Fig. 5.31)
InCl360 nm DU + IP28 O.oI fJ.gjl
specific
In 451 nm <0.1 fJ.gjl Br, I intf.
Uvispek Fat intf.;

Sepd. H2 InCl360nm
+ IP28 0.16 fJ.g
see text
I
Sepd. H2 InCl359 nm Zeiss PF5 + 0.06 fJ.g
intf. filter
Sepd. H2 InCl359 nm Zeiss PF5 +

intf. filter
ization of copper and the concentration of chlorine in the flame, the emission may rise
faster than the concentration of analyte at low concentrations. At higher concentrations
the formation of CuCI approaches a maximum and the analytical curve straightens out.
The exact character of the copper emission depends on details of the procedure or de-
sign. Many different forms of copper-sensitized halogen detectors have been built, as
shown in Table 5XXXIII. In most of them the response is probably due mainly to
342 NONMETALS [5
CuOH. This is true in particular of the van der Smissen (Dragerwerk) burner [564],
which normally emits only the green spectrum and gives a linear analytical curve from 0.1
to 10,000 (Lgjl.
The best temperature for the sensitizer is a matter of dispute. In the Dragerwerk burn-
er the copper must be kept below 300 °C and in an intermediate state of oxidation to
avoid loss of sensitizer and to maximize sensitivity. In Nolcken's burner [559], shown in
Fig. 5.29, the copper is kept above 1000 °C, close to melting. Nolcken claims that his de-
sign eliminates tailing by avoiding condensation of copper in cooler parts of the burner.
Hot sensitizers do not last long. Anthes [560] says that a pure copper element in his burn-
er (Fig. 5.30) lasted 14 hours, whereas the 3 % silicon-copper alloy that he recommends
lasts 100 hours.
Most modern copper-sensitized halogen flame detectors offer little or no discrimination
among the halogens. Even when the CuCI bands appear, the spectra of CuH and CuOH
impair their selectivity. But Mitscherlich, over a century ago, achieved excellent selectivity
by visual spectroscopy [549]. His first procedure (Table 5.xXXIII A) permitted easy detec-
tion of t % CI, t % Br and 1 % I - with practice, much less. For small amounts of
halogens, he precipitated them with silver (see the Table); he could then detect 0.1 % ofC!,
Br or I in the precipitate. With careful heating, the spectra of CuCI, CuBr and CuI
appeared in sequence. Mitscherlich claimed to be able to detect 0.1 ppm of iodide or bro-
mide in chloride by the flame. To do this, he added insufficient silver nitrate and let the
precipitate stand to concentrate the bromide and iodide. For example, in analyzing so-
dium chloride containing 10 ppm of sodium bromide, he was able to watch the CuBr
flame spectrum for 5 minutes. He could easily see the bromide in sea water. He deter-
Flame shield
, - - - . -- window
Coppe r disk
I'.
U~~~~_r-- Stoinltl'It., 1 disk
flame - - -11----\
1L-=-F'-- 8urn,r tip
Ineulotino
_I,.n Sto inl.:n ,tn l b;Jrner tube
Ai,
~
Oeroll ot coppe r
dis'" and
Sta inl." .fee l
disk
~:E~~~Ui=-Annu'o' spoce-~// for oir t r.try
c:!~r: -r=t~OJ=.-- Orific. plale
f ilter
disk'
Fig. 5.30. Anthes's halogen-detecting lamp.

5.14] CHLORINE 343
mined the halogens quantitatively by using two hydrogen flames with parallel sample
bulbs in the hydrogen tubes, one for sample and one for standard; the duration of the
spectrum was measured. But he admitted that this method was very difficult.
The Beilstein test can be positive with various non-halogen substances, most of them
containing nitrogen [309-314, 550, 552]; see Section 5.6.4 and Table 5.xXXIII. However,
the response is often weak, as with certain carboxylic acids [552]. The response of the
Beilstein test to fluorine has been mentioned (Section 5.13.2). Hull [554] and Gaugler
[555] imply a sensitivity to fluorine. But the fluorine response is much weaker than that
to chlorine. This may be due to the lower volatility of copper fluoride together with the
great stability of HF in the fl.ame.
5.14.8 COPPER-SENsmZED SOLUTION METHODS FOR CHLORINE
In developing their flame-spectrographic method for nitrogen (see Table 5.xI), Honma
and Smith [305] noticed that chloroacetonitrile yielded the CuCI spectrum in the inner
cone, the copper being contributed by the burner. They obtained an analytical curve for
the 4354-A band over the range 3-60 % chlorine, using the C 2 band at 4737 A as internal
standard. Honma next worked out a better method for chlorine in sea water, utilizing the
Beckman DU spectrophotometer with oxyhydrogen sprayer-burner flame [573]. He
used a very lean, small flame to suppress the CuH emission and enhance the CuCl.
Copper added progressively to a chloride solution raised the CuCI emission to a plateau
with a rounded edge at equimolar concentrations. Honma mixed the sea water with
2 parts of 1.25-M cupric nitrate and 1 part of distilled water. The analytical curve was
linear up to about 5000 ppm chlorine, becoming convex above that. The relative standard
error was 1.3 %, and the standard error at low concentrations was about 20 ppm.
Potassium and ferric chlorides could be analyzed under the same conditions; magnesium
and calcium chlorides required more hydrogen, and aluminum chloride and hydrochloric
acid still more. Nitrate enhanced and sulfate depressed the CuCI emission. Bromide and
iodide could not be distinguished from chloride. Carbon interfered spectrally and was
compensated with bicarbonate in the standard.
The method was applied to inorganic chlorides (DDT and 2,4-D) by Marsh [574], using
the same instrument and flame. She worked in the range 100-10,000 ppm, and added 8 %
copper octoate instead of copper nitrate. Reproducibility was 3 %. Interferences were
buffered. Each compound required a different analytical curve. Maruyama and Seno
[575], with the same flame and instrument, determined chlorine in various organic com-
pounds dissolved in dimethyl formamide containing 0.05-M copper nitrate. The analytical
curve was nearly straight up to 2000 ppm. The relative standard error was 0.9 %. The
detection limit was probably about 10 ppm chlorine. Recovery of chlorine was 98-102%
for solid organic compounds, 111 % for chloroform and 128 % for carbon tetrachloride,
referred to hexachlorocyclohexane as standard. The authors scanned from 428 to 442 nm
to get the net height of the CuCI peak at 435.4 nm. They show a recording from 424 to
460 nm with a slit of 0.05 mm, affording somewhat better resolution than Fig. 5.28;
the euo bands at 433.3, 441.2 and 449.4 nm are clearly resolved from their neighbours.
Even in the lean flame (0.45 l/min hydrogen) the CuH bands are distinct; in the dimethyl
formamide blank the CH band at 431 nm is weak and the C 2 bands are very weak. (More
hydrogen brings out the CuOH, CuH and C2 emission.) The CuCI band at 435.4 nm is
both the strongest and the least affected by background bands.
344 NONMETALS [5
5.14.9 FLAME EMISSION MEmODS WITH OTHER SENSITIZERS
Sensitized flame emission detectors for chlorine utilizing sodium, alkaline earths, nickel
and indium are listed in Table 5.xXXIII. A few of these are merely suggestions in patents.
No real effort has been made with the alkaline earths or nickel. The results of Zhitkevich
et al. [540] were described earlier; they pointed out that the alkaline-earth halide bands
could be used for the flame-photometric determination of halogens, although in their
flame the bands were relatively very weak. Only Friedlander [533] has done any analytical
work with these bands. He preferred barium, which offered the best selectivity and the
least interference from other elements. He could detect and distinguish 13 [Lg of chlorine,
15 [Lg of bromine and 17 [Lg of iodine. Andrade's observations [551] on iron, cobalt and
nickel as sensitizers are sketchy, but there is little or no other work on the utilization of
these metals.
Sodium has been used as sensitizer (Table 5.xXXIII C) more often than any other element
except copper. The work is all recent. Bendt in 1954 seems to have been the first to observe
or use the emission of sodium induced by chlorine [569], but his work passed unnoticed.
Anthes in 1957 studied the phenomenon more closely [560]. He tried various sodium-
containing sensitizers in his burner (Fig. 5.30), including electrolytic iron, 8-11 stainless
steel and pure copper, impregnated by heating with 5 % sodium amalgam under argon.
Many steels and copper alloys contain enough sodium naturally to serve as sensitizers.
Anthes favored Type 304 stainless steel, which keeps its sensitivity longest. It is run at dull
red heat; if the sensitivity falls, jarring the metal restores it by loosening the oxide film.
He used copper and sodium together, to widen the range. At low concentrations, above
15 ppm of chloride in air, the flame becomes yellowish from the sodium; above 150 ppm
the copper begins to contribute a bluish-green tint, turning purple, according to Anthes,
at higher concentrations.
Karmen [393] in 1964 first called the attention of analysts to sodium as a flame-emis-
sion sensitizer for halogens. He was more interested in sensitized flame ionization detectors
for gas chromatography, but others (Table 5.xXXIII C) have subsequently studied the
emission aspect of the phenomenon. As a matter of fact, Sternberg and Jones [263] in
1961 had noticed the sensitized flame emission of sodium with chlorine compounds in gas
chromatography, but this observation was not published. Karmen reviewed the phenome-
non in 1966 [399]. The most sensitive embodiment is the burner of Nowak and Malm-
stadt [544]. For halogens they consider the sensitized flame emission detector much better
than the sensitized flame ionization detector. Molar specificity factors with respect to
chlorine are as follows: carbon, 5000; sulfur, 500; phosphorus, 20; nitrogen, extremely
high. The detector drifts less than 1 % per hour, less than the ionization detector. It can
be used, of course, in both modes and also as a normal (unsensitized) flame ionization de-
tector, the small hydrogen flame (50 ml/min) being suitable for all three uses.
5.14.10 THE INDIUM BURNER
In 1965, seeking a better sensitized flame emission detector for chlorine, I considered all
the elements of the periodic table and selected indium as the most likely prospect. The
reasons for this choice are set forth in my paper [539]. I was thinking, however, only of the
use of the strong indigo line (4511 A) for the indirect, nonspecific detection of halogens. It
5.14] CHLORINE 345
turned out that this line does offer better sensitivity for chlorine, below 0.1 [.Lg/I, than has
been reported for any other sensitized flame emission detector except perhaps Nowak
and Malmstadt's. (From their data I judge that the concentrational detection limit would
be about 0.01 [.Lg of chlorine per liter of air entering their burner.)
It was the accidental discovery of the InCI emission in the ultraviolet that makes the
"indium burner" uniquely useful. The abnormally great intensity of the bands may be due
to a chemiluminescence. They lie in a region (360nm) where flame background, other in-
dium emissions and ambient light are weak. A quartz monochromator can easily sepa-
rate the bands from those of InBr and Inl. The selectivity for chlorine will be much
greater than that of other flame detectors; but the results of selectivity studies are not yet
available for publication.
The "indium burner" is shown in Fig. 5.31. Like the van der Smissen burner,it produces
a separated hydrogen flame. The indium should be so placed that it remains somewhat
above its melting point. The primary air, carrying the sample vapor,can flow at 0.3-1.5
l/min; the hydrogen/primary air ratio should be about 0.7. The InCI spectrum is shown
in Fig. 5.32 and listed in Table 5XXXIV. A sensitivity of 0.01 [.Lgjl (chlorine in air) has
been demonstrated, but I believe that it can be extended to 0.001 [.Lgjl. The response is
linear at least up to 20 [.Lgjl. The emission is exceedingly steady; peak-to-peak noise is as
low as 0.3 % at a time constant of 0.5 s.
The only other published work on the indium burner is the series of papers by Herr-
mann and his associates [570, 571, 572 ](Table 5XXXIII F). To introduce sample, they va-
porized a few microliters of solution in an electrically heated capillary tube and swept it
Outer Chim ney
Upper Flcme
Region of In CI
Emission
Indium - Coated
Tube
Inner Ch imn ey
Secondary
Air
Flame
Pr im ary
Air with
Sample
Hydrogen Inlet
Fig. 5.31. Modified van der Smissen burner with indium. Reproduced by permission of Analytical
Chemistry.
346 NONMETALS [5
TABLE 5.xXXIV THE FLAME SPECTRUM OF InCI

Wavelengths of InCPs heads (degraded to shorter wavelengths) of the A and B systems. For
the B system, P heads are listed; Q heads lie about 0.3A to shorter wavelengths. Wavelengths
marked "w & m" are from Wehrli and Miescher [587]; those marked "p & h" were measured
by Petrikaln and Hochberg [586], but these, as well as those marked "calc,"· are calculated
from the vibrational constants quoted in [79] from Wehrli and Miescher. Flame intensi-
ties were observed under the conditions of Fig. 5.32, on a scale of 100 for the strongest band.
System and /-dntensities

v',
I
Wavelength V" Source Notes
sequence w&m I Flame
I~
3344.6 6, 2 calc
B (n + 4, n) ~ 3344.7 5, 1 calc 0.1 (u)
I 3345.0 4,0 p&h
3379.8 6, 3 calc
B (n + 3, n) ) 3379.9
3380.7
3381.5
5,2
4, 1
3, 0
w&m
w&m
p&h
2
0
~ 0.8 (u)
!
3415.2 6,4 w&m 1
3416.1 5, 3 w&m 1
3416.9 4,2 w&m 3
B (n + 2, n) 3418.0 3, 1 w&m 3 7 (u)
1 3419.3
3421.0
2,0
2,0
w&m
(a)
3
3435.2 5, 1 calc
+ 4, n) ~ ~
I
A (n 4,0 p&h 0.2 (u)
3435.8
~
3452.4 5,4 w&m 1
B (n + 1, n) \ 3453.6
3455.0
3456.6(f)
4, 3
3, 2
2, 1
w&m
w&m
w&m
1
2
4
22 (u)
?
3458.5
3459.3
1, 0
1, 0
w&m
(a)
5
I
l !
3471.4 7, 4 w&m 1
3471.9 6, 3 w&m 1
A (n + 3, n) 3472.4 5,2 w&m 0 3 (u)
3473.4 4, 1 w&m 0
3474.5 3, 0 p&h
I(
3492.6 3, 3 calc
B (n, n)
) 3494.5
3496.5
3499.0
2, 2
1, 1
0,0
calc
w&m
w&m
3
8
50 (u)
3508.8 7, 5 w&m 1
3509.4 6,4 w&m 1
3510.4 5, 3 w&m 2
A (n + 2, n)
) 3511.6
3513.0
3514.6
4,2
3, 1
2,0
2,0
w&m
w&m
w&m
2
3
2
15
12 (8)
3516.4 (a)
I
3530.8 3,4 calc
3532.9 2, 3 calc
B (n, n + 1) 3535.3 1, 2 w&m 2 30
3538.0 0, 1 w&m 2 23 (8)
Notes: (a) InCI37 band lying at head of sequence, probably conspicuous; from w & m. (b) Bands
barely resolved by DU spectrophotometer. (c) Doubtfully resolved by DU. (d) Several peaks are
visible, but their identities are uncertain. (e) Peak seems unduly narrow on recording. (I) Mis-
5.14] CHWRINE 347
System and Intensities

Wavelength v', v" Source Notes
sequence
I w&m Flame
I Il
3548.9 5, 4 w&m 0
3550.4 4, 3 w&m 1
3, 2 w&m
A (n + 1, n) 3552.1
3554.0 2, 1 w&m
3
4
50 (u)
3556.2 1, 0 w&m 5
3557.1 1, 0 (a)
B (n,n + 2)
1
3569.5
3572.0
3574.7
3577.8
3591.9
3, 5
2,4
1, 3
0,2
3, 3
calc
calc
calc
p&h
calc
! 11
(u)
A (n, n)
) 3594.1
3596.5
3599.2
2,2
1, 1
0,0
calc
w&m
w&m
2
6 ~ 100 (u)
l
3606.2 4, 7 calc 4
)
3608.8 3, 6 calc 4
B (n,n + 3) 3611.6 2, 5 calc 4 (b)
3614.7 1, 4 calc 2
3618.1 0, 3 p&h 1
3632.2 3, 4 calc
A (n, n + 1) ) 3634.7
3637.5
3640.5
2,
1,
0,
3
2
1
calc
w&m
w&m
2
2
I 45
40 (8)
3648.7 3, 7 calc 2
B (n, n + 4) ) 3651.9
3655.3
3659.1
2, 6
1, 5
0,4
calc
calc
calc
(1·t)
1 ~ (c)
3673.3 3, 5 calc
+ 2) 3676.1 2,4 calc 15
~
A (n, n 3679.2 1, 3 calc 15
1 3682.6 0,2 p&h 8
(c)
(8)
3692.8 2, 7 calc 1
B (n, n + 5)
~ 3696.6
3700.7
I, 6
0, 5
calc
calc
I
1
t ~ (b)
!
3714.9 3, 6 calc 3t
A (n, n + 3) 3718.1 2, 5 calc 4
(b)
1 3721.6
3725.3
1,
0,
4
3
calc
calc
4
3
B (n,n + 6) 3743.0 0,6 calc t
I
3753.9 4, 8 calc
3757.2 3, 7 calc ~ 1
A (n, n + 4) 3760.8 2, 6 calc
3764.6 1, 5 calc t-l ?? ~
t-l (d)
3768.7 0,4 calc t-l ?
+ 5) 3808.6 I, 6 calc
A (n,n
~ 3812.9 0, 5 calc 0.5 (e)
A (n, n + 6) 3857.8 0, 6 calc 0.5 (d), (g)
printed as 3456.3 in [78]. (g) Higher members of the sequence are doubtless present. (8) Weak
shoulder on side of peak. (u) Unresolved by DU.
348 NONMETALS [5
into the burner with nitrogen at 480 ml/min. However, the sample does not pass through
the combustion zone of the lower flame. The authors did not measure vapor concentra-
tions, but utilized the peak height or area given by complete vaporization of the sample.
They burned hydrogen at 1.2 l/min and kept the indium at 200 °C. It lasted for over 500
analyses.
0 3
..
8
oi
<0
.,
,,; N
:;;~
'" '" coft
,.;
<00
"',f
'"'"
N I
U')~
.,..08
"'''',.;
on
ci~
I'"
.. .
... ==-
~~
~~
='0
","
!1~
j;)(\j
~~ ~:;;
"uc
ij
~8
on
",,,,
~ a)
iii iii ""<7
on",
"'., '" "
(/)
';'1
I'" I
N':
!!i~ A A
B
--
0_
crlaj
..,'"
"'''' B
B
340 355 360
Fig. 5.32. Spectrum of InCI in air-hydrogen flame.

Burner of Fig. 5.31. DU-2 spectrophotometer, slit 0.014 mm. Bands of the A and B systems are so
marked. Numbers in parentheses are the vibrationalleve1s of the upper and lower states. Wave-
length scale is zero-intensity line. Reproduced from [539] by permission of Analytical Chemistry.
Gutsche, Herrmann and Riidiger [570] tested several chlorinated insecticides separate-
ly and in mixtures, the latter showing marked departures from additivity. The analytical
curve was straight for Lindane at 1-20 (Jog dissolved in 2 (Jol of petroleum ether. The stan-
5.14] CHLORINE 349
dard error was 4.5% but this includes the pipetting error. Recovery of Lindane and DDT
from butter, after extraction, ranged from 43 to 87 %at 10-40 ILg of insecticide. The butter-
fat could not be directly injected, as it suppressed the chlorine response. In testing their
filter photometer, Gutsche and Herrmann [571] determined Lindane in butter with
recovery of 67-94 %at 20-40 ILg. In examining several different insecticides, they found
that the ratio of response to chlorine content varied by ±19%. Perhaps this variation of
specific response, the lack of additivity in mixtures, and the interference from fat might all
be lessened if the sample were passed through the lower combustion zone; the sensitivity
might also be improved.
5.14.11 NONSENSITIZED INDIRECT FLAME EMISSION
Indirect methods in which chloride is precipitated by silver and the excess silver deter-
mined by fiame photometry have been reviewed in [3 (p. 247), 4, 6 (p. 112)]. Perhaps
the best known is that of Menis, House and Rains [580], described also by Dean [2 (p.
264)]. They determined the excess silver in the linear range 5-40 ppm with an oxyhy-
drogen sprayer-burner. The detection limit was below 0.1 ppm of chloride. Alcohol
or acetone could be added for more sensitivity. Papers later than the above reviews
include those of Lang [581] and Gutsche et al. [582]. They used air-hydrogen sprayer-
burner flames at 3383 A. Lang determined chloride in 50 ILl of blood serum with a stan-
dard error of 0.75 % and Gutsche determined it in 50 ILl of milk with a standard error of
0.46%.
Chloride can also be determined in water via the sodium emission, when the chloride
is present essentially as sodium chloride [1 (p. 315)]. Maley [583] used this principle in
monitoring the chloride content of purified boiler water in nuclear power plants. A con-
stant-level weir supplied the water to an oxyhydrogen sprayer-burner.
Westerlund-Helmerson [584] analyzed zinc and lead oxides for chloride by boiling the
sample with silver nitrate and nitric acid and dissolving the washed chloride precipitate
in ammonia. The silver in the dissolved precipitate was then determined by atomic ab-
sorption. The percentual detection limit was equivalent to 0.03 ppm chloride in the final
diluted solution. Emission flame photometry would be equally useful in this procedure.
Christian and Feldman [9] used atomic absorption for determining the excess silver after
chloride precipitation.
Perchlorate was determined by Collinson and Boltz [585] by a method analogous to
that of Kumamaru for nitrate (see Section 5.6.5). Cuprous perchlorate forms a complex
with neocuproine that can be extracted at pH 3-5 into ethyl acetate. The copper is
determined in the extract at 3247 A by atomic absorption. The method is very sensi-
tive, with a detection limit of 0.03 ppm perchlorate in the original aqueous solution; it
is useful up to 5 ppm. The standard error was reported as 0.4 % at 3 ppm. Not over
10 ppm of nitrate, ammonium, magnesium or aluminum should be present.
350 NONMETALS [5
5.14.13 IONIZATION DETECTORS
The discussion of flame ionization detectors under Phosphorus and Nitrogen applies
largely also to chlorine (and bromine and iodine). These detectors are usually much more
sensitive to phosphorus, yet sufficiently sensitive to chlorine to be very useful. (Converse-
ly, the sensitized flame emission detector of Nowak and Malmstadt is more sensitive to
halogens than to phosphorus.) Refer also to the outline of sensitized detectors for exam-
ples of flame and electrical ionization detectors. The sensitized electrical ionization de-
tectors respond primarily to the halogens, not to phosphorus.
A precursor of the sensitized flame ionization detectors for halogens was the arrange-
ment of Phillips and Owens [578], who used an ordinary (unsensitized) hydrogen flame de-
tector with an abnormally hot flame that touched the platinum ring and gauze electrodes
and kept them red hot. This detector was selective for halogens. It seems likely that so-
dium on the platinum was acting as sensitizer.
To point out some of the literature of sensitized flame ionization detectors for chlorine
I refer here once again to the work of Karmen and Giuffrida [393, 397, 398, 399], Aue et
af. [394, 395], Jentzsch et af. [400], Abel et aZ. [401], Saturno and Cooke [403], Ives and
Giuffrida [316], Johnson et aZ. [321], Baldwin [405,545], Nowak and Malmstadt [544]
and the earlier study of flame ionization with halogens by Padley, Page and Sugden [404].
Karmen's device [393] detected 0.3 ng of chlorine. Jentzsch's was l.inear for chlorine from
3 to 300 ng and Abel's from 50 to 2000 ng. Abel made the detector more sensitive to
chlorine than to phosphorus by using oxyhydrogen instead of the usual air-hydrogen
flame.
The sensitized electrical ionization detector of Rice [546,577] has been mentioned. There
are quite a few other patents and papers on this type of device. Among them the paper
by Moesta and Schuff [579] describes a leak detector nearly specific to halogens, sensitive
to 0.01 microtorr of Freon (in a vacuum). They studied the mechanism of the phenome-
non, but it is complex and depends on many variables.
5.14.14 ELECfRIC DISCHARGES
The electrodeless argon discharge of McCormack et aZ. [88] (see S. 5.4.7), with chlorine
compounds, emits the CCI bands in the vicinity of 2788 A and several unidentified bands.
The CCI band permits detection of 0.8 ngjs of chlorine in chloroform; elsewhere in the
paper a sensitivity of 2 pgjs is mentioned. Bache and Lisk [408], with their low-pressure
helium plasma, obtained a sensitivity of 0.06 ngjs with the chlorine line 4794.5 A.
Moye's argon-helium discharge [409] offered a sensitivity of 10 ng for chlorinated insecti-
cides; an unidentified band at 2210 A was used. In Braman and Dynako's d.c. discharge
the Clline 7256.6 A and the CCI bands could be used. The red line offered the remarkable
detection limit of 0.02 ng, but its specificity was not outstanding: e.g., the chlorine-iodine
specificity factor was only 70.
The sensitized discharge emission detectors of Davis Instrument Division [547],
Midgley [548] and Snyder [576] were listed in the outline of sensitized detectors. The
Davis halide meter gives a different analytical curve for each halocarbon. With carbon
tetrachloride the sensitivity seems to be as high as 1 ppm in air; the range extends to about
300 ppm.
5.15] BROMINE 351
5.15 Bromine
5.15.1 NONMETALLIC FLAME SPECTRA
The first observations on the flame spectroscopy of bromine were those of Mitscherlich
[21], who burned hydrogen with bromine alone or mixed with oxygen or oxygen and air.
He said that these flames emitted only a continuum. The continuum was seen also by
Salet [17, 282]; bromine turned an air-hydrogen flame yellow (but Br2 emission was
probably also present). The bromine continuum was later studied by Urey and Bates
[526, 527] in oxyhydrogen and by Phillips and Sugden [529, 530] in nitrogen-diluted
oxyhydrogen. There are two kinds of continua, analogous to those of chlorine; see
Gaydon's discussion [34 (p. 218)].
The spectrum of Br2 may be seen in emission in various flames. The bands are very nu-
merous, closely spaced, and weak except at high concentrations of bromine. The stronger
bands extend from the mid-green into the red. They appear in the bromine-hydrogen
flame [34 (p. 219)], the oxygen-ethyl bromide flame [588], oxyhydrogen flames containing
bromine or methyl bromide, and air-hydrogen and separated oxyhydrogen flames with
methyl bromide [589]. The Br2 emission comes from the mantle, which it colors orange
or brown; it is accompanied by the continuum. The bromide additives in antiknock gas-
oline may give rise to Br2 bands in the exhaust flame of an engine [34 (p. 212)]. A diffuse
band of Br2 peaking at 2910 A occurs in the inner cone of an oxyhydrogen flame with
methyl bromide [34 (pp. 218, 234), 589]; there are similar, weaker bands at 3330, 3120
and 2750 A. Forliterature and the principal wavelengths of the Br2 spectrum, see [34 (p.
234), 78, 79]. For earlier work, see Kayser [91 (p. 174)].
The "ethyl bromide flame bands," due to Bra, are visible in the bromine-hydrogen and
oxyhydrogen-bromine flames [526, 527, 589], oxyhydrogen or air-hydrogen with methyl
bromide [589], and the flame of methyl [589] or ethyl [588] bromide with oxygen. The
bands appear just above the inner cone in a separated oxyhydrogen flame, where they color
the flame blue [34 (p. 218), 589]; ordinarily the color is masked by the orange of Br2.
The Bra spectrum covers the violet and blue and resembles that of Cia. It is faint
except with much bromine. For the wavelengths and intensities of the chief bands, see
[34, 78, 79]. A detailed analysis was made by Durie and Ramsay [591], who observed
Bra in absorption after flash photolysis of a bromine-oxygen mixture.
The CBr spectrum has not been detected in flames; the bands near 2920 A listed in
[79] under CBr, observed with bromine in an oxygen-hydrocarbon flame, are probably
the same as the Br2 band mentioned above [34 (p. 218), 589 (p. 176)]. In flash photolysis,
however, CBr bands near 3050 A have recently been identified [78 (Supplement, p. 352)].
The infrared rotation-vibration bands ofHBr near 3.6 pm are strong in bromine-hydrogen
flames [34 (pp. 177,219)]. Lastly, bromine in an air-methanol flame emits a weak, violet-
degraded band at 3670 A; the emitter is unknown [590].
5.15.2 METALLIC BROMIDE SPECTRA
The bands of CuBr are as persistent and conspicuous in flames as those of CuCl. They
lie in the blue, extensively overlapping the CuCI bands. Early observations are those of
Simmler [28], Mitscherlich [21], Diacon [509] and Salet [17] (see Chlorine). Diacon was
352 NONMETALS [5
able to distinguish CuBr and CuCI in a mixture by means of a spectroscope, although

Friedlander [533] could not. Visually, the flame colors can hardly be told apart. A piece
of copper in a bromine-containing hydrogen flame gives a blue color (CuBr) surrounded
by the green of the normal copper flame spectrum and a red outer region showing a con-
tinuum [17]. Derichsweiler [592] measured the spectrum in 1906; he vaporized copper and
ammonium bromides in an oxygen-illuminating gas flame. Lecoq [98] published a good
drawing and Eder and Valenta [104] a photograph of the CuBr spectrum in the Bunsen
flame. Kayser summarized the data in 1910 [91 (p. 417)] and 1932 [93 (p. 652)]. The
most thorough study of CuBr is that of Ritschl [512], whose principal data are found in
[78] and [79].
Other metallic bromides have occasionally figured in the analytical flame spectroscopy
of bromine. Mitscherlich [21] mapped the flame spectra of the bromides of calcium,
strontium, barium and bismuth. Diacon [509] observed distinctive blue and green bands
of bismuth bromide in the Bunsen flame; see [79] for wavelengths (in absorption).
Lecoq's book [98] contained the spectra of many bromides, according to Kayser. Fried-
lander [533] studied the alkaline-earth bromides in the Bunsen flame. In the experiments
of Zhitkevich et at. [540], described in Section 5.14.5, bromine was fed to the flame as
element at rates up to 330 mg/min. Good spectrograms showing the flame bands of CaBr,
SrBr and BaBr appear in Eder and Valenta's atlas [104]. Summaries are found in Kayser
and Konen ([92 (p. 99)] for BaBr; [93 (p. 378)] for CaBr). The strongest heads of MgBr
lie at 3864 and 3880 A, of CaBr at 6253 and 6278 A and (weaker) at 3917 and 3951 A, of
SrBr at 6513 and 6667 A and (weaker) at 4053 and 4108 A, and of BaBr at 5208 and 5360 A.
The sequences are close; the violet bands are degraded to red and the red bands to violet;
the green bands of BaBr are degraded to red rotationally but to violet vibrationally [78,
79].
The spectrum of InBr has now become important in connection with the "indium
burner." It was measured by Petrikaln and Hochberg [586] and by Wehrli and Miescher
[587] both in emission in an electrodeless discharge and in absorption. The strongest
bands lie at about 3630 (a complex sequence), 3651, 3700 (another complex sequence),
3727, 3758 and 3790 A [78, 79].
5.15.3 DETECTION BY SENSITIZED FLAME EMISSION
All of the sensitized flame emission methods or detectors for chlorine listed in Table
5.xXXIII are probably about equally sensitive to bromine. When the emission is indirect,
e.g., CuOH or Na, the halogens cannot be distinguished; when it is direct, e.g., CuBr or
BaBr, bromine can often be distinguished from chlorine and iodine to at least some degree.
Refer to the discussion of the Beilstein test in Section 5.14.7. Mitscherlich's method [549]
of detecting and determining the individual halogens was described there. Diacon's
method [509] was also selective. With barium, Friedlander [533] was able to detect 15 {Lg
of bromine selectively. Tait [311] mentioned the detection of bromine on battlefields (his
detector was invented during the first World War). In the visual copper-sensitized gas-chro-
matographic detector of Dubois and Monkman [565], the detection limit for ethyl bro-
mide was 0.2 fl.!. In the similar detectors of Eads and Payne [314], ethylene bromide,
bromobenzene, etc., were stated to color the tip of the flame bright blue. The sodium-
sensitized flame emission detector of Nowak and Malmstadt [544] is 4 or 5 times as sen-
5.15] IODINE 353
sitive to bromine as to chlorine on a molar basis, or twice as sensitive on a weight basis.

Its detection limit for bromine is presumably 0.05 ng (absolute) or 0.005 (J.g/I (concentra-
tion). Bromine is detectable also by the methods of [313, 394, 395, 542, 543, 553-555,
557-564, 566, 567, 569].
The indium burner [539,570-572] is now known [320,593] to be as useful for bromine
as for chlorine. With proper choice of wavelength, it ought to afford the best combination
of sensitivity, selectivity and precision yet available for the detection and determination of
bromine in gases, vapors or aerosols.
As for copper-sensitized solution methods (see Section 5.14.8), Honma [573] said that
even with the spectrophotometer, bromine and iodine could not be distinguished from
chlorine. Maruyama and Seno [575] stated that the CuBr and CuI bands, although less
intense than the CuCI bands, could be used for bromine and iodine; but they said
nothing about selectivity.
5.15.4 OTHER METHODS FOR BROMINE
The nonsensitized indirect methods described for chlorine will not normally distinguish
bromine. However, Menis, House and Rains [580] determined bromine in the presence
of chlorine by precipitating it with silver nitrate in 0.03-M ammonia. The ammonia con-
centration is critical; too little will not keep the silver chloride in solution, and too much
will dissolve the bromide.
The various flame ionization and electrical ionization detectors mentioned in Section
5.14.13 respond also to bromine. Jentzsch's detector [400] responds linearly to bromine
from 8 to 800 nanograms.
The microwave argon discharge of McCormack at al. [88] emits an unidentified line
at 2985 A in the presence of bromine. It affords a sensitivity of 0.2 (J.g/s. The helium
discharge of Bache and Lisk [408] emits the bromine line at 4785.5 A, offering the 104 _
fold better sensitivity of 20 pg/s. Braman and Dynako's d.-c. discharge offers a limit
of 0.3 ng or 15 pg/s at the bromine line 7348.6 A, with specificity factors of the order of
100 toward other halogens [275]. These characteristics make the discharge very attractive;
it deserves further study.
5.16 Iodine
5.16.1 NONMETALLIC FLAME SPECTRA
The bands of 10, called the "methyl iodide flame bands" by Vaidya [595], have been seen
in flames since the beginning of spectrochemistry. Indeed, Salet in 1873 [17] surmised
that they might be due to an oxide of iodine. Mitscherlich [21] burned hydrogen or car-
bon monoxide with iodine vapor plus oxygen or oxygen and air. He saw the 10 bands
plainly and made a fine drawing of the spectrum of the red-degraded bands in the blue
and green. Salet noted the greenish color imparted by iodine to the mantle of a hydrogen
or carbon monoxide flame; with much iodine the inner cone emitted a yellow continuum.
He saw the 10 bands in the mantle also when silicon tetraiodide was fed to a flame. Ko-
354 NONMETALS [5
nen in 1898 obtained the bands by supplying iodine to flames of hydrogen, ether, alcohol,
carbon disulfide or carbon monoxide [594]. Kayser summarized these findings in 1910
[91 (p. 562)].
In 1929 Urey and Bates [526, 527] measured the bands from an iodine-charged oxy-
hydrogen flame and ascribed them to 10. Vaidya [595] first analyzed the system. He ob-
tained the bands from methanol or gas burning with air or oxygen and charged with
methyl iodide; oxygen-gas was best. Iodine placed in a Bunsen flame also yielded the bands.
In a lean flame 10 colors the whole mantle green; in a rich flame the green shrinks to a
region above the inner cone. The spectrum was remeasured by Coleman, Gaydon and
Vaidya [590], using iodine in oxyhydrogen. Durie and Ramsay [591] obtained the 10
spectrum in absorption by flash photolysis and, with Legay in 1960 [597], they remeasured
the spectrum more accurately, using a diffusion oxyhydrogen flame charged with methyl
iodide. A study of the dissociation of 10 was carried out by Phillips and Sugden [530], by
means of the 5307-A band in a rich nitrogen-diluted oxyhydrogen flame with 0.5 % iodine
or methyl iodide. The excitation of 10 is thermal, and it can be used for measuring the
atomic oxygen content of a flame.
The 10 spectrum extends from 4189 to 6231 A. There are no outstanding bands; the
strongest heads lie at 4487, 4586, 4844 and 5307. Owing to the diffuseness of the bands,
earlier tables show discrepancies of several angstroms; the best list is that in Pearse and
Gaydon [78].
The visible spectrum of 12 has not yet been seen in emission in flames [34 (p. 241)].
However, Mitscherlich [21] noticed the absorption spectrum of 12 in a flame overloaded
with iodine, and Kayser [91] said that the 12 spectrum may appear at the top of a flame,
above the region of 10 emission. According to Gaydon, a diffuse band of 12 at 3425 A
occurs in the inner cone of organic iodide flames [34 (pp. 218, 241), 78 (p. 185)].
The band spectrum of IF is emitted by the iodine-fluorine and methyl iodide-fluorine
flames [78, 454]. It covers the visible. Iodine added to an air-methanol flame produces a
strong violet-degraded band at 4045 A; the emitter is unknown [590]. Iodine emits flame
continua analogous to those of bromine and chlorine. They are due to I + I and I + H
recombination [526, 527, 529, 530].
5.16.2 METALLIC IODIDE SPECTRA
The flame spectrum of CuI, like that of CuBrand CuCI, covers the blue and violet and part
of the green. Although the three spectra look different through a spectroscope, they overlap
so severely that little selectivity can be had with a spectrophotometer. Among early obser-
vations are those of Simmler [28], Mitscherlich [21,27,508], Diacon [509], Friedlander
[533] and Derichsweiler [592] (see Chlorine and Bromine). Diacon said that the copper
iodide spectrum was harder to discern than those of the bromide and chloride. Eder and
Valenta [104] published a good photograph of the Bunsen flame spectrum of copper
iodide. The early data on CuI were summarized by Kayser [91 (p. 417), 92 (p. 361), 93
(p. 652)]. Ritschl [512] tabulated the absorption spectrum; his principal data are quoted
in Rosen [79], whereas Pearse and Gaydon [78] present the chemiluminescent spectrum
measured by Mulliken. Quite recently Hollander [82] studied the behavior of CuI in
carbon monoxide and propane flames.
The flame spectroscopy of other metallic iodides runs parallel to that of the bromides.
5.16] IODINE 355
Mitscherlich in 1862 studied the Bunsen flame spectra of the iodides of calcium, strontium
and barium mixed with ammonium iodide [27,508]. Two years later he mapped the iodide
spectra of calcium, strontium, barium and bismuth, and Diacon [509] did the same.
Friedlander [533] also examined the alkaline-earth halides. Zhitkevich et al. [540] studied
the effect of iodine on the flame spectra of strontium and barium, including SrI at 4412 A
andBal at 5609 A (see Section 5.15.2). Spectrograms of Cal and SrI are found in Eder and
Valenta [104]. Kayser and Konen summarized data on Cal [93 (p. 378)] and Bal [92
(p. 99)]. MgI is known only in absorption; the chief bands are 3953 and 4110 A [79]. The
strongest flame bands of Cal lie at 6389, 6413 and 6361 A (in order); there are several
violet bands, the strongest being 4211 and 4289 A. SrI has violet bands at 4307 and 4412
A and neighboring wavelengths, as well as red bands. These are close sequences, de-
graded like the analogous bromide bands. Bal emits green flame bands at 5609 and 5382 A,
degraded to the violet [78]. The spectrum of Inl, needed for utilization of the "indium
burner", was measured by Wehrli and Miescher [587] (see Section 5.15.2). It differs
a good deal from the spectra of InBr and InCI; the strongest bands of Inl lie at 3993 and
4099 A.
5.16.3 DETECTION BY FLAME EMISSION
Alone among the halogens, iodine has been detected by unsensitized direct flame emission
in practical flame-spectrophotometric work. This is possible because of the readier exci-
tation of the 10 spectrum. Ohyagi [596] observed these bands in a study of metal deter-
mination in biochemical materials (leaves and blood serum), which he oxidized by
grinding with iodine and warming with nitric acid and hydrogen peroxide. He used
Hitachi and Beckman oxyhydrogen sprayer-burners and spectrophotometers. The 10
bands at 469-573 nm, projecting only slightly above the continuum, appeared above the
reaction zone when potassium iodate solution at 2000 ppm of iodine was sprayed into the
flame. Based on Ohyagi's small spectrogram, detection limits and practical "intensities"
for iodine in oxyhydrogen have been published in [3, 5, 110, 116, 117]. The detection
limit for the bands plus continuum is about 10 ppm, but the net band intensities above
the continuum afford a much poorer limit than that. They will therefore hardly find
use in iodine determination, especially since solutions other than iodate do not appear
to emit the bands in the oxyhydrogen sprayer-burner flame. Ohyagi could not detect them
with iodine (2000 fLg/ml) in ethanol or in 2 % aqueous potassium iodide with or without
iodine at 2000 ppm. The bands did appear, however, in a half-oxidized serum sample,
showing the presence of iodate; after oxidation was complete, the bands disappeared.
In the air-hydrogen sprayer-burner flame, Claus [479] was unable to detect the 10 bands
with aqueous potassium iodate and iodide, each at 1000 ppm iodine; neither, for that
matter, did he find them in oxyhydrogen. Only Ohyagi has reported them.
I have sought the most sensitive iodine lines in the oxycyanogen flame, using hydriodic
acid containing 7% iodine, but without success [138].
Regarding sensitized flame emission methods for iodine, see Sections 5.14 and 5.15,
especially Mitscherlich's method [549]. Diacon said that bismuth iodide gives the most
distinctive bands of any of the metallic iodides; it is better than copper iodide [509].
Friedlander [533] could detect 17 fLg of iodine selectively, using barium. Eads and Payne's
copper-sensitized detector flame turned dark green (presumably from 10) with methyl
iodide [314]. Nowak and Malmstadt's sodium-sensitized detector was about as sensitive
356 NONMETALS [5
to iodine as to bromine, on a weight basis [544]. It could detect 0.05 ng (absolute) or

5 ng/l (concentration) of iodine. It gave a linear response in the range 1-100 ng and could
be used up to 10 (J.g; however, below 1 ng and above 100 ng the response was sublinear,
i.e., the logarithmic slope was less than 1. The molar specificity factor toward phosphorus
was 100. The indium burner, as in the case of bromine, will detect iodine with high selec-
tivity [320,593] by means of the violet bands of InI. The 4099-A band, however, suffers
interference from the nonspecific emission of the In 4102-A line; the 3993-A band of InI
will probably prove best. Regarding sensitized solution methods [573, 575], see the re-
marks in Section 5.15.3.
In their indirect method for halogens, Menis, House and Rains [580] were able to de-
termine iodide in the presence of bromide or chloride by precipitating it with silver nitrate
in O.5-M ammonia, which keeps chloride and bromide in solution. The method thus be-
comes specific for iodide. Its sensitivity is about 0.2 ppm.
5.16.4 OTHER METHODS FOR IODINE
Atomic absorption methods for iodide have been proposed by Christian and Feldman [9].
These entail reduction of dichromate by iodide, extraction of the excess dichromate, and
determination of chromium in the flame; oxidation of ferrous iron to ferric, followed by
extraction and determination of the ferric iron; precipitation of selenite as selenium and
determination of the latter. A method for iodate was also proposed.
Concerning ionization detectors, see Section 5.14.13. The detector of Jentzsch et af.
[400] was linear for iodine in the range 0.1-1 nanomole. The detection limit was 10 ng.
The microwave argon discharge of McCormack et aZ. [88] provides the extremely good
detection limit of 0.07 pg/s for iodine at its 2062-Aline. This was observed with methyl
iodide. Using this instrument as a gas-chromatographic detector, Bache and Lisk [598]
determined Ioxynil and two of its metabolites. The sensitivity (at 2062 A) was 0.2-0.4
ng/sec, which is not nearly as good as the limit named above; but the authors had optimized
the instrument for reproducibility and they had no need of the ultimate sensitivity. In
another paper [407] they noted some enhancement of the 2062-A line on lowering the
argon pressure, but the background rose rapidly. In their low-pressure microwave helium
discharge, Bache and Lisk [408] observed a detection limit of 50 pg/sec with the iodine line
at 5338.2 A. With his 85 % helium-argon microwave discharge at 25 torr, Moye [409]
observed a limit of 0.03 ng for iodine in butyl iodide at 2062 A. Braman and Dynako
[275] utilized the iodine lines at 5464.6 and 6082.5 A in their noble-gas d.c. discharge and
reported a limit of 0.1 ng or 0.01 ng/sec, but these lines afforded practically no selectivity
against the other halogens or even hydrocarbons, which gave roughly the same response
at these wavelengths. Interferences are severe in this spectral region and there is little
doubt that the 2062-A line would be far more selective.
5.17 The Noble Gases
In the preparation of this monograph on one small pigeonhole of analytical chemistry

- the emission flame spectroscopy of the nonmetals - so many curious phenomena have
REFERENCES 357
turned up that I should not be surprised to see a straightforward flame emission method
for the noble gases discovered one day soon. Meanwhile, however, we have an indirect
flame emission method, an atomic absorption method, and several discharge methods for
these elements.
The negative flame emission gas-chromatographic detector of Overfield and Wineford-
ner [273] was described in Section 5.4.6. Tested with helium, it showed a detection limit
of 0.5 fJ.1. With argon the limit was 1.5 fJ.1. Expressed in terms of flow rate, the limits
were 0.6 and 3 fJ.g/s, respectively. The thermal-conductivity detector cannot do as well,
and the flame ionization detector does not respond to the noble gases. As a nonspecific
detector, this simple device has much promise.
Goleb [599, 600] has developed a sensitive, specific and fairly accurate method of de-
termining the noble gases by atomic absorption spectroscopy. The resonance lines lie far
in the vacuum ultraviolet; to make use of a more convenient optical region, Goleb excites
the gases to get their atoms into metastable states that absorb lines in the visible and near
ultraviolet and infrared. A water-cooled hollow-cathode tube [599] or a microwave dis-
charge [600] may be used to excite the sample at about 1 torr. A similar hollow-cathode
tube [599] or a Geissler tube [600] containing the analyte serves as emission source. Many
absorption lines were listed for helium, neon, argon, krypton and xenon [599]. Neon and
argon were determined in helium at 6402 and 8115 A, respectively, with precision and
accuracy of 2 % or better (relative standard error) [600]. The analytical curves were linear
up to 10 nanomoles and usable to 60 nanomoles; the helium sample amounted to 1.5
micromole. Mercury can interfere by deactivating the metastable states.
As for discharge methods, I have not made a literature search for the noble gases, but
a couple of methods should be mentioned by way of illustration. Chakrabarti, Magee and
Wilson [601] determined argon and carbon dioxide in mixtures of the two gases by means
of a high-voltage electrodeless discharge at 230 MHz. The argon line 2942.9 A and the
CO 2 band at 2896 A were employed. The gases were at -t torr. The analytical curve was
nonlinear below 9 % and above 90 % argon, but 1 % of either gas could be detected in the
other. The standard error was 3 % absolute. An analysis took one minute. McCormack,
Tong and Cooke [88], with their microwave argon discharge, already mentioned many
times in this chapter, were able to detect helium by its 5876-A line at a flow of 0.01 fJ.g/s.
The radiofrequency plasma torch of West and Hume [10], used in unpublished studies of
flowing gases, proved extremely sensitive to neon in helium [602]. The best available he-
lium emitted a strong neon spectrum.
References
After each reference is given the Chemical Abstracts (CA) or Chemisches Zentralblatt (CZ)
citation, if available. ZaC denotes an abstract in Z. anal. Chern. Other abstract journals are
sometimes cited. Titles of journal papers are omitted; instead, to help the reader judge
the pertinence of the paper, a brief statement of the subject is given after the abstract
citation. In this, attention is confined to topics of concern in the present chapter. The
usual chemical abbreviations are used, together with the following:
aas. = atomic absorption spectroscopy (spectrophotometry)
detec. = detection
358 NONMETALS [5
fl. flame
fp. flame-photometric
fpr. flame photometer
fpy. flame photometry
fs. flame-spectrophotometric
fsr. flame spectrophotometer
fsy. flame spectrophotometry
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2. J. A. DEAN, Flame Photometry, McGraw-Hill, New York, 1960. 354 pp.
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of fl. spectra, etc.
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pounds.
22. A. GoUY, Ann. chim. phys. 18, 5-101 (1879). First good fsr.; photometric study of elements in
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25. J. ATTFIELD, Phil. Trans. Roy. Soc. London 152, 221-4 (1862). Swan bands ascribed to C.
26. J. W. DRAPER, Phil. Mag. (iii) 32, 100-14 (1848). Cyanogen fl. spectrum, etc.
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REFERENCES 359
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36. T. M. SUGDEN, pp. 369-90 in Annual Review ofPhysical Chemistry, H. Eyring, C. J. Christen-
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37. A. G. GAYDON, Dissociation Energies, 2nd ed., Chapman & Hall, London, 1953.261 pp.
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39. P. T. GILBERT, pp. 171-215 in Proc. Xth Colloquium Spectroscopicum Internationale, E. R.
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40. L. CAPACHO-DELGADO and D. C. MANNING, Spectrochim. Acta 22, 1505-13 (1966). CA 65,
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41. J. E. ALLAN, Absorption flame photometry below 2000 A, 4th Australian Spectroscopy Con-
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42. J. H. GIBSON, W. E. L. GROSSMAN and W. D. COOKE, Anal. Chem. 35, 266-77 (1963). CA 58,
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43. H. L. KAHN and JANE E. SCHALLIS, Atomic Absorption Newsletter 7, 5-9 (1968). Ar-H2 fl.
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44. R. M. DAGNALL, K. C. THOMPSON and T. S. WEST, Atomic Absorption Newsletter 6, 117-20
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48. R. M. DAGNALL, K. C. THOMPSON and T. S. WEST, Analyst 93, 72-8 (1968). Fp. detn. of P
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49. P. T. GILBERT, Analyzer (Beckman Instruments, Inc.) 2, No.4, pp. 3-6 (Oct. 1961). Anal.
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50. KAREN ZACHA and J. D. WINEFORDNER, Anal. Chem. 38, 1537-9 (1966). CA 66, 16267. Fsy.
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51. M. D. AMOS and J. B. WILLIS, Spectrochim. Acta 22, 1325-43 (1966). CA 65, 4639 (wrong p.
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56. B. E. BUELL, private communication, July 19, 1961.
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58. B. E. BUELL, Ibid. 35, 372-82 (1963). CA 58, 10867. Continuation of above; data & spectra
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59. B. E. BUELL, Ibid. 38, 1376-81 (1966). CA 65, 16047. High-dispersion fsy. (4A fmm); detec.
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60. W. J. CARNES, Flame photometric studies. C. Studies of the reaction zone of an oxygen-acetyl-
360 NONMETALS [5
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63. J. A. DEAN and J. C. SIMMS, Anal. Chem. 35, 699-702 (1963). CA 59, 1090. Fs. detn. of
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64. A. P. D'SILVA, R. N. KNISELEY and V.A. FASSEL, Ibid. 36,1287-9 (1964). CA61, 4942. Fsy.
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65. V. A. FASSEL and D. W. GOLIGHTLY, Ibid. 39, 466-76 (1967). CA 66,101313. Detec.lirnits of
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66. P. T. GILBERT, Chemiluminescentflame spectrophotometry, American Chemical Society, Univ.
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84. P. T. GILBERT (to Beckman Instruments, Inc.), U.S. Patent 3,208,333, Sept. 28, 1965.
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85. P. T. GILBERT, Anal. Chem.34, 1025-6 (1962). CA 57, 6580. Powder spraying in fsy.
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87. C. L. CHAKRABARTI, R. J. MAGEE and C. L. WILSON, Talanta 9,43-8 (1962). CA 56, 13682.
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108. P. T. GILBERT, unpublished work at Beckman Instruments, Inc., 1947-1965.
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114. W. SCHMIDT, Beckman Instruments G.m.b.H., Munich, unpublished flame spectrograms,
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115. H. WATANABE, unpublished work at Beckman Instruments, Inc., Fullerton, Calif., 1955.
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119. N. L. SINGH, Proc. Ind. Acad. Sci. 29A, 424-30 (1949). CA 44, 2847. BO bands in fl.
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121. K. KONOPICKY and W. SCHMIDT, Z. anal. Chem. 173, 358-69 (1960). CA 54,17145. Fsy. for
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122. CARL ZEISS, Oberkochen, Germany, Flammenspektren, Bestellnummer A 50-812; 1961.
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125. A. A. MAL'TSEV and V. M. TATEVSKII, Reports of the Chemical Faculty of Moscow State
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362 NONMETALS [5
126. A. A. MAL'TSEV, V. K. MATVEEV and V. M. TATEVSKII, Dokl. Akad. Nauk SSSR 137, 123-5
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127. A. A. MAL'TSEV, V. K. MATVEEV, and V. M. TATEVSKII, Fiz. Probl. Spektroskopii, Akad.
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129. W. E. KASKAN and R. C. MILLIKAN, pp. 262-75 in Symp. Combust., 8th, Pasadena, Calif,
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131. A. D. RUSIN and V. M. TATEVSKII, Dokl. Akad. Nauk SSSR 139, 630-3 (1961); Proc. Acad.
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132. J. W. C. JOHNS, Can. J. Phys. 39, 1738-68 (1961). CA 57, 10662. Analysis of B0 2 spectrum.
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135. W. G. BERL, E. L. GAYHART, H. L. OLSEN, H. P. BROIDA and K. E. SHULER, J. Chem. Phys.
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138. P. T. GILBERT, Oxycyanogenf/ame photometry, Pittsburgh Conference on Analytical Chemis-
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141. W. GEILMANN and H. BODE, Z. anal. Chem. 129, 3-5 (1949). CA 43, 4603. Fl. detec. of B.
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Fl. detec. of B.
144. MACQUER-LEONHARDI, Chymisches Worterbuch, Vol. V, p. 566, Leipzig, 1785. Fl. test for B.
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145. E. J. CHAPMAN, Phil. Mag. (v) 2,459 (1877); Chem. News 35,36 (1877); CZ 48,69 (1877).
Turner's test for B.
146. G. MERZ, J. prakt. Chem. 80, 487-99 (1860). CZ 31, 1022 (1860). Fl. colors of many ele-
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147. F. STOLBA, ()ber das Kiese/fluorammonium und Kiese/fluornickel, Verlag k. b6hm. Ges. Wiss.,
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150. V. MERZ and W. WEITH, Ber. deut. chem. Ges. 6, 1518-20 (1873). CZ 45,212 (1874). Fl. test
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151. M. W. ILEs, American Chemist 6, 361 (1876). ZaC 18,269 (1879). CZ 50,351 (1879). Fl. test
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152. M. W. ILEs, Chem. News 35,204-6 (1877). ZaC 18, 269 (1879). Cf. Ref. 151.
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158. F. JONES and R. L. TAYLOR, J. Chem. Soc. 39, 213-9 (1881); CZ52, 402 (1881). Chem. News
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REFERENCES 363
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174. C. MANNICH and H. PRIESS, Chem.-Ztg. 32, 314 (1908). CA 2, 1729 (Priess misspelled). FI.
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175. K. ARNDT, Chem.-Ztg. 33, 725-6 (note) (1909). CZ 80 II, 559 (1909). FI. detec. of B.
176. ANON., Deutsches Arzneibuch V, 1910. (From Ref. 142). FI. test for B in meat inspection.
177. G. BERTRAND and H. AGULHON, Bull. soc. chim. France (iv) 7, 90-9 (1910); Ann. chim. anal.
et chim. appl. 15, 45 (1910). CA 4, 1439, 2080. Spectroscopic fl. detec. of B in foods, etc.
178. T. VON FELLENBERG, Mitt. Geb. Lebensmittelunters. Hyg. 1, 193-4 (1911); CA 5, 1469 (wrong
year). Apotheker-Ztg. 25, 805 (1911). CZ 82 I, 1248 (1911). FI. detec. of B in preservatives.
179. G. BERTRAND and H. AGULHON, Compt. rend. 155, 248-51 (1912). CZ 83 II, 1295 (1912).
Improvement of Ref. 177.
180. E. PIESZCZEK, Pharm. Ztg. 58, 850-1 (1913). CA 8, 1070 (date wrong, initial probably wrong);
ZaC 60, 370 (1921). FI. test for B and for MeOH.
181. P. JANNASCH and F. NOLL, J. prakt. Chem. (ii) 99, 1-33 (1919). CA 14, 162. Detn. of B by
duration of fl. color.
182. J. R. PARTINGTON, A Textbook of Inorganic Chemistry, Macmillan, London, 1921. 1062 pp.
183. G. LUNGE and E. BERL, Chemisch-technische Untersuchungsmethoden, 7th ed., Vol. 2, Spring-
er, Berlin, 1922; 1411 pp. Review in J. Am. Chem. Soc. 45, 1572-3 (1923).
184. F. BORDAS and F. TOUPLAIN, Ann,fals. etfraudes 16,356-60 (1923). CA 17, 3557. FI. detec.
of B in mineral waters.
185. F. KRAUSS, Chem.-Ztg. 50, 33 (1926). CA 20, 1190. Volatility of Ba bisulfate in B fl. test.
186. A. GABRIEL and H. G. TANNER, J. Am. Chem. Soc. 50,1385 (1928). CA 22, 2123. FI. detec.
ofB.
187. J. B. KASEY, Chemist-Analyst 19, No.2, p. 15 (March 1930). CZ 101 1,3217 (1930). FI. test
for B.
188. W. BOTTGER and BERTHA-MARIE SCHALL, Mikrochemie, Emich-Festschri/t 1930, 29-38. CA
25,3263; CZ 102 II, 277 (1931). App. for B fl. test.
189. W. STAHL, Acta Univ. Latviensis Kim. Fakultat. Serija 1, No. 13-17,369-400 (1930); Z. anal.
Chem. 83, 268-89 (1931). CA 25, 1455,2385. FI. colorimetric detn. of B, optimized method.
190. J. S. McHARGUE and R. K. CALFEE, Ind. Eng. Chem., Anal. Ed. 4, 385-8 (1932). CA 26,
5869. Fp. detn. of B with KMnO 4 cuvet to obscure bands.
364 NONMETALS [5
191. J. S. McHARGUE, J. Assoc. Offic. Agr. Chemists 16, 465-71 (1933). CA 28,433. Method of
Ref. 190 for plant analysis.
192. R. K. CALFEE and J. S. McHARGUE, Ind. Eng. Chem., Anal. Ed. 9, 288-90 (1937). CA 31,
6129. Dual-fl. colorimetric detn. of B.
193. H. C. WEBER and R. D. JACOBSON, Ibid. 10, 273 (1938). CA 32, 4461. Detn. ofB by duration
of fl. color.
194. A. P. Kru!SHKOV and S. S. VIL'BORG, Zhur. Anal. Khim. 3, 172-5 (1948). CA 42, 7661. Fl.
test for B with Et 4 Si0 4 •
195. S. D. BOON, Vlam-Fotometrie, Thesis, Amsterdam, 1945. 112 pp. CA 40, 5668. Filter fpr. for
Na, K, Li, B.
196. P. L. HOOGLAND, Trace elements and dental caries, Thesis, Amsterdam, 1948. 64 pp. Anal.
Chim. Acta 2,831-8 (1948). CA 43, 7998. Used Boon's fpr. for B.
197. P. L. HOOGLAND, Medel. Lab. Physiol. Chem. Univ. Amsterdam en Nederlands Inst. Volks-
voed. 11, No.3, 63 pp. (1948-49). CA 45, 2553. See Ref. 196.
198. B. LANGE, A new flame photometer, Dechema Monograph. 17, 149-59 (1951). CA 47, 3621.
199. L. KNv and J. RICHTER, Arzneimittelstandardisierung, Informdienst. 1,41-6 (1961). CA 61,
8136. Fp. detn. of B in drugs.
200. H. LUNDEGARDH, Die quantitative Spektralanalyse der Elemente, Fischer, Jena, Part I, 1929;
Part II, 1934.
201. H. LUNDEGARDH, Lantbruks-Hogskol. Ann. 3, 49-97 (1936). CA 31, 2958. New burner for fl.
spectrography of various elements.
202. A. D. RUSIN and V. M. TATEVSKII, Vest. Mosk. Univ., Ser. II, Khim. 17, No.3, 21-3 (1962).
CA 57, 10090. Spectral detn. of B0 2 in B2H6 explosion products.
203. P. T. GILBERT, R. C. HAWES and A. O. BECKMAN, Anal. Chem. 22, 772-80 (1950). CA 44,
7592. Early Beckman fsr.
204. P. T. GILBERT,Aflame spectrophotometer with integral burner-atomizer, Pittsburgh Conference
on Analytical Chemistry and Applied Spectroscopy, March 1951; Symposium on Molecu-
lar Structure and Spectroscopy, Ohio State Univ., Columbus, June 1951.
205. P. T. GILBERT, Ind. Labs. 3, No.8, 41-6 (Aug. 1952). Fsy. and detec.limits for many elements.
206. C. E. BRICKER, W. A. DIPPEL and N. H. FuRMAN, U.S. At. Energy Comm., NYO-794, Dec.
31, 1951; 9 pp. Nuclear Sci. Abstr. 6, No. 1655 (1952). Fs. detn. of B.
207. G. R. KINGSLEY and R. R. SCHAFFERT, Effect of organic solvents on the emission spectra of
cations in serum and aqueous solutions, American Chemical Society, Los Angeles, Mar.
16, 1953. Discussion: Bin org. solvents.
208. W. A. DIPPEL, Fundamental study of analytical flame photometry, Ph. D. thesis, Princeton
Univ., 1954. 167 pp. Dissertation Abstr. 16, 224-5 (1956). CA 50, 7649. Fsy. of B.
209. E. PuNGOR and (Miss) ILONA KONKOLY THEGE, Magyar Kem. Folyoirat 62, 231-4 (1956);
Acta Chim. Acad. Sci. Hung. 13, 39-46 (1958). CA 52, 6925. Fsy. of B.
210. E. BOVAY and A. COSSY, Mitt. Gebiete Lebensm. Hyg. 48, 59-63 (1957). CA 52, 14942. Fs.
detn. ofB. in fertilizer.
211. D. E. FORNWALT, U.S. At. Energy Comm., TIM-406, May 1957; 25 pp. Nuclear Sci. Abstr.
16, No. 12960 (1962). Fs. detn. of B in plating solns.
212. D. E. FORNWALT, Anal. Chim. Acta 17,597-603 (1957). CA 53,2873. See Ref. 211.
213. R. P. PORTER, J. Phys. Chem. 61, 1260 (1957). CA 52, 1570. Reaction of MeOH with B-contg.
glass.
214. H. D. DuBOIS and R. E. BARlEAU, Improved flame photometry by direct recording study of
selected flame area emission, 23rd Midyear Meeting, Div. of Refining, American Petroleum
Institute, Los Angeles, May 1958. Includes study of B.
215. B. E. BUELL, A study offlame photometric determinations of elements, report, Union Oil Co.
of Calif., Research Dept., Brea, Calif., Sept. 18, 1958. Data on B and other elements.
216. B. D. LA MONT, J. V. DERBY, C. A. MEINZ and J. D. JOHNSON, pp. 36-49 in Analytical chem-
istry in nuclear reactor technology, U. S. At. Energy Comm., TID-7568, Part 1, 1959. CA
54,9522; CA 57,5543; Nuclear Sci. Abstr.13, No. 12450 (1959). Fs. detn. ofB.
217. K. KONOPICKY and W. SCHMIDT, Z. anal. Chem. 174, 262-8 (1960). CA 55,2349. Enhance-
ment of B, etc., by fluoride in fsy.
218. J. A. DEAN, Analyst 85, 621-9 (1960). Nuclear Sci. Abstr. 15, p. 22 (1961). Review on fsy. in
metallurgy; 57 refs.
219. B. E. BUELL, pp. 365-7 in The Encyclopedia of Spectroscopy, G. L. Clark, ed., Reinhold,
New York, 1960. Reviewoffpy. in petroleum; 32 refs.
220. E. PUNGOR and ILONA KONKOLY THEGE, Ann. Univ. Sci. Budapest. Rolando Eotvos Nominatae,
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Sect. Chim. 2, 485-7 (1960). CA 56, 5401. Cf. Ref. 209.

221. W. J. MAECK, MAXINE E. Kussy, B. E. GINTHER, G. V. WHEELER and J. E. REIN, Anal.
Chem. 35, 62-5 (1963). CA 58, 3877. Extn. & fs. detn. of B.
222. H. LUNDEGARDH, Metallwirtschaft 17, 1222-6 (1938). CA 33, 937. F!. spectrography & spark-
in-fl. for many elements.
223. R. LORA-SILVA, M. CASTELLANOS-TAPIAS and A. ACEvEDO-GuzMAN, Rev. Univ. Ind.
Santander 5, 409-12 (1963). CA 60, 2033. Fs. detn. ofB in plants.
224. T. YOSHIZAKI, Anal. Chem. 35, 2177-9 (1963). CA 60, 7461. Fs. detn. ofB in org. compounds.
225. M. E. DoTY, Suppression effects in emission flame photometry, Ph. D. thesis, Kansas State
Univ., Manhattan. Univ. Microfilms (Ann Arbor, Mich.), Order No. 63-6793, 101 pp.
Dissertation Abstr. 24, 1367 (1963). Vaporization interferences of B, etc.
226. M. E. DoTY and W. G. SCHRENK, Develop. Appl. Spectry. 3, 196-206 (1963), Plenum, New
York, 1964. CA 61,11488. Cf. Ref. 225.
227. J. L. WATERS, The design and applications of a continuous recording flame photometer, Pitts-
burgh Conference on Analytical Chemistry and Applied Spectroscopy, March 2, 1961.
228. W. A. CRANDALL, pp. 11-28 in Analysis Instrumentation - 1964, Proc. Natl. Anal. Instr.
Symp., 10th, San Francisco; Plenum, New York, 1964. CA 63, 14320. Fsr. for monitoring
Na & B in reactor coolant.
229. M. BAUM, Sprechsaal97, 101-3 (1964). CA 61, 416. Fs. detn. ofB in refractories.
230. J. RAMIREZ-MuNOZ, Inst. hierro y acero 17, 44-50 (1964). Solvent extn.; detn. of B in plants.
231. N. S. POLUEKTOV, Techniques in Flame Photometric Analysis, translated by C. N. and T. I.
Turton, Van Nostrand, Princeton, 1966; 219 pp. Reprint of 1961 translation; pub!. 1959 in
Russian. Review in Analyst 92,204 (1967).
232. T. C. RAINS and T. A. RUSH, pp. 28-40 in Analytical Coordination Chemistry: Titrimetry,
Gravimetry, Flame Photometry, Spectrophotometry, Gas Evolution, and Isotopic Preparations,
July 1965-June 1966, Nat!. Bur. Standards, Tech. Note 402, Washington, 1966. Fsy. of B;
Te by aas.
233. E. J. AGAZZI, Anal. Chem. 39, 233-5 (1967). CA 66, 61487. Extn. and fs. detn. of B.
234. R. A. A. MUZZARELLI, Ibid. 39, 365-6 (1967). CA 66, 82048. Fs. detn. of B in U nitrate.
235. C. T. J. ALKEMADE, Ibid. 38, 1252-3 (1966). CA 65, 14412. Interpretation of solute vaporiza-
tion interferences.
236. R. S. BRAMAN and E. S. GORDON, ISA Proceedings, 17th Ann. ISA Conf., New York, 1962,
Paper 13.2.62, 6 pp. CA 60, 4754. Fp. borane monitor.
237. R. S. BRAMAN, Research and development of an automatic beryllium and boron monitor,
At. Energy Comm. Accession No. 28218, Rept. No. AD-608438, 1962. 89 pp. CA 64, 14850.
238. R. S. BRAMAN and E. S. GORDON. IEEE Trans. Instrumentation and Measurement, IM-14,
11-19 (1965). Cf. Refs. 236, 237.
239. R. DOBRINER, Electronic Design, Oct. 25, 1963, pp. 18,20. Cf. Refs. 236-238.
240. R. S. BRAMAN and W. A. LOSEKE, Flame photometric detection of toxic volatile compounds,
Mid-America Spectroscopy Symposium, Chicago, May 22, 1963.
241. E. BOVALINI, L. PUCINI and A. Lo MORO, Ann. chim. (Rome) 49, 1046-50 (1959). CA 54,
1167. Indirect fp. detn. of B.
242. J. RAMIREZ-MuNOZ, Atomic-Absorption Spectroscopy and Analysis by Atomic-Absorption
Flame Photometry, Elsevier, Amsterdam, 1968. 493 pp.
243. R. N. KNISELEY, The determination of refractory metals by atomic absorption spectroscopy,
Eastern Analytical Symposium, New York, Nov. 13, 1964.
244. Beckman Instruments, Inc., Fullerton, Calif., Beckman laminar flow burner for nitrous
oxide-acetylene, Bull. 7112, 1966.
245. J. RAMIREZ-MUNOZ, Flame Notes (Beckman Instruments, Inc.) 2, 26 (1967). Data on B in
aas.
246. A. HELL, J. RAMIREZ-MuNOZ and N. SHIFRIN, Nitrous oxide-acetylene burner with improved
sample delivery system, Pittsburgh Conference on Analytical Chemistry and Applied Spec-
troscopy, Feb. 1966.
247. H. BADER and H. BRANDENBERGER, Atomic Absorption Newsletter 7, 1-3 (1968). Detn. of B
by aas. in biological samples.
248. W. A. STRAUB, Spark-in-flame spectroscopy, Ph. D. thesis, Cornell Univ., 1958; 113 pp. Univ.
Microfilms (Ann Arbor, Mich.), L.C. Card No. Mic 58-2451. Dissertation Abstr. 19, 31-2
(1958). CA 52, 16116.
249. W. A. STRAUB, S. H. BAUER and W. D. COOKE, Spark in flame spectroscopy, Pittsburgh
Conference on Analytical Chemistry and Applied Spectroscopy, March 6, 1958.
366 NONMETALS [5
250. MILDRED S. VIGLER and J. K. FAILONI, Appl. Spectry. 19, 57-8 (1965). CA 63, 404. Plasma
arc for B in gasoline.
251. A. G. COLLINS, Ibid. 21,16-9 (1967). CA 66, 88477. Plasma arc for B, etc., in brines.
252. H. C. HOARE and R. A. MosTYN, Anal. Chem. 39, 1153-5 (1967). Induction torch spectrog-
raphy; detn. of B in Ni.
253. B. P. STOICHEFF, pp. 399-415 in Proc. Xth Colloquium Spectroscopicum Internationale, E. R.
Lippincott and M. Margoshes, eds., Spartan Books, Washington, 1963. Fl. spectra of laser-
vaporized B, etc.
254. H. I. S. FERGUSON, J. E. MENTALL and R. W. NICHOLLS, Nature 204, 1295 (1964). CA 62,
8549. Laser excitation of B, C, etc.
255. V. S. ROSSIKHIN and I. L. TSIKORA, Optika i Spektroskopiya 5, 202-4 (1958). CA 53, 7756.
Mechanism of excitation of C 2479 in 02-C2H2 fl.
256. J. PLUCKER and J. W. HI'ITORF, Phil. Trans. Roy. Soc. London 155, 1-28 (1865). Spectra of
S in fl. & discharge; OrC2N2 fl. spectrum; Cu halide spectra.
257. W. M. WA1TS, Phil. Mag. (iv) 49, 104-6 (1875). CZ 46, 145 (1875). Polemic on origin of C 2
bands; reply to Smyth (Ref. 100).
258. J. A1TFIELD, Ibid., 106-8 (1875). Further reply to Smyth (Ref. 100); cf. Ref. 257.
259. A. M. BASS and H. P. BROIDA, A Spectrophotometric Atlas of the Spectrum of CH from 3000
A to 5000 A, Natl. Bur. Standards, Monograph 24, 1961; 20 pp. CA 55, 13044-5.
260. D. W. GRANT and G. A. VAUGHAN, p. 413 in Vapour Phase Chromatography, D. H. Desty,
ed., Butterworths, London, 1957. Suggested fl. emission for detec. of org. compounds.
261. D. W. GRANT, pp. 153-63 in Gas Chromatography, Proc. Symp., Amsterdam 1958, D. H.
Desty, ed., Butterworths, London, 1958. CA 53, 16609. Implementation of suggestion of
Ref. 260.
262. P. J. COWAN and J. M. SUGIHARA, J. Chem. Educ. 36, 246-7 (1959). CA 53,19475. Fl. emis-
sion detector for GC.
263. J. C. STERNBERG and D. T. L. JONES, unpublished work at Beckman Instruments, Inc.,
Fullerton, Calif., 1961.
264. A. J. MCCORMACK, Emission detectors for gas chromatography, M. S. thesis, Cornell Univ.,
1963. Cf. Ref. 88.
265. R. S. BRAMAN. Anal. Chem. 38, 734-42 (1966). CA 65, 2981. Fl. emission detector for GC.
266. R. P. DURBIN, Gas chromatography. Part I. Characterization of the flame photometric de-
tector for gas chromatography, Thesis, Univ. Illinois. Dissertation Abstr. 27, 710B (1966).
267. R. S. JUVET, JR., and R. P. DURBIN, Anal. Chem.38, 565-9 (1966). Correction: Ibid., p.1740.
CA 65, 4. Cf. Ref. 266.
268. F. M. ZADO and R. S. JUVET, JR., Ibid. 38, 569-73 (1966). CA 65, 4. Continuation of Ref. 267;
selective or nonselective.
269. J. W. ROBINSON and V. SMITH, Anal. Chim. Acta 36, 489-98 (1966). CA 66, 33293. Emission
spectra of org. liquids in 02-H2 fl.
270. P. F. MCCREA, Emission spectrum characteristics of hydrocarbons in a hydrogen-air jlame,
M.S. thesis, Providence College, 1966.
271. P. F. MCCREA and T. S. LIGHT,Anal. Chem.39, 1731-6 (1967). Emission of hydrocarbons in
MeOH in OrH2 fl.
272. W. A. AUE and C. W. GEHRKE, Spectrometric determination of organic compounds by sodium-
dopedjlame, American Chemical Society, 2nd Midwest Regional Meeting, Lawrence, Kan.,
Oct. 28, 1966.
273. C. V. OVERFIELD and J. D. WINEFORDNER, J. Chromatog. 30, 339-43 (1967). CA 67, 121970.
Fl. emission detector for GC, detg. fixed gases by depression of OH band.
274. J. C. STERNBERG and R. E. POULSON, Ibid. 3, 406-10 (1960). CA 55, 5050. Tesla discharge
detector for GC.
275. R. S. BRAMAN and A. DYNAKO, Anal. Chem. 40, 95-106 (1968). D.-c. discharge emission de-
tector for GC, etc.
276. C. D. WEST, A comparison of 30 MHz and 2450 MHz plasmas for gas analysis, American
Chemical Society, 155th National Meeting, San Francisco, Apr. 1, 1968.
277. R. BUNSEN, Ann. Chem. Liebigs 138, 257-96 (1866). Fl. tests, including As, Se, Te.
278. W. HUGGINS, Proc. Roy. Soc. (London) 18, 546-53 (1870); Phil. Mag. (iv) 40,302-6 (1870).
CZ 41, 673,689 (1870). Fl. spectrum ofSi, etc.
279. AUGUSTA SYTY, Ph. D. Thesis, Univ. Tennessee, Knoxville, 1967. See Ref. 280.
280. AUGUSTA SYTY and J. A. DEAN, Appl. Optics 7,1331-6 (1968). Detn. ofP & S in liquid sam-
ples by HPO & S2 emissions.
REFERENCES 367
281. G. SALET, Compt. rend. 73,1056-9 (1871). CZ 42,753 (1871). Fl. spectra ofP, S, Si, Sn.
282. G. SALET, Traite etementaire de spectroscopie, Masson, Paris, 1888. Vol. 1.
283. C. J. LUNDSTROM, Proc. Roy. Soc. (London) 59, 76-98 (1895). Spectra of Bessemer converter fl.
284. W. N. HARTLEY, Ibid., 98-101. Same subject as above.
285. A. DE GRAMONT and C. DE WATTEVILLE, Compt. rend. 147, 239-42 (1908). CA 2,3192; CZ
79][, 1233-4 (1908). Fl. spectrum of SiO.
286. R. K. SKOGERBOE, ANN T. HEYBEY and G. H. MORRISON, Anal. Chem. 38, 1821-4 (1966).
CA 66, 25738. Excitation of Si, As, Se, Te, etc. in 0z-H 2 fl. with EtOH solvent.
287. CLAUDE E. JOHNSON, Nethercutt Laboratories, Los Angeles, personal communication, Feb.
19, 1964. Fs. detn. of Si. (Present address: 5402 Arbor Vitae, Los Angeles 90045.)
288. J. C. STERNBERG, W. S. GALLAWAY and D. T. L. JONES, Gas Chroma tog. Intern. Symp. 1961,
3,231-67 (Pub. 1962). CA 58,3865. Response mechanism of fl. ionization detector.
289. W. SLAVIN, A. VENGHIATTIS and D. C. MANNING, Atomic Absorption Newsletter 5, 84-8
(1966). CA 65,17678. Aas. by N 20-C 2H 2 fl.; Si.
290. J. S. CARTWRIGHT, C. SEBENS and D. C. MANNING, Ibid., 91-6. CA 65, 19292. Sullivan-Walsh
lamps for Si, Ti, V in aas.
291. J. RAMiREZ-MUNOZ, J. Forensic Sci. Soc. 7, 151-61 (1967). Beckman Instruments, Inc., Re-
print R-625 1. Applications of aas.; Si, Te in N 20-C 2H 2 fl.
292. J. J. McAuLIFFE, Atomic Absorption Newsletter 6, 69 (1967). Detn. of Si in Fe & steel by aas.
293. J. J. McAuLIFFE, Silicon analysis in cast iron and steel by atomic absorption spectroscopy,
Society for Applied Spectroscopy, 7th National Meeting, Chicago, May 13, 1968.
294. JUDITH A. BOWMAN and J. B. WILLIS, Anal. Chem. 39, 1210-6 (1967). CA 67, 78635. Aas. with
N 20-C2H2 fl.; detn. of Si in bauxite.
295. CONCETTA M. PARALUSZ, Trace organic silicon analysis using atomic absorption spectroscopy,
Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy, Cleveland,
March 4, 1968.
296. G. F. KIRKBRIGHT, A. M. SMITH and T. S. WEST, Analyst 92,411-6 (1967). Indirect detn.
of P & Si by aas. via Mo complex.
297. T. R. HURFORD and D. F. BOLTZ, Anal. Chem. 40, 379-82 (1968). Similar to Ref. 296.
298. E. HOFFMANN and G. HOLDT, Monatsber. deut. Akad. Wiss. Berlin 10/11, 693 (1965). Disk-
stabilized arc as emission source.
299. E. HOFFMANN and G. HOLDT, Canadian Spectry. 12, 10-5 (1967). CA 67, 16392. Disk-stabil-
ized arc; detn. of Si in rocks, P in C 2H 2.
300. R. H. WENDT and V. A. FASSEL, Anal. Chem. 37, 920-2 (1965). CA 63, 10872. Induction torch;
detec. limits for many elements.
301. H. C. DIBBITS, Ann. Physik 122, 497-545 (1864). FI. spectra of C 2N 2, NH 3, S, H 2S, CS 2
with air, O 2, N 20, etc.
302. K. B. HOFMANN, Ibid. 147, 92-101 (1872). CZ 43, 691 (1872). Spectra of P glow, P fl., P in
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303. T. M. SUGDEN, EuiBIETA M. BULEWICZ and A. DEMERDACHE, Chem. Reactions Lower and
Upper Atmosphere, Proc. Intern. Symp., San Francisco, Calif, 1961,89-108. CA 56, 13583.
Mechanisms & chemiluminescence of NH, NH 2, HNO, S2, SH, SO, & H 2S in H2 fl. with
NO orS02.
304. C. DE WATTEVILLE, Z. wiss. Photo 7, 279-85 (1909). CZ 80 II, 674-5 (1909). Spectra of N, P,
As, Sb in Bunsen fl.
305. M. HONMA and C. L. SMITH, Anal. Chem. 26, 458-62 (1954). CA 48, 6911. Fs. detn. of
organic N by CN 3883.
306. B. E. BUELL (Union Oil Co., Brea, Calif.), personal communication, 1960. Detec. of N in
02-H2 sprayer-burner fl. by CN band.
307. U.S. Naval Applied Science Laboratory, Brooklyn, N.Y., Flame photometer for atmospheric
contaminants, brochure distributed at exhibit of Instrument Society of America, Chicago,
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308. R. E. BEAUCHENE, A. D. BERNEKING, W. G. SCHRENK, H. L. MITCHELL and R. E. SILKER,
J. Bioi. Chem. 214, 731-9 (1955). CA 49, 10799. Fs. detn. of amino N by Cu substitution.
309. E. NOELTING and E. TRAUTMANN, Ber. deut. chem. Ges. 23, 3654-83 (1890). On p. 3664:
Beilstein test for hydroxyquinoline, etc.
310. H. MILRATH, Chem.-Ztg. 33, 1249 (1909). CA 4, 907. Beilstein test for ureas, quinolines, etc.
311. G. M. S. TAIT, U. S. Pat. 1,305,025, May 27, 1919. CA 13, 1960. Cu in ale. fl. to monitor
halogens, etc., in air.
312. J. VAN ALPHEN, Rec. traY. chim. 52,567-8 (1933). CA 27,5078. Beilstein test for trimidines.
368 NONMETALS [5
313. F. A. GUNTHER, R. C. BLINN and D. E. Orr, Anal. Chem.34, 302-3 (1962). CA 56, 9393. Cu
in ft. for detec. of Cl, Br, I, CN, SCN in GC.
314. E. A. EADS and D. A. PAYNE,JR., Ibid., 36,2373 (1964).CA62, 15432. Like Ref. 313; Cuin
burning CH 4 carrier gas.
315. A. M. BOND and T. A. O'DONNELL, Ibid., 40, 560-3 (1968). Aas. detn. of F and NH3 by
enhancement of Zr or Ti in N 2 0-C 2 H 2 •
316. N. F. Ivss and LAURA GIUFFRIDA, J. Ass. Offic. Anal. Chem.50, 1-4 (1967). CA 66,61612.
Thermionic ft. detector for N, P, As and CI.
317. C. WELLS, U.S. Food and Drug Administration Pesticide Workshop, Kansas City, Mo., May
1966. See Ref. 316.
318. W. A. Am, C. W. GEHRKE, R. C. TINDLE, D. L. STALLING and C. D. RUYLE (or Tindle,
Ruyle, Gehrke, Stalling and Aue), An alkali flame ionization detector specific for organic
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323. T. KUMAMARU, E. TAO, N. OKAMOTO and Y. YAMAMOTO, Bull. Chem. Soc. Japan 38,2204
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324. F. WOHLER, Ann. Chem. u. Pharm. 39, 252-3 (1841). FI. test for P.
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326. P. GEUTER, Z. wiss. Photo 5, 1-23, 33-60 (1907); Dissertation, Bonn, 1906. CZ78 II, 205
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328. E. B. LUDLAM, J. Chem. Phys. 3, 617-20 (1935). CA 29, 7798. HPO spectrum photographed;
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329. L. DUSART, Compt. rend. 43, 1126-7 (1856). CZ 28, 107 (1857). H ft. test for P.
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335. G. SALET, Bull. soc. chim. France 16, 195-8 (1871). CZ 43, 529 (1872). Spectra of P & S in
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336. A. SCHUSTER, Upon the present state of our knowledge of spectrum analysis. 1. Spectra of
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338. M. PEYRON, Spectroscopic study of the H atom-phosphorus atomic flame, U.S. Dept. Com.,
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339. LAM THANH M. and M. PEYRON, J. chim. phys. 59, 688-95 (1962). CA 58, 1045. Like Ref. 338.
340. LAMTHANH M. and M. PEYRON, Ibid. 60, 1289-93 (1963). CA 60, 10076. Identification of
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341. P. T. GILBERT, unpublished work at Beckman Instruments, Inc., 1963; supported by U. S.
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342. DRAGERWERK; H. and B. DRAGER; German Patent 1,133,918, July 26,1962. CA 57, 14444.
H burner for monitoring P and S in air.
343. C. E. VAN DER SMISSEN (to O. H. Drager, LUbeck), U.S. Patent 3,213,747, Oct. 26,1965. Cf.
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352. C. P. FENIMORE and G. W. JONES, Combustion & Flame 8, 133-7 (1964). CA 61, 11487.
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367. F. M. PAGE and D. E. WOOLLEY, Anal. Chem.40, 210-2 (1968). Mechanism of thermionic
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372. J. MALINOWSKI, Chem. Anal. (Warsaw) 4, 939-45 (1959). CA 59,3317; Anal. Abstr. 7, No.
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373. F. J. DINAN, A. DAVIS and L. E. TUFTS, Phosphorus determination by flame photometry,
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375. W. SCHMIDT, Beckman Report (Beckman Instruments G.m.b.H., Munich) No.3, 1964, pp.
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8-13. CA 65,16060. Fs. detn. ofP in organic compounds by PO bands & continuum.
376. M. BEROZA and M.e. BOWMAN, J. Agr. Food Chem. 14, 625-7 (1966). CA 66, 10159. GC detn.
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377. M. C. BOWMAN and M. BEROZA, J. Ass. Offic. Anal. Chem. 49, 1046-52 (1966). CA 66, 1835.
GC detn. of ehemosterilants with fp. detec. of P & S.
378. M. C. BOWMAN and M. BEROZA, Ibid., 1154-7. CA 66, 45522. Similar to Ref. 376.
379. M. E. GETZ, J. Gas Chromatog. 5, 377-9 (1967). CA 67, 72713. GC detn. of pesticides with
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380. M. C. BOWMAN and M. BEROZA, J. Ass. Offic. Anal. Chem. 50, 926-33 (1967). CA 67, 72515.
Similar to Ref. 379.
381. M. C. BOWMAN and M. BEROZA, Ibid., 1228-36. CA 68, 38221. Similar to Ref. 379.
382. R. K. STEVENS, Ibid., 1236-42. Similar to Ref. 379.
383. M. C. BOWMAN and M. BEROZA, J. Agr. Food Chem. 15, 465-8 (1967). CA67, 20675. Similar
to Ref. 376.
384. M. e. BOWMAN and M. BEROZA, Ibid., 651-3, CA 67,72508. Similar to Ref. 376.
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386. C. CORLEY and M. BEROZA, Ibid., 361-3. Similar to Ref. 376.
387. M. C. BOWMAN and M. BEROZA, Ibid., 399-402. CA 69,1853. Similar to Ref. 376.
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389. M. C. BOWMAN and M. BEROZA, Gas chromatographic analysis of pesticide residues with the
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390. M. BEROZA and M. C. BOWMAN, Environ. Sci. Tech. 2, 450-7 (1968). CA 69,2029. Similar
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391. M. C. BOWMAN and M. BEROZA, Anal. Chem. 40, 1448-52 (1968). Fpr. for simultaneous
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392. TA-CHIANG LIU, T'u Jang T'ung Pao (or Tu Sang Tung Pao), No.3, 53-5 (1964). CA 62,
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394. W. A. AUE, D. L. STALLING, C. W. GEHRKE, R. C. TINDLE and S. R. KOIRTYOHANN, Organo-
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395. W. A. AUE and e. W. GEHRKE, Spectral characteristics of the "thermionic" detector, American
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396. T. KUMAMARU, Y. OTANI and Y. YAMAMOTO, Bull. Chem. Soc. Japan 40, 429 (1967). CA 67,
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397. A. KARMEN and LAURA GIUFFRIDA, Nature 201, 1204-5 (1964). CA 60, 13860. Preliminary to
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398. LAURA GIUFFRIDA, J. Assoc. Offic. Agr. Chemists 47, 293-300 (1964). CA 61, 3611. FI. ioni-
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399. A. KARMEN, pp. 293-336 in Advances in Chromatography, Vol. 2, J. C. Giddings and R. A.
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403. T. T. SATURNO and W. D. COOKE, The mechanism of the Karmen-Giuffrida detector, American
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404. P. J. PADLEY, F. M. PAGE and T. M. SUGDEN, Trans. Faraday Soc. 57, 1552-62 (1961).
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406. C. A. BACHE and D. J. LISK, Anal. Chem. 37, 1477-80 (1965). CA 64, 1288. Detector of Ref.
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407. C. A. BACHE and D. J. LISK, Ibid. 38,1757-8 (1966). CA 66,1817. Similar to Ref. 406.
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408. C. A. BACHE and D. J. LISK, Ibid. 39, 786-9 (1967). CA 67, 17625. Microwave He discharge
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423. Beckman Instruments, Inc., Bull. 7106, Model 979 Atomic Absorption Spectrophotometer,
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424. H. L. KAHN, G. E. PETERSON and JANE E. SCHALLlS, Atomic Absorption Newsletter 7,
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429. L. P. PEPKOWITZ and W. C. JUDD, U. S. At. Energy Comm., KAPL-127, declassified 1949.
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439. G. MERZ, Repertoire de chimie pure 1861, p. 185. Blue of H2 fl. on H 2S0 4 ,
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441. G. SALET, Compl. rend. 68, 404-6 (1869); CZ 40,895 (1869). Bull. soc. chim. France 11, 302-
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453. F. BRINSLEY and S. STEPHENS, Nature 157, 622 (1946). CA 40, 5223. S2 bands in coal-gas fl.
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456. R. G. W. NORRISH, Science 149,1470-82 (1965). CA 63,14109. Spectral study of photoflash
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465. M. CHARTON, Combustion des melanges gazeux, Societe des Editions, Paris, 1958; p. 639.
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467. M. C. BOWMAN and M. BEROZA, J. Ass. Olfic. Anal. Chern. 50, 940-1 (1967). CA 67, 89829.
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470. D. C. CULLUM and D. B. THOMAS, Ibid. 85, 688-9 (1960). CA 55, 5236. Modification of Ref.
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471. D. ALT, Landwirtsch. Forsch.16, 278-84 (1964). CA 60, 13556. Indirect fp. detn. of sulfate via
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374 NONMETALS [5
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536. A. P. SMITH, Chem. News 39, 141 (1879). Blue fl. of NaCI on coal.
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542. F. BEILSTEIN, Ber. deut. chern. Ges. 5, 620-1 (1872). CZ 43, 617 (1872). Detec. of halogens by
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543. R. L. SHRINER, R. C. FUSON and D. Y. CURTIN, The Systematic Identification of Organic
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547. Davis Instrument Division, 130 W. Emerson St., Melrose, Mass., Davis Halide Meter, Bull.
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548. T. MIDGLEY, JR. (to General Motors Corp.), U.S. Patent 1,990,706, Feb. 12, 1935. Cu spark
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550. E. ERLENMEYER, JR. and G. HILGENDORFF, Ber. deut. chern. Ges. 43, 955-8 (1910). CA 4,
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553. D. E. DASHER (to General Motors Corp.), U.S. Patent 2,017,951, Oct. 22,1935. Cu-sensitized
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554. W. K. HULL (to Hull Mfg. Co.), U. S. Patent 2,106,147, Jan. 18, 1938. Similar to Ref. 553.
555. R. S. GAUGLER (to General Motors Corp.), U.S. Patent 2,134,552, Oct. 25, 1938. Similar to
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556. W. B. GRIESE (to Crosley Corp.), U.S. Patent 2,169,605, Aug. 15, 1939. Fl. color for testing
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557. W. G. TUEL (to Prest-O-Lite Co.), U.S. Patent 2,200,523, May 15, 1940. CA 34, 5790. Simi-
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558. A. c. SCHMIDT, The halide torch method of leak detection, U.S. At. Energy Comm., AECD-
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559. W. G. NOLCKEN (to Pressed Steel Co., Ltd., England), U.S. Patent 2,589,116, Mar. 11, 1952.
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561. H. A. MITCHELL (to Turner Brass Works), U.S. Patent 2,809,lOl, Oct. 8, 1957. CA 52, 13.
562. O. H. DRAGER, Brit. Patent 872,691, Appl. Aug. 21, 1959. Anal. Abstr. 8, 5039 (1961).
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563. DRAGERWERK; H. and B. DRAGER, German Patent 1,095,552, Dec. 1960. CA 56, 938. See
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564. C. E. VAN DER SMISSEN, U.S. Patent 3,025,141, Mar. 13, 1962. See Ref. 562.
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567. Her Majesty's Factory Inspectorate, Ministry of Labour, Methods for the detection of toxic
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568. Anonymous, "Halogen leaks can be detected by device which can operate as blow lamp,"
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569. P. J. BENDT (to General Motors Corp.), Brit. Patent 678,806, Sept. 10, 1952. CA 48,82. Na-
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570. MRS. B. GUTSCHE, R. HERRMANN and K. RUDIGER, Z. anal. Chern. 241, 54-66 (1968). In-
376 NONMETALS [5
dium-sensitized fl. detn. of organic CI.

571. MRS. B. GUTSCHE and R. HERRMANN, Ibid. 242, 13-7 (1968). Like Ref. 570, with filter pho-
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572. R. HERRMANN, The possibility of combining gas chromatography with flame photometry,
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573. M. HONMA, Anal. Chem.27, 1656-9 (1955). CA 50,4718. Fs. detn. ofCI in sea water by CuCI
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574. GRACE E. MARSH, Appl. Spectry. 12, 113-4 (1958). CA 53, 4011. Fs. detn. of organic CI by
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575. M. MARUYAMA and S. SENO, Bull. Chem. Soc. Japan 32, 486-90 (1959). CA 54, 3050. Fs.
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576. V. D. SNYDER, U.S. Patent 2,884,591, Apr. 28, 1959. Low-pressure Ni spark for detecting
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577. General Electric Co., Instrument Dept., West Lynn, Mass., Type H-2 Leak Detector, In-
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578. T. R. PHILLIPS and D. R. OWENS, pp. 308-15 in Gas Chromatography 1960. Proc. 3rd Symp.
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579. H. MOESTA and P. SCHUFF, Ber. Bunsenges. physik. Chem. 69, 895-900 (1965). CA 64, 4301.
Sensitized elec. ionization detector for halogens; theory.
580. O. MENIS, H. P. HOUSE and T. C. RAINs, Anal. Chem. 29, 76-8 (1957). CA 51, 4873. Indirect
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582. MRS. B. GUTSCHE, M. BAFI-YEBOA, B. CZERNICKI and R. HERRMANN, Deut. tieriirztl. Woch-
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583. L. E. MALEY, pp. 59-64 in Proc. 4th. Natl. Power Symp., 1961. CA 61, 15833. Fs. monitor
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584. ULLA WESTERLUND-HELMERSON, Atomic Absorption Newsletter 5,97 (1966). Aas. detn. of
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585. W. J. COLLINSON and D. F. BOLTZ, Anal. Chem. 40, 1896-8 (1968). Indirect aas. detn. of
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590. E. H. COLEMAN, A. G. GAYDON and W. M. VAIDYA, Nature 162,108-9 (1948). CA 42, 8084.
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592. R. DERICHSWEILER, The band spectra of the copper halides. Regularities in compound spectra,
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REFERENCES 377
(present address: Dept. of Chemistry, Occidental College, 1600 Campus Rd., Los Angeles,
Calif. 90041).
CHAPTER 6
ATOMIC EMISSION AND ABSORPTION SPECTROMETRY
OF THE RARE EARTH ELEMENTS
Richard N. Kniseley,
Velmer A. Fassel,
Constance C. Butler.
and Department of Chemistry
Iowa State University, Ames, Iowa, U.S.A.
6.1 Introduction
The striking similarity in the chemical properties of the rare earth group of elements pre-
cludes the use of classical techniques for the quantitative analysis of most rare earth mix-
tures. Consequently, the analyst has turned to measurements of physical properties of
these elements in order to obtain analytical data on mixtures of the rare earths. By far
the most useful analytical information has been obtained from intensity measurements
on the various characteristic spectra of these elements. Thus, optical emission spectra,
absorption spectra in the optical region and fluorescent spectra in the optical and x-ray
regions have been extensively employed [1].
6.2 Atomic and molecular emission spectra
The conventional arc or spark emission spectra of most of the rare earth elements are very
complex, possessing thousands of lines of rather uniform intensity and lacking the cha-
racteristically intense lines found in the spectra of other elements. Even under high dis-
persion the probability of line interference is high and difficulties are frequently encount-
ered in locating interference-free lines. The promise that simpler spectra can be obtained
under less energetic excitation conditions than those prevailing in arcs and sparks has led
several investigators to explore the spectra excited in conventional flames. LundegArdh [2]
first recognized the possibility of using flame spectra for the determination of several
elements in this group. In a series of papers published during the period 1929 to 1941,
Piccardi [3] described the principal features of the oxyhydrogen flame spectra of most of
the rare earth elements. Piccardi, as well as Lundegardh, introduced the rare earths into
the flames as aerosols of aqueous solutions. Under these moderate excitation conditions
both LundegArdh and Piccardi observed that most of the spectra were remarkedly devoid
Contribution No. 2272. Work was performed in the Ames Laboratory of the U.S. Atomic Energy
Commission.
380 ATOMIC EMISSION AND ABSORPTION SPECI'ROMETRY [6
of any atomic lines. However, Piccardi noted that most of the rare earth elements have a
tendency to form stable diatomic monoxide (MO) molecules in the flame. Since these
molecules are relatively stable, their presence in the flame was manifested by the charac-
teristic diatomic band emission spectra. Pinta [4] extended the observations to air-acety-
lene flames and made a thorough study of the analytical utility of these spectra. Mavrodi-
neanu and Boiteux [5] have listed the band heads for the monoxides bands of the rare
earths as emitted in oxy-acetylene and air-acetylene flames. General information on these
monoxide bands is also contained in other books dealing with molecular spectra [6-9].
Most of the monoxide band systems are concentrated in the wavelength region 4800-
6000 A, as illustrated in Figs 6.1 and 6.2. Although Piccardi [3] showed that these band
systems could be used to advantage in monitoring rare earth fractionations, the overlap
of the individual spectra greatly restricts the general analytical utility of these band
systems. The feasibility of applying appropriate interference corrections has been studied
by Pinta [4], but this approach is practically limited to simple binary or ternary mixtures.
There are several components in these band systems which occur in spectral regions
relatively free of interference. The most prominent of these are the LaO bands at 4372,
4418, 7403 and 7910 A. Although De Albinati [10], Ishida [11] and Menis et al. [12]
found that these bands were subject to various degrees of interference by other cations
present in the solution, Tremmel [13] observed that under his experimental conditions
other rare earths present in mixtures did not exert significant interelement effects or spec-
tral interferences on the 7910 A LaO band. A five-fold enhancement of the band intensity
y---
400
WAVE LENGTH (nm)
Fig. 6.1. Rare earth monoxide band emission spectra (from [13D.
6.2] ATOMIC AND MOLECULAR EMISSION SPECTRA 381
Ce -----~-'li
!
P'~
La
Nd
Eu---
Fig. 6.2. Rare earth monoxide band emission spectra (from [13]).
was observed by Tremmel when 25 % by volume of n-propanol was added to aqueous

solutions of the rare earths. According to Menis et al. [12], the 5600 A band system shows
a comparable enhancement in a 1 : 1 methanol-water solution, whereas the 7910 A band
was enhanced l00-fold when the lanthanum was aspirated into the flame from a 4-methyl-
2-pentanone solution.
The oxyhydrogen flame spectra of all the rare earths except cerium plus the elements
382 ATOMIC EMISSION AND ABSORPTION SPECTROMETRY [6
yttrium and scandium have been observed by Rains et al. [14]. They aspirated 4-methyl-
2-pentanone solutions of the rare earths into an oxyhydrogen flame. Rains et al. deduced
that the LaO band systems described above, the ytterbium atom line at 3988 A and the
NdO bands at 6606 and 7120 A should be useful for the determination of the parent ele-
ments in rare earth mixtures. Using air-acetylene flame excitation, Poluektov and Nikono-
va [15] employed the LaO emission at 7940 A, the YO emission at 5972 to 5988 A or
6132 to 6165 A, and the atom lines of ytterbium and europium at 3988 and 4594 A,
respectively, for determining the parent element in some rare earth mixtures. Since the
standard addition technique was used, the upper limit of determination was restricted
to the range 10-30 percent.
Several other authors [16-19] have also utilized the rare earth band spectra for analyti-
cal purposes. However, because of the high incidence of spectral interference among the
various rare earth monoxide band systems, it is unlikely that the analytical utility ofthe
band spectra will be extended significantly beyond the applications discussed above.
6.3 Production of free atoms
Although Lundegardh [2], Pinta [4], and Rains et al. [14] reported the presence ofa few
atomic lines in their flame spectra, the intensities were so weak that these lines were oflittle
or no analytical significance except in the cases of europium and ytterbium as discussed
above. There is strong experimental evidence and corroborative thermodynamic data which
suggest that stable diatomic rare earth monoxide molecule formation is the major control-
ling factor which limits the production of line spectra in oxygen supported flames. As
noted by Piccardi [3], the monoxide band systems are the most prominent features in the
oxyhydrogen flame spectra, indicating that the compounds are stable at the prevailing
flame temperatures. This conclusion is supported by the exceptionally high dissociation
energies exhibited by these molecules (Table 6.1). In view of these high dissociation ener-
gies it is really not surprising that oxyhydrogen flame spectra are so devoid of lines since
the formation of monoxide molecules should greatly reduce the free-atom concentration
in the flame. The actual number of atoms present under these circumstances therefore de-
pends on the degree of dissociation of the parent monoxide molecules.
Since these rare earth monoxides are not dissociated to any appreciable extent at ordi-
nary flame temperatures, Fassel, Curry and Kniseley [20] approached the problem of
free-atom formation from the standpoint of flame chemistry. Their study of the fuel-rich,
oxyacetylene flame showed that this flame provided a more favorable environment for the
existence of rare earth atoms in the flame gases. These flames contain appreciable concen-
trations of carbon-containing species such as solid carbon, CHn radicals, C 2 and possibly
atomic carbon [21,22].
Because of the highly exothermic nature of the reaction between atomic oxygen and
these species, lower atomic oxygen concentrations in these flames are not unexpected [23].
The position of the rare earth monoxide dissociation equilibrium is thus more favorable
for the existence of a higher concentration of free atoms in the flame gases.
Another interesting mechanism which may contribute to a greater free-atom popula-
tion in these flames is the reaction of atomic carbon with rare earth monoxide molecules
[20] in accordance with the equation:
C + MO = CO + Me (or M*).
For the rare earth monoxides, this reaction will always be exothermic.
6.3] PRODUCTION OF FREE ATOMS 383
TABLE 6.1 DISSOCIATION ENERGIES OF RARE EARTH MONOXIDES
Dissociation
Molecule Energy (eV)*
CeO 8.3
DyO 6.5
ErO 6.6
EuO 5.8
GdO 7.4
HoO 6.5
LaO 8.2
LuO 7.2
NdO 7.4
PrO 7.9
ScO 7.1
SmO 6.1
TbO 7.4
TmO 6.0
YbO 3.9
YO 7.3
• Values from L. L. Ames, Ph. D. Thesis, Ohio State University, Columbus, Ohio (1965). In a
later review (L. L. Ames, D. N. Walsh and D. White, Department of the Navy Report
AD 651562 (Defense Documentation Center, Arlington, Va.) May, 1967) the Do values quoted
are slightly larger, ranging from an increase of 0.02 eV for DyO up to 0.15 for YO.
There are scattered observations recorded in the literature which provide confirmation
that free-atom populations of other elements are increased in fuel-rich, reducing flames.
The enhancement of the line spectra of magnesium in highly reducing oxyacetylene flames
observed by Knutson [24] appears to be a manifestation of the same phenomena discussed
above. The dissociation energy of MgO reported by Schofield is 3.6 eV [25]. An enhance-
ment in the atomic absorption spectra should also be a discernible consequence of an in-
crease in the free-atom population in these flames. David [26] has reported that the ground
state, molybdenum-atom population in air-acetylene flames is critically dependent on the
air-to-acetylene ratio. For air-rich flames, negligible atomic absorption occurred for molyb-
denum concentrations at the 50 ppm level, whereas 35 percent absorption occurred in a
fuel-rich reducing flame. DeMaria et al. [27] have reported the dissociation energy of
MoO as 5.03 ± .65.
The success of Fassel et aI. [20] in obtaining analytically useful line spectra of the rare
earths is illustrated in Fig. 6.3. The spectra of dysprosium shown in this figure were all
observed at the same instrumental sensitivity. At the particularly low sensitivity employed,
spectral lines characteristic of dysprosium are not detectable in the oxyacetylene flame
spectra of aqueous solutions. For ethanol solutions, the strongest lines are just barely
detectable. A marked intensification of the line and band spectra was produced by fuel-
rich, oxyacetylene excitation of aqueous solutions, but the strongest line spectra were
observed for fuel-rich, oxyacetylene excitation of the perchlorates dissolved in absolute
ethanol. The enhancement factor attributable to ethanol ranges from 3 to 5 depending on
the element and the actual line measured for a given element.
4211.7
4186.8 A
Ethanol solution-fuel rich
Water solution-fuel rich
Ethanol solution-stoichiometric ---"-------"--
Water solution-stoichiometric
Fig_ 6.3. Oxyacetylene flame emission spectra of dysprosium (1000 [lg/ml).
The fuel-rich, oxyacetylene flame was obtained with flow rates of 2.72 and 3.371/min,
respectively, for oxygen and acetylene. Since both the oxygen and the acetylene are ex-
panded to atmospheric pressure before they are burned, the volume flow rates are roughly
proportional to molar flow rates. If air diffusion into the flame and the fuel contributed by
the ethanol solvent are neglected, these flow rates gave oxygen/acetylene mole ratios of
0.8. For a stoichiometric flame the required mole ratio is 1.5, if complete combustion to
carbon monoxide and water is assumed.
The original observations were made on fuel-rich, oxyacetylene flames obtained from a
total consumption burner (Beckman-type) which produces a highly turbulent flame. The
development of a premixed, oxyacetylene burner by Kniseley, D'Silva and Fassel [28, 29]
led to a large improvement in signal-to-noise ratio. Also, existence of distinct reaction
zones in the flame offered an opportunity for a more careful study of the fuel-rich pheno-
menon. As illustrated in Fig. 6.4, the more favorable conditions for the formation of rare
earth free-atoms appear to exist for only a restricted zone of the flame. Weak line emission
is observed in the primary reaction zone but the line emission is primarily confined to the
oxygen-deficient interconal zone. In the secondary reaction zone sufficient oxygen is
available to force the formation of the stable metal monoxides and only very weak atomic
line radiation emission is observed. Atomic absorption studies of the three flame zones in-
dicate a similar distribution of the free atoms. Thus, the optimum position in the flame
for observation of atomic emission and absorption for most of the rare earth elements
lies within the interconal zone of the fuel-rich flame.
6.3] PRODUCTION OF FREE ATOMS 385
OUTER ZONE
o o
(SECONDARY REACTION ZONE)
" "
....
([) ~
01" -
Vl
I
....
o
3.5 X SENSITIVITY o~t::
.... "'''''''
~
'"o
:z:
o
,......., o
.....,
"
Vl
m
'" ...
" ...'"0
til
INTERCONAL ZONE '"
"
til
'"
;;;
N
0 U
'"
;;;
Z
u
...m o
U
N ...
(I)
,.......,
U
N m
(I)
'"Zo
r'r 0
w
2':
f--
«
..J
W
a::
BLUE CONE
(PRIMARY REACTI ON ZONE)
...'"
;;;
m ~~ .
....
...'"
N
U
3500
Fig. 6.4. Flame emission spectra of scandium (1000 [Lgjml) observed in the three zones of the
premixed oxyacetylene flame.
The efficiency of free-atom formation is very sensitive to the oxidant/fuel ratio. In-
creasing the fuel-richness ofthe flame increases the concentration of the carbon-containing
species but also reduces the flame temperature. Thus, the optimum oxidant/fuel ratio is a
compromise between flame temperature and concentration of reductants. For elements
which form very stable monoxide molecules (e.g., La), very fuel-rich flames are necessary
in order to produce an appreciable concentration of free atoms. However, for other ele-
ments which do not form stable metal monoxides at ordinary flame temperatures (e.g.,
Eu), near stoichiometric flames produce the maximum emission line intensity.
The excitation of the atomic species, once they are present in the flame, appears to be
principally thermal in character. The intensities and excitation potentials of the observed
lines are exactly those expected from the type of energy distribution prevailing in flames
possessing temperatures in the 2800-3000 °C range. Thus, most of the lines, and all of the
intense ones, originate from excited states within 3.5 eV of the ground state of the atom.
A few weak ion lines, originating from excited states within about 3 eV of the ground
state of the ion, are also excited. Their appearance is not unexpected since the degree of
ionization ofrare earth atoms at the temperature ofthe flame is significant [30]. Once the
ions are formed, the lower excited states can be populated by a thermal excitation mecha-
nism, thus producing ion lines.
THUUUM
50,."11'11
401~AVEl.ENGTH tAl 4100
ERSIUM
50,.,/ml
I----- '--'---"~----- _ _ _ _.-J '-_~_ _ _ _ _ _ _-' '-_ _ __
.,.,. WAVELENGTH 117

HOlMIUM
50,.,""1
l ' I
407'WAVELENGTH '''7.&) 4DO
Fig. 6.5. Portions of the flame emission spectra of Tm, Er and Ho recorded under conditions for
analytical observations.
6.4] ANALYTICAL APPLICATIONS 387
The fact that free atoms of the rare earth elements are produced in fuel-rich oxyace-
tylene flames led Fassel and Mossotti [31,32] to study the atomic absorption spectra of
these elements. They utilized three Beckman-type burners in conjunction with a multipass
system, a continuum source and a 3.4 meter Ebert grating spectrograph and observed
atomic absorption spectra for all of the rare earth elements with the exception of cerium.
Amos and Willis [33] and Pickett and Koirtyohann [34] have shown that fuel-rich,
nitrous oxide-acetylene flames effectively produce free atoms of the rare earth elements.
In most instances they have found that the atomic absorption and emission in this flame
is comparable to that observed in the premixed, oxyacetylene flame.
The possibility of detecting atomic line radiation from the rare earths in the inner cone
of the air-acetylene flame has been explored by Ovchar and Poluektov [35]. According
to Ovchar and Poluektov, the intensities of the lines were weak and in most cases did not
allow determinations below 200 [Lg/ml.
The flame emission spectra of the rare earth elements are shown in the appendix at the
end of this chapter. These spectra were recorded at a fast scanning rate to compress them
into a size suitable for publication. This results in the impression that the spectra are com-
plex whereas in reality they are relatively simple. When the spectra are recorded under
more optimal conditions for analytical observation, this simplicity is plainly evident. For
example, Fig. 6.5 shows the spectra of Er, Ho and Tm in the wavelength region from 4000
to 4175 A. This series of spectra shows that there is an ample choice of interference-free
lines which are suitable for both major and minor constituent analyses. One of the most
complex of the rare earth spectra is sho'Wn in Fig. 6.6. In this example the spectrum of
samarium is recorded under more optimal conditions. Again the relative simplicity of the
spectrum is readily apparent.
Fig. 6.6. A portion of the flame emission spectrum of Sm recorded under optimal conditions. Sm
concentration is 100 [Lg/ml.
6.4 Analytical applications
6.4.1 FLAME EMISSION SPECTROMETRY
One of the most useful applications of the flame atomic spectra of the rare earths is the
analysis of rare earth mixtures, since classical chemical methods cannot be used. Flame
atomic emission spectra possess several advantages over the other spectra used for the
analysis of rare earth mixtures. First, the spectra are striking in their simplicity compared
TABLE 6.II
EMISSION SPECTROMETRIC DETECTION LIMITS FOR THE RARE EARTH
ELEMENTS
Detection Limits (fLgjml)
Element Wavelength Flame 2 Flame 3 Spark Excitation
(A) 1
Emission * Absorption Porous Cup 4
Ce 3942.75 25
4012.39 10
4186.60 3
5697.00 10
5699.23 10 n.d.
Dy 3407.79 2
4186.78 0.3
4211.72 0.1 0.2
Er 3372.76 2
4007.97 0.3 0.2
4151.10 1
5826.79 1
Eu 4205.05 0.5
4594.03 0.003 0.2
Gd 3422.47 4
3684.13 4
4346.46
4346.62 4
4519.66 2
Ho 3398.98 0.5
4103.84 0.1
4163.03 0.3
La 3337.49 0.3
3927.56 80
3949.10 1
5791.34 1
Lu 2911.39 0.5
3312.11 0.2 50
4518.57 0.5
Nd 4012.25 5
4634.24 2
4883.81 1
4924.53 1
Pr 4100.75 2
4939.74 2
4951.36 6
Sc 3613.84 0.05
3907.49 0.2
3911.81 0.07 0.2
4020.40 0.1
Sm 3634.29 3
4296.74 5
4883.77
0.6
4883.97
5175.42 0.8
Tb 3509.17 3
3901.35 4
4326.47 1 2
Tm 3131.26 2
4094.19 0.3 0.1
4105.84 0.2
Detection Limits ([lgjml)

Element Wavelength Flame z Flame 3 Spark Excitation
(A) 1 Emission Absorption Poroous Cup 4
Y 3242.28
3710.30
4077.38 0.3 0.3
I 0.2
0.1
4102.38 0.3
4128.31 0.5
Yb 3289.37 0.04
3987.98 0.05 0.04
1 Wavelengths of lmes from W.F Meggers, C. H. CorlIss and B. F. SCrIbner, NBS Monograph
32, Part. 1 (1961).
z From References [28] and [29].
3 From References [36] and [37].
4 From compilation in Reference [38].
* Approximately a factor of ten improvement in these emission limits has been obtained with
a NzO-CzH z flame burning on a conventional slot burner [47].
to the arc or spark spectra. It is therefore possible to achieve adequate spectral resolution
with small table-model spectrometers, whereas large, high dispersion spectrographs are re-
quired when arc or spark spectra are observed. Secondly, all of the rare earths exhibit line
spectra of sufficient intensity to possess analytical utility. This is further illustrated in
Table 6.II which lists the detection limits observed in a premixed, fuel-rich, oxyacetylene
flame together with the available data for atomic absorption and conventional spark-
excitation, optical-emission techniques. The group of rare-earth elements which evade de-
tection by the spectrophotometric techniques [1] are readily observed in the flame spectra.
In addition, there is no evidence of inter-element effects, and line interferences, even in
small monochromators, are rarely a serious problem. This contrasts sharply with the se-
lective enhancement and absorption effects observed in x-ray fluorescent spectrometric
measurements.
D'Silva et al. [39] have reported a method for the analysis of complex mixtures using a
fuel-rich, oxyacetylene flame from a Beckman-type burner. They obtained relative standard
deviations which ranged from ± 1.3 to 3.7% of the amount present. This method was later
adapted by the authors to use with the premixed, oxyacetylene flame. The lines which were
most satisfactory with the premixed burner together with their useful analytical range are
shown in Table 6.1II. These lines were selected for minimal spectral interference, especially
from neighboring atomic number rare earths, and thus are not necessarily the most
sensitive. For the analysis of some in mixtures, where fewer spectral interferences exist,
more sensitive lines may be used with a corresponding improvement in detection sensitivity.
A typical analytical curve is shown in Fig. 6.7. The concentration axis on the analytical
curve is in terms of the percentage of the element in the original sample. In certain instances
the analytical curves can be extended to lower concentration levels than the normal 1 to
100% range. A typical example is shown in Figure 6.8. The matrix composition in each
of the standards used to prepare this analytical curve was changed. All of the experimental
points cluster rather uniformly along a single congruent curve, with no apparent syste-
matic deviations for any of the matrices. This behavior documents the high degree of free-
dom of this technique from both spectral and interelement interferences.
TABLE 6.111
ANALYTiCAL LINES FOR FLAME EMISSION ANALYSIS OF COMPLEX RARE EARTH
MIXTURES
Wavelength Range of Analytical
Element (A) Curve (wt. %)
Ce 5223.49 3 -100
Dy 4589.37 0.2 -100
Er 4007.97 0.1 -100
Eu 4594.03 0.1 -100
Gd 4346.46
0.5 -100
4346.62
Ho 4163.03 0.1 -100
La 5930.68 0.5 -100
5930.62
Lu 3312.11 0.2 -100
4518.57 0.2 -100
Nd 4866.74 0.5 -100
Pr 5018.58 2 -100
8c 3269.91 1 -100
8m 4470.89 0.5 -100
Tb 4493.08 2 -100
Tm 3887.35 0.2 -100
Y 4643.70 2 -100
Yb 3987.98 0.01-100
5556.48 1 -100
100
50
10 50 100
z
CONCENTRATION Y 0 3 (%)
Fig. 6.7. Analytical curve for the determination of yttrium in rare-earth mixtures.
(Sm)e
100
Gd)
(Lui
50 Tm
(Ce+Pr)
,,"<D (La). (Tb)
'"<D'"
'"'2>- (Nd).
ScI
>- (Dy)
!::
<n (Tm).
z 10
.(Ha)
'"f-~ (y\Lu)
w
>
;:: Prj
«
.J
w
0:
(Dy)
.005 .01 .05 .10
CONCENTRATION Yb 2 0 3(%)
Fig. 6.8. Analytical curve for the determination of low concentrations of ytterbium in rare-earth
mixtures.
An indication of the accuracy of this flame emission method can be obtained from
Table 6.IV. The analytical results were obtained from a naturally occurring ore and were
analyzed by two independent methods. In both cases the rare earths were separated prior
to analysis and the values reported refer to the percent of each rare earth oxide in the ori-
TABLE 6.IV
COMPARISON OF ANALYSES ON A RARE EARTH ORE
wt % rare earth oxide in ore
Element X-ray Fluorescence 1 Flame Emission 2
Ce203 0.18 0.26
DY20 3 0.14 0.11
Er203 0.04 0.02
EU203 O.o? 0.03
Gd 2 0 3 0.17 0.15
Ho 2 0 3 0.02 0,0]
La203 O.o? 0.05
LU203 <0.01 <0.04
Nd 2 0 3 0.19 0.17
Pr6011 0.04 <0.07
Sm203 0.17 0.13
Tb 4 0 7 0.Q2 <0.04
Tm203 0.Q2 <0.01
Yb 2 0 3 <0.01 0.01
1 Analysis by Salt Lake City Metallurgy Research Center, Bureau of Mines. H. E. Peterson,
Supervisory Chemist.
2 Analysis by Ames Laboratory, Iowa State University.
ginal ore. Considering the difficulty of this analysis, the agreement between the x-ray
fluorescence and flame methods is good.
6.4.2 ATOMIC ABSORPTION SPECTROMETRY
In a systematic study on the absorption spectra of the rare earth elements in a fuel-rich,
oxyacetylene flame fed with ethanolic solutions of these elements, Mossotti and Fassel
[31,32] identified over 1000 absorption lines in the 2500 to 6500 A region. Many ofthese
lines were of sufficient intensity to be useful for analytical purposes. Skogerboe and Wood-
riff [40] observed europium, thulium, and ytterbium in absorption in a turbulent, fuel-
rich oxyacetylene flame. These investigators employed an oxyhydrogen flame fed with so-
lutions of the respective rare earth salts as primary sources. Because of the low intensity
and relative instability of these sources, the observed detection limits were not good.
Later work by Fassel et al. [41] provided detection limits for all of the rare earth elements
except cerium. A continuum primary source combined with a small 0.5 meter spectro-
meter were used for these observations. The development of a long-path slot burner de-
signed specifically for the observation of atomic absorption spectra of high burning velo-
city flames, such as oxygen-acetylene, led to an order of magnitude improvement in the de-
tection limits [42, 43]. The detection limits reported later by Amos and Willis for fuel-rich
nitrous oxide-acetylene flames compared favorably with those observed for fuel-rich
oxyacetylene flames [33].
When higher temperature flames are employed as absorption cells, the degree of ioni-
zation of the rare earths may be significant [44]. Since the degree of ionization in flames is
suppressed by the presence of other easily ionizable elements, enhanced absorbances may
be observed when other elements are introduced into the flame with the rare earths [33,45].
Published accounts of the application of atomic absorption spectra to the determination
of the rare earths are very limited. According to Kinnunen and Lindsjo [46], the absor-
bances of several rare earths in a nitrous oxide-acetylene flame were depressed significant-
ly by the presence of fluoride, silicon, and aluminium in the analyte solution. These same
investigators applied this flame to the determination of neodymium, yttrium, and europium
in rare earth concentrates separated from phosphate ores, but no accuracy data were
presented. Jaworowski et al. [45] studied the determination of erbium, dysprosium, ter-
bium, europium, and neodymium impurities in an yttria matrix, but the reported analyti-
cal results were inconclusive.
A comparison of the detection limits for the rare earth elements in flame atomic emis-
sion and absorption spectrometry (fable 6.II) allows certain conclusions to be made. The
fuel-rich oxyacetylene and nitrous oxide-acetylene flames are very effective in producing
free atoms of these elements and are the flames of choice for both atomic emission and
absorption analysis. The emission detection limits are equal to or better than those ob-
tained by absorption techniques, and thus flame atomic emission methods are, at present,
generally superior. Future improvements in hollow cathode discharge tubes (or develop-
ment of other primary sources) may lower the atomic absorption detection limits and
thereby make the two techniques more complementary. However, Kinnunen and Lindsjo
[46] have emphasized that locating the proper rare earth absorption line is sometimes
difficult because of the complexity of the spectra emitted by the hollow cathode lamps.
This could cause difficulties in routine analytical application.
A,6.I. EMISSION SPECTRA OF THE RARE EARTH ELEMENTS 393
APPENDIX 6.1
Emission spectra of the rare earth elements
These spectra were recorded on a 0.5 meter Ebert spectrometer with a reciprocal linear
dispersion of 16 A/mm. The scanning rate was 125 A/min. The burner used was the one
described by Kniseley, D'Silva and Fassel [26,27] and in each case the oxygen/acetylene
flow ratio was adjusted to provide the optimum signal/noise ratio. The changes in the
flame background are the result of these changes in the flame stoichiometry. In all cases
the solutions contained 500 fLg/ml of the rare earth element in absolute ethanol.
CH eN c,
c,
9.0
...
"
3000 4000 .4500 5000 5500

WAVELENGTH (A)
5500 6000 6500 • 7000 7500 6000

WAVELENGTH (A)
Fig. A.6.1. Flame background with pure ethanol

9.
3000 3500 4000 4500 5000 5500

WAVELENGTH (AI
9.
....
z
'"~6
iso
b
~
5500 6000 6500 • 7000 7500 8000

WAVELENGTH (AI
Fig. A.6.2. Flame spectrum of cerium

A.6.I. EMISSION SPECTRA OF THE RARE EARTH ELEMENTS 395
~I
3000 3500 ( 4000 4500 5000 ~~oo

WAVELENGTH (A)
9.
...z
w
~6 .
=>
'-'
~
J:
0..
3.
5500 7500 8000
Fig. A.6.3. Flame spectrum of dysprosium

4000 4500 5000 5500

WAVELENGTH (A)
5500 6000 6500 • 7000 7500 8000

WAVELENGTH (A)
Fig. A.6.4. Flame spectrum of erbium

3000 3500 4000 4500 5000 5500

WAVELENGTH (A)
3.0
0-
i:} 2.0
a:
a:
a
~
if:
1.0
8000
Fig. A.6.5. Flame spectrum of europium

3000 3500 4000 .4500 5000 5500

WAVELENGTH (A)
.."
9.0
I-
Z
""~6.0
i3
o
b
;,:
Q.
3.
5500 8000
Fig. A.6.6. Flame spectrum of gadolinium

9,0
...
"
..,>-z
~6 .0
...,
=>
e
o
"
Q.
3.0
3000 3500 4000 4500 5500

WAVELENGTH (AI
5500 6000 6500 • 7000 7500 8000

WAVE LENGTH (AI
Fig. A.6.7. Flame spectrumof holmium

400 ATOMIC EMISSION AND ABSORPTION SPECfROMETRY [6
3000 3500 4000 4500 5000 5500

WAVELENGTH (A)
9,
<l
c
I-
Z
w
~6,
a
~:x:
c..
5500 6000 6500 • 7000 7500 8000

WAVELENGTH (A)
Fig. A.6.S. Flame spectrum of lanthanum

A.6.I. EMISSION SPECTRA OF TIlE RARE EARTH ELEMENTS 401
.
c
>-
Z
UJ
~6.
::>
I.)
~:x:
0.
3.
3000 3500 4000 4500 5000 5500

WAVELENGTH (AI
>-
~ 2.0
a:
a:
::>
I.)
f!
o
:x:
0.
1.0
o 5500 6000 6500 • 7000 7500 8000

WAVELENGTH (AI
Fig. A.6.9. Flame spectrum of lutetium

.. c
....z
....
II:
a:
=>
l)
*
:r
Q.
3500 5500
WAV ELENGTH (A)
5500 6000 6500 • 7000 7500 8000

WAVELENGTH (A)
Fig. A.6.10. Flame spectrum of neodymium

A.6.I. EMISSION SPECTRA OF TIlE RARE EARTH ELEMENTS 403
3000 3500 4000 4500

WAVELENGTH (A)
'""
3.
5500 6000 6500 • 7000 7500 8000

WAVELENGTH (A)
Fig. A.6.11. Flame spectrum of praseodymium

3000 3500 4000 4500 5000 5500

WAVELENGTH (A)
5500 6000 6500 • 7000 7500 0000

WAVELENGTH (A)
Fig. A.6.12. Flame spectrum of samarium

3000 3500 4000 4500 5000 5500

WAVELENGTH (A)
5500 6000 6500 • 7000 7500 8000

WAVELENGTH (A)
Fig. A.6.13. Flame spectrum of scandium

3000 3500 4000 4500 5000 5500

WAVELENGTH (A)
:'OIJ~r
z
w
&: 6.0
a
5
'"<>.
3.0
6500 • 7000 8000

WAVELENGTH (A)
Fig. A.6.14. Flame spectrum of terbium

9.0
""
c
I-
Z
w
~6.0
::>
u
o
I-
o.
r
Q.
3.
3000 3500 4000 4500 5000 5500

WAVELENGTH (Al
5500 6000 6500 • 7000 7500 8000

WAVELENGTH (Al
Fig. A.6.1S. Flame spectrum of thulium

9.
I-
Z
'"
~6.
'"
<.>
~
:r
0..
3.
3000 3500 4000 4500 5000 5500

WAVELENGTH (A)
3.0
.."
I-
IEn: 2.0
0:
:>
'"0
0>:
0..
'] I
5500 6000
,~ 6500 • 7000
WAVELENGTH (A)
I
7500 6000
I
Fig. A .6.16. Flame spectrum of ytterbium

A.6.I. EMISSION SPECTRA OF THE RARE EARTII ELEMENTS 409
9.
<I
c
....
Z
!oJ
..,:::>~ao
[5
:t:
0..
3.0
3000 3500 4000 4500

WAVELENGTH (AI
9.0
<I
c
3.0
~~y~ ~
~ I
I
\Jl "- J..It..
I I ~ ~ I I
1500 8000
5500 6000 6500 • 7000
WAVELENGTH (AI
Fig. A.6.17. Flame spectrum of yttrium

References
1. v. A. FASSEL, Anal. Chem. 32, 19A (1960).
2. H. LUNDEGARDH, Die Quantitative Spektralanalyse der Elemente, Part II, Fischer, Jena (1934).
3. G. PICCARDI, Spectrochim. Acta 1, 533 (1941).
4. M. PINTA, J. Recherches Centre Natl. Recherche Sci. Labs. Bellevue, (Paris), 21, 260 (1952).
5. R. MAVRODINEANU and H. BOITEUX, Quantitative Spectral Analysis by Flame, (in French),
Masson, Paris (1954); Flame Spectroscopy, Wiley, New York (1965).
6. W. JENONS, Report on Band Spectra of Diatomic Molecules, University Press, Cambridge (1932).
7. G. HERZBERG, Molecular Spectra and Molecular Structure, 1, Spectra of Diatomic Molecules,
Van Nostrand, Princeton, N.J. (1960).
8. R. W. B. PEARSE and A. G. GAYDON, The Identification of Molecular Spectra, Wiley, New
York (1963).
9. A. GATTERER, J. JUNKES and E. W. SALPETER, Molecular Spectra of Metallic Oxides, Specola
Vaticano, Citta del Vaticano (1957).
10. J. F. POSSIDON! DE ALBINATI, Anales Asoc. Quim. Arg. 43, 106 (1955).
11. M. ISHIDA, J. Chem. Soc. Japan (Pure Chern. Sect.) 76, 60 (1955).
12. O. MENIS, T. C. RAINS and J. A. DEAN, Anal. Chim. Acta 19, 179 (1958).
13. C. G. TREMMEL, Masters Degree Thesis, Iowa State University, Ames, Iowa (1958).
14. T. C. RAINS, H. P. HOUSE and o. MENIS, Anal. Chim. Acta 22,315 (1960).
15. N. S. POLUEKTOV and M. P. NIKONOVA, Ukrain. Khim. Zhur. 25, 217 (1959).
16. V. PATROVSKY, Collection Czech. Chem. Commun. 26, 2445 (1961).
17. O. A. SHIRYAEVA and SH. G. MELAMED, Zavodsk. Lab. 30,183 (1964).
18. E. SUDO, H. GOTO and S. IKEDA, Sci. Rept. Res. Inst. Tohoku Univ. Ser A 12, 401 (1960).
19. L. A. OVCHAR, S. A. MISHCHENKO and N. S. POLUEKTOV, Zh. Prikl Spektr. 3,306 (1965).
20. V. A. FASSEL, R. H. CURRY and R. N. KNISELEY, Spectrochim. Acta 18,1127 (1962).
21. H. A. BROIDA and K. E. SHULER, J. Chem. Phys. 37, 933 (1957).
22. A. G. GAYDON and H. G. WOLFHARD, Flames, Their Structure, Radiation and Temperature,
(2nd Ed.), Chapman and Hall, London (1960).
23. C. P. FENIMORE and G. W. JONES, J. Phys. Chem. 62,178 (1958).
24. K. E. KNUTSON, Analyst 82,241 (1957).
25. K. SCHOFIELD, Chem. Rev. 67, 707 (1967).
26. D. J. DAVID, Nature 187, 1109 (1960).
27. G. DEMARIA, R. P. BURNS, J. DROWART and M. G. INGRAM, J. Chem. Phys. 32, 1373 (1960).
28. R. N. KNISELEY, A. P. D'SILVA and V. A. FASSEL, Anal. Chem. 35, 910 (1963).
29. A. P. D'SILVA, R. N. KNISELEY and V. A. FASSEL, Anal. Chem.36, 1287 (1964).
30. M. N. SAHA, Phil. Mag. 40, 472 (1960).
31. V. A. FASSEL and V. G. MOSSOTTI, Anal. Chem. 35, 252 (1963).
32. V. G. MOSSOTTI and V. A. FASSEL, Spectrochim. Acta 20,1117 (1964).
33. M. D. AMOS and J. B. WILLIS, Spectrochim. Acta 22, 1325 (1966).
34. E. E. PICKETT and S. R. KOIRTYOHANN, Spectrochim. Acta, 23B, 235 (1968).
35. L. A. OVCHAR and N. S. POLUEKTOV, Zh. Anal. Khim. 22, 45 (1967).
36. J. FIORINO, Masters Thesis, Iowa State University of Science and Technology, Ames, Iowa,
(1965).
37. W. SLAVIN, Appl. Spectry. 20, 281 (1966).
38. V. A. FASSEL and D. W. GOLIGHTLY, Anal. Chem. 39, 466 (1967).
39. A. P. D'SILVA, R. N. KNISELEY, V. A. FASSEL, R. H. CuRRY and R. B. MYERS, Anal. Chem.
36, 532 (1964).
40. R. K. SKOGERBOE and R. A. WOODRIFF, Anal. Chem.35, 1977 (1963).
41. V. A. FASSEL, V. G. MOSSOTTI, W. F. L. GROSSMAN and R. N. KNISELEY, Spectrochim. Acta
22,347 (1966).
42. J. A. FIORINO, R. N. KNISELEY and V. A. FASSEL, Spectrochim. Acta., 23 B, 413 (1968).
43. R. N. KNISELEY, Spectroscopic Properties and Analytical Applications ofFuel-Rich,Oxyacetyle-
ne Flames, Eastern Analytical Symposium, Nov. 13, 1964.
44. D. C. MANNING, Atomic Absorption Newsletter 5, 127 (1966).
45. R. J. JAWOROWSKI, R. P. WI!BERLING and D. J. BRACCO, Anal. Chim. Acta 37,284 (1967).
46. J. KINNUNEN and O. LINDSJO, Chem. Analyst 56, 25 (1967).
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CHAPTER 7
SOME RECENT SPECTROSCOPIC INVESTIGATIONS

OF LOW-PRESSURE OXYACETYLENE FLAMES
R. Bleekrode
Philips Research Laboratories
N. V. Philips' Gloeilampenfabrieken
Eindhoven, The Netherlands
7.1 Introduction
In this chapter we present a description of recent spectroscopic investigations of low-

pressure flames. In particular we shall be concerned with the reaction zone of low-pressure
oxyacetylene flames. As the effort devoted to such studies is relatively small this descrip-
tion is necessarily a short one. Very little, if any, attention has been paid to low-pressure
flames from the practical point of view. The greater part of spectroscopic research deals
with the visible and ultraviolet spectra of diatomic molecules like CO, CH, CN, C 2 , NH
and OH. An excellent review of the older literature can of course be found in Gaydon's
well-known book [1]. The studies of interest which specifically deal with metal atoms in
low-pressure flames are very limited in number. We may mention here the work of Gaydon
and Wolfhard [2] on the excitation of Fe, Pb and Tl in the reaction zone of various flames,
and that of Broida and Shuler [3] for Fe. Quite recently an interesting experiment with zri
was reported by Hollander and Broida [4] (see Section 7.5). In addition to these there are
the investigations of a somewhat preliminary character carried out by the author, which
will be treated at greater length in Sections 7.3 and 7.4.
Although the study of the physical and chemical processes occuring in the reaction
zone of low-pressure flames is of considerable interest, it is felt that an extensive discussion
lies beyond the scope of the present chapter. Information concerning the main combustion
reactions can be found elsewhere, for example in Fenimore's monograph [5]. Valuable
information has also been obtained from shock-tube investigations by Kistiakowsky [6],
Gardiner [7] and their associates. Ion formation and recombination processes have been
treated by several groups of investigators [8]. Valuable information has also come from
flash-photolysis experiments carried out by Norrish, Porter and co-workers [9]. Finally
attention may also be drawn to the studies of OH fluorescence by Carrington [10].
If one is solely interested in the direct analytical application of flames one may perhaps
find the present situation well described by the following quotation from Gaydon [1]:
"low-pressure flames do not appear very suitable for absorption studies." And further:
"although it is difficult to detect band spectra in absorption, for line spectra it has been
found that reversal temperatures can be measured quite well and lead to interesting con-
clusions about the lack of equilibrium in the flame front. " One might be tempted to con-
clude that since the determination of a reversal temperature is quantitative in character,
it will follow that quantitative absorption measurements are possible. This has been prov-
ed quite positively for molecules and atoms as well [11], [12].
412 RECENT SPECI'ROSCOPIC INVESTIGATIONS OF LOW-PRESSURE FLAMES [7
Before we begin our discussion of the various aspects of low-pressure flame spectroscopy
let us first consider the question of whether there are at present sufficient arguments to
justify the expenditure of further effort on low-pressure flames. From the flame spec-
troscopic point of view the answer is of course a simple yes. Yet it should be borne in mind
that an impressive number of flame phenomena have been studied in detail by spectrosco-
py for which at present no satisfactory answers can be given. Rather than study such
phenomena again and again in flames, one can also try to solve them through studies of
less complicated systems e.g., atomic flames [13] or atomic and molecular beam studies
[14]. On the other hand, the complexity of high-temperature combustion should by no
means stop investigations in this area. With better equipment and improved knowledge of
the electronic spectra of, for example, polyatomic molecules [15], new investigations will
eventually lead to new and interesting results in the area of combustion research.
From the practical point of view more than one argument may be advanced in favour
of a low-pressure flame:
a. In the first place low-pressure flames can be made to burn in a very stable manner.
h. Because of the low density at pressures between 1 and 20 torr the changes of refractive
index are relatively small.
c. The flame conditions can be varied over a wide range without great danger of flash-
backs. Thus the chemical composition can be changed and compound formation can be
reduced.
d. Volatile compounds and solutions can be added to the flame without danger and a large
number of flames, e.g., CH4 /0 2 ; C 2 H 2 /0 2 ; C2 H 2 /air; C 2 H 4 /0 2 ; H 2 /0 2 ; etc. can be stabi-
lized on the same burner. The use of other oxidants like N 2 0 falls in the same catagory.
e. Because of the low particle density (~10-5 mole/1 ~ 10 16 molecules/cm 3 ) the effect
of collisional broadening can be disregarded almost entirely. The final and perhaps the
most important property, it follows that the dominant broadening of absorption lines is
caused by the Doppler effect. This implies that for a given concentration of atoms (or
molecules) the absorption coefficient at the centre of the absorption line will be larger in a
low-pressure flame than in an atmospheric flame. Therefore, it can be expected that the
limits of detection can be lowered. In fact first indications for such a behaviour have
been found (see Section 7.4.2).
Practical knowledge of atmospheric flames has spread with the advance of flame emis-
sion spectrophotometry and flame absorption spectroscopy [16]. This is not the case as
far as low-pressure flames are concerned. Although the changes with respect to the flame
equipment originally used by Gaydon and Wolfhard [2] are not of a fundamental nature
a few remarks seem appropriate here. In the following section we shall therefore give a
more detailed description of the apparatus for emission and absorption measurements
[17]. Sections 7.3 and 7.4 will deal with the results of a few of our own studies of low-
pressure flames. In Section 7.5 a refined method for determining absorption coefficients
will be discussed. A short appendix dealing with the quantitative aspects of absorption
spectroscopy is added in order to free the text from algebraic calculations.
7.2 Experimental information
7.2.1 FLAMES
Low-pressure flames were burned in water-cooled metal reaction vessels. For emission
7.2] EXPERIMENTAL INFORMATION 413
Fig. 7.1. Reaction vessel used for the measurements of molecular absorption bands in low-press-
ure oxyacetylene flames.
and absorption studies of molecular bands a 501 stainless steel reaction vessel (Fig. 7.1)
was used in combination with a Galileo mechanical pump having a capacity of 60 m 3 Jh.
For the atomic emission and absorption studies a 150 I chamber was used in combination
with a 180 m 3 Jh Leybold pump. At pressures below 15 torr simple stainless steel burners
were employed, the slit dimensions being 10 x 1 and 20 xO.6 cm 2 • At higher pressures
watercooled flat flame burners were used and flames could be stabilized between 0.8 and
150 torr.
The ignition of a low-pressure flame may pose some problems. Usually an electrical
spark is used to start the reaction chains. We shall describe an alternative method with
which flashbacks and explosions in the high pressure chamber of the pump can be pre-
vented.
A discharge is excited in the oxygen inlet with a 10 MHz high-frequency generator.
The oxygen flow and discharge power are adjusted so as to give a green afterglow of the
reaction NO + 0--+ N0 2 *; N0 2 *--+ N0 2 + hv. Acetylene is then added through the
burner and the flame reactions start in the mixing region of the oxygen afterglow products
and acetylene. It often proved advantageous to premix the gases slightly, otherwise the
procedure is the same. It may be noted here that flames are more easily ignited in large
reaction chambers than in smaller ones. In the latter case the reaction chains are terminat-
ed by radical recombination or by deactivation processes at the wall.
In order to introduce Fe or Pb into the flames the latter were seeded with the vapour of
the volatile compounds Fe(CO) sand Pb(C2H s)4 or their solutions in benzene or toluene.
7.2.2 SPECTROSCOPIC EQUIPMENT
The elements used for the measurements are shown schematically in Fig. 7.2. For absorp-
tion measurements various light sources were used; a 500 W water-cooled mercury dis-
414 RECENT SPECTROSCOPIC INVESTIGATIONS OF LOW-PRESSURE FLAMES [7
A
B
E3.4
Fig. 7.2. Scheme of optical elements used for absorption measurements. A = light source; B =
aperture; C = chopper; D = lens, E1>2 and E 3 ,4 = mirrors of multiple reflection cell; Fl and
F 2 = viewing windows of 150 1 reaction vessel; G = mirror; H = slit of burner; I = monochro-
mator; J = photomultiplier; K = amplifier; L = recorder.
charge lamp or a 100 W compact source high-pressure mercury discharge lamp provided
the background continuum. The latter lamp has an exceptionally high surface brightness
which is of importance when narrow light beams are needed. The spectral lamps used are
of a recently [18] developed design. These lamps combine a narrow emission line (no
self-absorption) with a high spectral output. For all absorption measurements the flame is
placed in a multiple reflection cell. The mirrors, adjustable from the outside, were arranged
in a near-confocal configuration (Fig. 7.3). The number of passes through the flame
could be varied between 2 and 34, depending on the available light flux in the wave-
length region of specific interest. The precision polished mirrors were coated with SiO
to protect the reflective Al layer. The position of the burner slit was chosen parallel to the
multiple reflected light beams. The electronic detection of the light signals is described
elsewhere [17].
Fig. 7.3. Multiple reflection cell with 10 light passes drawn approximately to scale.
7.3 Emission
7.3.1 MOLECULAR BANDS
The electronic bands predominantly emitted by low-pressure oxyacetylene flames in the

visible and near ultraviolet are those of C 2 • CR and OR. In Fig. 7.4 a survey spectrum
shows these bands under low resolution. It may be noted that the "background" level
7.3] EMISSION 415
0) b)
~
i':-
~
:a
€,
.p
·iO
~
.!;
·r
Fig. 7.4. Survey emission spectrum of low-pressure oxyacetylene flame. a = premixed; b

diffusion. Note the increased emission in case h.
between the bands is relatively low, especially in a premixed flame. The spectra of these
bands have been studied in detail and their structure is well understood. Furthermore,
such quantities as the electronic oscillator strengths, Franck-Condon factors and the line
strengths of individual rotational lines are known either from experiment or from theory.
In some cases, however, the electronic oscillator strength is not known better than to
within a factor or two.
At first sight it might be conjectured that there would be very little to gain from a renewed
study of these bands. However, some time ago a number of interesting observations were
made in the C 2 "Swan" emission bands [11]. These form the well-defined vibrational
sequences throughout the visible part of the spectrum.
It seems worth devoting some space to these observations, not only because of their
possible implications with respect to the excitation of C2 in flames but also because a
better understanding of the phenomena may be of interest in the field of atomic and mole-
cular collision processes, especially those determining the excitation of certain species in
seeded flames.
The C 2 Swan emission spectrum from an oxyacetylene flame almost invariably shows an
intensity alternation, as can be seen from Fig. 7.5. The rotational lines originating from
even rotation levels (odd KH) of the A 3IIg (v = 0) state appear with higher intensity than
the lines originating from the odd rotational levels. In all likelihood the alternation is pre-
sent for all three spin components of the rotational lines. •
It was found that the degree of alternation depends on experimental conditions such as
pressure, flame composition and the position in the flame. A phenomenological descrip-
tion of the effects has been given previously [17], the results of which will not be repeated
here. However, a more detailed analysis revealed that at least part of the C 2 excitation in a
flame is due to the transfer of electronic energy from the electronic state to the radiating
A3IIg state [19].
* K is used for the rotational level numbering in order to avoid confusion with the particle
density N.
1("-
PI~
45
I I I
T JS
II I n II II11I i 111111111
25
R
K'
mWW~mWWjjEW~W~UIIiI
1 10 5
5165-2
Fig. 7.5. Part of 0-0 C z Swan emission band from a low-pressure oxyacetylene flame. The
P-branch lines clearly show alternating intensities.
7.3.2 SEEDED FLAMES: Fe AND pb EMISSION
The Fe I emission spectrum from low-pressure flames has been studied by Gaydon and
Wolfhard [2] and by Broida and Shuler [3]. From their experiments it has become clear
that the electronic excitation of Fe is a non-equilibrium One: lines originating from exci-
ted states up to about 8 eV have been observed and the energy distribution cannot be
described with a single parameter which would represent the electronic excitation tempe-
rature.
With the data at present available On transition probabilities [20] we are able to include
more lines in an analysis of the excitation of the Fe spectrum in a flame. Fig. 7.6 shows the
spectrum of Fe as emitted by a low-pressure oxyacetylene flame seeded with Fe (COh. The
spectrum of a Fe hollow cathode lamp is shown in Fig. 7.7 so that a comparison between
the two spectra can be made. About 120 lines of the spectrum were used for the analysis.
The intensity of an emission line between energy states Eu and E" l.m, is proportional to
the transition probability AUI and the number of excited atoms Nu:
(1)
The number of excited atoms Nu is related to the total number of atoms Nt through the
relation:
(2)
where the energy distribution over the electronic states is described with T. xe , gu is the
degeneracy of the upper state, k is Boltzmann's constant and Q e is the electronic partition
function. Combining (1) and (2) gives
(3)
7.3] EMISSION 417
l~ 11' llL
lBOO
I, ,I I ~.Lli W~ / ul .llOlI A.(A) 4 -
IlL 1.11 I. I .t Lt I
,..,
Fig. 7.6. Part of Fe emission spectrum of a low-pressure oxyacetylene flame seeded with
iron-carbonyl.
II I J~ J j J Ll t 1 IJU I. 1 JI
)"IA I 4 - -
Fig. 7.7. Part of Fe emission spectrum of a hollow-cathode discharge tube.
A semilogarithmic plot of gAy/! versus energy should therefore give a straight line with a
slope l/kTexc . Such a plot for the Fe spectrum of Fig. 7.6 is shown in Fig. 7.8. The first
thing one notices is that no unique quantity Texc can be defined. Roughly speaking the
broad-banded distribution is one which is far off thermal equilibrium. The straight line
corresponding to T"'=! 5600 oK is arbitrarily drawn in the graph. The curved line connects
data points indicated with crosses. These correspond to the emission lines chosen by
Broida and Shuler [3]. The deviation from a straight line begins at a value Eu = 32 x 103
cm-I, in reasonable agreement with the results of these authors.
Attention may also be drawn to the fact that in the spectral region which was consider-
ed the 3720 A line of Fe connecting the as D4 ground state and the ZS Fs ° excited state
(Eu = 26875 cm- l ) is not the strongest one. For typical analytical purposes some of the
more intense lines may be of interest if flame emission with Fe solutions is to be the subject
of investigation.
10 ,.
•
.. • I
-,
j
!
I
.
!!.
:;
~,
oil
Fig. 7.8. Semilogarithmic plot of statistical weight times transition probability times frequency
divided by the intensity versus energy of upper energy level for a number of iron lines emitted by a
low-pressure oxyacetylene flame seeded with iron carbonyl.
The results of the addition of tetraethyl lead to a low-pressure flame have also been
discussed by Gaydon and Wolfhard [2]. Among the observations of interest made by
them is that when a flame is photographed against the pole of a carbon arc the 2833 A
line is observed in absorption whereas other Pb lines remain visible in emission. We shall
presently mention an observation which is in qualitative agreement with the findings of
these authors, namely that the "excitation" temperature for the 2833 A is lower than for
many other emission lines.
Fig. 7.9 shows the emission spectrum of a low-pressure oxyacetylene flame between
3000 and 4000 A. The upper half is taken with Pb (C 2R s)4 added to the flame and shows
a number of Pb I emission lines together with bands of OR and CH. The lower half is the
spectrum without additive. As can be seen the 4057 A line is by far the stronger of the Pb
emission lines in this spectral region.
Fig. 7.10 shows a plot similar to that of Fig. 7.8 for a number of Pb lines. The value of
"T" ~ 5400 is in agreement with that previously found for Fe.
Another part of the spectrum is shown in Fig. 7.11. Quite unexpectedly it was found that
the 2833 A line is almost completely absent in the emission spectrum. The structure start-
ing on the high wavelength side of the 2802 A line is due to the unresolved rotational
structure of the 1-0 ultraviolet band of OR. It will be clear that this observation is closely
connected with that originally made by Gaydon and Wolfhard mentioned above. At pre-
7.4] ABSORPTION 419
~~ ~ 1 A ~
..,
~
fi; 000
"'GO'"
~ ....,.rU\ .., .., '" '"fi;
... CD CD
~
I
Fig. 7.9. Part of Pb emission spectrum of a low-pressure oxyacetylene flame seeded with tetra-
ethyllead (upper figure) and of an unseeded flame (lower figure).
sent no complete study of this phenomenon is available. A tentative explanation may be the
following.
At high concentrations of Pb atoms in the flame the effective lifetime of the Pb resonan-
ce level is completely determined by radiation trapping and collisional deactivation
(quenching). The probability of quenching may be increased considerably because of the
presence of relatively large amounts of OR. A large number of rotational levels of OR
lying within kT spread around the Pb resonance level.
7.4 Absorption
7.4.1 MOLECULAR BANDS
Because of the low concentrations, experiments to detect absorption in e.g., C z or CR elec-

tronic bands in the reaction zone of atmospheric flames have long been unsuccessful. For
low-pressure flames the situation is more favourable now. In addition to the results of
Gaydon, Spokes and Van Suchtelen [21], who observed absorption near the bandhead
420 RECENT SPECI'ROSCOPIC INVESTIGATIONS OF LOW-PRESSURE FLAMES [7
0.1L--L.i+-------L
40------L,,-----...,,J50
- Eu (103cm-')
Fig. 7.10. Semilogarithmic plot as in Fig. 7.8 for a number of lead emission lines emitted by a low-
pressure oxyacetylene flame seeded with tetraethyllead.
~ Ji
.... NO
'" "''''
N NN
Fig. 7.11. Part of Pb emission spectrum of a low-pressure oxyacetylene flame seeded with tetra-
ethyllead. The 2811 A resonance line ofPb is not observed.
7.4] ABSORPTION 421
of the 0-0 C z Swan band and weak absorption in the 3133 A Q branch of the CZE+-Xzll
band a number of bands of C z and CH have now been obtained in absorption with well-
resolved rotational structure [22]. This provides the information from which the con-
centrations of these radicals can be calculated. We place some emphasis on this here since
these results show that quantitative data with regard to atomic or molecular species can be
obtained in low-pressure flames, notwithstanding the relatively small oscillator strengths
of some of the transitions under consideration (between 0.001 and 0.03) and the small
concentrations as well.
There are two important reasons why these observations were successful in the end. In
the first place there are some considerations about the thickness of the reaction zone and
the difficulties of passing a beam of light through it at one atmosphere contrary to the
situation met in a low-pressure flame. Secondly, and in all probability of even more im-
portance, is the shape of the absorption line in the cases under discussion. At one at-
mosphere this shape will be largely determined by collisional broadening, whereas at
pressures of about 1-10 torr the shape will be primarily determined by Doppler broaden-
ing. The value of the absorption coefficient at the centre of a line is therefore larger for
a given concentration in a low-pressure flame than in an atmospheric flame. We have
as yet no data at hand as to the concentration of CH and C z in atmospheric flames but
it is difficult to see why these should be lower than in low-pressure flames.
50
4305 .p 4310
-A(A)
Fig. 7.12. Absorption spectrum of 0-0 band of the AZLI-XzII electronic transition of CH as
measured in a low-pressure oxyacetylene flame.
An absorption spectrum of CH (Az,J- XZlI) is shown in Fig. 7.12. It may be noted

here that these spectra were obtained with flames which were not, or only slightly, cooled by
the burner. With the efficient cooling of a brass burner it proved hardly possible to meas-
ure the absorption spectra of C z and CH. The absorption of OH, however, showed very
little dependence on cooling. These observations must be ascribed to the changes in che-
mical reactions involving the radicals C z and CH. In a similar manner such changes may
affect the results of absorption studies of metal atoms. Another absorption spectrum, that
of C2 (A 31Ig - X31Iu) is shown in Fig. 7.13.
1-1 45 4lJ 35 30 25 0-0 Kit

p
R
15 10 5 K
5130 5165
Fig. 7.13. Absorption spectrum of 0-0 band of the A3II g -X 3II u electronic transition ofC z as
measured in a low-pressure oxyacetylene flame.
With the aid of the following relations (see Appendix)
co
A.mD"/Io R:! (l/iJv.lIt) f k.dv (4)
o
and
co
f k.dv = nezNflmc (5)
o
the concentration of the absorbing molecules, Nx in rotational energy level Ex was cal-
culated. Using a relation of the type (1) but now valid for a rotational energy distribution
(6)
the total concentration N. of the relevant vibrational energy level can be calculated. Fi-
nally, after summation over all vibrational levels, the total concentration in the electronic
state from which the absorption originates is derived. The C z and CH concentrations
were found to vary in a pressure range between 2 and 10 torr between 1011 and 5 x 1012
cm- 3 and 1011 and 1012 for theX 311. andX 211 electronic states respectively.
7.4.2 SEEDED FLAMES
7.4.2.1 Fe absorption with a continuum source
Absorption of Fe is measured with a continuum source [12], [23] using 22 passes through
the multiple reflection cell, thus providing a sufficiently long optical path through the
flame. In Fig. 7.14 a number of Fe absorption lines are shown as measured in a low-
pressure oxyacetylene flame seeded with the vapour of a 1 % (vol) Fe(CO)s/C 6 H 6 solu-
tion.
In Table 7.1 the data necessary for an interpretation of the results are presented. It can
be seen that absorption is not only measured from energy levels belonging to the same
multiplet (as D) but also from excited states (as F) lying about 1 eV above the ground state.
7.4] ABSORPTION 423
o 100
==~-::-:~~~~~=1======:r~=_=========I~~ f
______________________ '-_________________ ___ ili
3737.13 l .!
~~~-~~===~~fff~~~~~~;~~=~~~~====~=====~~= ~== r
o 100
- Transmission ('10)
Fig. 7.14. Scan of six iron absorption lines measured in a low-pressure oxyacetylene flame seeded
with the vapour of an iron carbonyl-benzene solution.
TABLE7.I
SOME DATA CONCERNING A NUMBER OF OBSERVED ABSORPTION LINES OF Fe
Transition wavelength energy gili. g,

(A) (em- l )
1 zSF 3O-a s D 2 3745.56 704 0.24 5
2 zSF2o-a5Dl 3748.26 888 0.15 3
3 zSF 1 o_a5Do 3745.90 978 0.066 1
4 y5FOs-asFs 3734.87 I 6928 4.2 11
5 y5F4 O-a 5F 4 3749.49 7377 2.7 9
6 ySF30-asF3 3759.24 7728 2.2 7
In order to arrive at concentration data the following procedure was followed. Because
of the large absorption the approximation (4) is no longer valid (see Appendix). Hence
the method of the "total absorption" is applied which is independent of instrumental
factors. From the measured area (0) of the absorption line the quantity
AG = 2n I dv [l-exp(-kJ)] (7)
°
is calculated in a way also indicated in the appendix.
Although in the case of Fe it is necessary in principle to take account of complications
due to isotope splitting and hyperfine structure of the spectral lines, these can provisionally
be neglected since over 90% of the Fe atoms are of the 56Fe isotope which has zero
nuclear spin.
On the assumption that the translational temperature in the flame is of the order of
T R:! 2300 K (see below) the concentrations in a number of Fe atom energy levels can be
derived. In Table 7.11 a series of concentrations is given for a flame seeded with a trace
of Fe (CO)s' Similar results are obtained for solutions of Fe (CO) 5 in benzene or toluene.
TABLE 7.11
MEASURED VALUES OF TOTAL ABSORPTION, A G , AND CALCULATED CONCEN-
TRATIONS N FOR A NUMBER OF ABSORPTION LINES OF Fe IN A LOW-PRESSURE
OXYACETYLENE FLAME SEEDED WITH IRON CARBONYL
b = nLlvD/(ln 2)1/2.
wavelength energy A,/2b I Nd.,l/b N,/g,

(A) (cnc 1 ) - I (cm- 2 s) cm- 3
1 3745.56 704 1.31 I 40 1.3 X 1010
2 3748.26 888 1.12 I 28 1.4 x 10 10
3 3745.90 978 0.82 I 15 1.8 x 10 10
4 3734.87 6928 1.02 I 22 4.1 x 108
5 3749.49 7377 I 0.70 I 12 3.5x108
6 3758.24 7728 0.54 I 8 2.8x 108
At very low concentrations the concentrations in the excited F levels are too small to be
measureable. However, under favourable conditions it proved possible to measure ab-
sorption in the 3720 A line for concentrations down to 10- 7 ml Fe (COh/ml C 6H 6,
corresponding to 0.04 ftg Fe/ml C 6H 6.
7.4.2.2 Fe absorption with a line source
Measurements were also made with a spectral source emitting the Fe 3720 A line with
sufficient intensity to permit a large number of light passes through the flame in the
multiple reflection cell. The Fe (CO)s concentrations were varied between 10- 7 and 10- 3
ml Fe (CO)5/ml C6H6 correspondingto4x 10- 2 and 4x 102 ftg Fe/ml C 6H 6. The results
thus obtained are presented in Fig. 7.15. The heavily dotted curve refers to 18 passes
(I = 360 cm) and a rather high temperature of the spectral lamp. The other curve was ob-
tained with ten passes (I = 200) at a much lower power input level. Open circle data were
measured with the 1 m monochromator, the squares with a t m monochromator, giving
very little change in absorption. The different slopes are due, in all likelihood, to a differ-
ent Doppler width of the emission line, because of the different working temperatures of
the spectral lamps. The input power was much higher with 18 passes since a higher light
output was required.
The correspondence between the two calibration curves is not good from a quantitative
point of view. The percentage absorption found for a given concentration should differ
by at the most a factor of two (18 as against 10 passes). The differences are probably caus-
ed by two effects. In the first place we have found that the solutions age quite rapidly. Al-
though fresh solutions were used, this may explain part of the discrepancy. The other factor
is also of an experimental nature, being concerned with the difficulties involved with the
introduction of the sample into the flame. For a given concentration series the results can
be considered satisfactory. In order to obtain reproducible results, much more effort will
have to be devoted to the matters touched upon above. In any case, it is clear that in
principle very small amounts of a number of elements will be detectable in a low-pressure
flame.
7.5] SPECIAL TOPICS 425
c
.2
f
~1
\0-9 1()""8 10-7 lO-S 10-5 1CJ'o 10--1 1()""2 10-1
_ m l Fe (CO)5/ml CsHs
Fig. 7.15. Calibration curves of iron absorption in the 3720 A line measured with 18 passes (e)
and a continuum source and 10 passes of a special spectral lamp emitting Fe lines taken with high
resolution (0) and low resolution (0).
7.5 Special topics
7.5.1 ZEEMAN SCANNING
Hollander and Broida [4] have recently reported on a method of determining the profiles
of absorption lines, consisting of a determination of the frequency dependence of the
absorption coefficient kv. In their experiments the emission lines of Zn were split in a mag-
netic field (up to 15,000 gauss). One of the a-components was isolated and passed through
a flame burning at pressures between 50 torr and 1 atmosphere. Since the width of the
emission line was much smaller than the width of the absorption line, the absorption
coefficient was measured directly. By variation of the magnetic field the frequency of the
emission line was shifted, making it possible to measure the frequency dependence of the
absorption coefficient. In this manner the line profiles of the 3075.9 A line of Zn were
measured together with those of the R 1 (1) and R 1 (1) transition of OH. In the latter case
the 3072.06 A line of Zn was used for scanning purposes.
It should be mentioned here that apart from the importance of such measurements for
the data they provide on collision parameters (line widths and hence collision cross sections)
the method might well be very useful for absorption measurements as such. A rapidly
modulated small magnetic field superimposed on a slowly and linearly varying one could be
used to measure the absorption lines as is usually done in N.M.R. or E.S.R. spectroscopy.
A possible disadvantage is the fact that only a limited number of spectral lines used in a-
tomic absorption spectroscopy have simple Zeeman splitting patterns.
7.5.2 TEMPERATURE MEASUREMENTS
With the advance of absorption and emission spectroscopy, there is an increasing need in
almost every analytical laboratory to have available a rapid and reliable method of mea-
suring the translational temperature of the "exciting" medium. This can be a normal flame
or a hot N 2 0 supported flame or electrical discharge (plasma) as well. It may be interest-
ing, therefore, to realize that with many presently available "atomic absorption" equip-
ments one is able to set an upper limit to the flame temperature in a rather simple manner.
Essentially, one only has to determine a number of NK values of a molecular species or
NL values of an atomic species for different values of EK or EL respectively (see Section 7.3,
equation (2) and 7.4, equation (6». That is, one measures the concentrations of a number
of energy levels and the temperature is found from the exponential relationship.
This method was applied for the first time by Kostkowski and Broida [24] who deter-
mined the temperature of a premixed oxyacetylene flame using the OR radical as the
"thermometer." We have also tried to derive flame temperatures from absorption data
[25]. Instead of OR, which is normally present in flames, but not in plasmas, we have used
Fe atoms as the species for which the energy distribution is to be determined.
-E(cm-')
Fig. 7.16. Semilogarithmic plot of concentration divided by statistical weight versus energy for a
number of low lying 5 D and sF levels of iron measured in a low-pressure oxyacetylene flame seeded
with iron carbonyl.
7.6] CONCLUSION 427
Using the results of Table 7.II one can make a semilogarithmic plot of concentration
divided by statistical weight (N/g) versus energy. Such a plot is shown in Fig. 7.16. From
the slope the excitation "temperature" can be calculated. As the energy distribution over
the low lying energy levels is mainly governed by collision processes it is reasonable to
assume that this excitation temperature is very close to or equal to the translational tem-
perature of the system. For the case under consideration, that is for the low-pressure
oxyacetylene flame seeded with a trace amounts of Fe (CO)s, we find T ~ 2400 K.
So far we have used concentrations calculated from total absorption data but these can
only be obtained if relatively high resolving power is available. We can, however, also
apply the same procedure to a much simpler set-up provided with a spectral lamp instead
of a continuum source. One should be careful to avoid errors due to self-absorption effects
but in general the specific spectral absorption method for the measurement of tempera-
tures should be a convenient and simple one.
As a test of the latter method the temperature of a low-pressure flame seeded with
Fe(CO)s was measured with a Fe hollow-cathode lamp and compared with the results
obtained from total absorption data. The "temperature" value thus obtained was some-
what higher than the one measured with the continuum source, namely T ~ 2600 K.
As a first conclusion there seems to be no reason at all why the method could not be
extended and by suitable choice of the "thermometer" might well be applicable to a varie-
ty of high-temperature systems over a wide range of temperatures provided very high
absolute accuracy is not required.
7.6 Conclusion
The discussion of the properties of low-pressure oxyacetylene flames was centered around
the emission behaviour on the one hand and the quantitative aspects of absorption spec-
troscopy on the other. The molecular emission of radicals like CH and C z and the atomic
emission of e.g., Fe and Pb indicate the presence of strong overexcitation in the reaction
zone. This property suggests a possible application in flame emission-photometry especial-
ly for elements like Sb, As, Sn, Pt, etc. Due to the large volume of the reaction zone at re-
duced pressures and the stability of the flame, long-path absorption cells provide a means
of compensating for the loss in particle density when the pressure is lowered from 1 atm
to a few torrs. Besides, refractive index problems are less difficult to cope with.
A problem of great importance, namely that of the sample introduction into the flame,
was hardly touched upon in the course of the present investigations. We have limited our
attention solely to volatile metal compounds. Hence the applicability of the flame is still
very limited. However, we believe that solutions to this problem can be found. For
example, the analytical sample can be introduced as a fine powder with ultrasonic devices
or by spark pulverization. These methods have been applied successfully before.
In conclusion we would like to remark that it has not been our intention to present in-
formation concerning a completely new tool in the field of applied spectroscopy. We
rather wished to discuss some interesting results and properties of low-pressure flames.
Furthermore, investigations which have been carried out with low-pressure flames may
also be of interest to atmospheric flame research. Section 7.5 certainly may be looked at in
that sense.
The author acknowledges the helpful assistance of Messrs. Van den Eynden, Van
Benthem and Ponsen in various experimental stages of the investigations. Mr. van Gelder
kindly put the spectral lamps at our disposal.
Appendix
ABSORPTION FROM A CONTINUUM
The amount of light absorbed from a continuum at a spectrograph setting 'P. is given by:
00
A. =10 - I. = f d'PIvg('P- 'P,) [1- exp (-kvl)] (AI)
o
00
A. = 1.0 f d'Pg('P- 'P.) [1- exp(-k.l)] (A2)
o
Here 10 and I. are the 100% transmitted intensity and the transmitted intensity with the
absorbing medium in the light path respectively, kv is the absorption coefficient at fre-
quency 'P, 1 is the optical path length, g('P - 'P.) is the spectral response function of the in-
strument and Iv is the intensity distribution in the continuum which is assumed to be
constant over the frequency ranges of interest.
The response function will be defined as follows:
00
f d'Pg('P- 'P.) =gmax L1'P'llt = IolIv o
o
For small absorption, that is for small values of k), relation (A2) reduces to
00
A. Rj Iv 0 f d'Pg('P - 'Ps)kvl (A3)
o
If the slit function is broad compared to the absorption line width, this relation can be
simplified further and becomes
00 00
Asmaxi10 = (Iv 0 I10) g maxI f kvd'P = (II L1 'PSllt) f kvd'P (A4)
o 0
which is the relation used in equation (4).

The total absorption AG as defined by
00
AG = 2n f d'P[I - exp (-kvl)] (AS)
o
can be found from (AI) by integration over 'P.

00 00 00
o = fo Asd'Ps = 0f d'P. f d'PIvg('P - 'P.) [1 - exp (-kvl)] =
0
00 00
= Iv 0 f d'P. f d'Pg('P - 'Ps) [1 - exp (-kvl)] =
o 0
00 co
= Iv 0 f d'Psg('P - 'Ps) f d'P [1 - exp (-kvl)]
o 0
co
= 10 f d'P [1 - exp (-kvl)] (A6)
o
REFERENCES 429
where 0 is the total area of the measured absorption line. Hence it follows that
AG = 2nO/fo (A7)
which is the relation used in Section 7.4.1.
Values of AG for various values of kol have been calculated numerically for lines of
various shapes and in some cases they include hyperfine splitting and isotope effects
[26], [27].
IO.--------r-------.r-------,--------,
O.lL-----7-----f;;-------:-:=------'
_kol
Fig. 7.At. Curve of growth for a Doppler-broadened line. b = nLlVD/(ln 2)1/2, Llvo is the
Doppler width of the absorption line.
A plot of AG divided by the Doppler halfwidth versus kol is usually referred to as a cur-
ve of growth. In Fig. 7.Al such a plot (double logarithmic) is shown for a simple Doppler
broadened line.
References
1. A. G. GAYDON, The Spectroscopy of Flames, Chapman and Hall Ltd., London (1957).
2. A. G. GAYDON and H. G. WOLFHARD, Proc. Roy. Soc. A. 205, 118 (1951).
3. H. P. BROIDA and K. E. SHULER, J. Chem. Phys. 27, 433 (1957).
4. T. HOLLANDER and P. H. BROIDA, J. Quant. Spectroscopy Rad. Trans/.
5. C. P. FENIMORE, The International Encyclopedia of Physical Chemistry and Chemical Physics.
Topic 19. Gas Kinetics, A. F. Trotman-Dickenson, Editor, Volume 5, Chemistry in Premixed
Flames, Pergamon Press, Oxford (1964).
6. G. P. GLASS, G. B. KISTIAKOWSKY, J. V. MICHAEL and H. NIKI, J. Chem. Phys. 42, 608 (1965).
7. R. F. STUBBEMAN and W. C. GARDINER, J. Phys. Chem. 68, 3169 (1964).
8. H. F. CALCOTE, Tenth Symposium (International) on Combustion, The Combustion Institute
(1965) p. 605, also for other references.
9. R. G. W. NORRlSH, G. PORTER and B. A. TRUSH, Proc. Roy. Soc., A 216, 165 (1953); A 227,
423 (1955).
10. T. CARRINGTON, J. Chem. Phys. 30, 1087 (1959).
It. R. BLEEKRODE and W. C. NIEUWPOORT, J. Chem. Phys. 43, 3680 (1965).
12. R. BLEEKRODE, Appl. Spectr. 22, 536 (1968).
13. C. A. ARRINGTON, W. BRENNEN, G. P. GLASS, J. V. MICHAEL and H. NIKI, J. Chem. Phys. 43,
1489 (1965), also for other references.
14. Advances in Chemical Physics, Vol. X, Molecular Beams, (Editor, J. Ross), Interscience Publish-
ers, New York (1966).
15. G. HERZBERG, Molecular Spectra and Molecular Structure. III. Electronic Spectra of Poly-
atomic Molecules, D. van Nostrand, New York (1967).
16. R. MAVRODINEANU and H. BOITEUX, Flame Spectroscopy, John Wiley and Sons, Inc., New
York (1965).
17. R. BLEEKRODE, Philips Res. Rep. Suppl. 7, 1967.
430 RECENT SPBCTROSCOPIC INVBSTIGATIONS OF LOW-PRESSURE FLAMES [7
18. Z. VAN GELDER, Appl. Spectr. 22, 581 (1968).

19. W. C. NIEUWPOORT and R. BLEEKRODE, J. Chem. Phys. 51, 2051 (1969).
20. C. H. CORLISS and W. R. ROZMAN, Experimental Transition Probabilities for Spectral Lines
of Seventy Elements, NBS Monograph 53 (1962).
21. A. G. GAYDON, G. N. SPOKES and J. VAN SUCHTELEN, Proc. Roy. Soc. A 256, 323 (1960).
22. See ref. 11 and 17.
23. R. BLEEKRODE, XIII Colloquium Spectroscopicum Internationale, Ottawa, 1967.
24. H. J. KOSTKOWSKI and H. P. BROIDA, J. Opt. Soc. Am. 46, 246 (1956).
25. R. BLEEKRODE, Phys. Lett. 27A, 673 (1968).
26. C. VAN TIuOT, TJ. HOLLANDER and C. T. J. ALKEMADE, J. Quant. Spectr. Rad. Trans/., 5, 813
(1965).
27. C. VAN TIuGT, J. Opt. Soc. Am., 58, 669 (1968).
CHAPTERS
AGRICULTURAL APPLICATIONS
OF FLAME PHOTOMETRY
M. Pinta
Office of Scientific and
Technical Research Overseas (ORSTOM)
93-Bondy, France
8.1 Introduction
S.1.1 NATURAL MEDIA
In this chapter on the agricultural applications of flame emission spectrophotometry, we

are dealing basically with the chemical analysis of the following natural media:
a) rocks and soils
b) plants
c) water.
From the chemical point of view, we can distinguish between the major elements and
the trace elements in all these media; the major elements may be said in general to be
those present at a concentration of more than 0.1 %, and the trace elements are those at a
concentration of less than 0.1 %. It goes without saying that this limit between the major
and trace elements is quite arbitrary; in what follows, we will class a given element as
major or trace depending on its mean concentration in the medium in question. This gives
the following classification of the chemical elements in the different natural media:
a) Rocks and soils
major elements: Si, AI, Fe, Na, Ca, Mg, K
trace elements: Mn, Cu, Zn, Ba, Sr, Li, Rb ...
b) Plants
major elements: K, Ca, Mg, Na, Si, S, P
trace elements: Fe, Mn, Cu, Zn, B ...
c) Water. We will limit ourselves here to the types of water which are likely to be in-
volved in agricultural applications: water from streams, rivers and springs. It will be
clear that the concentrations mentioned above are not applicable to this case. We will
therefore define the major elements in water as those present at a concentration of more
than 1 mg/l, namely Na, Ca, Mg, Si, S, P, ... and the trace elements as those present at
concentrations below 1 mg/l, namely Fe, AI, Cu, Mn, Ba, Sr, Li, Rb ...
S.1.2 ELEMENTS WInCH CAN BE DETERMINBD BY FLAME PHOTOMETRY
Flame emission spectrophotometry cannot be used in practice for the chemical analysis
432 AGRICULTURAL APPLICATIONS OF FLAME PHOTOMETRY [8
of all elements. In general, the elements which can be determined by flame photometry
in the various media are as follows:
a) Rocks and soils: AI, Fe, Na, K, Ca, Mg, Mn, Cu, Sr, Li, Rb, Cs ...
b) Plants: K, Ca, Na, Mg, S, P, Mn, Fe, Cu .. .
c) Water: Na, K, Ca, Mg, S, Mn, Fe, Li, Sr .. .
It should, however, be mentioned that in special cases certain elements for which flame
photometry is not very sensitive (such as barium or caesium) can still be analysed be-
cause of their exceptionally high concentration in the medium under consideration.
8.1.3 ANALYTICAL METHODS
Classical flame photometry is a method for the determination of an element by direct

measurement of one of its spectral emission lines in a flame; this is of particular use for
K, Na, Mg, Mn, Cu ... There are, however, a number of indirect methods which are of
particular interest for the analysis of natural media. We may distinguish:
a) Methods based on interactions between elements.
Under certain conditions, aluminium ions or phosphate ions can form stable molecular
compounds with calcium or strontium in the flame, thus reducing the spectral emission
of the calcium or strontium. Since this reduction is a function of the concentration of the
aluminium or phosphate ions, it can form the basis of a method for the determination of
this concentration.
b) Methods based on the precipitation of metallic salts.
Sulphate ions can be determined by precipitation of the sulphate by means of a known
excess of barium (or lead), followed by photometric determination of the remaining
barium (or lead). Similarly, chlorides can be determined by the photometry of silver.
8.1.4 SAMPLE PREPARATION
Samples must be prepared in accordance with general analytical principles; in particular,

account must be taken of the possibility of interactions, of the sensitivity of emission of the
element to be measured in the flame, of the complexity of the medium and of the calibra-
tion method to be used.
We may mention a number of general principles which apply to this case.
a) The sample is generally dissolved in an acid medium - which should if possible
contain only one acid (HCI, HN0 3 , H 2 S04 , etc.) at a concentration of between 1 % and
5 %. The blank solutions should be made with the same acid medium, to reduce the inter-
action of anions.
Figs. 8.1 and 8.2 show the difference between the calibration curves for sodium and cal-
cium obtained with different acid media.
b) The solution used for analysis should be of such a dilution that the element to be
determined is present at the optimum concentration for the determination. For trace ele-
ments, preliminary chemical separation may be necessary to give a more concentrated so-
lution; for example, copper in plants can be determined by extracting the copper as a Cu-
dithiocarbamate complex, which is dissolved in the minimum volume of methyl isobutyl
ketone.
200 200
~ Hel
0
III HNO, Hel
150
~ H'50
z"
100
f~ H,SO. f6~
Ole
:§,g
HNO,
H, S04
H
100 8:J: 100
_"
",0
·~u
:!
.5
50 50
)J9 Najml )J9 Cajml

10/0 acid ,e/.acid
Fig. 8.1. Calibration curves for sodium Fig. 8.2. Calibration curves for calcium
c) Possible interactions which might interfere with the result of the determination must
be eliminated or compensated for. For example, to determine calcium in a soil extract,
either the aluminium present must be removed, or an "interaction corrector" must be
added to form a complex with the aluminium and thus release the calcium (see Section
8.2.2.1.3).
8.1.5 CALIBRATION METHODS
Various methods can be used for the calibration of a photometric method of analysis:
a) Calibration by means of simple synthetic solutions, containing only the element to be
determined in an acid medium (Figs. 8.1 and 8.2).
b) Calibration by means of simple synthetic solutions containing a spectral buffer as well
as the element to be determined. This spectral buffer is an inorganic or organic substance
which is intended to correct for interactions with other elements. Oxine, ethylene diamine
tetracetic acid (EDTA), glycerol, salts of potassium, strontium, lanthanum, etc., phospha-
tes, etc. are used as spectral buffers. The use of these reagents is discussed in each parti-
cular case.
c) Calibration by means of complex solutions, containing elements other than the ele-
ment to be determined, at concentrations corresponding to that at which they are to be
found in the analysed samples. This method is specially useful for the determination of
trace elements.
d) Calibration by means of simple solutions, also containing a spectral buffer to correct
for any interactions which may take place.
e) Calibration by the addition method. Known amounts of the element to be deter-
mined are added to the solution under analysis, and the spectral emission of the element
in question is plotted against the concentration added. The curve obtained has the form
shown in Fig. 8.3: the unknown solution, of concentration X, gives a spectral emission Y;
200
"
.Q
.~ 150
! 100
50 X 25 o 50 75
Concentration JJ9/rri.
Fig. 8.3. Calibration by the "addition method"
the solution containing X + NI gives Yh and similarly the solutions containing X + N2

and X + N3 give Y2 and Y3 • The line YABe (curve 1) is now extrapolated until it cuts the
axis of abscissae at a point corresponding to -X. This method presupposes that the cali-
bration curve is linear, and this can be checked beforehand with the aid of synthetic
solutions (curve 2).
8.1.6 EQUIPMENT (Fig. 8.4).
The quality and performance of the spectrophotometer are of prime importance for the
success of the analysis. Without going into details about all the models available commer-
cially, we may mention two main types; the choice between these depends on the aims of
the investigation.
Filter photometers can only be used for the determination of sodium, potassium, cal-
cium, sometimes magnesium and in special cases lithium and strontium.
Prism (or grating) spectrophotometers may be strongly recommended for pedological,
hydrological and agricultural analyses. They should preferably be equipped with:
1) an interchangeable flame source, for oxy-acetylene or oxy-hydrogen and air-acety-
lene flames;
2) a photomultiplier, which is indispensible for amplifying the signal obtained with
trace elements.
Pedological or geological surveys, fertilizer problems, and studies aimed at improving
crop yields often involve a large number of determinations. Flame spectrophotometry
is very suitable for routine analyses; the classical equipment can easily be automated
(Fig. 8.4):
1) by the inclusion of an automatic sampler for the solutions to be introduced into the
spectrophotometer, and
2) by replacing the galvanometer which gives the reading by a chart recorder (Figs. 8.5
and 8.6), or a digital recorder combined with a printer, which can present the results
directly in the desired units.
-""*-"1-+-- 3
Fig. 8.4. Flame spectrophotometer:

1. Automatic sample distributor (Le Materiel Physico-chimique, 94 - Neuilly-sur-Marne, France)
2. Spectrophotometer (Jobin & Yvon, 92 - Arcueil, France)
3. Recorder (Sefram. 75 - Paris. France)
3
1-+--:::::::::::'
2 4
Fig. 8.5. Automatic sample distributor
1. Solution for analysis, 2. Washing, 3. Suction tube, 4. Atomizer burner
436 AGRICULTURAL APPUCATIONS OF FLAME PHOTOMETRY [8
Fig. 8.6. Recorder

1. Reference solutions, 2. Unknown solutions
Flame spectrography, in which the flame spectrum is photographed, was first used by
Lundegardh [64a]. It has now been more or less replaced by flame photometry, but it
should not be forgotten, as it can be very useful for the determination of trace elements
in complex media giving a large number of spectral lines which are difficult to separate.
Reference: [1].
8.1.7 COMPARISON WITH OTHER METHODS
The methods presented here, although tested by years of application, are not claimed as
the best under all circumstances; it will be clear that for certain elements more precise or
more sensitive metp.ods can be found. For example, atomic absorption spectrophotome-
try often allows a higher sensitivity to be attained (e.g., with magnesium), and can be used
for the analysis of a number of elements which cannot be determined by flame photo-
metry (zinc, silicon, etc.); here, as elsewhere, comparisons are odious. Flame photometry
8.2] ANALYSIS OF ROCKS AND SOILS 437
is a physico-chemical technique which we try to use to the full, like any other. The methods
described below are presented with complete objectivity and criticized according to their
merits; each method has its own properties, which we try to bring out in each individual
case.
8.2 Analysis of rocks and soils
8.2.1 GENERAL PROBLEMS
The mineral media, rocks and soils, are generally brought into solution by the classical
method of treatment with acids; rocks are generally treated with a mixture of perchloric,
hydrofluoric and hydrochloric acids, and soils by a mixture of sulphuric, nitric and hydro-
chloric acids or by nitric acid alone. Treatment with alkalis - fusion with sodium hydrox-
ide or alkaline carbonates - is used less because of the large amounts of cations which it
introduces. It may, however, be used when treatment with acid is ineffective in bringing cer-
tain heavy minerals into solution, or when trace elements to be analysed are extracted
from the fusion product.
In the methods described below, acid treatment is used almost exclusively.
The analysis is carried out on a sample offrom 1 to 5 g, in a final volume of solution of
from 50 to 250 ml; however, it is important for flame photometry that silica and the ex-
cess of anions introduced by the acid treatment should be removed by evaporating to
dryness and redissolving the residue in a simple acid medium of known composition(Figs.
8.1 and 8.2).
Certain elements (iron, aluminium, etc.) can be determined directly in this solution,
after appropriate dilution and the addition of reagents which correct for interactions. It
may be necessary to remove interfering elements (iron and aluminium can be precipitated
as the hydroxides) before analysing for the alkaline-earth metals. Finally, and in parti-
cular for trace elements and elements which do not give a strong flame emission, the ele-
ments to be determined may be extracted from the original sample by precipitation, by
ion exchange (lithium, rubidium, caesium, strontium, barium) or by complexing with or-
ganic reagents (copper, aluminium, etc.).
Special techniques exist for the analysis of soils for agricultural purposes: the exchange-
able, soluble, assimilable alkali and alkaline-earth ions can be determined in suitable soil
extracts, prepared with ammonium acetate, dilute hydrochloric acid, water, etc.
As regards equipment, a prism or grating monochromator with a suitable optical sys-
tem and a photomultiplier receiver are needed for the determination of AI, Fe, Mg, Sr, Ba,
Li, Rb, Cs, Cu, Mn, etc.; filter photometers can only be used for sodium, potassium and
calcium.
Tables 8.1 and 8.11 give the concentration ranges of major and trace elements in rocks
and classical soils, together with the limit of detection by flame photometry.
8.2.2 DETERMINATION OF THE MAJOR ELEMENTS
We will now describe the various methods for the different elements in turn.
TABLE 8.1
MAJOR ELEMENTS IN ROCKS AND SOILS
Concentration ranges and detection limits by flame photometry
Granites Basalts Carbonates Soils and sediments
Coneen- Detee- Coneen- Detee- Coneen- Detee- Coneen- Detee-
tration tion tration tion tration tion tration tion
range limit range limit range limit range limit
(%) (%) (%) (%) (%) (%) (%) (%)
Al 0 -10 0.1 5 -10 0.1 1 -5 0.1 2 -30 0.1

Fe 0.5 -6 0.05 5 -10 0.05 0.5 -5 0.05 0.5 -20 0.05
Ca 0.1 -3 0.02 2 -10 0.02 20 -40 0.02 0.01-3 0.02
Mg 0.05-1 0.5 1 -4 0.5 2 -10 0.5 0.01-1 0.5
Na 1 -5 0.01 0.5-4 0.01 0.01-0.5 0.01 0.1 -2 0.01
K 1 -4 0.01 0.5-4 0.01 0.1 -0.5 0.01 0.01-1 0.01
TABLE 8.11
TRACE ELEMENTS IN ROCKS AND SOILS
Concentration ranges and detection limits
Granites Basalts Carbonates
I Soils and sediments
Coneen- Detee- Coneen- Detee- Coneen- Detee- Coneen- Detee-
tration tion tration tion tration tion tration tion
range
(ppm)
limit
(ppm)
range
(ppm)
limit
(ppm)
range
(ppm)
limit
(ppm)
range
(ppm)
I limit
(ppm)
I
Li 10-50 1 10-25 1 1-20 10 5-200 10
Rb 50-300 60 10-50 60 2-40 60 20-500 60
Cs 1-5 50 0.5-2 50 0.1-0.5 50 1-20 50
Sr 100-500 50 200-1000 50 200-1000 50 50-1000 50
Ba 200-1000 100 150-600 100 10-100 100 50-3000 100
Mn 200-800 2.5 800-3000 2.5 500-2000 2.5 100-3000 2.5
Cu 5-50 15 40-200 15 1-10 15 2-100 15
Cr 10-50 125 100-200 125 5-20 125 1-200 125
8.2.2.1 Aluminium
Although aluminium does not give strong emission in flames, this element can be deter-
mined under good conditions. In an oxy-acetylene or nitrous oxide-acetylene flame,
aluminium gives a line at 396.2 nm and a band at 484 nm; these are detectable down to
a concentration of 0.5 f1g/ml, but only in organic solution or in the presence of organic
substances. Alkaline-earth metals and fluorides interfere with the determination of
aluminium. There are three methods available for the determination of this element.
8.2.2.1.1 Determination of aluminium by the extraction of the Al-cupferron

complex in methyl isobutyl ketone
Reagents
Hydrochloric acid 1/10
Ammonia, M
Ammonium acetate
Aqueous solution of cupferron, 0.1 M
Methyl isobutyl ketone
Aluminium
Sample preparation
An aliquot of the solution prepared by acid treatment of the soil or rock, containing 1 to
10 mg of aluminium (pH 0) is shaken in a separating funnel with 10 ml of a 0.1 M solution
of cupferron and 25 ml of methyl isobutyl ketone. The following metals pass into the or-
ganic phase, which is removed:
Ga, Fe, Sn (IV), Ti, V, Zr.
The aqueous phase is now adjusted to pH 3.5 as indicated by a pH-meter, by addition
of ammonium-acetate/ammonia buffer, and mixed with 10 ml of 0.1 M cupferron and 20
ml of methyl isobutyl ketone. After shaking, the organic phase containing the aluminium
is removed for photometry.
The calibration curve is prepared with convenient samples of a solution of aluminium
in hydrochloric acid, containing from 1 to 10 mg of aluminium, extracted with cupferron
at pH 3.5 as described above.
Spectrophotometry
Flame: oxy-acetylene (very pure gases)
Wavelength: 484 nm
Sensitivity of the equipment: the galvanometer should be zeroed on the background level
at 484 nm, and adjusted to give full-scale deflection with the reference solution of 10 mg
Al 2 0 3 in 25 ml of methyl isobutyl ketone.
Slit widths: should be adjusted with the greatest of care.
Characteristics of the method
This is a fast method, which requires more than 1 mg of aluminium; other elements do
not interfere, and the error is less than 5 %.
References: Berthollay, [8], Fornaseri & Turi [40].
8.2.2.1.2 Determination of aluminium in aqueous solution
Aluminium can be determined in aqueous solution in the presence of large amounts of

organic compounds such as 8-hydroxyquinoline (Debras-Guedon & Voinovitch [26]).
Reagents
Hydrochloric acid, pure and 1/1
Glacial acetic acid
8-Hydroxyquinoline: 20% solution in 40% acetic acid

Pure aluminium
Sample preparation
An aliquot (less than 50 ml) ofthe unknown solution containing between 1 and 100 mg of
aluminium is mixed with 25 ml of the 8-hydroxyquinoline solution and 20 mlofhydro-
chloric acid, and made up to 100 ml with water in a graduated flask.
The solutions for the calibration curve are prepared in the same way from a solution of
aluminium in hydrochloric acid, to cover the range from 0 to 100 mg of Al 2 0 3 in 100 ml,
in the presence of 8-hydroxyquinoline and hydrochloric acid.
Spectrophotometry
Conditions similar to those for the previous method.
Validity 0/ the method
This method is suitable for the determination of Ah03 concentrations between 5 and
20 %; it is not very exact at low concentrations. Even in complex mixtures, the presence of
the 8-hydroxyquinoline reduces the effect of other elements.
Reference: Debras-Guedon & Voinovitch [26].
8.2.2.1.3 Indirect determination of aluminium with the aid of the inter-

action between calcium and aluminium
Aluminium reduces the intensity of the calcium emission spectrum in classical flames; it
appears that a molecular complex (AI 2 0 4 Ca) is formed, which binds the calcium respon-
sible for the emission. Under given spectrophotometric conditions and with a given con-
centration of calcium, the equilibrium between the calcium and the Al 2 0 4 Ca complex
is a function of the aluminium concentration introduced into the flame. The measurement
of the calcium emission spectrum thus allows the determination of aluminium. The precise
form of the interaction depends on the nature of the anion present (Fig. 8.7). Strong
variations in the iron or titanium content also have an effect on the results.
We will now describe the method as applied in practice to soils and rocks.
Reagents
Ammonia, concentrated
Nitric acid, 1/5
Calcium solution, 1000 [lg Ca/ml in 1 % nitric acid
Aluminium solution, 1000 [lg AI/ml in 1 % nitric acid
Iron solution, 1000 [lg Fe/ml in 1 % nitric acid
Sample preparation
A soil or rock sample weighing from 0.25 g to 0.5 g is brought into solution by treatment
with hydrofluoric and perchloric acids. The solution is evaporated to dryness, and the re-
sidue dissolved in 1/5 hydrochloric acid. An aliquot of this solution (containing between
15 mg and 30 mg of Ah03) is treated with just enough concentrated ammonia to precipi-
tate hydroxides, and filtered. The precipitate is redissolved in 1/5 nitric acid and collected
in a 100 ml graduated flask; 20 ml of the 1000 [lg/ml calcium solution is added, and the
~~------------------------~
~"-
<D I'1oHCt
.§ 150 @ I'1oH NO,
E!
"E
~
8
8 100
Ig.
50
o 100 ~ 300 400

,1'9 AtfmL
Fig. 8.7. Effect of aluminium on the determination of calcium
mixture made up to 100 ml, with addition of enough nitric acid to bring the final nitric
acid concentration to 1 %.
The approximate amount of iron present in the solution should be known.
The calibration curve is constructed with the aid of a series of solutions containing
from 0 to 200 [Lg Allml in 1 % nitric acid, in the presence of 200 [Lg Calml, and iron equi-
valent to the content of the sample solutions.
Spectrophotometry
Flame: air-acetylene or air-propane
Wavelengths: Ca 422.6 nm, or CaOH 553.5 nm or 623 nm
Detection limit: 10 (.Lg Al/ml.
Accuracy: 3-6 %
Note
The precipitation of the hydroxides can be avoided by determining iron and calcium be-
forehand, and adding a weighed amount of calcium to an aliquot of the solution so as to
bring the final calcium concentration to 200 [Lg Calml after making up to 100 ml.
References: Pinta & Aubert [77], Goushev & Kozhourarov [47], Cencelj [15].
8.2.2.2 Iron
Iron gives two high-intensity lines in the oxy-acetylene flame, at 372.0 nm and 386.0 nm.
A concentration of 2.5 [Lg Felml can be detected. These lines are used for the determina-
tion of iron in soils and rocks. Alkali and alkaline-earth metals and titanium do not in-
fluence the results appreciably; only magnesium shows interaction with the iron spectrum,
as a result of the superimposition of the MgO bands on the iron spectrum in the above-
mentioned region. The iron concentration determined will be higher than the actual one
unless this is taken into account. Aluminium interferes by reducing the intensity of the
iron lines. In addition, any other element present in large quantities can give rise to a
spectral background which will interfere with the results. Most of the interactions can
be corrected for by means of an internal standard; cobalt is particularly useful for this
purpose, as it interacts with aluminium in the same way as iron does.
8.2.2.2.1 Direct determination of iron
Iron can be determined directly in solutions obtained from rocks and soils, in concentra-
tions ranging from 2 % to 50 %. However, in the presence of large concentrations of mag-
nesium, calcium, barium or potassium (more than 5 %), it is advisable to separate the iron
by precipitation of ferric hydroxide and redissolving in hydrochloric acid.
The classical method (without separation) is as follows.
Reagents
Hydrochloric acid, 6 N
Iron solution in 0.3 N hydrochloric acid, 10 mg Fe/ml
Cobalt solution, 2 mg Co/ml
Sample preparation
An aliquot (5-15 ml) of the solution obtained by treatment of the soil (or rock),
containing between 1 mg and 7 mg of ferric oxide, is mixed with 5 ml of cobalt solution
(2 mg/m!) and made up to 25 ml in a graduated flask.
The reference solutions are made up in the same way, to contain from 0 to 10 mg of
Fe203 in 25 ml in the presence of the same amount of cobalt as in the unknown samples,
and with a constant hydrochloric acid content.
Spectrophotometry
Flame: oxy-acetylene
Slit width: 50 [Lm
Wavelength: 386 nm
The galvanometer is adjusted to read zero for the spectral background at 386 nm with
the blank sample, and to give full-scale deflection with the 10 mg Fe203/25 ml (280 [Lg
Fe/m!) reference solution.
Lines measured: Fe 386.0 nm and Co 387.1 nm
The calibration curve is obtained by plotting the intensity ratio IFe/Ico as a function of
the Fe203 concentration.
Note
This method with an internal standard does not correct completely for the effect of
magnesium. In order to correct accurately for the magnesium content, we must construct
a calibration curve giving the effect of increasing known amounts of magnesium on the
iron lines in the presence of cobalt, by measurements on synthetic solutions; the magne-
sium content of the solution to be analysed must now be determined, and the effect of
this on the iron determination can then be read off.
8.2.2.2.2 Determination of iron after extraction
When low concentrations of iron have to be determined in the presence of large amounts
of calcium and magnesium, the iron can be extracted with methyl isobutyl ketone.
The sample is brought into solution in 6N hydrochloric acid, and extracted by shaking
with methyl isobutyl ketone; there should be between 2 and 10 (Lg of Fe per ml of solvent.
The organic solution is then subjected to photometry in an oxy-hydrogen flame.
This method is particularly applicable to the determination of iron in calcite and dolo-
mite.
Reference: Goto & Sudo [46].
8.2.2.3 Sodium,potassium, calcium, magnesium
The principal spectral lines furnished by these elements are:
- sodium doublet at 589/96 nm, detectable at 0.001 (Lg/ml in an oxy-hydrogen flame, and
at 0.01 (Lg/ml in an air-acetylene flame;
- potassium doublet at 766/69 nm, detectable at 0.02 (Lg/ml, and a line at 404.4 nm
detectable at 1.7 (Lg/ml in an oxy-hydrogen flame;
- calcium line at 422.6 nm, detectable at 0.2 (Lg/ml and bands at 553.5 and 623 nm,
detectable at 0.1 (Lg/ml;
- magnesium line at 285 nm, detectable at 1 (Lg/ml, and MgO bands at 370 and 385 nm,
detectable at 1 (Lg/ml.
In classical rocks and soils, where these elements are generally present at concentrations
exceeding 1 %, iron and aluminium must be precipitated as hydroxides before the solu-
tion is analysed.
Sodium and potassium can be determined directly in the total soil solution if they are
present in concentrations exceeding 0.2 %; the calibration curve must then be prepared
with complex solutions containing iron and aluminium. Calcium interferes with the deter-
mination of sodium by superimposition of the background spectrum. A calibration curve
has to be prepared for the effect of calcium on the sodium spectrum, and the sodium
concentration obtained corrected for the calcium present.
The determination of calcium is affected by the presence of aluminium as the result of
the formation of a complex CaAh02 which does not dissociate in the flame (see Section
8.2.2.1.3). The addition of strontium reduces this complex, liberating the calcium atoms;
but large amounts of strontium have to be added (10 to 100 times the calcium).
In the determination of magnesium, the Mg line at 285 nm is not generally influenced
by the elements present in rocks and soils, but the MgO band at 370 nm on the other
hand is affected by Ca, Na and Fe. When Ca and Mg are to be determined, iron and
aluminium have to be precipitated first as their hydroxides.
We will now describe a method for the determination of the four elements after separa-
tion of the hydroxides (of Fe and AI), a method for the direct determination of sodium
and potassium in the total solution from soils or rocks, a method for the determination of
the cations in the aqueous or ammonium acetate extract of soils, and finally a method for
the determination of the ion-exchange capacity of soils.
8.2.2.3.1 Determination of the cations sodium, potassium, calcium and

magnesium in solutions of soils and rocks prepared by acid treat-
men t, after precipi ta tion of the hydroxides
A sample of 1 to 2 g is treated with sulphuric/nitric acid (2/3) and then with hydrochloric
acid; after the silica has been precipitated and the excess acid removed, the residue is re-
dissolved in 100-250 ml of 5 %hydrochloric or nitric acid.
Rock samples for analysis are treated with hydrofluoric acid and perchloric acid; the
sample size is sti111-2 g, and the final volume 100-200 ml in 5 % hydrochloric or nitric acid.
These solutions can now be used for the determination of the cations Na, K, Ca and Mg.
Reagents
Ammonium acetate, 5 N
Ammonium chloride solution, 5 %
Hydrochloric acid, concentrated
Nitric acid
Sample preparation
The solution from 1-2 g of rock (or soil) is mixed with 50 ml of ammonium acetate,
brought to the boil and neutralized with ammonia. Boiling is continued until the smell of
ammonia has gone; a few more drops of ammonia are now added. The solution is filtered,
and the contents of the illter washed with a tepid solution of ammonium chloride. The
filtrate is evaporated to dryness, 20 ml of nitric acid and 10 ml of hydrochloric acid are
added to eliminate ammonium salts, and the solution is evaporated to dryness again. The
residue is redissolved in 2 % nitric acid and finally made up to 50 ml.
The calibration curves are prepared with the aid of the following solutions:
Na: NaCI (10 mg Na/ml) in 1 % nitric acid
K: KCl (10 mg K/ml) in 1 % nitric acid
Ca: solution of Ca (10 mg Ca/ml) in 1 % nitric acid, prepared from CaC0 3 and HN0 3
Mg:MgS04 (10 mg Mg/ml) in 1 % nitric acid.
The calibration curves cover the range from 0 to 100 [Lg/ml for each element.
Spectrophotometry
Flame: air-acetylene for Na, K, Ca, oxy-hydrogen or oxy-acetylene for Mg and Ca.
Wavelengths: Na 589 nm
K 766nm
Ca 623 nm
Mg 285nm
Spectrophotometer and receiver: a filter photometer can be used for Na, Ca and K, if the
receiver is sensitive to the wavelengths used. A prism or grating spectrophotometer is
necessary for Mg.
Sensitivity: under the best spectrophotometric conditions, we can detect
Na 0.002%
K 0.002%
Ca 0.025%
Mg 0.050%
The accuracy is 5 %; errors are due to the preparation of the sample rather than to the
spectrophotometric determination. For calcium in particular, incomplete separation of the
hydroxides can lead to error. Sodium concentrations determined in the presence of large
amounts of calcium (calcareous rocks or soils) should be corrected for the influence of the
background of the calcium spectrum.
Reference: O.R.S.T.O.M. [74].
8.2.2.3.2 Direct determination of sodium and potassium
The sample is brought into solution by treatment with acid as described in Section 8.2.2.3.1,
or by fusion with alkalis; the latter procedure is better for rocks. The flux used is a mixture
of boric acid and lithium carbonate. The method as used in practice is as follows (Govin-
daraju [48]).
Reagents
Flux: 200 g H 3B03 + 60 g LhC03
Citric acid, 30 %
Sample preparation
A 0.2 g sample is mixed with 4 g of flux and placed in a graphite crucible which is heated to
960 °C in the oven. The fusion product is weighed and ground, and 500 mg of the powder
is heated to 80-90 °C in 25 ml of 2.5 % citric acid; the solution is filtered and made up to
50ml.
Calibration curves are prepared with synthetic mixtures of the oxides SiOz, Ah03,
Cao, MgO, MnO and TiO z with a composition representative of the samples to be ana-
lysed, containing amounts of NazO and KzO increasing from 0 to 2 %. The synthetic
mixtures are fused and prepared like the unknown samples.
Spectrophotometry
Flame: air-acetylene
Other conditions: see Sec. 8.2.2.3.1
Notes
1) The method is applicable to series of similar samples which justify the construction
of calibration curves in the range 0.1 %-5 % NazO and KzO. The relative error is less than
5%.
2) The accuracy can be improved by using lithium as internal standard.
3) Lithium tetraborate can also be used as flux.
It is also possible to determine the potassium content of soil samples directly: lithium
sulphate is added to the powdered soil, and the mixture is introduced into the flame by a
mechanical device. The potassium line at 770 nm and the lithium line at 670 nm are sepa-
rated by interference filters and subjected to photometry. The analytical error is less than
3.7% for potassium contents between 0.1 % and 1 % (Shipicyn & Kirjushkin [94]).
References: Govindaraju [48], Corbiere & Mariage [18] and Hameau & Legrand [50].
8.2.2.3.3 Analysis of soil extracts
This method is interesting for agricultural studies, and in particular for the determination
of exchangeable and soluble bases.
The exchangeable bases are extracted by percolation of a known volume (100-250 ml)
of normal ammonium acetate, pH 7, through a given amount of soil (10-50 g). The ca-
tions Na, K, Ca and Mg can be determined directly in this extract; there is no risk of in-
terference from aluminium or iron, as they are not extracted under these conditions. The
calibration curves are constructed with the aid of simple solutions of the elements to be
determined at concentrations from 0 to 200 (Lg/ml in normal ammonium acetate at pH 7.
If one of the cations Na or Ca is present in excess, it can interfere with the determination
of the other. The method is not sensitive enough for low magnesium contents.
The sensitivity can be improved and the interaction of other elements reduced by carry-
ing out the determination in the presence of 8-hydroxyquinoline (Delas [27]); for this
purpose, 25 ml of the ammonium acetate extract are mixed with 12.5 ml of 20 %8-hydroxy-
quinoline (200 mg of 8-hydroxyquinoline is dissolved in 400 ml of glacial acetic acid, and
the solution diluted to 1000 ml) and 10 ml of 50 % hydrochloric acid, and the mixture
made up to 100 ml. The solutions for the calibration curve are prepared in the same way.
This method is particularly useful for the determination of magnesium (detection limit
0.1 u.g/ml) and calcium (the influence of phosphates, sulphates and aluminium on the
calcium determination is reduced).
The soluble salts are extracted with water (10-50 g of soil is shaken with 100-250 ml of
water); depending on the type of soil, the extract may contain the chlorides, sulphates,
carbonates or humates of calcium, sodium, potassium and magnesium. The solution is
evaporated to dryness, treated with a few drops of sulphuric acid and again evaporated to
dryness; the organic substances must be destroyed with hydrogen peroxide before the resi-
due is dissolved in 50-100 ml of 1 %hydrochloric acid.
The extracts are subjected to flame photometry as above, with appropriate calibration.
Reference: Delas [27].
8.2.2.3.4 Determination of the ion-exchange capacity of soils and clays
A number of methods for determining the ion-exchange capacity of soils and clays are
based on the estimation of barium by flame photometry. The soil is saturated with barium
so as to displace the other cations, and the barium fixed in this way is extracted with am-
monium acetate and determined by flame photometry.
Reagents
Hydrochloric acid, 0.1 N
Barium chloride-triethanolamine solution, pH 8.1:
90 ml of triethanolamine are diluted with 1000 ml of water, and the pH is adjusted to
8.1 with HCI (280-300 ml of N HCI). This solution is made up to 2000 ml, and mixed
with 2000 ml of 5 % BaCb.2H 2 0.
Barium chloride solution, 2.5 % (2.5 g BaCI 2 .2H 2 0 in 100 ml)
Ammonium acetate, normal, pH 7
Sample preparation
The following solutions are percolated in turn through a 2.5 g sample: 25 ml of 0.1 N HCI,
50 ml of BaCh (pH 8.1), 50 ml of BaCh, 100 ml of distilled water and finally 100 ml of
ammonium acetate.
The calibration curve is constructed with the aid of a series of solutions of BaCl 2 in
normal ammonium acetate, covering the range from 0 to 200 [Lg Ba/ml.
Spectrophotometry
Flame: air-acetylene or oxy-acetylene
Wavelength: 873 nm or 553.5 nm
Note
This method can be used for most soils; soils rich in calcium carbonate should be given
a preliminary treatment with normal hydrochloric acid.
References: Pratt & Holowaychuk [83], Toth [96], Mehlich [69], Schroeder [92].
8.2.3 TRACE ELEMENTS
8.2.3.1 Lithium, rubidium, caesium
These elements emit readily in low-temperature flames (air-propane, air-acetylene); oxy-

hydrogen and oxy-acetylene flames are also used.
The high-intensity lines are found in the red and the near infra-red: Li 671 nm, Rb
780 nm and Cs 852 nm. The measurement of the intensity of these lines requires a receiver
with a photomultiplier which is sensitive for this region of the spectrum. The range of
conventional spectrophotometers does not always extend this far.
These elements can be detected at very low concentrations: Li 0.01 {lg/ml, Rb 0.1 and
Cs 0.1.
In the flame photometry of rocks and soils, the lithium, rubidium and caesium lines
are disturbed by a number of elements: aluminium, phosphorus, calcium, sodium and po-
tassium. Iron and aluminium must be precipitated as their hydroxides, and the determina-
tion carried out in a medium which is buffered for sodium, potassium and calcium.
Details o/method (after Pouget [82])

Reagents
Methyl red, 0.1 % in alcohol
Calcium carbonate
Sodium sulphate solution (5 mg Na20/ml)
Potassium sulphate solution (5 mg K 2 0/ml)
Lithium sulphate (too (lg Li/ml)
Rubidium sulphate (100 (lg Rb/ml)
Caesium sulphate (too (lg Cs/ml)
Buffer solution: 453 g of ammonium citrate and 453 g of citric acid in 21 of distilled water
Hydrogen peroxide, 3 % (to vol.)
Sample preparation
The sample (2 g) is brought into solution by treatment with sulphuric, nitric and hydro-
fluoric acids, and made up to 100 ml. Aliquots are taken and analysed for sodium and po-
tassium. A 50-ml aliquot is now taken, and sodium and potassium added until the final
amount of each of these elements is 100 mg; 5 drops of methyl red are now added, and
the solution neutralized with calcium carbonate until the colour changes from purple to
yellow. Ten drops of hydrogen peroxide are now added, and the solution boiled for 2
minutes and filtered into a 1OO-ml graduated flask containing 10 ml of buffer solution. The
contents of the filter are washed with water, and the solution made up to 100 ml.
The reference solutions are made up in the same way, from solutions of lithium, rubi-
dium and caesium sulphate of known strength; the final solutions should contain 1 gil
of Na20 and K 20, and the buffer solution, and should cover a range of 0.1-10 fLg/ml
Li, Rb and Cs (10-100 ppm in the analysed medium).
Spectrophotometry
Flame: oxy-hydrogen
Photo-cell: high-quality, sensitive to the red end of the spectrum
Wavelengths: Li 671 nm, Rb 780 nm, Cs 852 nm
Notes
The presence of the ammonium ions reduces the influence of sodium and potassium so
well that it is not necessary to know the precise content of these elements. The addition
of the calcium carbonate to the unknown samples and the standards stabilizes the calcium
content in view of the solubility of calcium sulphate (2 gIl).
The detection limits are: lithium 2 ppm, rubidium 10 ppm, caesium 10 ppm (in the
medium analysed).
References: Pouget [82], Horstman [56], Howling & Landolt [57], Vajshtejn & Lebedev
[100], Esikovet al. [35-36], Bradford & Pratt [12], Osterried [75], Rubeska [87].
8.2.3.2 Strontium, barium
Barium and strontium give high-intensity emission spectra in oxy-hydrogen or oxy-acety-

lene flames; the former is recommended for barium, and the latter for strontium.
Barium gives two lines at 455.5 and 553.6 nm, with detection limits of 3 and 1 fLg Ba/mI,
and one BaOH band at 828 nm, which can be detected down to 1 !Jog/m!. Strontium has
a line at 460.7 nm, detectable down to 0.06 fLg/ml. The intensity of this line is increased by
the alkali metals and calcium, and reduced by iron and aluminium.
The effect of the background spectrum due to the alkali metals, calcium and strontium
on the 828 nm barium line must also be taken into account.
8.2.3.2.1 Strontium
The sample of rock or soil to be analysed (1 g) is brought into solution as for the deter-
mination of calcium; the hydroxides of iron and aluminium are precipitated as described
in Section 8.2.2.3.1, and the filtrate treated in the same way and finally made up to 50 or
100 mI. The reference solutions cover the range 0-500 fLg Sr/mI, and should contain the
elements Ca, K, Na and Mg at concentrations representative of those found in the un-
known samples.
The errors due to variations in the calcium content should also be corrected for by
buffering the solutions (reference and unknown) with sodium chloride to 3 mg Na/l
(Esikov [35]).
Spectrophotometry
Wavelength: 460.7 nm
Range of concentrations: 1-500 fLg Sr/mI
Detection limit in the original sample: 50 ppm Sr
References: Esikovet al. [35-36], Vajnshtejn & Lebedev [100], Fornaseri & Grandi [38].
8.2.3.2.2 Barium
It is best to bring the sample into solution by fusion with alkalis, precipitate the hydroxi-
des and determine barium in the filtrate; in order to take the influence of the background
at 828 nm (BaOH band) into account, the barium is precipitated from an aliquot of the
solution, which is then used to adjust the zero of the galvanometer to the background
spectrum. This deals with the error caused by the background due to K, Na, Mg and Ca;
the small amount of calcium or strontium which may be precipitated with the barium does
not interfere with this correction.
Reagents
Sodium and potassium carbonate, equimolecular mixture
Hydrochloric acid, liS
Sulphuric acid, concentrated
Barium chloride, 1000 [Lg Ba/ml
Sample preparation
The rock or soil sample (0.5-1 g) is fused with 8 g of the sodium-potassium carbonate
mixture; the fusion product is dissolved in liS hydrochloric acid, filtered and diluted to
50 ml. Concentrated ammonia is added to the solution until a faint smell of ammonia re-
mains, so as to precipitate iron and aluminium as their hydroxides; the solution is heated
to 80°C and filtered. The contents of the filter are redissolved in 10-15 ml of liS HCI and
again precipitated with ammonia and filtered. The two filtrates are combined, evaporated
to 80 ml and then made up to 100 ml. This solution (solution A) is used for the determina-
tion of the barium. A 1O-ml aliquot is taken, and the barium precipitated as the sulphate
by addition of 2 drops of concentrated sulphuric acid. The barium sulphate is centrifuged
down, and the supematent (solution B) is used for adjusting the zero of the galvanometer.
The calibration curve is constructed by the addition method (Fig. 8.3): amounts of ba-
rium comparable with those in the unknown solution (100, 200, 400, 600, 800 and 1000 [Lg
of Ba) are added to two or three 1O-ml aliquots of solution A.
Spectrophotometry
Flame: air-acetylene
Wavelength: 828 nm (BaOH band)
Receiver: photomultiplier, sensitive in the near infra-red
Adjustment of the zero of the galvanometer: with solution B
Preliminary calibration with a series of barium solutions (0-500 [Lg Ba/ml) allows the
approximate barium content of the analysed solutions to be determined, so that the a-
mounts of barium to be added for the final calibration can be fixed at an appropriate level.
The sensitivity of the spectrophotometer is adjusted so that the galvanometer gives full-
scale deflection with solution A plus the largest amount of barium added, while zero de-
flection corresponds to the background spectrum, determined with the aid of solution B
as described above.
8.2.3.3 Manganese, copper, chromium, thallium
Flame photometry is not generally used for the determination of trace elements in rocks
and soils. Its application is limited to elements which are sufficiently excited in the flames-
namely, manganese, copper, chromium, thallium and perhaps one or two others, if these
elements are present in sufficient quantity in the sample to be analysed.
The spectral lines used are the following:
- manganese line at 403.3 nm, detectable at 0.1 flg/ml in an oxy-acetylene flame; errors
may be caused by the presence of potassium (K line at 404.4 nm) and gallium (line at
403.3 nm).
- copper line at 324.7 nm, detectable at 0.6 {Lg/ml in an oxy-acetylene flame.
- chromium line at 425.4 nm, detectable at 0.5 {Lg/ml in an oxy-acetylene flame.
If we assume that 1 g of the sample can be dissolved in 25 ml under the best conditions,
the detection limits in the soil and rock samples become:
manganese: 2.5 ppm
copper: 15 ppm
chromium: 12.5 ppm.
However, the concentrations of these elements in the samples analysed sometimes fall
below these levels. It may be possible to increase the intensity of emission with the aid of
organic solvents.
8.2.3.3.1 Manganese
The sample (0.5-1 g) is brought into solution by treatment with a mixture of sulphuric and
hydrofluoric acids; the acids are then evaporated off and the residue dissolved in 5 %
hydrochloric acid and made up to 25 or 50 ml. This solution is subjected to photometry at
403.3 nm; the background level is determined by measurement on each side of the line,
at 400 and 406 nm. The best calibration method is the addition method (Sec. 8.1.5.) The
manganese concentration in the solution used for photometry should be in the range
2-100 {Lg/ml; this corresponds to 100-5000 ppm in the original sample.
The manganese can also be determined by extraction of the manganese-hydroxyquino-
line complex at pH 8.9 in methyl isobutyl ketone, and atomization of the organic solution
in an oxy-hydrogen flame. This improves the sensitivity by a factor of 20 (Sudo & Goto
[95]).
Manganese can also be determined in the basic ion-exchange extract of soils (Kick [61],
Heidel [53]).
Ishida uses the photographic method to record and measure the manganese spectrum
(air-acetylene flame) [58].
References: Dippel & Bricker [30], Debras-Guedon & Voinovitch [25], Ishida [58].
8.2.3.3.2 Copper
The normal copper content in rocks (10-200 ppm) and soils (10-100 ppm) is often too low
to be determined by direct flame photometry on the solution obtained from the sample
(1 g in 50 ml), as these values are near the detection limit. The sensitivity can some-
times be improved by a factor of 3 by working in 80 % methanol.
However, the best method is based on extraction in an organic medium. Details of the
method are as follows.
The sample (2.5 g, containing 10-200 ppm of copper) is acid-treated and dissolved in
2.5 %nitric acid. The solution is buffered with 2 ml of 40 %ammonium citrate to complex
iron, and the pH is adjusted to 3.0 with concentrated ammonia. The copper is extracted
as the salicylaldoxime complex by shaking the solution three or four times with 5 ml of
salicylaldoxime (1 % in amyl acetate). The organic phases are combined and made up to
20 or 25 ml, and this solution is subjected to photometry at 324.7 nm in an oxy-acetylene
flame. The calibration curve is constructed with the aid of a series of solutions containing
0, 50, 100, 250, 500, 1000 and 2000 [Lg of copper in the form of copper sulphate, treated
and extracted as described above.
It is also possible to extract the copper as the Cu-diethyldithiocarbamate complex in
methyl isobutyl ketone, iron being complexed with citric acid or ethylene diamine tetra-
ceticacid.
Reference: Dean & Lady [23].
8.2.3.3.3 Chromium
Chromium can be detected at 0.5 [Lg/ml in aqueous solution, with an oxy-acetylene

flame; in an organic medium (methyl isobutyl ketone) the sensitivity is greater bya factor
of 50; chromium contents greater than 20 ppm in rocks and soils can be determined by
flame photometry after extraction in methyl isobutyl ketone.
A sample (2-5 g) containing from 50 to 1000 [Lg of chromium is dissolved in normal
sulphuric acid after fusion with alkalis. To this solution, we add 2 ml of 0.1 N silver nitrate
and 2 g of potassium peroxydisulphate, to oxidize the chromium to Cr03' The solution is
made up to 100 m!. A 5-10 ml aliquot is diluted to 18 ml with distilled water, and 2 ml of
10 N hydrochloric acid and 10 ml of methyl isobutyl ketone are added. The solution is
cooled and shaken; the organic phase is separated, and analysed in an oxy-acetylene flame.
The calibration curve is prepared with chromium solutions of known strength, prepared
in the same way to give a final concentration range of 0-20 [Lg Cr/ml in the organic phase.
The chromium lines used for photometry are those at 357.9 and 425.4 nm. High con-
centrations of iron (more than 500 [Lg Fe/ml in the aqueous phase) can interfere with the
determination (iron lines at 357 and 427.2 nm).
Reference: Bryan & Dean [13].
8.2.3.3.4 Thallium
Thallium contents of rocks and soils in excess of 0.2 ppm can be determined by flame
photometry. The thallium is extracted as the tetrabromide, HTIBr4, in amyl acetate as
follows.
The sample is brought into solution by treatment with a sulphuric-hydrofluoric acid
mixture, then oxidized by a solution of bromine in normal hydrobromic acid to give the
tetrabromide HTIBr4' The solution is then extracted with amyl acetate, and the organic
phase separated and subjected to flame photometry. The flame used is oxy-hydrogen; the
intensity of the TIline at 377.6 nm is measured and compared with that of a series of refer-
ence solutions prepared under the same conditions by oxidation and extraction with amyl
acetate.
Reference: Fornaseri & Penta [39].
8.2.3.4 Miscellaneous methods: Atomic fluorescence spectrophotometry; determination of

zinc, cadmium, mercury, gallium, thallium and indium
When atoms have been excited by radiation of a given wavelength, they are capable of
reversing this process and emitting radiation of the same or a lower wavelength. The
wavelengths emitted by fluorescence in this way are characteristic of the excited atoms
(Winefordner & Vickers [103]). Certain elements introduced into an oxy-hydrogen or
oxy-acetylene flame by atomization of a solution under conditions resembling those of
classical emission spectrophotometry give a fluorescence spectrum which allows highly
sensitive determination of the elements in question.
This new method should be applicable to the analysis of soils and rocks.
Table 8.111 gives some experimental data obtained by Mansfield & Winefordner [65]
with an oxy-hydrogen flame.
This method would seem to be very promising, but it still has to be tested in practice.
References: Winefordner & Vickers [103], Winefordner & Staab [104], Mansfield &
Winefordner [65].
TABLE 8.11I
OPTIMUM CONDITIONS AND DETECTION LIMITS OF ATOMIC FLUORESCENCE
FOR CERTAIN ELEMENTS
Spectral Height
Slit Detection
Element line above width Excitation source limit
nm burner (mm) ([J.g/ml)
(em)
Cadmium 228.3 6-6.5 2 Philips or Osram lamp 0.0002
Zinc 213.9 5.5-6.5 2 Philips or Osram lamp 0.0001
Mercury 253.7 8 1 electrodeless discharge tube 0.1
Thallium 377.6 4-4.5 0.2 Philips lamp 0.04
Indium 410.5 5-6 1 electrodeless discharge tube 10
Gallium 417.2 5-6 1 electrodeless discharge tube 10
8.3 Analysis of plants
8.3.1 GENERAL PROBLEMS
Plant matter, after destruction of its organic component, contains the following elements
in order of decreasing average concentration:
Potassium, calcium, magnesium, sodium
Silicon, phosphorus, sulphur, chlorine
Iron, manganese, zinc, copper, boron, cobalt, molybdenum, rubidium, aluminium.
The following elements may also be found, in very small quantities:
Lithium, strontium, barium
Vanadium, chromium, lead, tin, selenium.
We give below the classical methods for the determination of the major elements, to-
gether with certain techniques which are more specially applicable to trace elements.
The analysis of plant media is also affected by interactions between the various chemical
species present. The well known effect of anions can generally be dealt with by carrying
out the photometry in an acid medium of constant composition. However, this does not
8.3] ANALYSIS OF PLANTS 453
eliminate the effect of phosphates on the estimation of calcium and magnesium; this can
be corrected for with the aid of buffers.
Interactions between cations are generally either due to the background spectrum
(effect of calcium on sodium, sodium on calcium, and iron on magnesium), which can be
reduced by the use of a sufficiently dispersive monochromator, or result from the effect
of the easily ionizable alkali metals (K, Rb, Cs) on certain other ionization processes:
large amounts of the alkali metals increase the emission of calcium, magnesium and sodium
(Pinta & Bove [78]).
Chemical reactions in the flame can also have an effect on the results; phosphorus or
aluminium can affect the determination of calcium in this way, but the effect of aluminium
is generally negligible in plant media.
The sample should be prepared - i.e., brought into solution - in such a way as to re-
duce interfering effects; suitable calibration can in general deal with all other sources of
error.
Calibration by the addition method (Sec. 8.1.5) can be used if the measured emission is
proportional to the concentration of the element in the solution introduced into the flame.
This is the case with Ca, Mg, Fe and Mn, but not with sodium and potassium. In any
case, the addition method allows a check on the determination.
Reference: Mitchell [72].
8.3.1.1 Preparation of samples; general method
Two techniques are used to remove the organic component of plants: treatment with acids
(perchloric, sulphuric, nitric, etc.) and calcination followed by solution of the ash in an
acid. We will now give brief details of the second method, which permits the determina-
tion of quite a large number of elements.
A sample of 2 g of plant powder, prepared by heating in a platinum crucible at 80°C for
16 hours, is placed in a cold oven. The oven is heated to 450°C in two hours, and kept at
this temperature for a further two hours. After cooling, the ash is moistened with 2-3 ml
of water and 1 ml of concentrated hydrochloric acid, and warmed gently. The solution
is filtered into a l00-ml graduated flask; the contents of the filter are washed with luke-
warm water, and the washings added to the filtrate. The filter and its contents are now
calcined in the original 30-mm platinum crucible at 550°C. The residue is taken up in
5 ml of hydrofluoric acid to volatilize silica; the excess acid is evaporated off (not above
250°C), and the residue is redissolved in 1 ml of concentrated hydrochloric acid and a
little lukewarm water, and finally filtered into the l00-ml flask. The solution is now made
up to 100 ml.
This solution can be used to determine:
K, Ca, Mg, Na
Fe, Mn, Cu
P
Certain authors (e.g., Pinta & Bove [78]) remove interfering anions by ion exchange.
This can be done either by fixing the cations on a resin such as DOWEX 50, and then
eluting them by means of 3 N hydrochloric acid, or by fixing the anions, in particular
phosphates, on a resin like DOWEX 2X8 and determining the cations in the filtrate.
Reference: Pinta [76].
8.3.1.2 The chemical composition olplant media
Table 8.IV below gives typical concentrations of major and trace elements in plant media,
particularly leaves.
TABLE 8.IV
CONCENTRATIONS AND DETECTION LIMITS OF CERTAIN ELEMENTS IN
PLANT MEDIA
Major elements Trace elements
Detection Detection
Concentration Concentration limit
Element limit Element (ppm)
(%) (ppm)
(%)
K 0.4 -3 0.005 Fe 10 -1000 10

Ca
I 0.1 -2 0.01 Mn 10 -1000 5
Mg 0.01-0.4 0.04 Sr 0.2 -800 10
Na 0.01-0.2 0.005 Zn 2 -500 -
S 0.02-0.3 0.05 Rb 2 -600 50
Cl 0.03-0.3 0.03 Ba 1 -300 250
P 0.01-0.3 0.1 B 1 -100 25
Cu 1 -100 5
Pb 0.1 -50 -
Ni 0.1 -10 -
Mo 0.02-10 -
Se 0.1 -5 -
Sn 0.1 -5 -
Li 0.01-10 -
V < 0.01-2 -
Co < 0.01-1 -
Ag < 0.01-0.2 -
8.3.2 DETERMINATION OF THE MAJOR ELEMENTS
8.3.2.1 Potassium, calcium, magnesium, sodium
8.3.2.1.1 Potassium
Potassium and the other alkali metals should preferably be determined in a low-tempera-
ture flame, since errors due to the ionization of other elements are smaller under these cir-
cumstances.
For the analysis of plant media, we use either the lines at 766/9 nm, detectable down to
0.02 ~g/mI in an oxy-hydrogen flame and 0.1 ~g/ml in an air-acetylene flame, or the line
at 404.4nm, which is less sensitive: 2~g/mI in the oxy-hydrogen flame and 10 ~g/ml in the
air-acetylene flame. The lines at 766/9 nm are more often used.
There is practically nothing to interfere with the determination of potassium in plant

media.
Reagents
Hydrochloric acid, 1 %
Reference solution: KCI (1000 (log K/ml) in 1 % HCI
Sample preparation
The solution prepared as described in Sec. 8.3.1.1 is diluted with 1 % hydrochloric acid
until the potassium content is between 20 and 200 (log/ml.
The solutions for the construction of the calibration curve may be simple solutions con-
taining only potassium chloride in the concentration range from 0 to 200 (log K/ml in 1 %
HCl.
If the calcium content is high, the calibration solutions may have calcium added to
roughly the same level- between 100 and 500 (log/ml.
Spectrophotometry
Flame: air-acetylene or oxy-hydrogen
Prism or grating spectrophotometer, or simply a filter photometer
Receiver: sensitive in the near infra-red (766 nm)
The determination is very accurate: error less than 2 %, standard deviation less than
0.01.
8.3.2.1.2 Sodium
The sample is prepared as for the determination of potassium; it will not generally be ne-
cessary to dilute the solution (of 2 g of the plant in 100 ml). Photometry is carried out at
589 nm in an air-acetylene or oxy-hydrogen flame.
The calibration solutions should be complex, with the sodium concentration ranging
from 0 to 100 (log/ml and representative potassium and calcium levels. If the difference
between the calcium content of the sample and that of the reference solution is too great,
the effect of this on the sodium level found must be taken into account, especially when a
filter photometer or a quartz-prism spectrophotometer (which is not very dispersive in
the region around 590 nm) is used.
8.3.2.1.3 Calcium
The determination of calcium in plant media has been the subject of many publications,
all of which deal with the elimination of the effect of phosphorus on the results. There are
various possible solutions, such as removal of the phosphate ions by ion exchange, preci-
pitation of the calcium as the oxalate, correction of the calcium level found as a function
of the phosphate content, reduction of the interaction by means of a suitable choice of the
physico-chemical flame parameters, elimination of the interactions by means of inor-
ganic or organic spectral buffers; several methods have been proposed based on all these
different ways. The most recent methods have been based on the last-mentioned principle.
The phosphorus-calcium interaction can be corrected for with the aid of a curve giving
200~ ________________________ ~
l.,
c0
150
~
c11
0
u
u" 100
C
~
a.
a.
"
50
o 50 100 150 200

}Jg Pjml
Fig. 8.8. Effect of phosphorus on the determination of calcium
the calcium emission of solutions with a constant calcium content (50 [Lg/ml) and increas-
ing amounts of phosphate (0-100 [LgP/ml); see Fig. 8.8.
The depression of the calcium emission by phosphates can be reduced by the addition of
appropriate spectral buffers. The most widely used buffers are 8-hydroxyquinoline (Delas
[27], Popov [81]), lanthanum chloride (Yoke & Finkelstein [l05]), strontium salts
(Dinnin [29]), magnesium sulphate (Ebert [32]), ethylene diamine tetracetic acid (West
& Cooke [101], Greweling [49]) and glycerol (Heeney et aI., [52], d'Auzac & Danjard
[4]).
We have adopted a method based on the use of glycerol as a spectral buffer.
Reagents
Glycerol, redistilled, 25 %
Hydrochloric acid
Calcium chloride, 1000 [Lg Calml in 1 % HCI
Sample preparation
A 25-ml aliquot of the sample solution prepared as described in Section 8.3.1.1 is mixed
with 4 ml of glycerol and made up to 50 ml with 1 %hydrochloric acid.
The reference solutions, containing from 0 to 100 [Lg Calml, are prepared from the
1000 [Lg/ml calcium solution, diluted with 25 % glycerol and 1 %hydrochloric acid.
Spectrophotometry
Prism spectrophotometer, with photomultiplier
Accuracy: error generally less than 3 %
References: Havre [51], Delas [27], Yoke & Finkelstein [105], Heeney et aI. [52],
d'Auzac & Danjard [4], Popov [81], Didier de Saint-Arnand [28].
8.3.2.1.4 Magnesium
Flame photometry is neither very sensitive nor very accurate for the determination of
magnesium.
However, few elements have an appreciable effect on the determination of magnesium;
phosphates and sulphates cause a slight depression of the magnesium emission in the
flame, and potassium, calcium and sodium an enhancement. The addition of 8-hydroxy-
quinoline not only corrects for these effects, but also increases the intensity of emission.
In a solution containing 5 % of 8-hydroxyquinoline, the determination of 50 {lg Mg/ml
is not affected by 1000 {lg K, 400 {lg Na, 2000 {lg Ca, 10 {lg Al and 20 {lg Fe per ml
(Delas [27]).
We use the method described below.
Reagents
Hydrochloric acid, 50 %
8-Hydroxyquinoline, 20% in acetic acid
Magnesium sulphate, 1000 {lg Mg/ml in 1 % HCI
Sample preparation
A 25-ml aliquot of the prepared solution (Sec. 8.3.1.1) is mixed with 12.5 ml of 8-hydroxy-
quinoline and 5 ml of hydrochloric acid in a 50-ml graduated flask, and made up to 50 ml.
The reference solutions, containing from 0 to 100 {lg Mg/ml, are prepared in the same
way from the stock solution containing 1000 {lg Mg/ml.
Spectrophotometry
Flame: oxy-hydrogen
Spectrophotometer: quartz-prism or grating
High-quality photomultiplier receiver
Galvanometer zero adjusted to the background of the blank solution.
Characteristics oj the method
Sensitivity: 0.01 % Mg can be detected in plant media
Accuracy: error less than 4 %
8.3.2.1.5 Determination of potassium. sodium and lithium in plants without

incineration of the sample
This very simple method (Gavva et al. [41]) may be useful for investigations into the
role of minerals in nutrition.
It is based on the extraction of the metals from the plant tissues by a solution of ammo-
nium ethylene diamine tetracetate (ammonium EDTA).
Reagents
Ammonium EDTA, 0.1 M (29.2 gil)
Potassium chloride, 1000 {lg K/ml
Sodium chloride, 1000 {lg Na/ml
Lithium chloride, 1000 {lg Li/ml
Sample preparation
A suitable amount of the air-dried plant (0.5 g for the determination of K and Na, 3-5 g for
Li) is placed in 100 ml of the solution of ammonium EDTA in a 200-mllong-necked flask
and placed in a rotary shaker for 1 hour. The mixture is then filtered into a 200-ml gra-
duated flask, the original flask rinsed and the solution made up to 200 ml. The reference
solutions, containing
Na or K: 0 to 100 [Lg/ml
Li: 0 to 10 [Lg/ml
are prepared in 0.01 M ammonium EDTA. The solutions are subjected to photometry
under classical conditions. The method is very reproducible.
8.3.2.2 Sulphur
The flame photometric determination of sulphur makes use of an indirect method;

sulphates are precipitated by an excess of barium chloride, and the excess barium is then
determined. Sulphate contents from 5 to 100 [Lg SImI of solution can be determined in this
way; this corresponds to 0.05 %-1 % S in the original plant material.
Method of analysis, sample preparation (after Alt [2])

Reagents
Nitric acid (specific gravity 1.39)
Perchloric acid (s.g. 1.53)
Hydrochloric acid (s.g. 1.16)
Hydrochloric acid, 10 % (278 ml of 1.18 HCl in 11)
Sodium formate, 0.34 % (34 g of sodium formate and 191 ml of pure formic acid dissolved
in 1 litre of water; this solution is diluted 10 times before use. The pH should be 3.5.
Barium chloride, 89 g BaCl2 in 1 litre of water; this solution is diluted 10 times before use,
giving a final barium content of 5000 [Lg Balm!.
The organic plant material is destroyed by treatment with perchloric acid: a 500 mg
sample of the powdered dry plant material is placed in a lOO-ml Kjeldahl flask with 20 ml
of nitric acid and 4 ml of perchloric acid, and the mixture is heated gently until decoloriza-
tion is complete; it is then evaporated to dryness and the residue taken up in 4 ml of
hydrochloric acid, again evaporated to dryness, and taken up in 20 ml of 10 % hydrochlo-
ric acid. This solution is heated to boiling, cooled, made up to 50 ml and then filtered.
Twenty ml of the filtrate is placed in each of two graduated flasks (a and b). Two ml of
sodium formate is added to each flask, and 2.5 ml of barium chloride to precipitate the
sulphate in flask (a) only. The solutions are made up to 25 ml, shaken and left to stand for
12 hours. These solutions are used for the determination.
For the preparation of the reference solutions, 40 ml of nitric acid, 8 ml of perchloric
acid and 8 ml of hydrochloric acid are evaporated to dryness together; the residue is taken
up in 40 ml of 10 % hydrochloric acid, transferred to a lOO-ml flask and made up to 100 mI
with water. Five 4-ml aliquots of this solution are placed in 50-ml graduated flasks with
4 ml of sodium formate and from 0 to 2.5 ml of barium chloride (5000 [Lg Balm!). The
barium content of these reference solutions thus varies from 0 to 250 [Lg/ml, which corres-
ponds to sulphate contents in the original solution of from 58.5 to 0 [Lg SimI.
Spectrophotometry
Flame: oxy-hydrogen
Wavelength: 513 nm.
The barium spectrum has a band-head (BaO) at this wavelength, which can be used
for the determination. The bands at 828 and 873 nm can also be used for photometry
if a sensitive photomultiplier is available. The Ba line at 553.5 nm cannot be used,
because of interference from the CaO emission at this wavelength. It would thus seem
that the band-head at 513 nm is the best for the determination, i.e., the most intense
compared with the background (measured at 522 nm); it is the difference between these
two emissions (1513-1522) which is used as a measure of the barium content.
Sensitivity: The sensitivity of the spectrophotometer is adjusted so that the entire scale of
the galvanometer corresponds to the range of concentrations covered by the reference so-
lutions (0-250 [Lg Ba/ml).
The intensity of the samples (solution a) at 513 and 522 nm is now measured. In order
to check that the difference (1513-1522) is not affected by changes in the background due to
the other elements present, this difference is also determined for solution (b); if the value
for solution (b) is not zero, it is subtracted from that for solution (a).
Notes
Under these conditions, not much calcium can co-precipitate with the barium; the
error resulting from this is less than 3 %; iron and aluminium do not interfere with the
determination.
Anothermethodconsists of precipitating the barium sulphate, separating it and redissolv-
ing it in 10 ml of 2 % ammonium ethylene diamine tetracetate (ammonium EDTA). The
barium content of this solution is then determined by flame photometry; 100 [LgBa
corresponds to 23.2 [Lg S (Cunningham [20], Odler [73]).
References: Alt [2], Shaw [89-90], Burriel-Marti et al. [14], Cunningham [20], Odler [73],
Robinson [86].
8.3.2.3 Chlorine
Chlorine can be determined indirectly by precipitation of silver chloride and determina-
tion of the excess silver. Various papers have been published on this method.
The following procedure may be used for plant material.
The sample (1 g, containing between 0.3 and 3 mg of chlorine) is calcined, and the
ashes dissolved in 100 m1 of 1 % nitric acid.
A 50-ml aliquot, containing between 150 and 1500 [Lg CI, is mixed with 2.5 ml of a so-
lution of silver nitrate containing 2000 [Lg Ag/ml in 1 % nitric acid. This mixture is diluted
to 100 ml, centrifuged and subjected to photometry.
The reference solutions are prepared from sodium chloride solutions containing 0, 250,
500, 750, 1000 and 1500 [Lg CI in 1 %nitric acid by addition of 2.5 ml of AgN0 3 (2000 [Lg
Ag/ml in 1 % HN0 3 ) and dilution to 100 ml. These solutions are then centrifuged and
photometered.
The chlorine precipitated is equivalent to the initial silver less the silver found by photo-
metry; 10 [Lg Cl corresponds to 32 [Lg Ag.
Spectrophotometry
Flame: oxy-hydrogen
Wavelength: 328 nm
Sensitivity: the zero of the galvanometer is adjusted to correspond to the reference solu-
tion containing 15 fLg Cl/ml, and full-scale deflection to the blank (0 fLg Cl/ml, 50 fLg
Ag/ml)
Characteristics of the method: detection limit 0.5 fLg Cl/ml, relative error less than 5 %,
effect of phosphates is negligible.
References: Menis et al. [71], Lang [63], Honma [54].
8.3.2.4 Phosphorus
One way of determining phosphates would be to'make use of the interaction ofP04 3- ions
and calcium in flame photometry (line at 422.6 nm, bands at 553.5 and 623 nm) (Fig. 8.8).
This interaction is more sensitive at lower flame temperatures.
In order to determine phosphorus in this way, we have to know the calcium content of
the solution under investigation. In general, the calcium concentration should be higher
than that of phosphorus.
Dippel et al. [30] studied the determination of phosphates in the presence of the
standard cations calcium, sodium, potassium and magnesium, and came to the conclu-
sion that it is best to separate the cations by ion exchange and to add a known amount of
calcium to the anion-containing filtrate.
Details of method
The plant solution prepared as described in Section 8.3.1.1 (25-50 ml containing between
1 and 10 mg of P), in 1 % hydrochloric acid, is passed through a cationic ion-exchange
column (DOWEX 50). The filtrate is collected in a loo-ml graduated flask containing
10,000 fLg Ca (10 ml of solution with 1000 fLg Ca/ml), and made up to 100 ml.
The reference solutions are prepared so as to contain 100 fLg Ca/ml, 1 % HCI and a
phosphorus content increasing from 0 to 100 fLg P/ml.
The solutions are photometered in an air-acetylene flame at 422.6 nm (calcium line).
It is possible to work with a wider range of phosphorus concentrations, from 0 to
1000 fLg P/ml; the calcium content should then be made 1000 fLg Ca/ml.
The error of the determination is less than 1 %.
References: Dippel et al. [30], Ratner [85].
8.3.3 DETERMINATION OF TRACE ELEMENTS
The determination of lithium has been little studied, as this element does not seem to be of
much importance in plant physiology, while on the other hand it is present at very low
concentrations. There is hardly any literature on the determination of lithium in plant
material.
The determination of rubidium and caesium seems to be of greater interest. The spec-
tral emission of these elements (Rb line at 780nm, Cs line at 852nm) is enhanced by the
presence of potassium, sodium and calcium, and depressed by phosphates.
The effect of potassium and sodium can be corrected for by the use of reference solu-
tions containing roughly the same amounts of these elements as the unknown solutions, or
by adjusting the rubidium and caesium concentrations found (mainly as a function of the
potassium content).
The effect of calcium is slight, and may be neglected if the calcium content of the so-
lution under investigation is less than 0.1 %. The effect of phosphates is negligible if the
phosphate (P0 4 ) content is less than 0.04 %.
If large amounts of phosphates and calcium are present, they can be precipitated by the
addition of enough ammonium carbonate to make the pH between 8 and 9.
The method given below is applicable to the general case, and does not make use of this
separation.
Details 0/ method
The plant sample (2-5 g, containing between 50 and 1000 fLg of rubidium and caesium)
is calcined, silica is volatilized off with hydrofluoric acid and the residue is redissolved in
10-50 ml of hydrochloric acid (2.5 % or 5 %). This solution is photometered; the sodium
and potassium contents are assumed known.
The reference solutions have representative sodium and potassium contents, and con-
tain increasing amounts of rubidium and caesium; for example, a set of reference solu-
tions might have the compositions shown in Table 8.V.
TABLE S.V
REFERENCE SOLUTIONS FOR THE DETERMINATION OF RUBIDIUM AND
CAESIUM
1 2 3 4 5
K fLg/ml 2000 2000 2000 2000 2000
Na fLg/ml 500 500 500 500 500
Rb fLgjml 0 50 100 150 200
Cs fLg/ml 0 25 50 75 100
HCI % 2.5 2.5 2.5 2.5 2.5
The spectrophotometry requires a high quality monochromator of sufficient dispersivi-

ty, and a photomultiplier which is sensitive in the near infra-red; the solutions are photo-
metered in an air-acetylene flame at the following wavelengths:
rubidium: 780 nm
caesium: 852 nm.
As a result of the high sensitivity demanded of the instrument, the error may amount
to as much as 10 %.
References: Kick [62], Glendening et al. [45].
8.3.3.2 Strontium, barium
No particular study of the determination of barium in plant material has been made; this
element does not give a high-intensity flame emission spectrum, its concentration in plants
is low and its physiological role does not appear to be important.
However, several works exist on the determination of strontium. This element is pre-
sent in plants at a concentration of between 0.2 and 800 ppm; concentrations of more
than 10 ppm can be determined by flame photometry. Like calcium, strontium has a
flame emission spectrum which is affected by the presence of phosphates and aluminium.
It is preferable to separate the cations by ion exchange.
Details 0/ method, preparation 0/ sample
A suitable amount of the sample (between 0.5 and 5 g, containing between 50 and 5000
[Lg Sr) is freed from organic matter as described above and dissolved in 50 ml of 1 %
hydrochloric acid. All or part of this solution is passed through a cation-exchange column,
saturated with hydrogen ions by the preliminary passage of 5 N hydrochloric acid and
washing with water. The rate of passage of the solution should be less that 0.8 ml/min.
The column is then washed by passage of 40 ml of 0.5 N Hel, and the cations (including
strontium) are eluted by means of 60 ml of 5 N hydrochloric acid. The eluate is evapo-
rated to dryness and taken up in 50 ml of 1 % hydrochloric acid.
Calibration is by the addition method (see Sec. 8.1.5):
a) The approximate strontium concentration is determined on one 5-ml or 10-ml aliquot;
b) a second lO-ml aliquot is diluted to 20 ml with 1 % hydrochloric acid;
c) suitable amounts of strontium (1 and 2 times the amount found in a) are added to two
other 10-ml aliquots, and the mixtures diluted to 20 ml.
Spectrophotometry
Flame: oxy-hydrogen (with flow rates controlled appropriately)
Quartz or glass spectrophotometer, with sensitive photomultiplier receiver.
The sensitivity of the instrument is adjusted with the aid of the solution with the largest
amount of strontium added, and the other solutions are measured under the same con-
ditions. It may be necessary to change the sensitivity of the instrument for the solution
without added strontium, depending on its concentration.
Strontium concentrations ranging from 10 to 1000 ppm in plant material may be de-
termined in this way. The error of the method is less than 10%.
References: Scharrer & Heilenz [88], Kick [61].
8.3.3.3 Manganese, iron, copper
These elements cannot be determined directly in a solution of plant ashes prepared as

described in Section 8.3.1.1. It is better to separate them from a suitable sample by preci-
pitation with 8-hydroxyquinoline. The precipitate is calcined and redissolved in the
smallest possible amount (5-10 ml) of 0.1 N hydrochloric acid.
Details o/method (after Bemeking & Schrenk [7])
Reagents
Hydrochloric acid, concentrated
Hydrochloric acid, 0.1 N
Ammonium acetate, 2 N
Acetic acid, 2 N
8-Hydroxyquinoline, 5 % in 2 N acetic acid

Ammonia, 1/1
Aluminium chloride solution, 4000 [Lg AI/ml
Iron, stock solution, 2000 [Lg Fe/ml
Copper, stock solution, 2000 [Lg Cu/ml
Manganese, stock solution, 2000 [Lg Mn/ml
Sample preparation
A sample of the plant material (2-5 g, containing 20-2000 [Lg of iron, 10-1000 [Lg of
manganese and 2-100 [Lg of copper) is freed of organic matter (Sec. 8.3.1.1) and dissolved
in 8 ml of concentrated HCI and 70 ml of water.
We now separate the iron and copper from the manganese: the solution prepared as
described above is mixed with 0.5 ml of the aluminium chloride solution, 10 ml of 8-
hydroxyquinoline, and enough ammonia to bring the pH to 1.2-1.3 (as determined by
a pH-meter); 40 ml of ammonium acetate are now added, with stirring, and enough am-
monia (1/1) to bring the final pH to 5.1 (determined by pH-meter). The solution is allowed
to stand for 16 hours, then filtered and the filter washed.
The precipitate contains the iron and copper, and the filtrate the manganese.
The precipitate is calcined at 850°C for 16 hours, and redissolved in 3 ml of concen-
trated hydrochloric acid and 10-12 ml of water. This solution is again evaporated to
dryness, and finally taken up in 5-10 ml of 0.1 N hydrochloric acid; this solution (a) is
used for the determination of iron and copper.
The filtrate containing the manganese is mixed with 0.5 ml of aluminium chloride,
5 ml of 8-hydroxyquinoline and enough 1/1 ammonia to bring the pH to 7.1. The mixture
is stirred, and left for 16 hours. It is then filtered, and the precipitate treated as described
above for iron and copper.
A blank solution is prepared in the same way.
The reference solutions are prepared by dilution of the stock solutions of iron, copper
and manganese in 0.1 N hydrochloric acid to cover the ranges:
iron: 0-200 [Lg Fe/ml
manganese: 0-100 [Lg Mn/ml
copper: 0-100 [Lg Cu/ml
Spectrophotometry
Flame: oxy-acetylene (gas flow adjusted separately for each element)
Wavelength: Fe: 373 nm (solution a)
Mn: 403.3 nm (solution b)
Cu: 324.7 nm (solution a)
Spectrophotometer: quartz-prism or grating for ultraviolet, with high-quality photomulti-
plier; in particular the determination of copper makes the highest demands on the sensiti-
vity of the instrument.
Notes
The aluminium is used to facilitate the precipitation of the trace elements; it does
not interfere with their determination (Scott & Mitchell [93]).
Iron should be determined in the absence of manganese, as the latter interferes with
the emission spectrum of iron.
The following concentration ranges can be covered in this way:

iron: 2 - 200 ppm
copper: 1 - 10 ppm
manganese: 1 - 100 ppm
Accuracy: the relative error is generally less than 20 %.
Copper can also be determined after extraction as the dithizonate in chloroform or kero-
sene (Massey [68]).
References: Berneking & Schrenk [7], Scott & Mitchell [93], Pinta [76], Massey [68],
Mitchell [72].
8.3.3.4 Boron
Aqueous solutions of boron give rise to a fairly low-intensity band spectrum in an oxy-
acetylene flame, with bands at 492, 518 and 546 nm. The intensity of the bands is 7 times
greater in 1/1 water/methanol, and 17 times greater in 1/9 water/methanol. From 1 to
3 !Jog B/ml can be detected in this way (Dean & Thompson [24]).
The determination of boron in plant materials has been studied by Lora-Silva et al. [64];
although the method has not been completely worked out yet, the general principle is
worth mentioning here; at present, it is only useful for high boron contents (more than
200 ppm).
The plant sample (2 g) is calcined in the presence of calcium hydroxide at 600 °C, and
the ashes are taken up in 15 ml of 1/100 sulphuric acid. A 3-ml aliquot ofthis solution is
mixed with 3 ml of methanol; the precipitated calcium sulphate is separated by centri-
fugation and the solution is photometered in an oxy-acetylene flame at 492 and 518 nm.
The background spectrum is appreciable in this range; it is measured at 505 nm.
Calibration is performed by the addition method (Sec. 8.1.5).
Certain elements present in plants can interfere with the determination of boron; in
particular magnesium and calcium give bands which are superimposed on those of boron.
The acid concentration of the solution used for analysis is also important: an increase in
the hydrochloric acid content depresses the boron bands at 492 and 518 nm.
References: Dean & Thompson [24], Lora-Silva et al. [64].
8.4 Analysis of water
8.4.1 GENERAL DETAILS
We are mainly concerned here with natural water, or other types of water of agricultural
significance.
Tables 8.VI and 8.VII give representative concentrations of various elements in rain
water, stream water and river water; these values are very approximate, as they depend on
many factors such as the nature of the rocks, the type of soil, the vegetation, the flow rate
of the water, the temperature, etc.
8.4] ANALYSIS OF WATER 465
TABLE S.VI
CONCENTRATION OF THE MAJOR ELEMENTS IN WATER
Rain and stream water

Element
ILg/ml
Na 0.2 - 10
K 0.2 - 5
Ca 0.2 - 10
Mg 0.1 - 5
S04 0.1 - 3
CI 0.5 - 5
P0 4 0.1 -
Si0 2 5 - 25
TABLE S.VII
CONCENTRATION OF CERTAIN TRACE ELEMENTS IN WATER
Element Rain and stream water River water

ILg/I ILg/I
Li 1 - 20 5 - 50
Rb 0.5 - 5 5 - 25
Cs 0 - 5 0 - 10
Sr 10 - 100 50 - 200
Ba 2 - 50 10 - 100
Ti - 200 50 - 500
V 0.1 - 10 0.1 - 10
Cr 5 - 25 5 - 500
Mo 0 - 2 0.5 - 3
Mn - 200 5 - 200
Fe 10 - 100 25 - 500
Co 0 - 4 0 -
4
Ni 1 - 10 2 - 50
Cu 4 - 20 2 - 10
Al 10 - 100 5 - 50
Sn 0 - 2 0 - 2
Pb 0 - 5 0 - 5
Flame photometry is very suitable for the determination of the following elements:
major elements: Na, K, Ca, Mg
trace elements: Li, Rb, Cs, Sr, Fe, Ni, Co, Cu, Mn, Cr, AI.
Under conventional conditions, flame photometry allows the determination of con-
TABLE 8.VIII
DETERMINATION OF ELEMENTS IN WATER BY FLAME PHOTOMETRY
Concentration range Wavelength

Element Flame
([J.g/ml) nm
Na O.oI - 50 [J.g/ml 589 oxy-hydrogen

K 0.1 - 100 [J.g/ml 766 oxy-hydrogen
Ca 0.5 - 250 [J.g/ml 422.6 oxy-acetylene
Mg 2 - 250 [J.g/ml 285.2 oxy-acetylene
Li 0.1 - 10 [J.g/ml 671 oxy-acetylene
Rb 2 - 50 [J.g/ml 780.0 oxy-hydrogen
Cs 2 - 50 [J.g/ml 852 oxy-hydrogen
Sr 1 - 50 [J.g/ml 460.7 oxy-acetylene
Fe 0.5 - 50 [J.g/ml 372.0 oxy-acetylene
Ni 0.5 - 50 [J.g/ml 352.4 oxy-acetylene
Co 0.5 - 50 [J.g/ml 242.5 oxy-acetylene
Cu 0.2 - 20 [J.g/ml 324.7 oxy-acetylene
Mn 0.1 - 20 [J.g/ml 403.3 oxy-acetylene
Cr 1 - 100 [J.g/ml 425.4 oxy-acetylene
Al 2 - 50 [J.g/ml 396.2 oxy-acetylene
centrations (in the solutions introduced into the flame) in the ranges shown in Table 8. VIII.
The sensitivities given in Table 8.VIII can be improved by the addition of organic com-
plexing agents or miscible organic solvents, or by solution in a pure organic solvent.
However, it may be seen from the table that most of the elements present in water cannot
be determined by conventional flame-photometry methods. It thus becomes necessary to
treat the sample in one of the following ways before flame photometry:
a) concentration by evaporating some of the water off;
b) destruction of organic substances;
c) separation on ion-exchange resins;
d) extraction of the metal complex in an organic solvent; this can lead to a considerable
increase in the sensitivity.
8.4.2 DETERMINATION OF THE MAJOR ELEMENTS: SODIUM, POTASSIUM, CALCIUM, MAGNESIUM
The sample should be colourless and clear. If the water contains organic matter, a known
volume of water should be evaporated to dryness, the organic matter destroyed by hydro-
gen peroxide and the residue taken up in a known volume of 1 % or 2 %hydrochloric acid.
If the error of the determination is to be less than 2 %, the concentration in the photo-
metered solution should be:
Na: between 2 and 50 {Jog/ml
K: between 5 and 100 {Jog/ml
Ca: between 10 and 250 {Jog/ml
Mg: between 20 and 250 {Jog/mi
The anions in the sample should also be of as constant a composition and concentra-
tion as possible.
It may thus be necessary to concentrate or dilute with fresh water sample. Concentration
by a factor of 5 or 10 is generally sufficient for the determination of sodium, potassium and
calcium in rain water. Magnesium demands a higher concentration, e.g., by a factor of 100;
this can be achieved by means of ion exchange.
A simple and rapid method for routine analyses of average sensitivity and accuracy
(error 5 %) is to add 0.5-1 ml of hydrochloric acid to a 50-ml sample to remove carbonate
and bicarbonate ions, and to adjust the concentration of the principal anion remaining to
a constant value.
Another method is to evaporate a suitable sample (50 ml) to dryness, to treat the residue
with hydrochloric acid, to evaporate to dryness and finally to dissolve the residue in 50 ml
of 1 % hydrochloric acid.
The method given below is of more general application, as it involves the elimination
of the anions present by ion exchange, and allows the sample to be concentrated by a
factor of from 5 to 100 or more.
Details 0/ method (after Podobnik et al. [79])

Reagents
Anionic ion-exchange resin, DOWEX 2X8
Hydrochloric acid, redistilled
Hydrochloric acid, 2 N
Stocks solutions for calibration:
Naa, 1000 (Lg Nalml in 10% HCI
KCI, 1000 (Lg Klml in 10% HCI
CaC0 3 , 1000 (Lg Ca/ml in 10% HCI
MgS04 , 1000 (Lg Mglml in 10% HCI
Sample preparation
From 250 to 1000 ml of water is acidified with 2.5-5 ml of concentrated hydrochloric acid
if the water contains carbonates or bicarbonates. The mixture is brought to the boil, and
after cooling its pH is adjusted to 4. The solution is now passed through an ion-exchange
column (diameter 2.5 cm, height 10-15 cm) at a rate of 2-3 ml/min; before passage of this
solution, the resin is saturated with chloride ions by the passage of 2 N hydrochloric acid
followed by washing with water. The first 100 ml of the filtrate of the sample for analysis
are rejected, and the next 250 or 500 ml are collected for flame photometry either directly
or after concentration by a factor of 5-10, or if necessary after dilution.
The reference solutions may be simple solutions of sodium, potassium, calcium and
magnesium covering the desired concentration range (in which case it may be necessary to
correct for the interaction between the different elements), or complex solutions with all
four elements in suitable concentrations, e.g., as shown in Table 8.IX.
Spectrophotometry
Flame: oxy-hydrogen (flow rate suitably adjusted for each element); an air-acetylene flame
can be used for sodium, potassium and calcium.
The spectrophotometer should have one photomultiplier receiver sensitive in the ultra-
violet (350-500 nm) and another for the visible and near infra-red (400-900 nm).
TABLE S.IX
REFERENCE SOLUTIONS FOR THE DETERMINATION OF Na, K, Ca AND Mg
1 2 3 4 5
Na fLg/ml 0 10 20 50 100
K fLg/mi 0 5 10 25 50
Ca fLgjmI 0 20 50 100 200
Mg fLgjml 0 5 10 25 50
HCI fLg/mi 2N 2N 2N 2N 2N
TABLE S.x
PHOTOMETRY CONDITIONS
Spectral line Background Concentration range

Element nm
nm fLg/ml
Na 589 595 0.1 - 100
Na 330 331 10 - 1000
K 766 756 0.2 - 100
K 404 407 20 -1000
Ca 553.5 541 2 - 500
Ca 623 630 0.5 - 250
Mg 370 376 1 - 250
The sensitivity of the instrument should be adjusted for each element so that full-scale
deflection corresponds to the most concentrated reference solution; the background
spectrum near the line (or band) measured should be zero, or near the value found for the
blank at the wavelength in question; otherwise, allowance should be made for the differ-
ence (Table 8.x).
Characteristics of the method: in general, sodium and potassium are determined with
less than 2 % error, calcium with less than 4 % and magnesium with less than 5 %.
Notes
a) Certain authors have proposed that the solutions (unknown and reference) should
be buffered for the ions being determined, to reduce their influence on the results (Enaki
[33]); for example, when sodium is to be determined in the presence of variable amounts
of K, Ca and Mg, the solutions can be buffered with large, constant amounts of potassium,
calcium and magnesium.
b) Sodium and potassium can be determined in an air-acetylene or air-propane flame.
c) Filter photometers can be used for calcium, sodium and potassium; the influence of
the background spectrum should be carefully studied.
References: Podobnik et al. [79], Uzumasa et al. [99], Pudilo et al. [84], West [102].
8.4.3 DETERMINATION OF THE TRACE ELEMENTS LITlUUM, RUBIDIUM, CAESIUM, BARIUM AND
STRONTIUM

These elements are often present in natural water at concentrations which can be deter-
mined by flame photometry. They are generally to be found together with the alkali metals
sodium and potassium: in other words, if the water is rich in sodium and potassium, then
lithium and rubidium and sometimes caesium may be expected too. If on the other hand
the water has a low sodium and potassium content, the lithium, rubidium and caesium
contents will be very low. Even in the latter case, however, the water can be analysed for
these elements after concentration by a factor of 5-25. If the water has a low content of
major elements, it should be quite possible to concentrate it by simple evaporation; the
only substance which is likely to be precipitated is silica, which should be filtered off be-
fore making up to a definite volume.
8.4.3.1.1 Lithium
This determination is carried out on water which has been subjected to ion exchange as
described in Section 8.4.2. It may be possible to photometer the solution obtained from the
ion-exchange column directly, or it may be necessary to concentrate it. Measurements are
made with an air-acetylene flame, on the Li line at 671 nm (the background is measured
at 676 nm). The lithium concentration in the solution photometered should be between
0.1 and 10 {lg/ml.
Sodium, strontium and calcium may interfere with the results by superimposition of
the background spectrum. The reference solutions should contain a suitable amount of
sodium; the background due to sodium may also be reduced by means of a suitable opti-
cal filter (Jonsson [60)). The effect of the CaOH band at 623 nm and the SrOH bands at
666-672 nm may be eliminated by the addition of aluminium; as we have seen
(Sec. 8.2.2.1.3), this element forms a complex with calcium and strontium in the flame,
thus reducing the intensity of their emission.
It may be noted that the intensity of the lithium spectrum can be increased con-
siderably by carrying out the photometry in an aqueous medium to which acetone/amyl
alcohol (4/1) has been added.
References: Uzumasa et al. [97], Podobnik et al. [79], Jonsson [60], Fishman [37],
Bradford & Pratt [12], Collins [16].
8.4.3.1.2 Rubidium, caesium
The low concentration ofthese elements in water (often less than 1 (lg/ml) does not permit
direct determination. One way of concentrating the sample to be analysed is to remove the
alkali-metal ions by ion exchange; this gets rid of calcium and magnesium, in particular.
Rubidium and caesium contents of the order of 0.1-0.2 (lg/ml can be determined under
these conditions.
Another possible method is that used by Collins [17] and Eristavi & Dzhincharazade
[34], which is based on the extraction of potassium, rubidium and caesium as tetraphenyl-
borates in an organic solvent - nitroethane or methyl ethyl ketone/methanol/water
(7/1/2). The extract is photometered in an air-acetylene or oxy-hydrogen flame, the rubi-
dium being determined at 780 nm and the caesium at 852 nm.
Reagents
Buffer solution of M sodium citrate, adjusted to pH 6.6 with 0.5 M nitric acid
Sodium hydroxide, N
Hydrochloric acid, N
Sodium tetraphenylborate, 0.05 M
Nitroethane
Details of method
A water sample containing from 5 to 50 [log of Rb and Cs is placed in a beaker with 25 ml
of the citrate buffer, and the pH is adjusted to 6.6 with sodium hydroxide or hydrochloric
acid. The solution is now diluted to 100 ml and placed in a Teflon separating funnel with
2 ml of the tetraphenylborate solution and 10 ml of nitroethane. The mixture is shaken for
2 minutes and left to stand for half an hour. The aqueous phase is removed, and the or-
ganic phase is filtered and used for the determination of rubidium and caesium.
The reference solutions are prepared by extracting synthetic solutions containing the
major elements under the same conditions.
References: Uzumasa [98], Collins [17].
8.4.3.2 Barium, strontium
The barium content of water cannot generally be determined by flame photometry; it does
not give a detectable flame spectrum (measured at 455 or 828 nm) below a concentration
of 2 [log/mI. Strontium, which is often present in river water at a concentration of 0.2
[log/ml or more, can be determined.
Details of method
The sample is prepared as for the determination of the major elements (Na, K, Ca, Mg);
in particular, it is advisable to pass the water through an anionic ion-exchange resin and
to concentrate the filtrate a further 4 to 10 times.
The sample generally contains large amounts of calcium as well as the strontium;
this calcium can interfere with the determination. This is taken into account in the prepa-
ration of the reference solutions, which contain a representative concentration of calcium
(determined by separate measurements) and a strontium content increasing from 0 to
25 [log Sr/m!.
Photometry is carried out in an oxy-hydrogen flame at 460.7 nm (strontium line), the
hackground being measured at 455 nm.
Notes: The sensitivity of the method can be increased by adding n-butanol to the solution
obtained by ion exchange; 0.1 [log Sr/ml can be determined in this way (Jonsson [59]).
References: Podobnik et aI. [79], Uzumasa et aI. [99], Jonsson [59].
8.4.4 DETERMINATION OF THE TRACE ELEMENTS IRON, NICKEL, COBALT, COPPER, MANGANESE,
CHROMITUM,ALUNITNnJ:M
8.4.4.1 Iron, cobalt, nickel, copper
These elements are extracted as the ammonium pyrrolidine-dithiocarbamates in methyl

S.4] ANALYSIS OF WATER 471
isobutyl ketone. Carbonates should be removed first by treatment with hydrochloric acid.
Reagents
Ammonium acetate, pure
Hydrochloric acid
Ammonium pyrrolidine dithiocarbamate, 1 % in water
Sample preparation
Enough ammonium acetate is added to 250-500 mI of decarbonated water to give a final
concentration of 0.2 M, and the pH is adjusted to 4.8 with ammonia and hydrochloric acid.
Five mI of the dithiocarbamate solution is added, and the metals are extracted with two
lots of methyl isobutyl ketone, which are then combined and made up to 25 mi.
This solution is photometered in an oxy-hydrogen flame; the region of the flame about
30-40 mm above the burner should be used, as the lines are most intense here. The follow-
ing lines are measured, and the background subtracted: Table S.x1.
TABLE 8.xI
SPEcrRAL LINES AND BACKGROUND FOR Fe, Ni, Co, Cu, Mn
Spectral line Background

Element nm nm
Fe 372.0 370
Ni 352.4 353.4
Co 352.8 353.5
Cu 324.7 325.1
Mn 403.3 406
The detection limits in methyl isobutyl ketone (!Lg/ml) are:

Fe 0.06 Ni 0.02 Co 0.03 Cu 0.02.
The reference solutions are prepared from solutions of Fe, Ni, Co and Cu extracted
under the same conditions to give the following concentration ranges in methyl isobutyl
ketone: Table s.xn.
TABLE 8.Xn
CONCENTRATION RANGES OF REFERENCE SOLUTIONS OF Fe, Ni, Co, Cu
Fe 0.1 - 2 [.Lg/ml
Ni 0.05 - 1 [.Lg/ml
Co 0.05 - 1 [.Lg/ml
Cu 0.05 - 1 [.Lg/ml
8.4.4.2 Aluminium
The determination is carried out on the aluminium-cupferron complex in methyl isobutyl

ketone.
Reagents
As in Section 8.4.4.1, plus
Cupferron, 0.1 M in water
Sample preparation and determination
A water sample containing more than 10 fLg Al is mixed with enough ammonium acetate
to give a final concentration ofO.2M, and the pH is adjusted to 4.5; 5 ml of cupferron and
5 ml of methyl isobutyl ketone are now added, and after shaking, the organic phase is se-
parated and photometered in an oxy-acetylene flame at 484 nm. The background is
measured at 482 nm; all measurements are made 40mm above the burner. The detection
limit is 0.4 fLg/ml in the methyl isobutyl ketone.
The reference solutions are prepared by extracting aluminium solutions containing from
2 to 100 fLg Al under the same conditions as the unknowns.
8.4.4.3 Chromium
This element is determined as the oxychloride (HCr03CI) in methyl isobutyl ketone.

Reagents
Sulphuric acid
Ammonium persulphate
Silver nitrate, 0.1 N
Hydrochloric acid
Sample preparation
A water sample containing 5-10 fLg of Cr(III) is mixed with enough sulphuric acid to
give a concentration of 1 M, then with 2 g of ammonium persulphate and 1.5 ml of silver
nitrate. The mixture is boiled for 10 minutes and allowed to cool; hydrochloric acid is
then added to a final concentration of 1.5 M. The complex formed (HCr03Cl) is ex-
tracted by 10 ml of methyl isobutyl ketone. The organic phase is separated and photo-
metered immediately in an oxy-hydrogen flame at 425.4 nm, the background being mea-
sured at 426 nm. (The measurements have to be carried out without delay, as the organic
solution is unstable.) A series of reference solutions are prepared by extracting Cr (VI)
solutions in 1.5 M hydrochloric acid with methyl isobutyl ketone.
If the chromium in the water is already present as Cr(VI), it can be extracted directly
from 1.5 M hydrochloric acid.
8.4.4.4 Manganese
This element can be determined directly in the filtrate obtained from ion exchange. The
water sample is acidified to pH 2 and passed through the anionic resin DOWEX 2X8
8.5] ANALYSIS OF FERTILIZERS 473
(saturated with chloride ions before passage of the test solution) to remove the anions.
The filtrate is photometered in an oxy-hydrogen flame at 403.3 nm, the background being
measured at 406 nm.
The detection limit is O.OOS [Lg/ml. The reference solutions are made from complex
solutions containing the major elements in representative amounts as chlorides, and
manganese at concentrations ranging from O.OS to 1 [Lg/ml.
References: Podobnik, Dular & Korosin [80], Mitchell [72], Marsh [66], Pinta [76],
Schoffman [91], Scott & Mitchell [93].
8.5 Analysis of fertilizers
The main elements involved in fertilizer analysis are phosphorus, nitrogen, potassium and
calcium, with sodium, iron, manganese, zinc and some others being of subsidiary in-
terest.
Not many works have been published on the flame photometry of these elements in
fertilizers, except for potassium; the flame photometry of potassium in fertilizers has even
been the subject of some official publications. However, the methods described for soils
and plants can often be used for the analysis of fertilizers, once the sample has been
brought into solution.
8.S.1 POTASSIUM
This determination can be carried out either on the entire fertilizer after treatment with
sulphuriclperchloric acids, or on an extract obtained with an aqueous solution of am-
monium oxalate or carbonate.
The method described below involves extraction with ammonium carbonate and re-
moval of the anions by ion exchange.
Reagents
Ammonium carbonate, SO g in 1000 ml water
Methyl red, 0.2 % in alcohol
Nitric acid, 1/10
Ion-exchange resin, Amberlite IR-4B
Potassium nitrate, 1000 [Lg Klml
Sample preparation
A sample of fertilizer (1-2 g) is placed in a 2S0-ml flask with 100 ml of water and 20 ml
of ammonium carbonate, and boiled for S minutes. The mixture is then allowed to cool,
filtered and made up to 2S0 ml.
A 10-ml aliquot is placed in a 2S0-ml beaker with 1 drop of methyl red and neutralized
with 1110 nitric acid; the neutral solution is then passed through the ion-exchange column.
The ion-exchange column is prepared beforehand by passage of 5 %sodium hydroxide and
washing with water; it is packed in a 2S x2.S-cm glass tube, to a height of IS-20 cm.
The fertilizer solution is passed through this column at a rate of 2 drops per second, and
the filtrate is collected in a 2S0-ml graduated flask. The column is then washed with 100 ml
of water, which is collected in the same flask, and the solution is made up to 250 ml and
photometered.
The reference solutions are prepared from a stock solution of potassium nitrate diluted
to cover the range from 0 to 100 !log K/ml.
Spectrophotometry
Flame: air-propane
Prism spectrophotometer or filter photometer, with receiver sensitive at 766 DID.
Wavelength: 766 nm.
Range of K 2 0 concentrations in fertilizer covered; 5 %-50%.
Notes
a) Lithium may be used as an internal standard; it is introduced into the solution to be
photometered at a concentration of 50 !log Li/ml, and measured at 671 nm.
b) The sample size depends on the potassium content, and should be chosen so that
the solution photometered contains from 50 to 100 !log K/ml.
c) The ion exchange is not always necessary (Mevel et al. [70]).
d) The method can be automated (Gehrke et al. [42]).
e) The solution for photometry can be prepared in a more concentrated state, and the
measurement carried out on the K line at 404.4 nm (Blackwell et al. [9]).
References: Austin et al. [3], Blackwell et al. [9], Crooks [19], Gehrke et al. [42], Giel-
frich et al. [44], Martens [67], Mevel et al. [70].
8.5.2 DETERMINATION OF OTHER ELEMENTS
The method described above can also be used for Na, Ca and Mg.
The determination of sodium has been studied specially by Gersten [43], who proposed
a method which is completely analogous to that for potassium. The sample size depends
on the sodium content of the fertilizer. If the potassium content is high, potassium must
be included in the reference solutions as well as sodium.
The determination of calcium and magnesium has been studied by Bovay & Cossy [11].
The same authors [10] also proposed a method for the determination of boron by the
flame photometry of a fertilizer solution after ion exchange.
References:
Determination of sodium: Bovay & Cossy [11], Gersten [43].
Determination of calcium and magnesium: Bovay & Cossy [11].
Determination of boron: Bovay & Cossy [10].
Analysis of superphosphates: Dobreanu [31].
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49. GREWELING, T., Flame photometry of calcium in ash plant materials; resolution of anion inter-
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CHAPTER 9
THE APPLICATIONS OF FLAME PHOTOMETRY

IN BIOLOGY AND MEDICINE
R. Herrmann
Department of Medical Physics
University of Giessen
Giessen, West Germany
9.1 The history of the biological and medical applications of flame photometry
Quantitative flame photometry was first developed by Lundegardh [1] in 1928-30, in

conjunction with his plant-physiological investigations. He required rapid methods for
the determination of various elements, e.g., potassium, in order to investigate their ab-
sorption as plant nutrients from the soil. Lundegardh was also the first to apply his
quantitative methods to medical questions. The development of the first commercial
flame photometer by Zeiss (Waibel [2]) was stimulated by the demands of agricultural
biology. The early development of flame-photometric methods in the USA by Barnes [3]
was due to the requirements of military medicine in the last World War, when it was found
necessary to determine rapidly the concentration of certain elements in the blood or
serum of wounded soldiers, so that threats to the life of the patients could be quickly diag-
nosed and adequately treated.
In the past 20 years, quantitative flame photometry has undergone an explosive ex-
pansion regarding both equipment and methods. While other fields of application have
been opened, the biological and medical applications still remain the most important.
The specific, rapid method of flame emission spectrophotometry is no longer the only
one which comes into consideration. Since 1955, the work of Alkemade [4] and Walsh [5]
has brought atomic absorption spectrophotometry to prominence, and from 1964 atomic
fluorescence spectrophotometry has been pioneered by Winefordner [6]. Since the appli-
cations of atomic absorption and atomic fluorescence methods in biology and medicine will
be described in a separate chapter, we will be concerned mainly with the use of flame
emission spectrophotometry (henceforth simply called flame photometry) in biology and
medicine. However, we will devote the next section to a discussion of the relative merits
of the emission and absorption methods.
9.2 Emission or absorption methods in flame photometry?
Each method has its advantages and disadvantages, depending on the analytical problem
to be solved in the particular medical or biological application, and the choice between
the two must be made on the facts of each individual case [7-9]. The choice of a method
480 FLAME PHOTOMETRY IN BIOLOGY AND MEDICINE [9
in its turn affects the equipment to be purchased; this will be discussed in more detail be-
low. We will now discuss the various considerations which determine this choice.
9.2.1 DETECTION LIMIT
When the analyses are carried out near the detection limit of the method, e.g., for the in-
vestigation of trace elements, it may be necessary to choose the method with the lower
detection limit. For example, flame emission photometry has a lower detection limit for
sodium than the atomic absorption methods, while for zinc analyses, the absorption
methods give the lower detection limit.
9.2.2 PRECISION
When the measurements have to be made within a narrow range of naturally occurring
values (e.g., 144.7 ± 10 mEqjl for serum sodium analyses), the precision of the method
(and the instrument; see below) plays an important role. According to the College of
Clinical Pathologists, the precision should be sufficient to allow the distinction of at least
16 sub-ranges in the range contained within 2 standard deviations of the mean. In the
example given above, the standard deviation (10) is about 7 % of the mean (144.7). If the
measurement is to divide the 7 %on each side of the mean into 8 sub-ranges, the precision
will have to be appreciably better than 1 %. In this respect, emission photometry is better
than absorption photometry - as long as we only compare single-beam methods with
one another, and double-beam methods with one another. The lower precision of atomic
absorption methods with single-beam instruments is due to the fact that the variation in
the intensity of the primary radiation source is superimposed on the variation of the indi-
cated value. Double-beam methods are more precise, but here too emission photometry is
better than absorption photometry.
9.2.3 BIAS
The bias of a measurement is a measure of the systematic error involved. The systematic
error of a measurement is the difference between the mean value found and the correct
value; unfortunately, the systematic error can in general be determined only with a certain
inaccuracy. For example, if the reference solution used for the calibration of a flame-
photometric method gives a reading different from the nominal value, all the results of
measurements will be in error by a constant amount, even though the reproducibility
(precision) of repeated measurements on the same biological solution may be excellent.
In fact, the user of routine analytical results, e.g., a medical doctor, may be unaware of,
or overlook, the systematic error, and thus regard the mean result as "correct." The
presence of a systematic error is not always a serious matter; as long as the systematic
error is constant, it does not prevent the detection of a pathological value (a value which is
greater than or less than the mean by two standard deviations). The systematic error in
general will only be important when results from different laboratories are compared with
one another, or when results from one laboratory are compared with tabulated standard
values. Atomic absorption methods are better than emission methods in this respect, be-
9.2] EMISSION OR ABSORPTION METHODS IN FLAME PHOTOMETRY 481
cause the systematic error caused by too great a difference between the reference solution
and the unknown, such as the omission of the protein from the reference solution for
measurements on sera, is lower than with emission methods. This is because the omission
of organic components in the reference solution can lead to variations in flame tempera-
ture [12]. While emission methods are very sensitive to these variations, atomic absorption
methods are unaffected by the flame temperature changes to a first approximation.
It should be noted, however, that differences between the reference solution and the un-
known also have a certain effect in atomic absorption methods since the flame temper-
ature does influence the evaporation and dissociation of the aerosol in the flame [10, 11].
9.2.4 SCANNING THE SPECTRAL RANGE
If the spectral range to be covered is scanned by a drive on the monochromator during the
evaporation of the solution in the flame, so that several elements can be determined one
after the other, the emission method offers better possibilities than the absorption method.
However, an instrument which measures at several wavelengths simultaneously is prefer-
able for biological and medical applications, as the amount of material required for ana-
lysis is less. This is true for both emission and absorption methods; in fact, the two
methods can be used simultaneously with an instrument of this type [13, 14].
9.2.5 CONCENTRATION RANGE COVERED
With the emission method, the only point which is fixed on the calibration curve is the
origin (and even this can be shifted under certain circumStances). The reading for any given
concentration (above the detection limit) can be adjusted to almost any desired value by
means of the sensitivity control. The concentration range covered can be varied over many
orders of magnitude in this way. It is more difficult to adjust the concentration range with
absorption methods (excepting the A10 method [15]), since both the 0 and the 100%
points on the scale are fixed. Here too, it is possible to vary the concentration range cover-
ed by several orders of magnitude by selecting a spectral line of lower absorption, but
this is a more complicated procedure. Of course, it would also be possible to choose a less
sensitive line with the emission method, but there is usually no need to do this. The above-
mentioned advantage of the emission method is not so apparent in biological and medical
applications, especially those involving a series of routine measurements on fairly uniform
samples, as the natural variation in the concentration of a given element from sample to
sample is generally small. There are, however, exceptions to this rule, such as in
toxicological investigations.
9.2.6 ELEMENTS WITH mGH DISSOCIATION ENERGIES
If the concentration of elements in compounds with a high dissociation energy is to be

determined, emission methods are preferable: the undissociated compounds often give
measurable emission bands, while the absorption of such bands is so weak that the ab-
sorption method gives very poor results [16].
9.2.7 SIMPLICITY OF TIlE REFERENCE SOLUTION
We have mentioned above that absorption methods give a more "unbiased" result with
comparable reference solutions and unknowns. Emission methods can only be brought
up to the same standard by increasing the outlay on the preparation of the reference solu-
tions. For example, it would greatly complicate the preparation of the reference solutions
if the protein content of part of the unknown sample had to be determined before the
flame photometry proper, so that the reference solution could be made up specially to con-
tain the same amount of protein. Moreover, proteins consist of different fractions with
different physical and chemical properties. These fractions can occur in different propor-
tions, thus altering the physical properties of the solution to be evaporated. The difficulty
of obtaining protein sufficiently free from electrolytes may also be mentioned. Apart from
the fact that the intensity of spectral emission lines increases exponentially with the tem-
perature, the background influence in emission spectra due to the presence of proteins
and similar components of biological mixtures is generally greater than that in absorption
methods. The reference solutions for absorption methods therefore can be simpler in com-
position than those for emission methods.
9.2.8 REQUIREMENTS TO BE MET BY TIlE MONOCHROMATOR
Since the effective spectral bandwidth of an absorption method as a whole is basically

fixed by the narrow width of the absorbing spectral lines in the flame and of the emission
lines in the primary radiation source, and not by the slit width of the monochromator, the
spectral half-width of the instrument or some similar factor, the monochromator or filter
in the absorption method can generally have a wider transmission band and hence be less
expensive than that for the emission method. This is important for the wider adoption of
the absorption method in biological and medical laboratories. In the absorption method,
the effect of closely neighbouring lines can be eliminated by a suitable combination of op-
tical and electrical measures, while in the emission method the only way this can be dealt
with is by increasing the optical resolution of the monochromator.
9.2.9 REQUIREMENTS TO BE MET BY TIlE OPERATING PERSONNEL
Since the energy which has to be supplied by the flame in the absorption method is the
dissociation and atomization energy, as compared with the excitation energy for the emis-
sion method, the flame temperature can often be lower in the former method. A cooler
flame is not as dangerous, and requires less supervision by the laboratory staff with
regard to the water cooling, compliance with safety regulations, etc. The absorption
method does not have this advantage in the case of easily oxidizable elements like AI, for
which N 2 0 flames have to be used in both absorption and emission methods; these flames
are more dangerous, and require more care [17-19].
The emission method has the advantage that the equipment is simpler (the hollow-
cathode discharge tube, the power supply unit and the associated measuring instruments
are not necessary), which means that measurements take less of the laboratory staff's
time.
9.3] THE CHOICE OF THE INSTRUMENT 483
9.3 The choice of the instrument
The rapid advances made in the field of instrument design and construction have been
described in another chapter. Therefore we will not go into this here but will merely dis-
cuss the factors which determine the choice between the various instruments available
for a given medical or biological application.
There are about 80 different flame photometers or spectrophotometers on the market
at present, which can be used either for the emission (E) method or for the absorption (A)
method - or sometimes for both; simultaneously or in succession. In principle, any good
instrument can be used to advantage for medical and biological investigations.
9.3.1 THE ELEMENTS TO BE DETERMINED
First of all, we must consider which elements have to be determined with the aid of the
instrument. In general, the more elements that have to be determined with the same in-
strument, the bigger and more expensive it will have to be. Since the operating costs
generally rise with the price of the instrument, many laboratories will find it advantageous
to buy two instruments, one for routine analyses and the other for the less frequently occur-
ring but more difficult cases. The first instrument, which is used for the determination of
the common element concentrations, e.g., Na, K and Ca, should be as simple as possible to
operate, so that it can be used by semi-skilled staff. Filter photometers are to be preferred
to monochromator instruments for this purpose. The instrument used for the more diffi-
cult analyses should be more sensitive, with lower detection limits for considerably more
elements; in general, this should be used only by skilled laboratory staff. For large-scale
clinical applications, it might be worthwhile installing an automatic analyser, which can
carry out determinations for a large number of elements at the same time without the aid
of an operator, no matter whether all these determinations are needed for each sample.
Such an instrument (e.g., the Jarrell-Ash 82-600) will only come into consideration where
several clinics or institutes share a central laboratory.
9.3.2 DETECTION LIMIT
The instrument chosen must be able to carry out the analyses in question down to the de-
sired detection limit. It should be remembered in this connection that in most analytical
methods it is found convenient to dilute the biological material by a factor of 10 or more
so that the surface tension and viscosity of the sample do not differ too much from those
of the aqueous reference solution. Furthermore it should be remembered that the detec-
tion limits quoted by the manufacturer generally apply to simple solutions, for example
aqueous solutions of one single salt. The presence of a large number of other substances,
as in biological materials, increases the detection limit; this is especially true of trace ana-
lyses by the E method.
9.3.3 AMOUNT OF SAMPLE REQUIRED
Many flame photometers or spectrophotometers require quite a large sample. This does
not matter for many industrial applications, but it definitely does matter for most medical
and biological investigations. For example, we cannot take large amounts of blood from a
patient for a trace analysis which requires preliminary chemical enrichment. If the detec-
tion limit for a given element is very low, then the sample can actually be diluted before
analysis; for example, samples in which Na is to be determined can often be diluted 500
times. In such cases, the size of the sample taken from the patient is not so critical. In
other words, the amount of sample required is a function of the concentration of the ele-
ment to be determined and its detection limit. We will be discussing micro-methods, which
only require very small amounts of material, in more detail below.
9.3.4 PRECISION
We have already discussed the general significance of the reproducibility of methods for
biological investigations. As far as the choice of instrument is concerned, we should re-
member that the reproducibility quoted by the manufacturer (like the detection limit men-
tioned above) is generally for simple aqueous solutions of salts. When the sample contains
appreciable amounts of organic components, in particular fibrin, proteins and the like,
the reproducibility may be poor, due to frequent clogging of the sprayer, encrustation of
the burner, etc. Before buying an instrument, it is therefore desirable to get each of the in-
struments considered for purchase on trial for a brief period, so that the reproducibility
can be checked by recognized statistical methods with the material which is actually to be
analysed.
9.3.5 BIAS
We have already discussed the bias of a determination in our general remarks. As far as
the choice of an instrument is concerned, it should be noted that the construction of the
instrument can have a considerable influence on the magnitude of the systematic errors
to be expected and hence on the correctness of the results obtained. For example, emission
flame photometers with medium-high flame temperatures (about 2500 °e,produced by an
air-acetylene flame) and a direct sprayer are quite sensitive to the presence of phosphorus,
aluminium, etc. when used for the determination of alkaline-earth metals [20, 21], while
errors due to this cause are often negligible in instruments equipped with indirect spraying
and provided with spraying vessels which prevent large drops from getting into the flame.
The behaviour of the instrument in this respect will have a considerable influence on the
method of analysis to be used and in particular on the sample preparation. In other words,
the sample preparation which precedes each analysis can often be appreciably simplified
if the right instrument for the analysis is chosen in the first place. Similar remarks
may be made in connection with ionization errors; for example, if the instrument chosen
can only be used with high-temperature flames such as oxy-acetylene and N 2 0-acetylene,
then ionization errors will always give trouble in the determination of easily ionizable ele-
ments such as sodium and potassium. It is true that these difficulties can be largely elimi-
nated by suitable sample preparation, such as the addition of caesium compounds to the
unknown, blank and reference solutions [22, 23]; however this method is more compli-
cated and may introduce impurities which can interfere with trace analyses. Instruments
9.3] THE CHOICE OF THE INSTRUMENT 485
which can be used with low-temperature flames such as propane-air are therefore re-
commended for alkali metal analyses, as they give negligible ionization errors.
9.3.6 CLOGGING AND ENCRUSTATION
The sample preparation should preferably be as simple as possible; ideally, the sample
should be introduced into the flame photometer as it is or, if necessary, after dilution.
Methods which involve a complicated chemical preparation of the sample are less likely
to form the basis of routine analyses. However, if samples of biological materials are
sprayed as they are, or after only a slight dilution, the sprayer capillary can easily become
clogged by gradual deposition of e.g., serum fibrin on its wall, or the burner nozzle can
become encrusted with e.g., coagulated protein. The instrument chosen for medical and
biological investigation should therefore have a sprayer and burner constructed in such
a way that this trouble either does not arise or is signalled and consequently corrected
when it does arise. For example, when an internal standard is used, the instrument can be
provided with a device which gives an acoustic or optical signal when the intensity of the
reference spectral line falls below a certain level. It may be mentioned in this connection
that in direct sprayer-burner combinations, the gas and air inlets can be interchanged. This
can be used to avoid encrustation of the burner nozzle [24, 25]. No matter what type of
instrument is chosen for medical or biological investigations, it should preferably have a
straight sprayer capillary, with a polished inner wall. Such capillaries have less tendency to
clog and generally can be cleaned easily with a wire. This consideration is of special impor-
tance with automatic instruments, which are required to operate for long periods of time
without supervision.
9.3.7 OPERATING COSTS AND AUTOMATION
Instruments chosen to be used for hundreds of routine analyses for the same elements
should require as little work as possible from the laboratory staff. Semi-automatic or auto-
matic instruments offer great advantages in this connection, and can reduce labour costs
considerably. If the number of laboratory staff is kept constant, the introduction of auto-
mation can mean a widening of the analytical program, with consequent advantages for
the patients or for the research being carried out.
It is also important that the results of the analysis should be available as soon as possible.
While this is particularly important with out-patients, where the physician would like to
have the results before the examination is finished, there are cases with in-patients, e.g.,
dangerous hypocalcemias, where the provision of an analytical result within a few minutes
could help to save the patient's life.
Hence, it is advantageous to choose an instrument which has automatic sample input
and perhaps even automatic sample preparation. Automatic display of the results, prefer-
ably directly to the user, is also desirable. Among other things, this will allow reliable ana-
lytical results to be obtained even when the laboratory is lightly staffed or empty (e.g., at
night or on sundays).
When such semi-automatic or fully automatic instruments are used, great care should
be taken to check that the calibration curve is either linear or of constant curvature, since
only under these conditions can the associated analog or digital computer unit calculate
the results correctly from the measured intensities. It is also important that the instrument
be stable over long periods of time; instruments which work with internal standards are
to be preferred in this respect.
In conclusion, the proper choice of a flame photometer for routine analyses can save a
lot of time in sample preparation and in the evaluation of the results.
9.4 Properties of the starting material in medical and biological investigations
9.4.1 STATE OF AGGREGATION
The substances involved in a medical or biological investigation may be solid (bone,

teeth, wood, etc.), liquid (urine, serum, lymph, sputum, etc.) or even gaseous (dissolved
CO 2 , CO, O 2 , etc.). We may also have substances which occupy an intermediate position
between two of these groups (muscle tissue, faeces, etc.). We will assume from now on
that all samples should be prepared in liquid form for introduction into the flame. It may
be remarked in passing, however, that methods have been developed for the flame photo-
metry of powders [26,27], while gases can also be introduced into a flame.
9.4.2 CHEMICAL COMPOSmON
Unlike many applications of flame photometry in the chemical industry, geology, the
ceramic industry, etc., in biology and medicine we are dealing mainly with organic sub-
stances; although inorganic substances, e.g., electrolytes such as NaCl, play an important
role too. The presence of these organic substances makes the sample preparation more
difficult. It should also be realized that although certain elements often occur in relatively
high concentrations in biological materials, e.g., Na in serum and Ca in bone, many other
elements cannot be detected at all in biological materials (apart from cases of poisoning),
even by the most sensitive trace-element detection methods available today; these ele-
ments include the rare earths, the actinides, the rare gases, B, Ga, Ge, Au, In, Ir, as, Pt,
Rh, Ru, Te, Si, W, Zr, and others. The elements which can be detected by flame photo-
metry occur in widely differing concentrations in different media. It may very well happen
that elements (e.g., zinc) which are present as trace elements in one organ are present at
concentrations higher by one or more powers often in other organs (e.g., the prostate) [28,
28a]. This remark has an important bearing on the method of sampling used; great care
must be taken that the sample taken is really representative of the material to be analysed,
and does not include enough of the surrounding tissue to falsify the results. The following
table (Table 9.1) gives a survey of the elements which so far have been determined in bio-
logical material by flame photometry, arranged according to the number of methods
published for each element. The number of published methods may be taken as a measure
at the same time of the importance of the element and of the difficulty of its determination.
The elements are listed separately for the emission and absorption methods. A cross ( +)
in front of an element means that an excitation source of relatively high temperature, e.g.,
a plasma-arc burner, was used. An asterisk (*) after an element means that the analytical
method was indirect, e.g., the determination of chloride by means of silver determination.
It may be seen from this table that emission methods have been used mainly to deter-
9.4] PROPERTIES OF THE STARTING MATERIAL 487
mine the elements potassium, sodium and calcium, while absorption methods have been
used mainly with magnesium, zinc and cadmium. Of the less frequently investigated ele-
ments, some (e.g., lithium) have been mainly investigated by emission methods, and some
(e.g., mercury) by absorption methods. The choice between the emission and absorption
methods must therefore be made for each case depending on the concentration of the
element to be determined.
TABLE 9.1.
ELEMENTS WHICH HAVE BEEN DETERMINED IN BIOLOGICAL MATERIAL BY
THE EMISSION METHOD AND THE ABSORPTION METHOD, ACCORDING TO THE
NUMBER OF PUBLICATIONS.
Emission method Absorption method

Element Element
No. of publications No. of publications
K 138 Mg 39
Na 135 Zn 34
Ca 63 Ca 28
Mg 27 Cu 21
Sr 8 Fe 17
Cu 7 K 13
Li 4 Pb 13
+Be 3 Ni 12
Fe 3 Na 11
Pb 2 Cr 9
Rb 2 Hg 4
S04* 2 Sr 4
Al 1 Bi 3
Cl* 1 P* 2
Cr 1 Li I
Cs 1 Se 1
+P 1 Sn 1
+Si 1 Te I
Zn I Ti 1
V 1
* Determined by indirect method

+ Solution atomized in plasma-arc burner
In general, flame photometry only gives the over-all concentration of the element in
question in the material investigated. For example, the flame-photometric determination
of magnesium in a sample will give the total magnesium concentration, no matter whether
the magnesium is present as the chloride, the carbonate, or in an organic complex. How-
ever, it is sometimes possible to separate the various compounds involved by suitable
chemical treatment before photometry, and then to measure each compound separately.
Naturally, this gives more information about the chemical composition of the material
under investigation.
9.4.3 SURFACE TENSION
The solution to be analysed is generally introduced into the flame with the aid of a sprayer;
the fine drops which this produces are carried to the flame in the stream of compressed
air or oxygen, or in certain exceptional cases in the gas stream. The rate of evapora-
tion of the sample has an appreciable effect on the observed intensity of the absorption or
emission line. Small drops evaporate faster than big drops; in indirect sprayers, most of the
big drops are separated in the sprayer chamber, and never get to the flame [10,21,29,30].
If the flame-photometeric determination is to be correct, i.e., without systematic error, it is
very important that the droplets of the reference or blank solution should have the same
properties as those of the unknown, induding the same size distribution. Under given
experimental conditions (same sprayer, same gas, same gas flow rate, same temperature
conditions, same pressure differences, etc.) the droplet size distribution depends strongly
on the surface tension of the solution. Unfortunately, organic solutions do not have
the same surface tensions; moreover, solutions of the same type can differ considerab-
ly in surface tension; with sera, for example, this may be due to differences in the bili-
rubin or bile acid content. These oifferences in surface tension lead to differences in size
distribution of the sprayed solution, and hence to differences in evaporation rate; and the
differences in evaporation rate will lead to errors in the result when the unknown is com-
pared with the reference solution, of constant surface tension. The following methods
may be used to remove this property of biological solutions:
a) The starting material is calcined, thus destroying the substances which cause the var-
iation in surface tension.
b) The sample is diluted until the difference in surface tension is negligible.
c) An excess of surface-active substances is added to the unknown, the blank and the re-
ference solution, so that the surface tension is constant and no longer depends on the
original content of organic substances. We will return to this method in our descrip-
tion of the sample preparation.
d) An internal standard is used.
9.4.4 VISCOSITY
The biological starting material is often more or less viscous. This can lead to systematic
errors when the test solution, sprayed without much dilution, is compared with an aqueous
reference solution. The magnitude of this possible error is generally over-estimated in
practice; apart from reducing the rate of flow of liquid to the sprayer jet, the viscosity
also has other effects which act in just the opposite direction [10, 21, 31].
In a pneumatic sprayer, the amount of energy supplied by the air or oxygen current to
the liquid emerging from the sprayer jet is independent of the amount of liquid in question.
If a more viscous liquid is sprayed, less liquid will emerge from the capillary per unit time;
this liquid will therefore receive more dispersion energy per unit volume, and will thus
be more finely divided. As a result of the improved droplet size distribution, the liquid will
evaporate faster, thus raising the intensity of the emission or absorption line produced.
This partly, but not entirely, compensates for the drop in intensity due to the increased
viscosity. The following methods may be used for further compensation of the viscosity
effect:
a) Calcination.
b) Further dilution.
c) Addition of viscous substances such as glycerol to the unknown, blank and reference
solutions, to raise the viscosity to a high but fairly constant level.
9.5] SAMPLE PREPARATION AND EXECUTION OF THE METHOD 489
d) Use of an internal standard.
9.4.5 INTERFERENCE DUE TO CHEMICAL REACTION WITH OTHER SUBSTANCES
Any chemical analysis can be interfered with by the presence of elements other than the
one under investigation; flame photometry is no exception to this rule, although the dis-
turbing elements and the disturbing reactions may differ from those found in other cases.
We have just discussed the effect of differences in surface tension and viscosity on the re-
sults; here we will consider the effect of chemical reactions with other substances on e.g.,
the rate of evaporation in the flame. Alkemade [32, 33] and Schuhknecht [34] have shown
that phosphorus or aluminium can react with alkaline-earth metals in the flame to form
relatively stable compounds, which cannot easily be evaporated in the usual flames. For
example, phosphorus or phosphorus compounds which are present during the flame photo-
metry of calcium can bind some of the calcium; this bound calcium will not be determin-
ed, since the method is sensitive only to atomic calcium. We will be returning to this
possible source of error and its correction below; here we will only mention that the main
elements which cause errors in this way in the flame photometry of biological materials
are phosphorus, aluminium, titanium and sulphur [29, 37-81].
9.4.6 INTERFERENCE DUE TO PHYSICAL REACTION WITH OTHER SUBSTANCES
The main effects of this type found during the flame photometry of biological material
are the influence of Na on the determination of K and vice versa. The mechanism of this
effect is the same as in other flame-photometric analyses, and has already been investigat-
ed by a number of authors [9,21,35, 36]; therefore, we will not go into this any further
here, but merely will point out the various ways in which this effect can be avoided.
a) Use of flames of low temperature, i.e., low ionization energy, such as air/propane
flames.
b) Addition of an excess of electron donors, e.g., caesium saits, so that the electron con-
centration in the flame depends on the added caesium content, and not on how much
Na or K happens to be present. This method can also be used for the other easily
ionizable elements; details will be given under the individual elements.
9.5 Sample preparation and execution of the method
9.5.1 INTRODUCTION
Instructions for use, including instructions for analyses of biological and medical im-
portance (e.g., serum sodium, potassium and calcium) accompany many commercial in-
struments. These instructions are worked out specifically for the instrument in question,
and are to be recommended - as long as the manufacturer's development staff has not
overlooked any point of importance. It should be stressed, however, that such instruc-
tions, which apply to a definite instrument, a definite material under investigation and a
definite method (emission or absorption), cannot in general be applied to another instru-
ment, material or method. With certain limitations, the same may be said of the treat-
ment given to the starting material before analysis.
In other cases, recourse may be made to the literature, as long as the published method
refers to the same starting material and the same instrument. Even here, however, it
should be borne in mind that differences can exist between different instruments of the
same type. We refer the reader to the papers cited below and at the end of the chapter
[7, 82-86]. Apart from the fact that a method designed for one instrument cannot be
relied upon to work with another instrument, we would like to stress once more that
instructions relating to a particular analytical task and a particular test solution (prepar-
ed in a standard manner from a sample taken in a standard manner) need not be applica-
ble to a similar substance of different composition, even though the instrument used is the
same in both cases. This is due to the above-mentioned differences in viscosity and sur-
face tension, in the concentration of the element to be determined and of other elements
which might interfere with the determination.
When relevant instructions are not delivered with the instrument, and analysis of the
material in question is not dealt with in the literature - or when one is working with an
instrument of one's own construction - the guidelines given below should suffice for the
elaboration of an appropriate method.
9.5.2 CHOICE OF THE SPECTRAL LINE
The following points should be considered when choosing the most suitable spectral line:
1. The useful spectral sensitivity range of the instrument, which is largely determined by
the optics and the nature of the radiation receiver.
2. The concentration to be determined. If the element in question is present at a high con-
centration (as may be the case with sodium), and if one does not use a higher dilution,
it may be advisable to change to a less sensitive spectral line. This avoids working in the
range where the calibration line is curved, due to self-absorption of the over-sensitive
resonance lines at high concentrations.
3. The nature of the method chosen, emission or absorption. There are fewer lines to choose
from in an absorption method, as only resonance lines show adequate absorption. In
emission methods, any other lines may be used, especially when higher concentrations are
involved. Details of the wavelength and sensitivity of many lines are given in the litera-
ture [3,21,87-93]. It may be mentioned in this connection that in emission methods, band
intensities as well as line intensities can be used as a measure of the concentration in ques-
tion. For example, the calcium bands at 622 nm and 554 nm can be used for this purpose.
Band intensities cannot be used for the analysis of biological material by the absorption
method, as they do not give enough sensitivity.
4. The flame used. The choice of the spectral line is influenced by the choice of flame,
because when low-temperature flames are used in the emission method, the lines available
for analysis are mainly in the long-wavelength region. Short-wave lines require higher
excitation energies, which are not provided to a sufficient extent by low-temperature fla-
mes. No excitation energy is required in the atomic absorption method, so that this method
can be used in the short-wave UV with low-temperature flames as well as under other
conditions.
9.5.3 SAMPLE PREPARATION
9.5.3.1 Taking and preserving the sample
The proper taking of the sample and its preservation until it is required for analysis are
of critical importance for the quality of the final analytical results. Unfortunately, the
need for care at this stage is often overlooked, and poor analytical results (e.g., low
reproducibility) are often due to the use of inadequate sampling methods; not knowing the
cause of these poor results, the user may imagine that it is the photometric method (emis-
sion or absorption) itself which is at fault.
It would take us too long to go into details about the precautions to be taken when
sampling all the different kinds of biological materials. We will merely discuss a couple
of examples here to illustrate the kind of problems involved. For further details, the reader
is referred to two textbooks [21, 86] where the method of sampling is described at length
for each individual case.
a) Inhomogeneity 0/ the starting material
Let us suppose that we have a big orchard of citrus fruit, and that we want to determine
the mean concentration of a given element in the juice of this fruit. While it is to be expect-
ed that the average concentration for one tree will differ to a greater or lesser extent from
that for another tree, differences in the composition or physical condition of the soil, in
the amount of fertilizer applied to various parts of the ground, in the amount of pesticide
applied to the various trees, etc., will influence the growth conditions of the trees in such a
way that we should not be surprised to find different concentrations of the element in
question in the fruit juice sampled in different parts of the orchard. In such cases, the
person who has commissioned the test should make up his mind, before sampling begins,
precisely what he wants. If he really is interested in the inhomogeneity, it will be necessary
to take samples from various well defined parts of the orchard, and to plot the analytical
results obtained on a plan of the orchard. If however all that is wanted is the mean value,
care must be taken to have samples collected at random from all over the field; these
samples can then be mixed to give one large common sample.
Similar problems are encountered in medical applications. If for example a sample of
blood serum is kept in the refrigerator for a long time (e.g., a day) after centrifugation
and removal of the blood clot, and small amounts of serum are pipetted off for determina-
tion of the serum calcium, then quite large differences may be found between the different
determinations for the same sample [94]. One of the reasons for this is that when serum
stands for a long time, the lipid-containing material tends to rise to the top. This ma-
terial contains relatively little calcium; moreover, the material at the surface of the serum
can react with the carbon dioxide of the air to form calcium carbonate, which is insoluble
and gradually settles out. In other words, when serum is allowed to stand for a long time
and consequently separates out, the upper layers will contain relatively little calcium, and
the lower layers much more. Mixing the serum before sampling does not help much. The
samples used in flame photometry are very small, e.g., 10 fll [95-98], and inhomogeneities
caused by micelle formation will not be adequately evened out by shaking. It is therefore
advisable to measure out the individual samples needed for flame photometry immediate-
ly after centrifugation, to store them separately, and to dilute them before analysis with a
weakly acid diluent 1, so as to dissolve the precipitated calcium carbonate and similar
compounds [21]. If for some reason it should not be possible to take the samples at once,
then fairly big samples should be taken, so that· the inhomogeneities are more or less
evened out.
1) E.g., Titrisol No. 9979, Merck AG, Darmstadt.

b) Variation o/the composition o/the starting material with time

An even greater problem in the sampling of materials for medical purposes is that the
very act of sampling can cause changes in the organism under investigation. Let us suppose,
for example, that we take a number of blood samples in succession from the same patient
in the following way: we insert a needle in a vein, and allow the blood to drip out slowly
into a number of test tubes. Each blood sample is centrifuged individually, and prepared
individually for flame photometry in the usual way. We would then expect all samples to
give the same serum potassium level, since they are all taken from the same person. How-
ever, investigation has shown this not to be the case [21,99]. While the first sample shows
a relatively high potassium content, the level found in subsequent samples falls until a
minimum is reached after about 2.2 minutes (see Fig. 9.1). After that the potassium con-
tent rises appreciably slower, and does not generally reach the starting value since the
needle clogs up. This sharp drop in potassium content just after veinpuncture is due to the
effect of the veinpuncture itself on the patient (fear of the prick, pain causes by the prick,
etc.).
,I
18.0
I,\
-
mg,/100cm
17. 5
t 17.0
~ . /r-.
\ r'\...
",.
E
.il l/
.§ 16.5 ./
If - ./
16.0
50 100 150 200 250 300 350 ~ 450 500 550 sec
t-
Fig. 9.1. The fall in the serum potassium content of a number of blood samples taken in succession
from the same patient. The experimental points represent the mean of six series of measurements
[99].
This effect can be eliminated by taking the blood samples in the same way, except that the
patient is under general anaesthesia [99]. If a local anaesthetic is used at the spot where the sample
is to be taken, a drop in the potassium level will again be observed, but it will be less pronounced.
It will be clear from the above discussion that the sampling method itself does have an effect on
the potassium level found. Furthermore, when the patient gets used to giving blood, and no
longer feels the pain of the prick so badly, it has been found that if samples are taken from the
same patient at intervals of 1-2 hours, the drop in the potassium content becomes smaller and
smaller [100].
It has further been found that the temperature of the room in which the blood sample
is taken has an appreciable influence on the serum electrolyte content [101]. The compo-
sition of the atmosphere in which the patient is situated, such as the ozone content, can
also have an effect on the concentration found [102].
To improve the reproducibility of the results in the above-mentioned example, it is
advisable to take all samples at the same time of day, with the same period of time between
the insertion of the needle and the collection of the last drop of blood, in a room of con-
stant temperature and an atmosphere of constant composition.

As implied above, the diurnal rhythm plays an important role in all medical investiga-
tions of this type. This means for example that the serum potassium level found for a
patient at 8 a.m. is not directly comparable with the level found for the same patient at
noon [103]. It is advisable to carry out such determinations at a time of day when the
diurnal variations are least, so that inevitable differences in sampling time will not have
too great an influence on the result. Fig. 9.2 shows one such diurnal variation, by way of
example.
Sodium
~ 110
g 100 j
..~
~ 90
Potassium
~ 120
g 110 J
.2
"0100
E
.g 90
.§
Calcium
1120
g
~ 100
110
J
e
r1::1 Chloride
11 14 17 20
100 +-___.-..11.........,1-...ill---=l:::::~-
23 5 ehour
~-::=::::!:=-:::..:L7"""
90
Fig. 9.2. The diurnal rhythm of the serum potassium level (after [103]).
9.5.3.2 Dilution
In certain cases, the sample can be used for analysis as it is taken; this may be the case
with urinalyses. In slightly more difficult cases, simple dilution of the sample will suffice
to prepare it for analysis. The dilution needed for serum sodium analyses is generally
between 1.:100 and 1 :1000, and for serum calcium or potassium generally between 1:10
and 1 :50. In still more difficult cases, dilution with distilled water is not enough. If an
internal standard is to be used, then e.g., lithium (in the form of lithium chloride) can be
added in the diluent [104]. If interfering effects, such as that of phosphorus on calcium,
have to be eliminated, then lanthanum salts can be added in the diluent [105-107]. There
are, of course, other ways of eliminating such effects, e.g., by the "saturation method." If
a relatively high-temperature flame has to be used because elements with a high excitation
energy have to be determined by the emission method, the diluent often contains caesium
salts in addition to one or more ofthe above-mentioned salts; these caesium salts compen-
sate for the mutual effect of the alkali-metal ions on one another's ionization. In other
applications of flame photometry, organic solvents are often used to improve the eva-
poration of the liquid sample and thus increase the intensity of the emission or absorption
line. This cannot be done directly with most biological samples, as the addition of such an
organic solvent will either precipitate protein and some of the metal under investigation
may be co-precipitated with it [108], or it will cause a gelatinous mass to be produced which
is not easily sprayed [109]. These difficulties can be obviated by deproteinization or by cal-
cination, which will be discussed in further detail below. Once this has been done, there
is no objection in principle to the use of an organic solvent. If an organic solvent is used,
the extraction method and the organic solvent should be chosen to give the best results
with the flame-photometric method used. The organic solvent should fulfill the following
conditions:
a) It should be polar, so that the substance under investigation will be soluble enough
in it after e.g., calcination.
b) It should have a low vapour pressure at room temperature, so that the concentration
will not be increased artificially by undue evaporation of the solvent during the sample
preparation and atomization.
c) It should be fairly easy to get, not too expensive and of sufficiently high, constant qua-
lity.
Isobutyl ketones seem at the moment to meet all these requirements best.
9.5.3.3 Deproteinization
Many methods for the removal of protein from biological materials have been given in
the literature [37,47,57, 110-112]. Therefore we will not go into details about this here
but merely will mention a number of points which should be kept in mind when deproteini-
zation is to be used for flame photometry.
a) The deproteinizing agent should not introduce into the sample any of the elements
which are to be determined; for example, when sodium analyses are to be carried out, no
sodium tungstate should be added, and when chloride has to be determined no trichlor-
acetic acid should be used.
b) The deproteinizing agent should also be added to the blank and reference solutions,
so that any influence it may have on the analytical results due to evaporation effects, disso-
ciation effects, ionization effects, temperature effects, etc. will be the same for the un-
known and comparison solutions, and will thus cancel out.
c) In each individual case the possibility of the deproteinizing agent causing some of the
element under investigation to be co-precipitated must be checked. This co-precipitation
may be due to the fact that the element in question was adsorbed on, or in some way che-
mically bound to, the protein - or the element may just happen to be contained in part of
the solution which is trapped in the interstices of the precipitate. The best way of testing
for this phenomenon is to calcine the protein precipitate after centrifugation, redissolve
the ashes and test this solution for the element in question. If the amount of the element
co-precipitated is not too great, it may be possible to correct the analytical results for
the effect ofthe protein [108]. It should be realized however that both the amount and the
nature of the protein present can vary appreciably from sample to sample, and the correc-
tion should really vary accordingly. The correction itself thus represents the source of a
certain error in the analytical results. The magnitude of this possible error can be esti-
mated by statistical analysis of the results obtained with a large number of different sam-
ples.
9.5.3.4 Calcination
In general the sample to be analysed will only be calcined if no other method of treatment
is possible. It should be remembered that calcination involves quite a lot of work on the
part of the laboratory personnel, is relatively time-consuming, and always involves a cer-
tain risk due to the possible loss of the element to be determined, or contamination from
the reagents or vessels used.
Three different calcination procedures can be distinguished:
a) Wet calcination. The sample is heated in a Kjeldahl flask after wetting with nitric or
sulphuric acid or a mixture of the two, possibly with the addition of perchlorates or per-
chloric acid. Details ofthis method are given in the literature [50, 113-117]. The advanta-
ges of the method are that no special equipment is required, and that it is faster than either
of the other two methods described below. The disadvantages are the risk of contamina-
tion by the acids added (since the acids are added bit by bit, as needed to keep the sample
moist, it is difficult to tell in advance how much acid is needed, and thus difficult to correct
for this effect by adding corresponding amounts of acid to the blank and reference solu-
tions); the risk that material will be lost by sputtering; the risk that part of the sample,
e.g., that around the neck of the flask, will not be redissolved after calcination; and the risk
that the whole sample will be lost if the flask is broken by over-heating [156].
b) Dry calcination. This is carried out in a muffle furnace in a suitable container, e.g., a
platinum boat [47,48,52,55,56,82,113, 115, 118, 119]. The risk of contamination is less,
since no acid is used, but there is still the risk that substances evaporated from the wall of
the furnace will condense on the cooler platinum boat. A further advantage is that there is
no need to stand over the sample, as in the previous method, and add acid from time to
time; if need be, the sample can be left unattended to calcine overnight.
The main disadvantage is that relatively volatile elements, such as mercury, cadmium,
gallium, tin, arsenic, etc., can evaporate as a result of the strong heating; and if the
temperature is lowered to reduce this risk, the calcination takes an excessively long time.
The calcination temperature is generally chosen between 550 and 650°C, and the calci-
nation time between 10 and 24 hours. This method is recommended for the following ele-
ments: [48] AI, Au, B, Be, Ca, Co, Cu, Fe, Mn, Ni and Sr.
High-temperature dry calcination is not advisable with the following elements:
Hg, As, Cd, Cs, Ga, In, K, Li, Mg, Na, P, Pb, Rb, S, Se, Sn, Zn.
c) Cold calcination at reduced pressure and temperature, in a stream of atomic oxygen.
Most of the disadvantages mentioned above are avoided with this method [120]. For
this purpose, the sample is placed in a partially evacuated vessel, and while pumping is
going on, a slight current of oxygen is allowed to enter the vessel. Before reaching the
sample this oxygen passes through a high-frequency discharge which converts molecular
oxygen to atomic oxygen, and this atomic oxygen is responsible for the calcination of the
sample.
The method has the advantage of negligible evaporation losses, as it can be carried out
at temperatures between 100 and 160°C. Since no chemicals are added, there is no danger
of contamination. The process is largely automatic and does not require supervision.
The disadvantages are that the equipment needed is expensive, and requires highly
skilled staff for its operation, and that the calcination time is relatively long.
9.5.3.5 Extraction
a) Physical separation. The liquid part of leaf material, fruit, or human or animal tissue
can be physically separated from the solid part, e.g. by cutting the material into small
pieces and then squeezing or centrifuging it. After this liquid has been purified by further
centrifugation or filtration through an ash-free filter, it can be used for flame photometry
as it is or after dilution. Centrifugation is to be preferred to filtration, as the filter paper can
easily introduce impurities into the material to be analysed.
It should be clearly realized that such physical extraction methods really only give cell
fluid; nothing is taken from the connective tissue. Depending on the problem, this may
be what is wanted or not.
b) Chemical extraction. In chemical extraction methods, the metal under investigation is
generally complexed by the addition of a complexing agent such as dithizone, diethyl-
dithiocarbaminate, 8-hydroxy-quinoline, etc., and this complex is then extracted by
shaking with a suitable organic solvent. A large amount of literature on such techniques
exists [50, 121-127, 160].
It should be remembered, however, that such extraction methods in general cannot be
applied to biological material. As we have seen above, shaking a biological sample with
an organic solvent generally leads to precipitation of protein, and some of the element to
be analysed will often be carried down with the precipitate as a result either of adsorption
or of occlusion. Such extractions are therefore generally preceded by deproteinization or
calcination of the material as discussed above.
When an extraction method is used for the purposes of flame photoreetry, the organic
solvent chosen must be suitable. Extraction methods using e.g., carbon tetrachloride
(CCI 4 ) are not very suitable for use with flame photometry; when this solvent is burnt in
the flame, toxic or bad-smelling gases are produced. Moreover, the chlorine compounds
produced by the combustion can corrode metal objects in the laboratory including the
electronics of the photometer. Although the latter difficulty can be largely avoided by the
use of an efficient fume cupboard or hood to extract the fumes, little can be done about
the corrosion of the burner. It might be possible to use a special glass or quartz burner or
to coat the surface of the burner with a layer of silicone lacquer or heat-resistant plastic,
but the best thing to do is not to use a solvent with such unfortunate properties. Isobutyl
ketone is likely to be satisfactory. If absolutely necessary, a two-stage extraction can be
carried out. The complex is first extracted with e.g., carbon tetrachloride, the extract is
evaporated to dryness and the residue on the walls of the flask is redissolved in a suitable
solvent for flame photometry, e.g., isobutyl ketone. It is, of course, preferable simply to
extract the complex with e.g., isobutyl ketone in the first place.
Two papers give particularly useful details of such extraction methods for the flame pho-
tometry of biological materials [50, 127]. The first paper is especially interesting, as it
describes the use of pre-formed flocks to improve the efficiency of precipitation of trace
elements. It is possible to determine 0.005 ILg of Cs in 8 litres of water in this way; this
corresponds to a detection limit of 6 x 10- 6 ILg Cs/ml.
In conclusion, a chemical extraction is required to be selective, i.e., it should extract the
desired element to the exclusion of all other elements. However, an extraction method for
the purposes of flame photometry need not be very selective, as flame photometry is itself
a highly selective method of analysis. Thus there is no reason why group extraction
should not be used [170]. The object of the extraction is simply to remove substances which
might interfere with the determination, to get rid of elements present in very high concen-
trations, and if necessary to enrich the solution with trace elements so that these can more
easily be determined by flame photometry. All that is really required of the extraction
method is that none of the element to be determined should be lost, and conversely that
this element should not be added in unknown amounts as a contamination of the reagents
used in the extraction.
9.5.3.6 Precipitation reactions
Precipitation reactions can be used in two different ways:

a) The element in question is separated from the other elements present, in particular from
those which might interfere with the determination, by means of a specific precipitation re-
action; the precipitate containing the element is then redissolved and analysed.
b) The other elements are precipitated, and the remaining solution is subjected to flame
photometry.
The precipitation of Ca and Mg by oxine (8-hydroxyquinoline), followed by flame pho-
tometry of the redissolved precipitate for these elements, has been well worked out
[37, 52, 114, 128-131]. The use of other precipitation reactions in medical investigation
has also been reported [37,55,57,153,170].
Precipitation reactions are also involved, in a slightly different way, in indirect determi-
nations, e.g., the determination of chloride by silver precipitation. We will be returning
to this below.
9.5.3.7 Ion exchange
Ion exchange may be used in two different ways for flame photometry.
a) Elements which might interfere with the determination are replaced by elements which
do not interfere by passage through an ion-exchange column [53].
b) An ion-exchange column can be used for the enrichment of certain elements which
could not otherwise be detected [132].
9.5.4 THE SPECTRAL LINES OR BANDS USED FOR THE ANALYSIS OF PARTICULAR ELEMENTS
General considerations concerning the choice of the spectral line were given in Section
9.5.2. The recommended spectral lines are listed in Table 9.II, in the order of the frequen-
cy with which they are used in medical and biological investigations.
We will now discuss each of these elements in the same order as in Table 9.II.
TABLE 9.11.
RECOMMENDED SPECTRAL LINES FOR MEDICAL AND BIOLOGICAL INVESTI-
GATIONS USING THE EMISSION METHOD 1 •
Element Recommended spectral line (nm) References
K 766.49 + 796.90 or 404.41 + 404.72 Many references

Na 589.00 + 589.59 or 330.23 + 330.30 Many references
Ca I 422.67, 622b 2 , 554b 55, 152, 153, 168, 169
Mg 285.21, 381-383, 4b 14, 37, 39, 51, 56, 82, Ill,
140, 151, 156
Sr 460.73 52, 55, 132, 152, 157
Cu I 324.75; 327.40 I 50,58
Li 670.78 158, 159
Be Plasma burner, 313.0 166
Fe 238.20; 237.36 I 160
Pb Glow discharge, 363.96 169
Rb 780.02; 794.76 161
S04 Indirect with Ba 171
CI Indirect with Ag, 338.29 I 162, 163
Cr I 427.48 168
Cs 852.11 127, 164
N Indirect with Cu, 324.75 167
P Plasma burner, 213.6 165
Si Plasma burner, 251.6 172
Zn Glow discharge, 213.86 155
1) The elements are given in the order of the frequency with which they are determined by flame
photometry in the laboratory, as given in Section 9.4.2, Table 9.1.
2) "b" signifies bands
9.5.4.1 Potassium
The most widely used spectral lines are those at 766.5 and 769.9 nm. Most instruments do
not separate these two lines. Interference with this doublet from the background or from
the superimposition of other bands seldom occurs. With instruments of low resolving pow-
er, interference may sometimes be caused by the rubidium line. In such cases, measure-
ments can be made at 404.5 nm; however, it should be remembered that the K line at this
wavelength is more than 100 times less sensitive. Potassium, like other alkali metals, does
not give bands in flames.
9.5.4.2 Sodium
The most widely used sodium line is the doublet at 589.2 nm. At relatively low sodium
concentrations and relatively high calcium concentrations, the neighbouring Ca band
system can interfere with the determination. This can be dealt with by:
a) using an instrument of higher resolving power;
b) suppressing the Ca bands by the addition of phosphates or aluminium salts (e.g., alu-
minium nitrate [113]).
The reverse situation, with high sodium concentrations and low concentrations of the
other elements to be determined, can also arise. The difficulty here is that at high
concentrations the sodium resonance line can give self-absorption and self-reversal lead-
ing to a curvature of the calibration line. This problem can be solved in two different
ways.
a) A higher dilution is used for the sodium analyses, so that these are carried out in the
linear part of the calibration curve. The other elements are estimated at a lower dilution.
b) If it is undesirable to use two sets of solutions, then under certain circumstances it is
possible to use another sodium line which does not give curvature of the calibration line,
namely the line at 330.3 nm. Use of this line for medical investigation has already been
reported [134].
The determination of sodium - and also of potassium - should preferably be carried
out with low-temperature flames to avoid ionization effects.
9.5.4.3 Calcium
Unlike the two above-mentioned elements, calcium should be determined in relatively

high-temperature flames, to minimize interference from phosphorus, aluminium, iron and
similar elements. There are two Ca band systems which can be used for analysis, at 554
and 622 nm, and also a Ca line at 422.67 nm. Phosphorus and aluminium can influence
the intensity of the Ca bands as well as that of the line; thus there is nothing to choose be-
tween the line and the bands in this respect. The line is to be preferred at extremely high
temperatures when a spectrophotometer of high resolving power is used; at such high
temperatures, the bands are hardly measurable, while the instrument with its high resolv-
ing power can separate the line clearly from the bands. In all other cases, especially when
filter photometers are used, it is better to measure the Ca bands. At the present time more
and more use is being made of the band system at 622 nm, where interference from other
lines is less marked. It appears worth mentioning that high, variable sodium concentra-
tions can give rise to error in the determination of Ca; this can easily be seen by measur-
ing the intensity of the Ca band at 622 nm for a series of solutions of constant Ca content
but different Na contents. This effect may have two causes:
a) The spectrophotometer transmits part of the light from the sodium line. The solution
here is to improve the resolving power. The simplest way of doing this is to insert a di-
dymium nitrate filter in the optical system; this suppresses the sodium line more than the
desired calcium band [135].
b) When sodium is present in flames in high concentrations, it gives rise to a genuine
continuum, which is ascribed to non-quantized recombination phenomena [136]; this is
difficult to eliminate. One conceivable way would be to remove all the sodium from the
sample before flame photometry, but this is very difficult and in many cases impossible to
do. Improving the resolving power does improve the calcium-bruid/sodium-continuum
ratio, but does not get rid of the error completely. In such cases, it is best to use a special
calibration method (e.g., the parameter method, described on pages 510,514) in which the
sodium content is determined each time a sample is analysed and is taken into account in
the calibration; another solution is to use the Ca line at 422.67 nm, where the Na conti-
nuum is weaker and can more easily be separated by optical means.
9.5.4.4 Magnesium
The magnesium line at 285.21 nm is generally used for Mg analyses. The Na doublet at
285.28 and 285.30 nm can interfere with the determination especially when the sodium is
present at an appreciably higher concentration than the magnesium. If the instrument has a
high resolving power, the Mg line can be separated from the Na doublet, but with an in-
strument of lower resolving power the Na line contributes to the background. If there is
reason to suspect that Na is contributing to the background - and this contribution is gen-
erally not very high, and practically constant - it can be allowed for by adding corres-
ponding amounts of sodium to the blank and reference solutions. Less commonly, use
may be made of the Mg bands at 370.2 and 381-383 nm. The Mg line also lies between
relatively strong OR bands, which provide another reason for the use of an instrument of
high resolving power [58, 114, 137-140], e.g., one with a double monochromator [137,
140].
The Mg band at 370.2 nm is not very suitable for analyses, as it is subject to interference
from other band systems in this region, such as those of iron [56,86,141]. It is advisable
to measure the background e.g., at 360 nm and to correct for this if the above-mentioned
band is used [141]. The Mg band at 383 nm has also been used for analyses [142, 143].
The Mg line at 285.21 nm has a high excitation energy - 4.4 eV - and it is therefore
advisable to use a high-temperature flame (e.g., oxy-acetylene) when the emission of this
line is used for analyses. The Mg line is particularly easy to measure in strongly reducing
flames, e.g., one with an excess of acetylene [51, 111]. Chemical interference from other
elements, such as phosphorus or aluminium, will be discussed separately below.
9.5.4.5 Strontium
The strontium line at 460.73 nm is the only one recommended for strontium analyses. A
fairly high-temperature flame is generally used to suppress interference from phosphorus.
The flame is sometimes surrounded by an oxygen mantle, which gives an even higher tem-
perature than burning in air [55, 152, 157]. Calcium is often used as a spectral buffer in
strontium analyses [42]. In this case, the instrument used should not have too Iowa re-
solving power, because of the Ca line at 423 mn.
Strontium is quite often used as a spectral buffer itself, to reduce interference with the
determination of the other alkaline-earth metals. Then, of course, the strontium is no
longer part of the sample for analysis, and the strontium lines are regarded as interferen-
ce.
9.5.4.6 Copper
Two copper lines, at 324.75 and 327.40 nm, are available for copper determinations. In
normal flames and constant concentrations, the line at 324.75 nm is about twice as strong
as the other. However, the OH-band background at 324.75 nm is appreciably stronger
than that at 327.4 nm - especially when the sample is further diluted to avoid interference
from proteins (see below).
9.5.4.7 Lithium
The only line recommended for lithium analyses is the lithium line at 670.78 nm [158, 159].
Interference may be caused by the neighbouring Ca bands, or by the background due to
Na or K recombination. Ionization effects can also interfere; for this reason, low-tempera-
ture flames with little intrinsic radiation are generally used. Since the chemical separation
oflithium from the other alkali metals gives difficulties, it is usually preferable to separate
the lithium line spectroscopically from its surroundings, e.g., by the baseline method [158].
This spectroscopic separation is much simpler if we are dealing not with physiological
serum lithium concentrations, but with the concentrations found in serum after lithium
therapy, which are about 20 times higher. The line can then quite easily be picked out by
means of filters. Since lithium therapy must be carried out within quite narrow limits, the
method should have a good reproducibility in this case.
In all cases, no matter for what the lithium analysis is used, OH-free flames (e.g., CO/air
flames) should be used, since lithium has a tendency to form LiOH in flames; this latter
compound does not give an emission spectrum.
9.5.4.8 Beryllium
The determination of Be in biological material by normal flame photometry is not to be

recommended, as the Be lines have a high excitation energy (3.95 eV and more), and this
element also has a tendency to form relatively stable oxides in flames. A plasma-arc
burner is to be preferred for this purpose. The plasma arc may be regarded as a stabilized
electrical arc discharge, in which the sample is sprayed into it in much the same way as
into a flame [166]. Suitable lines for the analysis are the Be lines at 234.86, 332.13 and
330.4 nm.
9.5.4.9 Iron
The detection limit for Fe in biological materials by direct flame photometry is generally
higher than the Fe concentration to be determined. Therefore it is usually necessary to
concentrate the sample [160]. The Fe lines at 302.06, 337.36, 338.20, 371.99, 373.71 and
374.7 nm may be used for the analysis.
9.5.4.10 Lead
With the exception of cases of lead poisoning, the lead concentration in biological material
is generally too low for determination by flame photometry, unless the sample can be very
considerably enriched beforehand. Yurek's method [169], which can deal with amounts of
lead down to about 10- 12 g, may be mentioned in this connection; however, this method
does not use a flame, but a helium glow discharge, for the excitation.
9.5.4.11 Rubidium
Rubidium is quite easy to determine by flame photometry with the Rb resonance line at
780.02 nm, which has the low excitation energy of 1.59 eV. The only source of interferen-
ce is likely to be the generally very strong K lines at 766.49 and 769.90 nm, which can only
be separated from the Rb line by an instrument of high resolving power. The chemical
similarity of these two elements makes it difficult to separate them by a chemical method.
Background due to Na or K recombination may also make itself felt. It is therefore ad-
visable to record the whole rubidium line profile, so that the background on either side of
the line can be determined and subtracted. It is advisable to use a flame with a low intrin-
sic background, e.g., air/hydrogen [161].
9.5.4.12 Sulphate
Sulphur (as S04 - -) does not give an emission spectrum in flames because of its high
excitation energy (more than 7.86 eV). However, sulphate contents of biological or me-
dical interest can quite easily be determined by flame photometry, by an indirect method
[171 J. For this purpose, a known excess of BaCh is pipetted into the solution to be in-
vestigated, precipitating the sulphate as BaS04. The remaining Ba, which is determined
by flame photometry of the BaOH band at 873 nm, is a measure ofthe sulphate concentra-
tion of the original solution. A wider range of sulphate concentrations can be covered if
two barium solutions of different concentrations are available. This method can be
used, for example, in the detection of renal insufficiency.
9.5.4.13 Chlorine
The excitation energy of chlorine is even higher than that of sulphur - namely, more
than 10.3 eV.1t is therefore quite out of the question to hope for atomic chlorine spectra in
flames. However, chloride contents can be determined by an indirect method, similar to
that described above for S04 - - [162,163]. A known excess of silver nitrate is pipetted in-
to the solution in question; this precipitates the chloride as silver chloride. The silver re-
maining, which can be determined by flame photometry of the Ag line at 338.29 nm, is a
measure of the chloride content of the original solution.
Covalently bound chlorine, involved in the detection of residues of insecticides such as
DDT in biological material, must be determined by a different method. The principle
suggested by Gilbert [174] has been used as the basis for a number of sensitive, specific
methods for the determination of organochlorine compounds [172, 173]. The organo-
chlorine compounds extracted from the sample are evaporated, and the vapour is allow-
ed to pass over a hot (200 0c) indium cylinder. Indium chloride (InCI) is formed under
these conditions; this gives characteristic InC! bands at 359.9 nm in an air/hydrogen flame.
9.5.4.14 Chromium
The detection limit for chromium in normal flames is so high that the Cr concentrations
found in biological material cannot be determined without very considerable preliminary
enrichment. However, it is sometimes necessary to determine Cr contents in biological
materials which lie appreciably above the physiological level. For instance, chromium
sesquioxide (CrZ03) is sometimes used in investigations of metabolism, as a nontoxic
salt which does not occur in the human body, it is given in constant concentration in
a meal. It is not absorbed by the alimentary canal, but passes through and is excreted.
The chromium level in the faeces thus acts as an indicator of the inevitable variations in
the rate of excretion [168]. If one is interested e.g., in the metabolism of calcium,
one can eliminate the effect of these variations by using the ratio of the calcium concen-
tration found at any given time to the chromium concentration found at the same time.
The chromium content is found after dry calcining, by measurements on the Cr line at
427.48 nm with a spectrophotometer.
9.5.4.15 Caesium
Caesium can be determined by a suitable method in a number of biological materials, e.g.,

urine. Measurements are made on the Cs line at 852.11 nm [164]. When direct flame
photometry is not sensitive enough, the sample should be enriched by a suitable method
[127]. The background can be corrected for by recording the whole line profile, and sub-
tracting the mean background level found.
9.5.4.16 Nitrogen
The detection limit of nitrogen in normal flames is quite high; indirect methods for ni-
trogen determinations have therefore been developed. An indirect method for the flame
photometry of amino nitrogen with the aid of copper is described in the literature [167].
Five ml of a copper-phosphate suspension are pipetted into the solution containing the
amino acids. The mixture is allowed to stand for 5 minutes and is then centrifuged. The
remaining copper phosphate concentration is a measure of the amino-nitrogen content of
the original solution. The copper is determined in the usual way, as described above.
9.5.4.17 Phosphorus
Phosphorus lines in normal flames (without chemiluminescence) are not of sufficient in-
tensity to be used for analysis. The P bands are also unsuitable for investigations of
biological materials. It is advisable to use a hot plasma-arc burner for the determination
of phosphorus; the sample of biological material for analysis is sprayed into the arc as
into a flame [165]. The P line at 213.6 nm is generally used.
9.5.4.18 Silicon
Silicon does not give an emission spectrum in normal flames either. Here too, as with
phosphorus, the sample of liquid for analysis (e.g., urine) can be sprayed into a hot
plasma-arc burner. The Si line at 251.6 nm is used for analysis [172].
9.5.4.19 Zinc
When normal flames are used, zinc is generally analysed by the atomic absorption method,
which has an appreciably better detection limit than the emission method for this ele-
ment. In special cases, an emission method can be of use, but not with chemical flames;
ultra-micro-analysis of amounts of zinc of the order of 10- 12 g can be performed using a
glow discharge [155]. The line used for analysis with the glow discharge, as with the
atomic absorption method, is that at 213.86 nm.
9.5.5 THE PREPARATION OF REFERENCE AND BLANK SOLUTIONS
It would take us too far to describe how to make reference and blank solutions for all
kinds of samples, sample-preparation methods and instruments. For details in each parti-
cular case, the reader is referred to the literature cited above. We will, however, give here
a number of points which should be borne in mind when preparing reference and blank
solutions for the analysis of biological material.
9.5.5.1 The blank
The blank solution is sprayed into the flame in the usual way, and the photometer is ad-
justed to read zero under these conditions; alternatively, the photometer reading obtain-
ed with the blank can be noted, and subtracted from the reading obtained with all unknown
and reference solutions. We will assume below that this subtraction has already occurred.
What we are interested in at the moment is whether either of the above-mentioned methods
for correcting or adjusting the zero reading with the aid of a blank solution is likely to give
an exact result.
Ideally, the blank solution should contain all the elements present in the unknown solu-
tion, apart from the element to be analysed; and all these other elements should ideally be
in the same state of combination as in the material investigated. However, this ideal case
is seldom realized. Let us take the example of human serum which is to be analysed for
calcium by flame photometry. There is no natural serum which contains all the other com-
ponents in their natural state, including all the protein fractions, but no calcium, and it is
impossible to precipitate the calcium from the serum without precipitating some of the
protein with it .. Therefore our blank solution is no longer an ideal blank. We may remind
the reader that the protein sprayed into the flames has an effect on the flame temperature,
and hence on the form and intensity of the flame spectrum, including the magnitude of the
background and consequently the position of the zero on the concentration scale. Corres-
ponding difficulties arise with the reference solutions discussed below; we shall not go
into this point in detail here.
Fortunately, however, there are many cases where the departure of the blank solution
from the ideal does not seriously affect the use of emission flame photometry for the ana-
lysis of biological materials, because the background due to components of the solution
which are difficult to get in the exact natural state and concentration (e.g., proteins) is not
appreciably affected by the differences which occur. The error caused by ignoring these
effects is thus negligible.
Simpler blank solutions can be used in the following cases:
1. When the element to be detected, say Na, has a very low detection limit, and is pre-
sent in the sample of biological material to be analysed, for instance serum, in very high
concentrations, so that the sample can be diluted from 100 to 1000 times before analysis.
The blank and reference solutions must then be diluted to the same extent, but under these
conditions the other components of the sample, such as proteins, are so greatly diluted
that their effect is negligible. In such cases the blank solution can be very simple, sometimes
just a solution of a sodium salt in distilled water; the same distilled water should then
be used to dilute the reference serum and the unknown serum too.
2. Even when the dilution is not so great (e.g., 1 :1), it will be quite in order to omit the
organic components from the blank solution, if the sample for analysis has been depro-
teinized or simply calcined. However, the blank should contain other salts, e.g., Na and K
salts for the analysis of Ca, as we have already mentioned several times above. It will be
recalled that the addition of Na and K to the flame gives rise to recombination effects
which produce an additional continuous spectrum. In such cases, the blank should also
contain the same amount of acid or deproteinization agent as was used in the treatment
of the unknown sample.
3. The situation is simpler if a chemical or physico-chemical separation, e.g., a relatively
selective precipitation of the element to be determined, is used before flame photometry.
Both the blank and the reference solutions can then be made appreciably simpler. They
should, however, contain acid in an amount equal to that used for the dissolution of the
precipitate.
Despite the qualifications mentioned above, our somewhat pessimistic remarks at the
start of this section should not be forgotten. In particular, the reader should be warned
against treating the question of the blank too lightly.
How can one determine whether the blank is correct? This can be done relatively
simply by dividing a fairly large sample with a low concentration of the element to be
determined into a number of aliquots; increasing amounts of the element in question
are then added to successive aliquots, which are subsequently subjected to flame photo-
metry. If the measured intensities, corrected for the blank, are plotted against the con-
centration, the curve obtained, if straight, should go through the origin. If it does, the
blank is satisfactory. If it does not, investigations should be made to determine which of
the simplifications made in the preparation of the blank solution was unjustified.
9.5.5.2 The check solution
The check solution is used at regular intervals, for instance after every other determina-
tion, to check and if necessary to adjust the sensitivity of the instrument. This solution
should contain the element to be determined, and all other elements and substances pre-
sent in the unknown, in representative amounts. The remarks made above about possible
simplification of the blank solution apply here too.
9.5.5.3 Reference solutions
The reference solutions are used once to construct the calibration curve for the method,
and may be re-used occasionally to check that the calibration curve still holds. They con-
sist of a series of solutions with increasing amounts of the element to be determined, all
other substances present in the unknown sample being present at constant concentrations.
These reference solutions can be used to determine whether the calibration curve is linear
or curved, and if it is curved whether its curvature remains constant.
Another set of reference solutions should also be made, with the element to be determin-
ed at a constant, average concentration and the other substances present at varying con-
centrations; these are used to determine the effect of the other substances present on the
results. The experienced flame photometrist will generally know which substances should
have their concentrations varied (e.g., phosphorus and aluminium in analyses of the
alkaline-earth metals; sodium and potassium in analyses of the other alkali metals). The
beginner must try more variations, unless he can rely on published work which is applicable
to his own particular case. It should be stressed here that use can be made of published
results only when the flame conditions (composition, flow rate, shape of flame) are the
same in both cases. The various sources of error are discussed in detail in Section 9.6.
In general, we may state that when only a few analyses have to be made by flame photo-
metry, it will save work to simplify the complicated calibration procedure described above
and to give the sample a preliminary chemical treatment to suit it for a simplified method,
even when the chemical treatment is relatively time-consuming. If on the other hand
thousands of routine analyses have to be made by the same flame-photometric method, it
will be worthwhile calibrating the method thoroughly; this only has to be done once, and it
will take much less time than giving each of the thousands of samples a preliminary che-
mical treatment.
9.5.5.4 Intermediate standards
Standard sera of various commonly occurring types are commercially available (e.g.,
Moni-trol, Lab-trol, Patho-trol, Versatol and similar products marketed by Dade
Reagents Inc., Miami, Florida). These products, which are prepared from natural sera
by suitable treatment, can be used for calibration. These standard sera only differ from
natural sera in that certain chemical perservatives may have been added and certain frac-
tions of the original material removed so that they will keep better; apart from these slight
differences, they may be regarded as natural sera. They are supplied with relatively accu-
rate data on their composition. The only reason why such standard sera should not be
used for the check solutions (for checking the sensitivity of the photometer at intervals
during routine tests) is that they are quite expensive. The following less expensive method
of providing checks may be suggested. Serum residues from clinical laboratories can be
pooled, homogenized, divided into portions and stored in the deep-freeze for use in check
solutions. A number of these lots would then be measured against one or more commercial
standard sera, to give average concentration data for the pooled serum. Subsequently, this
inexpensive pooled serum with its known average concentration can be used (after ap-
propriate dilution) as the check solution instead of the expensive commercial product.
Unfortunately, no corresponding blank solutions for flame photometry which bear a suf-
ficient resemblance to serum are available.
A number of firms supply synthetic standards and blank solutions which can be used
for the calibration of their flame photometer in the most commonly occurring cases. We
may mention in this connection Merck's check solution Titrisol No. 9976, their diluent
No. 9979, the blank for potassium analyses No. 9977 and the blank for calcium analyses
No. 9978. The diluent contains acid to suppress the precipitation of calcium as the car-
bonate, and a wetting agent to bring the surface tension down to the relatively low value
found with natural sera. Such synthetic sera have only a limited range of application be-
cause in fact they do not resemble natural sera very closely. (The synthetic sera mentioned
above, for example, are only suitable for use with indirect sprayers, i.e., where the sprayer
and burner are separate.) Within their range of application, however, they are appreciably
less expensive than the pooled serum suggested above, and just as good for check solutions.
Synthetic sera made by a given firm for use with their own instrument will not necessa-
rily give good results when used with other instruments; for instance, when a synthetic
serum intended for use with an indirect sprayer is used with a direct sprayer (where spray-
er and burner are combined), the increased sensitivity to interference from other compo-
nents of the solution can lead to appreciable errors.
9.5.6 SPECIAL ANALYTICAL CONSIDERATIONS
9.5.6.1 Automation
Flame photometry is so time-saving when compared with the conventional chemical

methods which were commonly used for clinical or biological applications that many ana-
lysts are willing to carry out manually the standard flame-photometric method, with perio-
dic checks as described above. However, the increasing shortage of laboratory staff and
the general trend towards the centralization of laboratories into large clinical centres and
agricultural or biological research institutes is leading to an increasing need for semi-
automatic or completely automatic analytical methods. In order to meet this need, a
number of automatic instruments have been developed which offer considerable advanta-
ges compared with manually operated instruments when large numbers of measurements
have to be made.
If flame photometry is to be automated, it is very important that the instrument be
able to operate at sufficiently constant sensitivity for long periods of time without super-
vision, and that it should, if necessary, switch itself off if a problem arises (e.g., extinguish-
ing of the flame due to an empty gas cylinder or clogging of the sprayer or burner).
One method of automatic "supervision" often used with biological or medical analyses
is based on the addition of an "internal standard" such as Li to the diluent, so that after
dilution all samples have a constant lithium concentration. The measurement proper
can be arranged to give the quotient of the concentration required to that of lithium, e.g.,
Na/Li, K/Li, CalLi, etc. A number of temporary failures such as partial clogging of the
sprayer or burner have no effect on the value of this quotient, since both numerator and
denominator are affected in practically the same way; thus, these defects do not interfere
with the determination [175]. However, the concentration of the internal standard must
not be too small, since the results become inaccurate as the denominator of the quotient
approaches zero. This potential cause of error can be eliminated by arranging for a contact
to be actuated when the lithium content falls below a certain value. This relay can switch
off the instrument and cause an optical or acoustic signal to be given. The laboratory
staff can then clean the sprayer or the burner, after which the automatic measurements
can be resumed.
Apart from keeping the sensitivity constant, which can be done with an internal stan-
dard as described above, an automatic flame photometer should provide for automatic
introduction of the samples, if necessary coupled with automatic sample preparation
(e.g., by means of an Auto-Analyser). It should also present the results in a suitable analog
or digital form, print out, and if necessary arrange for data transmission.
The simplest way to do this is to use a large sample distributor, which can be filled with
numerous samples and which will automatically bring each one in turn under the sprayer
intake. One vital problem in this connection is the assurance that each sample be asso-
ciated with the right result on the chart or printed record. Difficulties can arise when large
numbers of samples have to be analysed. Two possible methods of providing checks are:
a) the regular inclusion of blank or reference solutions, giving constant results which are
easily recognizable on the record and can be correlated with the position of these solutions
as noted in the experimental notebook;
b) the use of markings e.g., magnets on the sample containers, which give additional
signals on the record thus helping in assigning the results.
Much can also be done to save labour in the presentation of results. It should be possi-
ble to read off the results directly in the desired concentration units. Some instruments can
do this automatically once the conversion factor has been set manually; while some can
even take the curvature of the calibration curve into account by means of analog or digi-
tal computations [176]. The results can be presented on punched tape or punched card, if
required, with details concerning the patient, hospital department, etc., so that with ade-
quate system design the results can be delivered automatically to the right place. The use
of punched cards or punched tape, which generally possesses some means of checking for
coordination mistakes, eliminates reading and copying errors and greatly increases the
reliability of the results.
Also connected with automation are the provisions available for automatically sub-
tracting the background from the signal (line + background). We shall be discussing this
further in the next section in connection with the background as a source of error.
9.5.6.2 Micro- and ultramicro methods
The amount of material available for biological or medical investigations is often very
small, as in the case of studies made on small organs or parts of organs. In other cases,
the amount of starting material is quite large, but after enrichment for a trace element of
interest only a very small sample is left.
Presently most commercial flame photometers are designed to operate with such small
amounts of material that they can often be used for micro-analyses [52,95,97,98,177].
In this section, we will discuss various ways of reducing the size of the sample needed for
analysis even further.
a) When choosing the instrument, one should look for the one with the lowest detection
limits. When a given amount of sample is available, the higher sensitivity of the instru-
ment allows this sample to be diluted to a greater extent, and when the amount of solu-
9.6] INTERFERENCE AND WAYS TO REDUCE IT 509
tion needed for an analysis is given (it is usually 1 ml), the amount of sample to be dissolv-
ed in this can be smaller. Instruments which make especially good use of the substance are
very valuable in this connection, i.e., instruments with highly efficient spraying and trans-
port of the sample mist into the flame.
b) For the same reason, it is important that the instrument once chosen should be care-
fully adjusted to give optimum performance for the analysis in question: the best gas
mixture should be chosen for the analysis, the best mixing ratio should be determined, the
best height for measurement in the flame should be found, etc.
c) When choosing the solvent, one should remember that in emission methods the use of
an organic solvent can sometimes improve the detection limit a hundredfold or more.
However, it should also be remembered that when solutions of many biological materials,
e.g., those with a high protein content, are treated with an organic solvent, protein is preci-
pitated, and some or all of the elements under investigation may be co-precipitated. This
problem can sometimes be solved by preliminary deproteinization, calcining or extraction.
d) When the concentration of several elements in the same sample has to be determined,
the normal method is to determine the concentration of each element by flame photometry
of a separate aliquot; the amount of material required is naturally higher under these cir-
cumstances. A similar case is found when the spectrum given by a certain solution has to
be recorded over a fairly wide spectral range. Since the recording time will then be relati-
vely long, and solution has to be sprayed into the flame the whole time, more material
will be required here too. In such cases it is advisable to use a multi-channel instrument,
which can measure at several different wavelengths at the same time [13, 104, 178-180].
e) When measurements are made on a given element, analytical solution can be saved by
use of a special high-speed method [181].
f) The flame can be replaced as an excitation source by some system which does not con-
sume any material. It may be recalled that a flame is in dynamic equilibrium, which means
that the supply of analytical solution to the flame must balance the amount carried off in
the flame; in other words, the flame must be continuously fed with appreciable quantities
of material. Closed systems have the advantage that the analytical material is not con-
sumed, but remains available for analysis for a long time. Strictly speaking, such analyti-
cal methods can no longer be called "flame photometry." Hollow-cathode discharge
tubes [182-184] and other gas discharge tubes with facilities for the introduction of sample
material [185-186] have been used for this purpose.
It goes without saying that several of the above-mentioned methods can often be com-
bined, thus saving even more material.
9.6 Interference and ways to reduce it
There are many sources of error in the flame photometry of material of biological or me-
dical importance, just as there are in any other branch of flame photometry. We may
mention, as an example, the ionization effects which can lead to error in the determination
of potassium in the presence of large amounts of sodium. In this section we will give a
brief survey of these sources of error and ways of reducing them, with special reference to
biological and medical applications. We shall also discuss in detail a number of sources of
error which are almost entirely limited to biological and medical studies.
We shall assume in all cases that the equipment is working properly, that no dust gets
into the flame (this can give rise to flashes of light which disturb the photometer reading),
that the fuel gas and the compressed air used are sufficiently pure, that the sprayer is not
clogged up (unfortunately, fairly concentrated biological solutions do quite often clog the
sprayer), and that the burner is clean, i.e., encrustation round the burner nozzle does not
interfere with the flow through it.
9.6.1 INTERFERENCE WITH THE ZERO LEVEL
We are dealing here with errors in the measurement of the signal (line +background), due
to variation in the background level caused by the other substances present in the analy-
tical solution. As we have discussed in detail in the section on calibration, the average
contribution of the background to the total intensity can be corrected for by use of a
blank solution - which is of course the same for all samples of a given type. When the
inevitable variations in the concentrations of the substances in the sample (other than the
element to be determined) do not cause the background to vary appreciably from its mean
value, this use of a uniform blank solution is recommended. In this case, the blank reading
is subtracted from the total reading, and the difference serves as a measure of the concen-
tration to be determined. If, however, the variation in the concentration of the other sub-
stances does have an effect on the background level, then, strictly speaking, a separate
blank, like the sample in all respects except that it does not contain any of the element
to be analysed, should be prepared for each sample. This can only be done if the con-
centration of all other substances in the sample had been determined by preliminary
analyses, which would take much too long in practice. In general one uses the same blank
solution for all samples of a given type, correcting the results if necessary with the aid of a
family of calibration curves (parameter method).
It might be thought that a much better method would be to record the whole line pro-
file including the background on both sides, so that the background level could be found
accurately by a baseline method [187]. While this is indeed an excellent method when possi-
ble, it is not always to be recommended when biological materials are to be investigated.
The reader will recall that recording a whole line profile takes a relatively long time, dur-
ing which the analytical solution must be supplied continuously; the amount of sample
required is thus increased. Moreover, use of this procedure makes automation more dif-
ficult, and the outlay on equipment will be greater, as filter photometers are often not
suitable for this application. If an increased outlay for equipment is considered worth-
while, it would be much better to choose a double-beam instrument which can measure
the background at a suitable wavelength at the same time as the line, and subtract the
background reading automatically from the total reading [180]. This method requires no
more sample than just measuring the line alone.
Errors due to the background are most difficult to estimate accurately when simple
filter photometers are used, since it is not always possible to measure just next to a line
with these instruments.
Background errors may be due to various causes. One is inadequate resolving power,
due e.g., to transmission of the filter at the wrong wavelengths, scattered light of other
wavelengths (which can also occur with simple monochromator instruments), etc. The
resolving power can be increased by using more than one filter in series, using a double
monochromator, combining a simple monochromator with a filter, etc. Another source
of error is an increase of the background level which cannot be removed completely by
optical means. An example of this is the continuous spectral component due to recombi-
nation of ions and electrons - a non-quantized process. This interference can be re-
moved by the use of low-temperature flames which do not exhibit ionization effects. Some
improvement is obtainable by the use of instruments with a narrow bandwidth, or by
measurement at another wavelength, generally in the short-wave region where the con-
tinuous radiation is not so strong.
9.6.2 NON-SPECIFIC EFFECTS
By non-specific effects one means effects which are the same for all spectral lines or bands
measured, such as effects due to differences in viscosity or surface tension between aqueous
reference solutions and solutions of protein-containing biological materials. These biolo-
gical substances affect the spraying of the solution (droplet size distribution in the aerosol)
and hence the evaporation of the solution in the flame. Effects of this kind are caused not
only by the various protein fractions but also by fibrin, bile acids, bilirubin, etc. It is diffi-
cult to reproduce the effect of these substances in the blank and reference solutions, as we
have already mentioned in our discussion on calibration. When a flame photometer with
direct spraying is used, comparison between the protein-containing test solution and the
aqueous blank or reference solution can thus give rise to systematic errors. Apart from
this, biological materials can also affect the flame temperature. We will be discussing this
in the next section on specific effects, as variations in flame temperature affect each line
differently, since each line has its own excitation parameters. Errors due to non-specific
spraying effects can be reduced in the following ways:
a) Making the biological solution more like the aqueous blank or reference solution by
1. further dilution with the same solvent (can only be done when the detection limits allow
it) ;
2. deproteinization (see above);
3. calcination, wet or dry (see above).
b) Making the blank or reference solution more like the biological solution by
1. using large batches of natural solutions (e.g., pooled serum) for the reference solution;
these solutions are analyzed in some other ways, e.g., chemically;
2. using suitable commercially available standards (see above);
3. adding suitable substances (glycerol, agar-agar, etc.) to the blank and reference so-
lutions, so as to make their spraying properties (viscosity and surface tension) roughly
equal to those of the sample;
4. adding surface-active substances or high concentrations of other salts to the blank and
reference solutions and to the biological solution as diluted for analysis, so that the
surface tension of all these solutions is given by the additions, not by the original
contents.
c) Chemically treating the biological solutions by
1. separation (e.g., by ion exchange);
2. precipitation, followed by the solution of the precipitated element in acid;
3. complex formation, and extraction of the complex with an organic solvent;
d) using an internal standard (see above);
e) using correction methods. The magnitude of the error in question is determined on a
number of samples. If the error is found to be more or less proportional to some measur-
able parameter of the sample, it can be used as a correction factor.
We may remark in closing that errors of this type depend very strongly on the equip-
ment used, in particular on the sprayer. Operating instructions, and, even more so, correc-
tion factors, which apply to one instrument cannot in general be used for another instru-
ment; in fact, errors of this kind can vary during the operation of one and the same in-
strument, as a result of e.g., gradual clogging of the sprayer.
9.6.3 SPECIFIC EFFECTS
In this section we will discuss effects which lead to errors in the measurement of line in-
tensities of different elements, and in some cases of the different lines of the same element.
Such errors cannot, therefore, be eliminated by means of a correction factor or term which
is the same for all elements [21].
9.6.3.1 Temperature effects
When biological solutions with a relatively high content of organic substances such as
protein are sprayed into a flame, especially if a direct sprayer is used, these organic sub-
stances act more or less like an organic solvent (e.g., alcohol) mixed with a corresponding
concentrated salt solution. As a result, the flame generally will be hotter than when the
aqueous blank or reference solution is sprayed into the flame [12, 188, 189]. This in-
crease in temperature will affect the intensity of each spectral line differently, because of
the differences in activation energy; thus, lines with higher activation energies will be
affected more. A further complication is that the line intensity varies not linearly but ex-
ponentially with the temperature. Also, these temperature influences are generally com-
bined with the non-specific influences mentioned above. It is difficult to separate these
various effects in practice, and to give generally applicable rules for their correction.
The practical implications of the above-mentioned effect are illustrated in Fig. 9.3,
which shows the intensity of the Ca line at 423 nm, after subtraction of the background,
for natural sera. The measurements where made on a spectrophotometer with a direct
sprayer, and compared with the results for blank and reference solutions of appropriate
concentration. The apparent Ca concentration is plotted against the relative H2 pressure
in the flame; the ratio of fuel gas to oxygen thus increases from left to right in the graph.
It will be seen that the "measured" calcium concentration can be given practically any
value by a suitable choice of the hydrogen/oxygen ratio in the flame.
We will not go into the question of whether these unfortunate results are due only to
temperature effects; it seems likely that evaporation effects also playa role [54].
In principle, the same means can be used to correct these errors as for the non-specific
effects, with certain limitations; as we have just mentioned, it is difficult to find a uniform
method which will deal adequately with all surface-tension, viscosity and temperature
effects. The usefulness of an internal standard is also limited since the temperature effect
on a spectral line varies with the excitation energy; strictly speaking each line in question
should have its own internal standard, with the same excitation energy. This is hardly
possible in practice, and compromise solutions have to be sought. Fortunately, the tem-
perature effect has the same diversion for all lines, so that the use of an internal standard
will at least give a smaller error than measurement of the line alone.
Finally, we may mention that indirect sprayer-burners, with a separate sprayer and a
_ 20
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0
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en
E
c 15
~
0
~
c. I----
u
c
0
u 10
0
U
C
~
0
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5
<
o
o 0.5 1.0 1.5 2.0
Relative Hz pressure
Fig. 9.3. The apparent Ca concentration measured in serum as a function of the hydrogen pressure
of the direct sprayer-burner (after [54 D. For explanation, see text.
separate burner, may be preferable in difficult cases since direct sprayer-burners (with
almost 100% transport efficiency), are much more sensitive to the interfering effect of other
substances present in the solution.
9.6.3.2 Ionization effects
Easily ionizable elements, such as potassium, will be partially ionized in flames; the pro-
portion of potassium ions increases with the temperature. These potassium ions are not
excited in the flame and will therefore not be detected by flame photometry. This fact alone
makes the use of low-temperature flames advisable in such cases. However, a further
complication should also be considered in this connection. If potassium were the only
element present in the analytical solution, then at a given temperature a given proportion
of the potassium would be present as neutral atoms, which can be detected by flame pho-
tometry. This situation is relatively simple to deal with. However, the law of mass action
also applies to ionization in flames; this means that electrons from any source can affect
the concentration of potassium ions in the flame. If another easily ionizable element,
such as sodium, is added to the potassium solution, the added sodium will give rise to
additional electrons, which will affect the degree of ionization of potassium. Thus the po-
tassium concentration determined by flame photometry will depend on the sodium con-
tent of the solution [21].
Similar ionization effects will be found with all easily ionizable elements in flames. The
magnitude of the effect depends strongly on the ease of ionization of the element in
question, the flame temperature, and the nature and concentration of other substances
present.
514 FLAME PHOTOMETRY IN mOLOOY AND MEDICINE [9
The following ways of reducing ionization effects may be used.

1. Choice of low-temperature flames. This can only be done if no elements which are dif-
ficult to excite or to dissociate have to be analysed in the same flame [21, 35].
2. Determination of the quantitative influence of the other substance present. This in-
fluence can be represented by making different calibration curves for different concen-
trations of the substance in question (parametric representation). This method is only
advisable when there is basically only one substance influencing the results [21].
3. Determination of the average concentration of the other substances in solution by pre-
liminary experiments. These same concentrations can then be added to the blank and
reference solutions. This method is advisable only when the concentration of the other
substances is so nearly constant that their variation (and hence the variation of the
ionization effect) about the mean does not cause any appreciable additional error [21].
4. Use of the addition method for calibration. The calibration curve determined in this
way can be used to deduce the form of the calibration curve without interference [190,
191], or the calibration curve can be determined afresh each time.
5. Use of the normalization or saturation method (these methods are also known as
buffer methods). A very easily ionizable element (e.g., caesium) is added to the solu-
tion in large concentration (normalization method) or very large concentration (sa-
turation method). This means that the partial pressure of electrons in the flame will be
high, no matter what the concentration of the element to be determined. The degree of
ionization will therefore be constant.
6. Use of lower dilutions. Since ionization effects are stronger for solutions of lower con-
centration, it is advisable not to dilute the solution too much - or even to enrich it
[127]. The sodium line at 330.2 nm is particularly useful in this connection [134], as it
gives a linear calibration curve up to high concentrations.
7. Observation at an optimum height. Since the flame temperature and the electron con-
centration in the flame vary with height in the flame, the ionization effects will also
vary with height. Selection of the right height for observation can reduce the ionization
effects considerably.
More than one of the above-mentioned methods can be combined, if one alone is not
enough to reduce the ionization effects sufficiently.
9.6.3.3 Evaporation effects
The intensity of the spectral lines or bands of elements of the second group of the periodic
system (calcium, magnesium, beryllium, zinc) is depressed by the presence of phosphorus,
aluminium or iron in the same solution. This depression is proportional to the concentra-
tion of the element causing it only in a narrow range; at high concentrations, saturation is
observed. The width of the proportionality range and the point at which saturation begins
to make itself felt depend on many factors, such as the concentrations of the element caus-
ing the change and the element affected, the flame temperature, the solvent used, the ob-
servation height, etc. [20,21,29,32-34, 37]. We will not go into the mechanism of the
"evaporation effects" here, but will merely mention briefly how they can be corrected in
biological and medical applications.
1. The element to be determined can be separated from the interfering elements [37, 151].
For example, when calcium is to be determined in the presence of phosphorus, the calcium
can be precipitated as the oxalate, the precipitate washed and dissolved in acid [153].
9.6] INTERFERENCE A~D WAYS TO REDUCE IT 515
2. The elements causing interference can be chemically separated from the element to be
determined [55].
3. The element to be determined can be treated chemically to give a compound which eva-
porates very easily in the flame, and which prevents evaporation effects from influencing
the results of the analysis [39, 132, 166, 193]. For example, when calcium is to be deter-
mined, it can be complexed with ethylene diamine tetracetic acid (EDTA); phosphate ions
present will then no longer influence the evaporation. Extraction of the complex before
flame photometry reduces the chances of interference even further [48, 50].
4. The variable influence of interfering substances, e.g., phosphate, can be eliminated by
the addition of large amounts of a substance with a similar evaporation effect, e.g., sul-
phuric acid [150].
5. The interfering substance itself can be added in such high concentrations that the satu-
ration range is reached, and the depression in intensity is constant [56,155]. The original
variations in the concentration of the substance in question then no longer have any effect.
The disadvantages of this method are that, since we operate in the saturation range, the
depression produced is relatively high, i.e., the measured emission is lower; furthermore
in vestigation has indicated [54] that the saturation depression may depend on the organic
carbon content of the solution (probably in fact on the protein content). Therefore this
method can be used only with relatively simple solutions.
6. Both the analytical solution and the reference solutions can be diluted so much that the
interference is reduced to a negligible level. This is, of course, only possible if there is
enough sensitivity available, as is the case with calcium analyses. This method is generally
out of the question for the analysis of magnesium, and even more so for the other group-
II elements, which are present at even lower concentrations.
7. A buffer can be added in such high concentration as to bind all the phosphate (or what-
ever else is interfering with the results), so that the element to be determined, with its low-
er concentration, is no longer affected. All group-II elements, apart from the element to be
determined, can be used for this buffer [52, 82, 155]. In certain cases, an element which is
naturally present at higher concentrations, e.g., Ca, can be used as a buffer for elements
present in a lower concentration [137].
8. The diluent used for preparing the sample can contain a substance which enhances the
evaporation of the aerosol in the flame. Glycerol, lanthanic acid and the perchlorates of
other elements, among others, can be used for this purpose [53, 148, 149].
9. It is advisable to use an excess of fuel gas in the flame, as it has been found that these
evaporation effects are reduced in flames low in oxygen [51, 111]. Since, as we have men-
tioned above, an excess of fuel gas is useful for magnesium analyses anyway, we are
eliminating two interferences at the same time.
10. Flames which are very hot and low in oxygen can be used [51, 111, 152]. It has been
found in practice that evaporation is practically complete under these circumstances, so
that evaporation errors are nearly eliminated; N 2 0jC 2 H 2 flames have proven useful
for this purpose [132].
11. Observations can be made in the flame at a level where evaporation effects are slight. It
has been found by experience that this is usually the case towards the top of the flame [21 l.
12. Sprayer-burner combinations which give a relatively fine droplet-size distribution
should be used; an indirect sprayer is best for this purpose, as nearly all the larger droplets
are trapped in the sprayer chamber [20, 54 l.
It goes without saying that more than one of the above-mentioned measures can be com-
bined if one alone is not sufficient to reduce evaporation effects. We may, however, re-
mark here, as we have already done in other connections, that experience gained with
one particular instrument or type of solution cannot necessarily be applied to another
instrument or solution type, as too many factors are involved which might have an in-
fluence on the evaporation effects (droplet-size distribution, flame temperature, oxygen con-
tent of flame, transit time of the evaporating droplet through the flame, etc.). Therefore
it will be necessary to determine the magnitude of the effect in each new case.
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CHAPTER 10
ATOMIC ABSORPTION SPECTROMETRY
J. B. Willis
CSIRO
Chemical Research Laboratories
Division of Chemical Physics
Clayton, Victoria, Australia
10.1 Introduction
The first application of atomic absorption spectra to chemical analysis was made over
100 years ago by Kirchhoff [1], who demonstrated the presence of various elements in
the solar atmosphere. Together with Bunsen he demonstrated shortly afterwards that
atomic spectra, whether in emission or absorption, could be the basis of a powerful method
of chemical analysis [2-4].
Since that time emission methods of spectrochemical analysis have been widely devel-
oped and have culminated in the direct-reading spectrographs which provide multi-
component analyses at high speed for the metallurgical industries. In biochemistry and
allied sciences, where interest was for many years confined mostly to the elements sodium,
potassium and calcium, emission analysis has generally been carried out with a much
simpler instrument, the flame photometer.
Whereas emission methods have been firmly established for many years, absorption
methods were for long almost completely overlooked except by the astrophysicist in the
determination of the compositions of solar and stellar atmospheres. Admittedly, the
determination of mercury vapour as a contaminant in laboratory atmospheres has been
carried out for nearly 30 years by an atomic absorption method [5], but it was not until
1953 that Walsh [6] recognized the potential advantages of the absorption method over
emission methods and devised simple and versatile apparatus applicable to the routine
analysis of solutions of a wide range of elements.
In 1955 Walsh [7] and Alkemade and Milatz [8, 9] published papers describing the
application of atomic absorption techniques to chemical analysis. Walsh's paper surveys
the theoretical factors involved in atomic absorption analysis and discusses the advantages
to be expected in the use of absorption rather than emission measurements. These advan-
tages are that atomic absorption is independent of the excitation potential of the transi-
tion involved and that it should be less subject to temperature variation and interference
from extraneous radiation or energy exchange between atoms.
Numerous reviews and several books [10-13] have appeared in recent years describing
the rapidly growing volume of work on this topic. The present chapter will discuss briefly
the theoretical basis of atomic absorption spectroscopy, the different types of instruments
used, the factors involved in making measurements, and will finally give a summary of the
526 ATOMIC ABSORPTION SPECTROMETRY [10
work which has been done on the determination of different elements by atomic absorp-
tion spectroscopy.
In a previous article [14] the author covered fairly fully the literature up to early 1962.
Today (mid-1967) it would be both difficult and tedious to try to refer to all the papers
and reports which have been published in this field. Fortunately, however, several excel-
lent bibliographies are available [15-17] and these are kept up-to-date by periodic supple-
ments.
10.2 Theoretical
The production of atoms from a molecule of a chemical compound requires the absorp-
tion of energy, and heat is usually the most convenient form in which to supply this ener-
gy. When vaporized by heating in a flame, a compound such as sodium chloride is partially
or wholly broken up into its elements in the gaseous form, and some of the atoms are
further excited to a state from which they can emit radiation when they return to the
unexcited, or ground, state.
The relation between the number of atoms in an excited state and in the ground state is
given by
(1)
where N J and No are the numbers of atoms in the excited and ground states, respectively;
PJ and Po, the corresponding statistical weights; EJ> the energy difference of the two states;
k, Boltzmann's constant; and T, the absolute temperature. The higher the value of EJ> i.e.,
the shorter the wavelength of the spectral line corresponding to the transition between the
ground and excited state, the smaller will be the fraction of atoms in the excited state.
Table 10.1 shows the fraction of atoms in the first excited state for several elements at
different temperatures.
It can be seen that at any easily attainable temperature only a small fraction of the
atoms of even the most easily excited metal (cesium) is raised above the ground state, and
that for metals such as zinc only an insignificant fraction of atoms is excited. It is for this
reason that flame photometry, while very sensitive for the alkali metals, is less satisfacto-
ry for metals such as magnesium or zinc. H, however, the absorption of light by the atoms
in the highly populated ground state is measured, this difficulty disappears, and the same
order of sensitivity can be expected for zinc as for cesium. It is this measurement which is
the basis of the technique of atomic absorption spectroscopy.
TABLE 10.1
VALUES OF Nj/No FOR VARIOUS RESONANCE LINES a
Resonance Pi NI/No
Line Transition -- T= T= T= T=
A Po 2000K 3000K 4000K 5000K
Cs 8521.1 2S112"2P3/2 2 4.44xtO-4 7.24 x 10 3 2.98x10 2 6.82 x 10-2
Na 5890.0 2S11Z-2P3/2 2 9.86x 10-6 5.88x 10-4 4.44 x 10-3 1.51 x 10-2
Ca 4226.7 IS0-IPl 3 1.21 X 10-7 3.69x to- 5 6.03 x 10-4 3.33 x 10-3
Zn 2138.6 IS0-lpl 3 7.29 X 10-15 5.58x to- IO 1.48 x to- 7 4.32 x 10-6
a Reproduced, by permission of Spectrochimica Acta, from reference [7].
10.2] THEORETICAL 527
40,000
T
E
u
W~
20,000
.« .« .« ,« ,« ,« 0«
0 Gl
eIJ elJlO ro 0 Lil
.neIJ 0>
rtl ro roO rtl "-
rtl eIJ eIJeIJ 1\j ~ !:::
No Mg Zn p
Fig. 10.1 Energy levels and resonance lines of sodium, magnesium, zinc, and phosphorus.
A toms in the ground state can only absorb radiation at a limited number of wavelengths
corresponding to their resonance lines, and Fig. 10.1 shows schematically the resonance
lines and energy levels involved for sodium, magnesium, zinc, and phosphorus. In atomic
absorption spectroscopy it is nearly always the first resonance line which is used, i.e., the
line corresponding to the transition from the ground state to the lowest excited state. For
metals with complicated electronic structures, such as iron and manganese, or for those
with low-lying multiplet components in the ground state such as aluminium and tin, there
are frequently several resonance lines which absorb to a roughly similar degree. For most
metals, however, the choice of absorbing line is simple.
In Table 10.11 are shown the lines which have been found most useful for the measure-
ment of a large number of metals.
The natural width of most atomic lines is inherently very small (ca. 10- 4 A), and even
when the broadening due to various factors (Doppler, pressure, resonance broadening,
etc.) is taken into account, the width is still only 0.01-0.1 A [25,26]. Ifacontinuous source
of radiation were used, as in an ordinary spectrophotometer, accurate measurement at the
peak of an atomic spectral line would require a spectral slit width of about 0.005 A. Such
high resolution is beyond the power of most spectrographs and monochromators, though
under favorable circumstances it may be possible to make useful measurements with a
continuous source of radiation (Section 10.3.1.6).
TABLE 10.11
SENSITIVITIES OF METALS DETERMINED BY ATOMIC ABSORPTION
SPECTROSCOPY
Approximate
Sensitivity (b)
Metal Line, A Flame (a) !l-g/ml for 1 % Notes Reference
absorption
Aluminium 3092.7 N 1 c 18
Antimony 2175.8 C 1 d, e 19
Arsenic 1937.0 H 1 20,21
Barium 5535.5 N 0.4 I 18
Beryllium 2348.6 N 0.Q2 c 18
Bismuth 2230.6 C 0.4 d,g 19
Boron 2497.7 N 50 e, h 18
Cadmium 2288.0 C 0.02 g 19
Calcium 4226.7 A 0.08 c 22
Cerium 5200 N 83 i 23
Cesium 8521.1 C 0.15 g,j 22
Chromium 3578.7 A 0.15 22
Cobalt 2407.3 A 0.1 d,g 19
Copper 3247.5 C 0,07 g 19
Dysprosium 4211.7 N 0.7 c,1 18,24
Erbium 4008.0 N 0.9 c,1 18,24
Europium 4594.0 N 0.8 I 18,24
Gadolinium 4078.7 N 17 c,1 18,24
Gallium 2874.2 C 2 g 19
Germanium 2651.6 N 1.5 h 18
Gold 2428.0 C 0.3 g 22
Hafnium 3072.9 N 14 e, h, k 18
Holmium 4103.8 N 1.5 f,h 18,24
Indium 3039.4 C 0.4 g 19
Iridium 2088.8 A 3 c, d 19
Iron 2483.3 A 0.1 d,g 22
Lanthanum 5501.3 N 42 I 24
Lead 2170.0 C 0.4 g 21
Lithium 6707.8 C 0.02 19
Lutetium 3359.6 N 12 c 18
Magnesium 2852.1 A 0.008 g 22
Manganese 2794.8 C 0.06 g 22
Mercury
I 2536.5 C 5 g, I 19
10.2] THEORETICAL 529
Approximate
Sensitivity (b)
Metal Line, A Flame (a) flog/ml for 1 % Notes Reference
absorption
Molybdenum 3132.6 N 0.4 18

Neodymium 4634.2 N 10 J,h 18,24
Nickel 2320.0 C 0.1 d, e 19
Niobium 3349.1 N 24 h 18
Osmium 2909.1 N 1 19
Palladium 2476.4 C 0.2 d,g 19
Platinum 2659.5 A 5 d,g 22
Potassium 7664.9 C 0.03 g 22
Praseodymium 4951.4 N 13 J,h 18,24
Rhenium 3460.5 N 12 h 18
Rhodium 3434.9 A 0.3 g 22
Rubidium 7800.2 C 0.04 g 19
Ruthenium 3498.9 A 0.9 c 19
Samarium 4296.7 N 9 I 18,24
Scandium 3911.8 N 0.6 c,1 18,24
Selenium 1960.3 H 0.5 c 21
Silicon 2516.1 N 2.5 e, h 18
Silver 3280.7 C 0.05 g 22
Sodium 5890.0 C 0.02 g 19
Strontium 4607.3 A 0.15 c 22
Tantalum 2714.0 N 11 h,k 18
Tellurium 2142.8 C 0.3 g 19
Terbium 4326.5 N 7.5 I 19,24
Thallium 2767.9 C 0.5 g 19
Thorium 3245.8 N 850 j 23
Thulium 3717.9 N 0.5 I 19
Tin 2246.1 H 0.5 c 20,21
Titanium 3642.7 N 3.5 h,k 18
Tungsten 2551.4 N 5 h 18
Uranium 3584.9 N 120 c, d 18
Vanadium 3184.0 N 1.5 h 18
Yttrium 4102.4 N 1.5 c,1 18,24
Ytterbium 3988.0 N 0.2 c,1 18,24
Zinc 2138.6 C 0.02 g 19
Zirconium 3601.2 N 15 h,k 18
Notes to Table 10.11:

a A = air-acetylene
C = air-coal gas
H = air-hydrogen
N = nitrous oxide-acetylene
b Concentration giving 1 % absorption when sprayed as an aqueous solution into a 10 cm pre-
mixed flame (5 cm for nitrous oxide-acetylene mixtures).
c Slightly fuel-rich flame.
d Absorbance markedly dependent on spectral slit width.
e Absorbance-concentration curve flattens markedly at high concentrations.
f Ionization suppressed with 1000 {Lg/ml. potassium ion.
g Absorbance markedly dependent on lamp current.
h Fuel-rich flame.
Heated spray chamber used.
j Spectral lamp used in place of hollow-cathode lamp.
k Measured in presence of 2 % hydrofluoric acid.
I Mercurous salt used.
However, if a source giving out a strong, sharp line of the appropriate wavelength is
available, then radiation from this source can be shone through the atomic vapour and
into the monochromator, which need now be only good enough to separate the desired
line from any others which the source may emit. If the width of the emission line from the
source is negligible compared with that of the absorption line in the atomic vapour, and if
it is assumed that the shape of the latter is determined entirely by Doppler broadening,
then the relation between the absorption co-efficient (Kmax) at the peak of the line and the
concentration of atoms in the vapour is given by
K
2A2
=--
(In2)1/2 -neN /
2
(2)
max D;. n me 2
where D;. is the Doppler width of the line; A, its wavelength; e and m, the electronic
charge and mass, respectively; e, the velocity of light; N, the number of atoms per cm 3
which are capable of absorbing light of wavelength A; and/the oscillator strength, which
is the average number of electrons per atom which can be excited by the incident radiation.
This implies a linear relationship between absorbance and concentration, which in prac-
tice is approached at low concentrations. At high concentrations the width of the line is
principally determined by factors other than the Doppler broadening.
Since the effective resolution of the system is determined by the width of the lines
emitted by the sharp-line source (ca. 0.01 A) the use of a sharp-line source containing one
isotope of an element may allow the determination of this isotope in the atomic vapour.
This requires, however, that the vapour be produced at temperatures sufficiently low that
the half-width of the absorption line is less than the peak separation of the isotopic lines.
Since for most metals except lithium and uranium the isotope separation is less than 0.01
A, vaporization of the specimen by means of a flame, which leads to half-widths greater
than this [27], will usually be impracticable.
10.3] INSTRUMENTAL 531
10.3 Instrumental
The atomic absorption spectrometer, shown schematically in Fig. 10.2, thus consists
of:
1. A light .source emitting, under conditions which ensure the production of extremely
sharp lines, the spectrum of the element to be determined.
2. A means of producing an atomic vapour of the sample to be analyzed.
3. A wavelength selector to separate the resonance line required.
4. A detector, amplifier, and readout system (meter, recorder, digital indicator, or print-
er).
Fig. 10.2. Schematic diagram illustrating operation of an atomic absorption spectrometer.
10.3.1 LIGHT SOURCES
10.3.1.1 Spectral lamps
For the more volatile elements such as the alkali metals and mercury, the most convenient
source is the spectral vapour lamp, in which an arc is struck between two electrodes in the
vapour of the metal. To minimize self-reversal and consequent broadening of the reso-
nance line the lamp current must normally be reduced to the lowest value which will
give a stable discharge. Suitable lamps are available from Osram and Philips.
10.3.1.2 Hollow-cathode lamps
For the great majority of metals, hollow-cathode lamps (Fig. 10.3) are found to be the
most satisfactory sources. A tube of this kind consists of an anode, usually of zirconium
or some other gettering material [28], and a hollow cylindrical cathode made of or con-
taining the metal whose spectrum is desired. The electrodes are mounted in a sealed tube,
fitted with a glass or quartz window, and filled with argon, neon, or helium at low pressure.
When the tube is connected to a source of current providing a starting voltage of about
4OOV, the discharge taking place is concentrated inside the hollow cathode, and bombard-
ment by rare-gas ions causes free atoms of the metal to be sputtered off the cathode. These
atoms are excited by collision with the rare-gas atoms and emit a strong, sharp line spec-
trum of the metal.
The early hollow-cathode tubes used in high-resolution spectroscopy required conti-
nuous circulation of purified gas, butJones and Walsh [29] succeeded in making perma-
nently sealed-off tubes, and this type which is now made and sold for atomic absorp-
tion spectroscopy by several manufacturers. Satisfactory hollow-cathode lamps are
available for most of the metals in Table 10.11, but the performance of a few lamps,
particularly arsenic and selenium, still leaves something to be desired.
Fig. 10.3. Hollow-cathode lamps with single and double cathodes. Courtesy Spectrochimica Acta.
In order to reduce the number of tubes required for the analysis of a range of metals it
is possible to incorporate two or more hollow cylindrical electrodes of different metals in
one tube; anyone of these may then be made the cathode, another serving as the anode
[29]. The metals which can be paired in this way are usually limited to those having fairly
similar melting points and volatilities, e.g., calcium and magnesium, silver and gold,
copper and iron, zinc and cadmium.
A more convenient technique, which allows the radiation from each metal to follow
the same light path through the flame and into the monochromator, consists of incorpo-
rating several metals in a single cathode. Cathodes made of alloys are not always satis-
factory, owing to preferential loss of the more volatile metals by sputtering, and the cur-
rent tendency is to fabricate cathodes either by sintering mixed metal powders pressed
into a die [30], or by pressing rings of various metals into a single supporting cathode
[31, 32].
A simpler, though probably less satisfactory, way of carrying out multi-element anal-
ysis is to use an iron hollow-cathode lamp [33]. The spectrum of this metal happens to
contain lines lying close enough to the resonance lines of barium, copper, magnesium,
manganese and nickel to enable atomic absorption measurements on these metals to be
carried out.
Demountable hollow-cathode lamps, into which the cathodes of different metals can
be inserted, have been used by some authors [34-38]. The interchange of cathodes re-
quires facilities for evacuation of the lamp and purging with argon or neon.
The hollow-cathode lamp is run from a stabilized power supply furnishing direct current
modulated at an appropriate frequency (Section 10.3.4) at a current which can be varied
up to a maximum of 10-30 rnA. It must provide for a starting voltage of about 500 V,
though the potential drop across the lamp while running is not more than about 200 V.
It is usual to incorporate a ballast resistance in the lamp circuit in order to improve lamp
stability.
10.3.1.3 High-intensity hollow-cathode lamps
In the ordinary hollow-cathode lamp the emission of light occurs as the result of a two-
stage process, in which the cathode material is vaporized by sputtering and this vapour
is then excited by the rare-gas ions formed by the electrical discharge. As the current
through the lamp is raised the intensity of the light emitted by the cathode increases, but
this is accompanied by an increase in the temperature of the metal vapour and may thus
lead to line broadening and self-absorption. Sullivan and Walsh [39] separated the
vaporization and excitation functions of the lamp by using the hollow cathode merely
to produce the metal vapour, which was then excited by an auxiliary discharge of
about 500 rnA between two electrodes in the space in front of the cathode (Fig. 10.4).
The emission of the ground state (resonance) lines of the cathode material is enhanced
relative to that of the upper-level, ion, and rare-gas lines by as much as loo-fold.
glass
restricting
aperture
auxiliary
electrode
cathode
anode
Fig. 10.4. High-intensity hollow-cathode lamp.

Courtesy Spectrochimica Acta.
Dawson and Ellis [40] have recently described a method of increasing the emission in-
tensity of a hollow-cathode lamp, without increase in line width or self-absorption, by
pulsing the current supplied to the lamp. With pulses having a frequency of 300 Hz, a
pulse width of 15 [L s, and a peak amplitude of about 600 rnA, enhancements of between
50- and BOO-fold relative to ordinary lamps were found for the emission intensities of
several metals, the rare-gas emission remaining unaltered. The greatest enhancement was
found for metals oflow melting point such as magnesium, calcium and strontium.
10.3.1.4 Selectively modulated hollow-cathode lamps
Bowman, Sullivan, and Walsh [41] have described a method of "isolating" the resonance
lines of an element by passing the radiation from a d.c.-operated hollow-cathode through
a pulsating cloud of atomic vapour of the same element produced by an a.c.-operated
hollow-cathode discharge. The resonance lines emitted by the first hollow-cathode are
modulated by absorption in the pulsating cloud of metal atoms, while other lines pass
through the vapour without modulation and produce no signal at the output of an a.c.
detection system. This type of source is useful where a non-absorbing line lies close to the
resonance line whose absorption it is desired to measure, and allows the use of much
larger spectral slit widths than are normally required (see Section 10.3.3.1).
10.3.1.5 Other line sources
Probably the simplest and most versatile source of line spectra for many elements is a
flame into which a solution of the metal is sprayed, and, using such sources, atomic ab-
sorption measurements have been reported for sodium [8], lithium [42] and three of the
rare-earth metals [43]. Flame sources, however, are generally less steady and less bright
than hollow-cathode lamps, and their widespread use is unlikely. High-frequency excited
lamps have been used for selenium [44], cadmium [45], and other metals [46], and would
probably be superior to arc discharge lamps for the alkali metals [47].
10.3.1.6 Continuous sources
Use of a continuous source, such as a tungsten lamp for the visible or a hydrogen lamp for
the ultraviolet, together with photographic recording, allows a comprehensive examina-
tion of the absorption spectrum to be made so that the most sensitive lines in a complex
spectrum may be identified [4B-50].
In the hope of developing a method of determining a wide range of metals without the
need for a range of hollow-cathode lamps, Gibson, Grossman, and Cooke [51] calculated
the value of the ratio of observed absorption to peak absorption for varying ratios of
spectral slit width to line width, and showed that the reduction in sensitivity, at any rate
for lines in the visible and near ultraviolet, was not intolerable. With a half-metre focal
length instrument fitted with a grating ruled with 30,000 lines/inch used in the second
order, these authors demonstrated that useful absorption could be measured, and found
that the loss in sensitivity was partly offset by the better signal-to-noise ratio of the
tungsten lamp as compared with their hollow-cathode lamps.
Later authors [45,52-54] have extended this work further into the ultraviolet and have
found it best to use a xenon arc and a scanning monochromator in order to obtain stable
and reproducible absorption readings. The calibration curves obtained, however, are
0'8
o Hollow Cathode lamp

o Xenon Arc
I
0·6
0·04
0·2
o 10 20 30 40 50
Yb,l'9/mi.
Fig. 10.5. Calibration curves for ytterbium at 3988.0 A.

o Hollow-cathode lamp source, nitrous oxide-acetylene flame, ionization suppressed by addition
of 1000 (Lg/ml potassium [19].
o Xenon-arc source, triple passage of light through three turbulent-flow oxygen-acetylene flames
[53].
strongly bent at high concentrations (Fig. 10.5) and this, together with the need for
scanning across the absorption line, will probably limit the usefulness of continuous
sources in practical analysis. Recently, however, Winefordner and his colleagues have
discussed quantitatively the relative merits of continuous and sharp-line sources and have
concluded that under the right conditions the limit of detection for many metals is approxi-
mately the same for both types of source [55, 56].
10.3.2 ATOMIZATION OF THE SAMPLE
10.3.2.1 Non-jlame methods of atomization
Although this book deals with flame spectroscopy, it seems desirable to mention briefly
some other methods which have been used to atomize 1 materials, particularly from the
solid state, without the need to prepare solutions. One of the first of these was the catho-
dic sputtering technique of Walsh [57-59], which has also been used by Goleb and co-wor-
kers [60, 61] for isotopic analysis of lithium and uranium metals. It has been shown to
have useful absorption sensitivity, though accompanied by some inter-element interferen-
ce, for solid salts deposited inside a hollow-cathode [62, 63].
Probably the most sensitive means of detecting traces of metals by atomic absorption
measurement uses vaporization by means of an arc-heated graphite crucible [64-66], but
the difficulty of quantitatively handling solid samples of 10- s g or less, combined with
1) In this chapter the word "atomization" will be used in its exact sense to mean "production of
atoms" rather than in its colloquial sense meaning "production of a fine spray." Thedevice
used for spraying a solution into a flame will be referred to as a "nebulizer."
the need for argon circulation through the crucible, has hindered the application of this
technique in practical analysis.
Rapid vaporization of solid specimens by means of pulses of radiation from a capacitor
discharge lamp, in conjunction with a continuous source of radiation and photographic
recording, has been used to measure qualitatively the presence of impurities in metals
[67] and there is no doubt that a laser source can be used similarly [68].
For metals such as cadmium, with fairly high vapour pressures at low temperatures,
it is possible to atomize a sample solution by spraying into a fused quartz tubular absorp-
tion cell maintained at about 1250 °C [69].
Recently, a completely novel approach to the problem of analyzing solids (and liquids)
without the necessity of preparing solutions has been described by Venghiattis [70]. The
sample is mixed with a solid-base propellant and pressed into a pellet, which is then burn-
ed just below the light beam of the atomic absorption spectrophotometer. Correction is
necessary for scattering and absorption of light by the other substances present in the
flame.
Induction-coupled plasmas have recently been used [71, 72] to atomize solutions for
atomic absorption work, and sensitivities for several metals approaching those found by
flame methods have been achieved.
10.3.2.2 Flames
Almost all workers in atomic absorption spectroscopy atomize the sample by spraying a
solution of the material into a flame. This is hardly surprising, since convenient and effi-
cient nebulizers and burners have been developed for flame photometry and are commer-
cially available. While the flame has certain disadvantages, the equipment required is
simple, inexpensive, easy to use, and well adapted to rapid measurement of a series of
different solutions, so that it is unlikely that any other method of atomization will replace
it for the great bulk of analytical work.
It is not possible here to consider in detail the physics and chemistry of various types of
flames, the design of burner systems, or the methods of feeding them with the solution
to be vaporized. These questions are treated at length elsewhere [73-75]. Nebulizer-
burner equipment, however, can be divided into two types which appear in the literature
under several different names.
Turbulent-flow burners. The characteristic feature of this type of burner is that the fuel gas
and the combustion-supporting gas are not mixed until the point at which they enter the
flame, and the solution to be sprayed is also introduced at this point. Thus the burner is
actually a combination nebulizer-burner. It is also known as a "direct-injection" or "total-
consumption" burner since all the liquid aspirated enters the flame and is converted to a
spray at the point of entry. This type of burner is llsed in many emission flame photometers,
as it is particularly well suited to safe operation with gas combinations having high burn-
ing velocities sllch as oxygen-hydrogen or oxygen-acetylene. It has been used for atomic ab-
sorption work by several workers following the early work of Robinson [76, 77].
The turbulent-flow burner gives a tall narrow flame which, while well adapted for
emission measurements, provides only a very short light path for absorption work. An in-
genious way of utilizing the height of the flame to achieve a long light path and hence
greatly improved sensitivity is to direct the flame into a tube [37,78-82] made of suitable
heat-resistant material such as quartz, alundum, or ceramic (Fig. 10.6). The transmission
of light down a long narrow tube is dependent on multiple reflections at the inner surface,
e:J0
HOLLOW-CATHODE EXHAUST
LA\, ~ INSULATION MONOCHROMATOR
=EJ ~ wmn===J
COLLIMATING
L ENS
BUR~ FOCUSSING
LENS
SAMPLE __
Fig. 10.6. Schematic diagram illustrating the long-tube technique for achieving high sensitivity
in atomic absorption spectrometry.
and is altered by deposit of solid material from the flame, so that it is frequently necessary
to insulate [37, 81] or heat [82] the outside of the tube to minimize this effect. The long-
tube technique is likely to be useful for these metals which do not readily form oxides in
the flame, and sensitivities 10-100 times those obtainable in an ordinary flame have been
reported, particularly for cadmium, zinc, and the noble metals. It is sometimes necessary
to correct for non-specific absorption when using this technique (Section 10.4.4.5).
Laminar-jlow burners. In this type of system the combustion-supporting gas aspirates the
liquid sample and produces an aerosol which passes into a spray chamber where the
larger droplets (usually 80-90% by weight of the total) settle out. The fuel gas may be
added either before or after the spray chamber, and the mixture of fuel gas, support gas,
and fine droplets proceeds to a burner where it is burned. This system, which is also
known as a "pre-mix burner" or "indirect atomizer-burner," was popularized for emis-
sion measurements by Lundegardh [83] and was introduced into atomic absorption work
by Allan [84] and David [85]. It is the one favoured by most workers in the field.
The actual design of the spray chamber and burner depends somewhat on the mixture
of gases to be burned. A typical arrangement is that shown in Fig. 10.7, in which the sup-
port gas (air or nitrous oxide) and liquid spray emerging from the nebulizer impinge on a
glass "impact bead," which serves to break up the drops further [75,86]. After admixture
liqu id Somple
'"
Fig. 10.7. Typical arrangement of atomizer, spray chamber, and laminar-flow burner [137].
Courtesy Spectrochimica Acta.
with the fuel (coal gas, propane, hydrogen, or acetylene) the spray strikes the walls of a
tapered spray chamber where the larger drops settle out, the fine drops being carried on
into the flame. In another design, based on that of a commercial flame photometer [87],
the spray formed by the nebulizer is mixed with coal gas or acetylene and passed through
two sets of vanes fixed in a cylindrical spray chamber; the swirling motion thus imparted
to the spray assists in the mixing of the gases and causes the larger drops to settle out. In
instruments with larger spray chambers it is customary to add the combustible gas after
the aerosol leaves the spray chamber so that there is only a small volume of gas mixture to
explode if flashback occurs.
A typical burner consists of a block, or tube, usually of stainless steel or other chemi-
cally resistant metal, containing either an array of holes or grooves [36, 88-90] or a slot
[18,91,92] at which the flame bums. Some workers find water-cooling advantageous both
in order to minimize salt deposits on the underside of the burner surface and also to en-
sure stable absorption readings, but in general this is not essential.
The total area of the burner opening is determined chiefly by the speed of combustion
of the gas mixture and by the rate at which it is supplied to the burner. In some instru-
ments the total gas flow, and hence the size of burner opening that may safely be used, is
increased by augmenting the air supplied via the nebulizer with a separate air supply
direct to the spray chamber [93].
The requirement that the light beam pass entirely through the flame limits the geometry
of the latter somewhat. Ideally the light beam should be very narrow, to allow the use of
a flame burning at a long, narrow slot, which will give highest sensitivity. The need for
the monochromator to accept sufficient light to give a satisfactory signal-to-noise ratio
usually means that a light beam of finite width is required, and this needs a shorter, wider
flame. In work with resonance detectors (Section 10.3.3.2) this limitation is particularly
important. Dimensions of typical burners for use with different fuel mixtures are shown
in Table 10. III.
Boling [94] has described a sheet-metal burner in which, by use of three parallel slots,
the effective width of the air-acetylene flame is increased without commensurate increase in
the explosion hazard, and somewhat similar burners made from a stainless steel block
have been used in work with resonance detectors [95].
TABLE 1O.III
TYPICAL SLOT DIMENSIONS FOR LAMINAR-FLOW BURNERS
Slot Size
Fuel mixture
Length, mm I Width, mm
Air-coal gas 100 1.5 B
Air-propane 100 1.5

Air-hydrogen 100 1.0
Air-acetylene 100 0.5
Nitrous oxide-acetylene 50 0.5 b, c
a Air-coal gas mixtures will also burn satisfactorily at burners designed for air-acetylene.
b Owing to the heat generated by this flame a burner of massive construction is required LI8].
e Such burners will also burn air-coal gas or air-acetylene mixtures satisfactorily.
Rawson [96] has recently described an ingenious burner with a slot of adjustable width,
which is made from two concentric stainless steel tubes forming a sliding fit with each
other.
Relative merits of turbulent-jlow and laminar-jlow burners. The relative merits of the two
kinds of burner have been widely discussed and are summarized below. Both types have
been extensively used; it seems significant, however, that almost all the commercial
instruments currently produced use laminar-flow burners.
The turbulent-flow burner gives a flame which is tall and narrow. While ideal for flame
photometry, it provides a much shorter light path and hence poorer sensitivity than does a
laminar-flow burner. This disadvantage can be overcome for some metals by use of the
long tube adaptor mentioned earlier, by using several burners in series, or by several
passages oflight through the flame [49].
The uptake of solution by the turbulent-flow burner is usually less than that of the la-
minar-flow system, and since all the solution aspirated enters the flame it should be a
more efficient producer of atoms than the laminar-flow system. However, there is evidence
that some of the liquid aspirated in the total-consumption type of burner passes through
the flame without being fully vaporized [97,98].
No quantitative comparison of the stability of atomic concentration in the flame at the
two types of burner under similar conditions seems to have been made, but one would
expect the fluctuation level to be worse for the turbulent-flow burner than for the laminar-
flow type, if only because of the presence, mentioned above, of large drops in the flame.
Changes in the temperature of the flame, on introduction of liquid, are very much smaller
in the laminar-flow burner than in the turbulent-flow one [75]. Even the addition of a
small pre-mixing chamber above a turbulent-flow burner improves the signal-to-fluctua-
tion level and reduces the intensity of emission by the flame gases [99, 100].
Chemical interferences, which are discussed in detail in Section 10.4.4.4, arise in part at
least from incomplete vaporization of the solid particles formed from the larger drops
entering the flame and are known to be worse with turbulent-flow than with laminar-
flow burners [101].
There is no doubt that the turbulent-flow burner is inherently safer than the laminar-flow
type, since the fuel and support gas do not mix until the actual point of entry to the flame,
and thus flashback is impossible. When particularly explosive gas combinations, such as
oxygen-acetylene or oxygen-cyanogen, are used it is almost mandatory to use this type of
burner. One drawback of the turbulent-flow burner, however, is the unpleasantly loud
audible noise which it emits while running; the laminar-flow burner on the other hand
is almost completely silent in operation.
10.3.3 WAVELENGTH SELECTORS
10.3.3.1 Conventional jilters and monochromators
The basic requirement for a wavelength selector is the ability to separate the desired re-
sonance line from the other lines emitted by the sharp-line source. If any background ra-
diation is emitted by the source, a curved calibration graph (absorbance-concentration)
will be obtained, but the curvature can be minimized by using a narrow-pass monochro-
mator to reduce the proportion of unabsorbed light.
For the alkali metals, whose spectra contain little but the resonance lines, a simple glass
or gelatine filter should suffice; indeed, for sodium determinations a very simple instru-
ment has been constructed [102] in which no wavelength selector whatsoever is used,
since the radiation from a sodium laboratory lamp is concentrated almost entirely in the
resonance lines comprising the yellow doublet.
For other metals with comparatively simple spectra, such as the alkaline earths and
magnesium, interference filters are satisfactory [103], but the difficulty and expense of
making selective interference filters of high transmission in the ultraviolet limits the use-
fulness of this technique considerably. Interference filters are unsuitable ifmuch background
radiation is emitted by the sharp-line source, as this radiation will be transmitted over
the band width of the filter. For instance, in the determination of calcium. using an inter-
ference filter to isolate the resonance line at 4226.7 A, a neon-filled hollow-cathode lamp
tube gives more satisfactory results than an argon-filled one, as the latter emits numerous
argon lines in this neighbourhood.
The commonest and most versatile wavelength selector is a monochromator which can
be set to pass any wavelength between 2000 and 9000 A, such as that from an ordinary
spectrophotometer. Quartz prism spectrographs have also been successfully adapted for
atomic absorption work by placing a pair of slits at the appropriate place in the focal
plane [84, 85].
10.3.3.2 Resonance monochromators
If the radiation from a line source such as a hollow-cathode lamp is passed through a
cloud of atoms of the same element, the resonance line or lines will be absorbed and re-
emitted in all directions, whereas the non-resonance lines, which are not absorbed, will
pass through unchanged. If the atomic cloud is viewed by a photomultiplier at right angles
to the light beam, the signal registered will be proportional to the intensity of re-emitted
resonance radiation, which in turn is proportional to the intensity of the resonance lines
in the light beam incident on the atomic vapour.
Sullivan and Walsh [95, 104] have used this principle in the construction of "resonance
monochromators" for the isolation and measurement of the resonance lines of a number
of metals. These instruments function as monochromators having an effective slit width
of about 0.01 A. Two techniques have been used for the production of atomic vapour:
(1) For metals having a relatively high vapour pressure at temperatures below their melt-
ing point, e.g., the alkali and alkali earth metals, zinc, cadmium, lead, etc., the vapour
may be produced thermally, by electrically heating a small block of the metal. An atomic
absorption spectrometer employing a resonance monochromator of this type is shown
in Fig. 10.8.
(2) For metals of higher melting point and lower vapour pressure the vapour is produced,
as in a hollow-cathode lamp, by cathodic sputtering.
ATOMICR£~
RADIATION
Fig. 10.8. Diagram of an atomic absorption spectrometer employing a resonance lamp as

monochromator. Courtesy Spectrochimica Acta.
With detectors of type (1) an ordinary hollow-cathode lamp serves as the primary
source of radiation. For those of type (2), where the electrical discharge involved in the
sputtering process necessarily results in the emission of radiation in the visible and ultra-
violet regions ofthe spectrum, it is necessary to use a high-intensity lamp modulated at the
frequency of the a.c. amplification system.
Resonance monochromators have the following advantages over conventional ones:
(1) The widths of the lines in the resonance spectrum are determined solely by the physi-
cal conditions, such as the temperature and pressure prevailing in the resonance mono-
chromator, whereas with a conventional monochromator the spectral band-pass of the
output signal due to the resonance line is determined by the width of the resonance line
emitted by the spectral lamp, and not by the monochromator.
(2) The random noise due to light emitted by the flame can only be produced by that por-
tion of the radiation which falls within the absorption region of the atomic vapour in the
resonance lamp. Such noise is therefore less than in a conventional spectrometer
where random noise can be produced by any radiation from the flame which passes
through the monochromator, the spectral slit width of which is much greater than the
width of the lines in the absorption spectrum of an atomic vapour.
(3) Unlike a conventional monochromator, where the wavelength setting may alter
through mechanical or thermal drift, a resonance monochromator is permanently tuned
to the wavelength of the resonance line it is designed to isolate.
There may, however, be disadvantages in using resonance monochromators for some
applications of atomic absorption spectrometry:
(1) In order to achieve an adequate signal at the photomultiplier a high-aperture optical
system is desirable, but unfortunately this conflicts with the need to use long, narrow
flames if maximum sensitivity is to be obtained using laminar-flow burners. A compro-
mise frequently has to be made between length and width of the flame used.
(2) For metals which have several resonance lines, all these lines will be detected by the
resonance system, but with efficiencies which will depend on the relative oscillator
strengths. In such cases it is usually not possible with the resonance monochromator to
isolate only the resonance line giving the greatest sensitivity in absorption, as would
normally be done with a conventional monochromator. For instance, when determining
potassium the resonance monochromator passes both resonance lines (7664.9 A and
7699.0 A) and thus the slope of the calibration curve is less than that with a conventional
monochromator which isolates the more sensitive line at 7664.9 A.
(3) When multi-element analysis is to be carried out, a range of resonance monochroma-
tors is required, which may involve more expense than buying a single conventional mo-
nochromator. However, it is possible to some extent to make a resonance monochromator
to pass the resonance lines of a pair of metals, such as calcium and magnesium. In this
particular case a glass filter is interposed between the monochromator and the photo-
multiplier when the calcium line (4226.7 A) is to be measured, and an ultraviolet-trans-
mitting but visible-opaque filter (e.g., Chance OX7, Schott UG5, or Coming CS 7-54) when
it is desired to measure the magnesium line (2852.1 A).
10.3.4 DETECTORS, AMPLIFIERS, AND READOUT SYSTEMS
The intensity of the resonance line transmitted by the monochromator is measured, with
and without the sample in the flame, by a photoelectric detector such as a vacuum photo-
cell or photomultiplier. Although photocells such as those supplied as standard equipment
with most manual spectrophotometers are satisfactory for metals having simple spectra
of high intensity, a photomultiplier is essential if the best results are to be achieved in the
determination of heavy metals. Most spectrophotometers now have provision for the
attachment of a photomultiplier instead of a photocell.
Several workers (84, 105-108) have satisfactorily carried out atomic absorption mea-
surements on metals whose resonance lines lie below about 3500 A by using a hoUow-
cathode lamp operated on direct current and feeding the output of the detector to a galva-
nometer or to a d.c. amplifier and meter. In the ultraviolet the emission from the flame is
usually negligible or can be compensated for by "backing-off" (Section 10.5.2.2). For
general use, however, it is desirable to modulate the output of the light source, either with
a mechanical "chopper" or, more conveniently, by supplying the source with alternating
current or modulated direct current, and feeding the output of the detector to an a.c.
amplifier whose output is rectified before being fed to a meter. In this way any signal
caused by continuous emission from the flame is rejected. However, any fluctuations in
flame emission may give rise to an appreciable a.c. component, and it is best to tune the
amplifier fairly closely to the modulation frequency of the light source. This is particularly
necessary where highly luminous or very hot flames are used.
Much of the published work on atomic absorption has been done with single-beam in-
struments of the general type described here. However, when the accuracy of absorption
measurement with such an instrument is limited by fluctuations and drift in the light
source, a double-beam technique is preferable. The first atomic absorption spectrophoto-
meter [28] was in fact a double-beam instrument. The light from the hollow-cathode lamp
was split into a sample beam modulated at a frequency /, which passed through the flame,
and a reference beam, modulated at a frequency 21. which passed through an equivalent
air path; the two beams were recombined on the entrance slit of the monochromator and
the photomultiplier output was fed to a homo dyne amplifier. The amplifier signals from the
two beams were separated and their ratio recorded on a pen recorder. The difficulties en-
countered in setting up and maintaining in adjustment the optics and electronics of this
instrument, however, proved considerable. Other double-beam instruments, with null-
point detection, have been described by Baker and Garton [109], Hinson and Kitching
[110], and Kahn and Slavin [111]. The latter instrument features 30-fold scale expansion
and is manufactured commercially.
Malmstadt and Chambers [112] have described a null-point instrument in which the
concentration of a reference solution is adjusted by addition of known volumes of stan-
dard solution until the absorption when sprayed into the flame is the same as that of the
sample.
When the performance of the instrument is limited, not by fluctuations in the emission
of the hollow-cathode lamp, but by fluctuations in the concentration of atoms in the
flame, there may be little advantage in using a double-beam instrument in place of a single-
beam one. In such cases an integrating system may be used, in which the output of the
detector, with no sample sprayed, is fed to a condenser for a fixed length of time, and the
resulting voltage measured. Then the corresponding signal with the sample is integrated
for a similar length of time and the ratio of the two voltages measured [113].
The demand for rapid routine analysis of large numbers of samples has led to the devel-
opment of digital read-out and print-out units, whose output can in some cases be scaled
to read directly in concentration units [114, 115]. These devices are particularly valuable
when used in conjunction with an automatic sampling device so that the instrument can
be left to work unattended for considerable periods of time.
An instrument for carrying out simultaneous determination of up to six metals has
been described by Butler and Strasheim [32]. In this instrument light from a multi-ring
cathode [31] passes through the flame into a spectrograph equipped with a pair of exit
slits and a photomultiplier at the wavelength corresponding to each metal. It is sometimes
difficult, however, to arrange for a flame having optimum path length and atomizing con-
ditions for all metals at the same time.
10.3.5 COMPLETE INSTRUMENTS
Box and Walsh [116] described an atomic absorption spectrometer (Fig. 10.9) on
the principles of which are based most of the single-beam instruments in use today. It
employed a Beckman DU monochromator and the nebulizer, spray chamber, and air-
coal gas burner from a commercial flame photometer. The hollow-cathode lamp was
supplied with stabilized current modulated at 50 or 100 Hz and the output from the
photomultiplier detector was amplified by a broadband a.c. amplifier, rectified, and read
on a microammeter. Later instruments differ mainly in having provision for longer flames,
a wider choice of gas mixtures, and more highly tuned electronics.
Fig. 10.9. Atomic absorption spectrometer described by Box and Walsh [1161. Courtesy
Spectrochimica Acta.
Atomic absorption instruments are made under license [6] to the Commonwealth
Scientific and Industrial Research Organization, Australia, by several manufacturers. At
present licenses are held by the following firms:
Hilger and Watts Ltd., London, England.
Unicam Instruments Ltd., Cambridge, England.

Evans Electroselenium Ltd., Halstead, Essex, England.
Southern Instruments Ltd., Camberley, Surrey, England.
Optica (U.K.) Ltd., London, England.
The Perkin-Elmer Corporation, Norwalk, Conn., U.S.A.
Beckman Instruments, Inc., Fullerton, Cal., U.S.A.
Atomic Absorption and Electronics Corp., New York, U.S.A.
Bausch and Lomb, Rochester, N.Y., U.S.A.
Carl Zeiss, Oberkochen, West Germany.
Optica Milano, Milan, Italy.
Jobin-Yvon, Arcueil (Seine), France.
Instrumentation Laboratory, Inc., Watertown, Mass., U.S.A.
Fisher Scientific Company, Waltham, Mass., U.S.A.
S.A.F.A.S., Monaco.
Varian Techtron Pty. Ltd., North Springvale, Victoria, Australia.
Aztec Instruments, Inc., Westport, Conn., U.S.A.
Shimadzu Seisakusho Ltd., Tokyo, Japan.
Jarrell-Ash (Europe) S.A., Le Lode, Switzerland.
Elwell and Gidley [10] give a detailed comparison of the characteristics of commercial-
ly available instruments.
10.4 Atomic absorption spectrometry and flame photometry
Although, as mentioned in Section 10.3.2.1, the use of a flame is not essential to atomic
absorption spectrometry, it is natural that this technique should be compared with
that of flame photometry, since injection of a solution into a flame is such a convenient
means of atomization. In general it may be said that almost all analyses which can be
carried out by flame photometry can be done at least as well by the atomic absorption
method, while the latter technique makes possible many analyses which cannot be carried
out at all by flame photometry in its present form.
10.4.1 SCOPE AND LIMITATION OF THE TWO TECHNIQUES
The atomic absorption method requires the use of resonance lines, and for most elements
there is little choice ofline if high sensitivity is required. In flame photometry, particularly
if a hot flame is used, there is sometimes a choice of lines, and some metals such as the
alkaline earths form compounds in the flame which emit measurable band spectra.
Since the non-metals and metalloids mostly have their resonance lines below 2000 A
(Table lO.IV) special difficulties arise in both techniques, as the strong absorption at
these wavelengths by the oxygen of the air requires not only a monochromator which can
be evacuated or purged with nitrogen but also a means of atomizing the sample which
does not introduce absorbing gases into the light path. Arsenic, selenium, and tellurium
absorb at wavelengths where air-hydrogen or air-acetylene flames transmit sufficient light
to enable measurements to be made. The remaining elements have not so far been measur-
lOA] ATOMIC ABSORPTION SPECTROMETRY AND FLAME PHOTOMETRY 545
TABLE 10.lV
RESONANCE LINES OF TYPICAL NON-METALS
Element Resonance Line, A
Carbon 1657
Phosphorus 1775
Arsenic 1890, 1937, 1972
Sulphur 1807, 1820, 1826
Selenium 1960, 2040, 2063
Tellurium 2143, 2383, 2386
Bromine 1488
Iodine 1830
ed in absorption, except that carbon and phosphorus have been determined in steel [117]
using the sputtering technique of Gatehouse and Walsh [58].
The limit of detection in flame photometry is set by the ability to distinguish the line
emitted by the metal from the background emission of the flame. In atomic absorption
spectrometry, however, the limiting factor is the measurement of the small change
in the intensity of the sharp-line source caused by absorption by the metal atoms in the
flame. The limit of detection or "minimum detectable concentration" of the metal being
determined is usually taken as the concentration which produces a signal (in emission)
or a change of signal (in absorption) equal to twice the r.m.s. fluctuation in the output
current of the photodetector. A quantitative discussion of the factors affecting the limit
of detection in both techniques has been given by Winefordner and co-workers [118, 119],
while practical examples of limits of detection in atomic absorption have been given by
others [120, 121].
Fassel and Golightly [l21a] have recently measured limits of detection in emission
for 67 elements sprayed as ethanolic solutions into an oxygen-acetylene flame. Of these,
43 were found to be comparable with or superior to the limits published for the atomic
absorption of aqueous solutions by Slavin [121 b J. In practical analytical work, however,
where other constituents of the sample may increase the background emission of the
flame, the situation is likely to be very different.
The effect of interferences in the two techniques will be discussed later.
10.4.2 USE OF DIFFERENT FLAME TYPES
1004.2.1 General considerations
For metals which are completely atomized in the flame, the sensitivity of the atomic ab-
sorption method is usually slightly higher with a cool flame than with a hot one [22, 122].
This is probably due to the lower degree of expansion of the flame gases and correspond-
ingly higher concentration of metal atoms per unit volume; furthermore, the peak ab-
sorption is inversely proportional to the Doppler width of the absorption line and hence
inversely proportional to the square root of the flame temperature. In flame photometry,
of course, the intensity of emission increases with the temperature of the flame, but fre-
quently this advantage of a hot flame is nullified by the higher background radiation and
increased interferences by other components of the sample.
In flame photometry it is sometimes possible to use the emission from a band system,
e.g., the MgOH band near 3710 A or the CaOH bands near 5440 and 6220 A. Although
the emission intensity of such bands is usually critically dependent on flame conditions
and is subject to interferences, their use sometimes provides higher sensitivity in emission
than does the use of the resonance line. Measurements of the absorption spectra of mole-
cular species have not as yet been used in analytical work, and the whole problem of in-
creasing the sensitivity and freedom from inter-element interference in atomic absorption
measurements lies in the achieving of complete conversion of the sample solution into a
cloud of atoms in that part of the flame through which the light beam passes.
Some metals are incompletely atomized when their compounds are sprayed into a
flame, and in such cases the degree of atomization varies with the type of flame, for on the
temperature and relative proportions of the flame gases depends the metal-metal oxide
equilibrium. The achievement of high temperatures, which are usually considered neces-
sary to break down refractory oxides, involves flames having high burning velocities. This
means that to prevent flashback a high rate of gas flow through the burner POl;t must be
maintained, which in turn requires that the total area of the burner port must be small.
Table 10.V shows the characteristics of some flames commonly used in atomic absorption
work, together with some which have been investigated but have not proved generally
useful.
TABLE 10.V
CHARACTERISTICS OF FLAMES SUITABLE FOR ATOMIC ABSORPTION
SPECTROSCOPY
Maximum Flame Maximum Tempera-I References

Gas Mixture Speed (cm 5- 1 ) ture COC)
Air-coal gas ca. 55 1840 75
Air-propane 82 1925 75
Air-hydrogen 320 2050 75, 123
Air-acetylene 160 2300 75, 123
50 % oxygen + 50 %
nitrogen-acetylene 640 2815 123
Oxygen-acetylene 1130 3060 123
Oxygen-cyanogen 140 4640 75
Nitrous oxide-propane-
butane 300 2550 l23a
Nitrous oxide-hydrogen 390 2650 p4,124a
Nitrous oxide-acetylene 180 2955 124
680 2795 123a,124b,
l24c
Nitric oxide-acetylene 90 3095 124
Nitrogen dioxide-acetylene 160 ? 124
10.4.2.2 Low and medium-temperature flames
Air coal-gas and air-propane flames have proved useful for the determination of the alkali
10.4] ATOMIC ABSORPTION SPECTROMETRY AND FLAME PHOTOMETRY 547
metals and a number of heavy metals such as copper, silver, lead, etc. The alkaline earth
metals are partially atomized in such flames, but the very large chemical interferences
experienced make the use of a hotter flame almost imperative in the determination of these
metals.
Air-hydrogen flames have recently been found [20, 21, 125] to give somewhat better
sensitivity than higher-temperature flames for arsenic, selenium, and tin. The best sensiti-
vity is normally obtained with a fuel-rich flame, but interferences, at any rate in the deter-
mination of tin, may be more troublesome than in higher-temperature flames [19]. One
advantage of the air-hydrogen flame over the air-acetylene one is that in the 1940-2400 A
region less light is absorbed by the flame gases themselves [20].
The air-acetylene flame is without doubt the most widely used one in atomic absorption
work. All the metals which can be determined in the air-coal gas or air-propane flame can
also be determined with air-acetylene, though sometimes with slightly reduced sensitivity.
In this flame most of the alkali earths are atomized sufficiently to enable useful measure-
ments to be made, and such chemical interferences as occur can usually be controlled by the
techniques described in Section 10.4.4.4. A number of other metals such as chromium,
molybdenum, ruthenium, and rhodium are more efficiently atomized in a fuel-rich air-
acetylene flame than in lower-temperature flames. Fig. 10.10 shows that the exact ratio of
air to acetylene and the height above the burner at which the absorption is measured are
very critical for metals such as tin and molybdenum, for which reasonably efficient ato-
mization is only achieved under the right flame conditions [22, 126, 127]. Rann and Ham-
bly [128] have measured the distribution pattern of the atoms of a number of metals in
the air-acetylene flame and have shown that restriction of the light beam to a very small
area of the flame can lead in some cases to a considerable enhancement of the sensitivity.
Unfortunately, however, this can usually only be achieved at the expense of reducing the
signal-to-noise level because the aperture of the monochromator is no longer filled with
light.
1'0
0'8
~ 06
~
< 0·4
0·2
o
HEIGHT IN FL.M£ I>&NE BURNER TOP, mOl.
Fig. 10.10. Effect of varying air-fuel ratio and height of absorption path in the flame on the ab-
sorption of 100 fLg/ml molybdenum. The air flow was kept constant at 5.51./min. and the acetylene
flow varied as shown.
10.4.2.3 High-temperature flames
The many metals forming refractory oxides, such as aluminium, boron, beryllium, tita-
nium, vanadium, tungsten, zirconium, etc., are not significantly atomized even in the air-
acetylene flame, and considerable effort has been expended to devise satisfactory flames to
enable the determination of these metals by atomic absorption spectroscopy. Robinson
[77] was able to detect such metals by emission, though not by absorption, in the very hot
oxygen-cyanogen flame, but more success was achieved by workers using the oxygen-
acetylene flame [49, 129, 130]. This flame, however, has the disadvantage of requiring the
use of a turbulent-flow burner and solutions in organic solvents, and the first successful
absorption measurements using a premixed high-temperature flame were those of Amos and
Thomas [131]. These workers succeeded in determining aluminium using the flame of
acetylene burning with a mixture of 50% oxygen and 50% nitrogen at a slot 3 cm long,
and later work [18] showed that the same technique could be extended to many other
metals which form refractory oxides.
The oxygen-nitrogen-acetylene flame, however, has some disadvantages in routine
work since it requires the provision of either ready-prepared oxygen-nitrogen mixtures or
fairly complex gas-mixing equipment to prevent the inadvertent use of mixtures too rich
in oxygen. Furthermore, the size of burner slot seems limited to about 3 em in length, on
account of the high burning velocity of acetylene with gas mixtures sufficiently rich in
oxygen to give adequate atomization of metals forming refractory oxides. A more generally
useful flame is that of acetylene burning in nitrous oxide [18, 132]. Here the burning velo-
city is relatively low, and the high temperature of the flame is due in part to the energy
liberated by the decomposition of the nitrous oxide. This flame can safely be burned at a
slot as long as 10 cm, though a 5 em slot is found to be optimum for most metals.
The lower burning velocities and higher flame temperatures attainable by burning ace-
tylene with nitric oxide or nitrogen dioxide suggest that such flames might be valuable, but
the expense and corrosive nature of these oxides of nitrogen militates against their use.
Slavin and co-workers [133] have found that the sensitivity for several metals is slightly
greater in the nitric oxide-acetylene than in the nitrous oxide-acetylene flame, but the sta-
bility of the flame is poorer so that the detection limits are usually worse than in the latter
flame.
10.4.3 NEBULIZATION CONDITIONS
10.4.3.1 Drop size in spray

An analysis of the factors influencing drop size is given elsewhere [73-75], but it may be
noted here that the mean drop size of the spray produced by a nebulizer of the type used
in most flame photometric and atomic absorption work can be calculated approximately
from the empirical equation of Nukiyama and Tanasawa [134] and for aqueous solutions
normally lies in the region 5-30 [J.m. Measurements on turbulent-flow nebulizer-burners
have shown that the mean droplet size with aqueous solutions is at least 20 [J.m [135], while
with nebulizer systems employing spray chambers the mean drop diameter of the spray
entering the flame is 8-12 [J.m [86,136] or perhaps somewhat less than this [137]. With the
help of an adjustable nebulizer [138] the mean drop size has been found to increase, and
the fraction of the liquid reaching the burner to decrease, with increasing rate of liquid up-
take. Fig. 10.11 shows the relation between the liquid uptake rate and the yield of liquid in
the flame for the nebulizing system shown in Fig. 10.7.
lOA] ATOMIC ABSORPTION SPECTROMETRY AND FLAME PHOTOMETRY 549
0'$
o 2 4 6 8 .,
LIQUID lFTAKE RATE mil..,;..
Fig. 10.11. Dependence of solution yield in flame on liquid uptake rate for the nebulizing system
shown in Fig. 10.7 [137]. Courtesy Spectrochimica Acta.
1004.3.2 Efficiency of nebulization
As has already been pointed out, the turbulent-flow nebulizer-burner allows all the liquid
aspirated to enter the flame, even though some of the larger drops may pass through it
without being fully vaporized. With laminar-flow systems, however, some 85-95 percent
of the aspirated liquid is condensed out as large drops in the spray chamber and runs to
waste. Clearly, a significant increase in analytical sensitivity would be achieved if all the li-
quid aspirated reached the flame and were efficiently vaporized there. This may be done
by providing sufficient heat to the spray chamber to evaporate the solvent before the drops
can condense out, so ensuring that all the solid particles formed enter the flame. Two ap-
proaches have been made, one by pre-heating the air supplied to the nebulizer [96, 139],
and the other by heating the inside of the spray chamber by radiant heat [140]. It is ne-
cessary to pass the resulting mixture of solid particles and solvent vapour through a water-
cooled condenser to condense out the solvent (usually water) which otherwise tends to
extinguish the flame. By such means eight- to tenfold enhancements in sensitivity for
many metals have been obtained, though usually at the cost of some instability or drift in
the absorption readings and of carry-over from one sample to the next, particularly when
solutions of high solid content are sprayed.
1004.3.3 Effect of solvent
The mean diameter of the drops produced by nebulizers of the type used in atomic ab-
sorption work is approximately proportional to the square root of the surface tension; thus
the average size of the drops, and consequently ofthe solid particles formed on evaporation
of the drops, will be reduced if water is replaced by an organic solvent. The effects of the
organic solvent will include: (1) increased rate of transfer of solution through the nebulizer
(unless the organic solvent is very viscous); (2) a larger fraction ofthe drops reaching the
flame, in instruments with spray chambers, due to the smaller drop size; and (3) more com-
plete vaporization of the material during the limited time it is in the flame, due again to
the smaller particle size.
These effects will lead to enhancement of both emission and absorption by atoms in the
flame, but the slight increase in flame temperature caused by spraying an organic solvent
instead of water will only affect emission intensity to any marked extent. The enhancement
of emission intensities, even with identical experimental conditions and solvent, varies
widely both between one metal and another, and between different emission lines of the
same metal [73).
The effect of organic solvents on the atomic absorption intensity of metals has been
studied by several workers. Robinson [141), using a total consumption burner of the Beck-
man type which burned oxygen and cyanogen, found for the 3414.8 A line of nickel an
enhancement relative to water of between 8- and 18-fold for a wide range of solvents;
acetone even gave a 36-fold enhancement. The same system in emission gave enhance-
ments of 4- and 9-fold only. Sachdev and co-workers [142) have found that the absorp-
tion of solutions of vanadium in organic solvents is increased even further by the presence
of long-chain compounds such as oleic acid. For laminar-flow burners use of organic sol:
vents enhances the absorption signal by only two- to fivefold, and this enhancement is
accounted for almost entirely by the greater rate at which solution reaches the flame [10,
143, 144). This explanation is supported by recent work [96, 145) showing that when the
spray is completely dried out to solid particles in a heated spray chamber the use of an
organic solvent in place of water gives no increase in sensitivity. It seems clear that the
change of flame temperature caused by spraying organic solvents is small and contri-
butes little to sensitivity in absorption. Ikeda and Atsuya [146) stress the role that im-
proved atomization of the particles plays in the enhancement brought about by use of
organic solvents.
10.4.3.4 Efficiency ofatomization inflame
The behaviour of an aqueous solution introduced as a fine spray into a flame may be con-
sidered to proceed in several stages. The droplets must first evaporate and the solid
salt particles formed may then undergo physical changes (evaporation, melting, boiling)
together with chemical changes such as interaction between the various inorganic sub-
stances present, oxidation, reaction with the flame gases, etc. Since the time spent by a
particle in the part of the flame traversed by the light beam is only of the order of milli-
seconds, the conversion of droplets into vapour must take a small fraction of this time if
the production of atoms is to be efficient. It is clear that the drop size will playa major part
in determining to what degree this process approaches completion, and what experimental
evidence is available bears out this view [137). The chemical factors influencing the de-
gree of atomization of metals in flames are still poorly understood, but it is known [147,
148) that several of the alkali metals are incompletely converted to atoms in low-tempe-
rature flames due to the formation of hydroxide molecules, and that the alkali earths si-
milarly give rise to molecules such as CaOH [148, 149). Recent work [150) suggests that
many other metals are incompletely atomized, even in the air-acetylene flame.
Fassel and coworkers [150d, 150e] have shown that in oxygen-acetylene and nitrous
oxide-acetylene flames the production of atoms from metals that form refractory oxides
is highly dependent on the stoichiometry of the flame gases and the location in the flame.
10.4.4 INTERFERENCES
Interference with the determination of one metal, caused by the presence of another con-
stituent ofthe sample, is a well-known and troublesome phenomenon in all forms of emission
analysis, whether the excitation is effected by the flame, arc, or spark. Several types of in-
terference may be distinguished, and their occurrence differs in emission and absorption.
10.4.4.1 Spectral or radiation interference
In flame photometric measurements, light is emitted not only by the element being deter-
mined but also by other elements in the sample and by the flame itself. If the wavelength of
this radiation lies close enough to that of the line being used, it will be passed by the filter
or monochromator and thus be recorded along with the signal being measured. This type
of interference, which causes a positive analytical error, is particularly likely to occur
with filter-type flame photometers.
For instance, in the determination of small amounts of magnesium in the presence of
large amounts of sodium (a situation which frequently occurs in biological work) the
2852.8 A line of sodium will make some contribution to the measured intensity of the
magnesium line at 2852.1 A, since most monochromators are unable to separate these
lines completely [151 J. Such interference has usually to be corrected for by adding a simi-
lar amount of sodium to the calibrating solutions, a procedure which is inconvenient if
the approximate composition of the sample is not already known.
In the determination by emission of small amounts of sodium in the presence of large
amounts of calcium, the monochromator transmits not only the sodium yellow lines at
5890.0 A and 5895.9 A, but also the molecular bands of calcium hydroxide which are
emitted in this region. Even when using a spectral slit width of 1 A the total calcium hy-
droxide emission in this wavelength range may be several times that due to sodium.
Under these conditions the background correction needed will be large and to some extent
uncertain.
In the determination of copper, using the strong lines at 3247.5 A and 3274.5 A, similar
difficulties arise from the OH band emission in this region.
In the atomic absorption method, on the other hand, the only absorption which can
be measured is that at the wavelength of the resonance line emitted by the source, which
has a width of ca. 0.01 A. This ensures that the effective resolution of the system is far
higher than in emission methods and results in correspondingly increased freedom from
radiation interference. Of course, if an unmodulated light source is employed, emission
from the flame may become important, particularly at wavelengths above about 3000 A,
but the use of a modulated system avoids this difficulty. However, even with a detecting
system closely tuned to the modulation frequency of the light source, light emitted by the
flame will give rise to random noise which may be appreciable if the ratio of flame emis-
sion to source intensity is sufficiently high.
10.4.4.2 Excitation interference
In emission methods many interferences are attributed to "excitation interference," which

is due to the change in the number of excited atoms when the introduction of another
atomic species produces a change in the effective temperature of the radiating vapour. This
type of interference is more commonly encountered in arc and spark work, but it probably
exists also in flame emission, though it has not been identified separately from the other
types of interference.
As can be seen from Table 10.1, only a small change in temperature is required to pro-
duce a large change in the number of excited atoms and thus in the intensity of emitted
radiation. The total number of these excited atoms is so small that the number of unexcit-
ed atoms can be regarded as constant and equal to the total number of atoms, so that no
counterpart to excitation interference is found in atomic absorption.
10.4.4.3 Ionization interference
Even a low-temperature flame such as air-coal gas possesses enough energy to ionize an
appreciable fraction of the atoms of the alkali metals. The ionization of an atom M to its
positive ion M+ and a free electron e- is assumed to behave as a dissociation process,
governed by the equation
(3)
and having an equilibrium constant K,

[M+] [e-]
K= [M] (4)
where x is the degree of ionization and P the partial pressure, in atmospheres, of the elec-
trons and the metal in all its forms in the burnt gases.
The dependence of the degree of ionization on temperature is given in the Saha equa-
tion [152]
- 5,040 E, gM +
T
+ ~ log T - log P + log -
gM
- 6.18 (5)
where E, is the ionization potential of the metal, in electron volts, Tthe absolute tempera-
ture, and gM and gM + the statistical weights of the neutral and ionized atom respectively.
It can be seen that the degree of ionization increases rapidly with increase of tempera-
ture and with decrease of concentration of metal in the flame. Fig. 10.12 and Table 10.VI
show the calculated degree of ionization for a number of metals assuming the wet flame
temperatures shown and a value for P of 10- 6 atmospheres [73, 153].
In the presence of a second metal which loses electrons even more readily than the one
being studied, the free electrons produced by the second metal will suppress the ioniza-
tion of the first, and the intensity of emission or absorption by the neutral atoms will
thereby be increased. Such effects have been frequently encountered in flame photometry
and have been studied in detail by Foster and Hume [153] and by Fukushima [154]. In
absorption work various authors have found a similar enhancement [18, 109, 155,
156], and Fig. 10.13 shows the effect of increasing concentrations of the readily ionized
metal potassium on the absorbance of calcium, strontium, and barium in the nitrous
oxide-acetylene flame. With increasing potassium concentration, absorption of the ionic
_ Alkali metals2S~-'so
--- Alkali earth metals lS0...JS'h
-~--- {~:."r:rium etc.2Ph,2P~_lSo
0·8 Total metal P. P.• IO "6atmos.
0·2
Be IONIZATION POTENTIAL,VOLTS
I I I II I I !I I
Cs Rb K Net Li Sr AICo Mg
Fig. 10.12. Degree of ionization, calculated by the Saha equation, for various metals in the air-
acetylene and nitrous oxide-acetylene flames. A total metal partial pressure of 10- 6 atmospheres
has been assumed.
TABLE 10.VI
CALCULATED DEGREE OF IONIZATION OF METALS IN FLAMES
Metal Ionization Air-propane (a) Hydrogen- Acetylene- Nitrous
Potential, eV 2200K Oxygen (a) Oxygen (a) Oxide-
2450K 2800 K Acetylene (b)
3230K
Li 5.39 0.000 0.009 0.16 0.68
Na 5.14 0.003 0.05 0.26 0.82
K 4.34 0.025 0.32 0.82 0.98
Rb 4.18 0.135 0.44 0.90 0.99
Cs 3.89 0.283 0.70 0.96 1.00
Be 9.32 .. . .. . ... 0.00
Mg 7.64 ... .. . . .. 0.03
Ca 6.11 0.000 0.010 0.073 0.43
Sr 5.69 0.00 0.027 0.172 0.71
Ba 5.21 O.ot 0.086 0.428 0.92
Al 5.98 .. . .. . ... 0.17
Eu 5.67 .. . .. . ... 0.61
Yb 6.2 .. . .. . I ... 0.36
a From references [731 and [1531
b Reference [191
species Ca +, Sr+ , or Ba + falls as that of the neutral atoms increases, and it can be seen
that ionization of these alkali earth metals can be completely suppressed by addition of a
sufficient excess of potassium.
Fig. 10.14 and 10.15 show the effect of ionization on the calibration curves for strontium
and barium in the nitrous oxide-acetylene flame. In the absence of a readily ionized metal
such as potassium the calibration curves bend slightly upwards, since, according to
equation (4), the degree of ionization decreases with increasing metal concentration in the
flame.
Fig. 10.13. Effect of increasing concentra-

tion of potassium on the absorbance of
calcium (5 fLg/ml), strontium (5.5 fLg/ml),
and barium (30 fLg!ml) in the nitrous oxide-
acetylene flame [18]. Courtesy Spectrochi-
mica Acta.
O-s
K2S,OOOpg/ml
K10,000pg/ml
w 0-6 KIOOOpg/ml
u
Z
:I
.
'"
0
'"«
0-4
K Opg/ml
0-2 KIOOO;'9/ml
(air-ace:fylene)
Fig. 10.14. Effect of potassium concentra-

tion on the calibration curve for strontium
[172]. Courtesy Analytical Chemistry.
o 6
- • - Air-acetylene flame.
Sr,pg/ml - 0 - Nitrous oxide-acetylene flame.
0'6
i..«
0-4
Kl000pg/ml
~
::l
«
0-2
Fig. 10,15. Effect of potassium concentra-

ne)
tion on the calibration curve for barium
[172], Courtesy Analytical Chemistry.
o ~=-~~~~~~2~0==~~~30~====~40 - • - Air-acetylene flame_
Ba P9/ml - 0 - Nitrous oxide-acetylene flame.
TABLE 10.VII
MEASURED DEGREE OF IONIZATION IN FLAMES
Degree of Ionization x
Concentration
Ionization in Solution Reference
Metal Potential, eV Air-acetylene Nitrous Oxide-
fAog/ml Flame acetylene Flame
Be 9.32 2 ••• (a) 0.00 [18]

Mg 7.64 2 0.00 0.06 [18]
Ca 6.11 5 0.03 0.43 [18]
2 ... 0.38 [156]
Sr 5.69 5.5 0.13 0.84 [18]
Ba 5.21 30 0.0 (b) 0.88 [18]
50 ... 0.92 [156]
Al 5.98 100 .... 0.14 [19]
Eu 5.67 50 .... 0.64 [19]
100 .... 0.58 [19]
Yb 6.2 15 ••. (c) 0.20 [18]
a No appreciable atomization
b Atomization very inefficient
c Potassium chloride suppresses absorption almost completely
The degree of ionization can be obtained by measuring the ratio of absorbances with
and without the addition of excess potassium, and the results of typical measurements are
shown in Table 10.VII. The agreement between these values and the ones calculated from
the Saha equation (Table 10.VI) is surprisingly good, since neither the temperature of
the nitrous oxide-acetylene flame nor the value of P under the experimental conditions is
accurately known; furthermore the addition of potassium chloride may affect the efficien-
cy of vaporization of the metallic salts in the flame.
Ionization interference is overcome where necessary in practical atomic absorption
work by adding to the standards the same concentration of interfering elements as
in the test solution. Alternatively, a large excess of the interfering element may be added
to each. The use of such a "radiation buffer" is open to far less objection in atomic ab-
sorption spectrophotometry than in emission flame photometry, since the errors due to
increased background emission, etc. seldom occur.
10.4.4.4 Chemical interferences
Another important type of interference encountered with flame methods of vaporizing the
sample is due to chemical combination oftheelement to be determined with other elements
or compounds in the flame. Well-known examples are the combination of calcium with
phosphorus and the combination of calcium and of magnesium with aluminium. Clearly,
this type of interference will be expected to affect emission and absorption methods in
much the same way.
In the last few years some progress has been made towards the understanding of the
mechanism of chemical interference and of the methods which are known to overcome it.
The subject is complicated by the dependence of the extent of interference on flame type
and temperature, so that it becomes very difficult for one investigator to reproduce exact-
ly the experimental conditions used by another. In all cases interference is least in hot
flames, and generally decreases in the upper parts of the flame. It is also dependent on
drop size, being least for the finest sprays [109, 137, 157], so that direct-injection burners
show higher levels of interference than do laminar-flow systems [101, 158].
The atomization of magnesium and of the other alkaline earth metals in low-temperature
flames has been fairly extensively studied, and is known to be highly dependent on the
presence of other cations and anions in the solution [159-163]. Halls and Townshend [161]
have pointed out that the direct dissociation of many inorganic magnesium salts to give
magnesium atoms in the flame is not a reasonable concept. While magnesium chloride
boils at a relatively low temperature, 1412 DC, the salts of oxy-acids decompose on heating
to magnesium oxide, which sublimes as magnesium oxide molecules at a temperature
(2700 0c) well above that of the air-coal gas, air-propane, or air-acetylene flame. These
authors suggest that the most important reaction in the atomization of magnesium is the
interaction of hydrogen atoms, supplied by the flame, with the surface of the magnesium
oxide particles.
In the presence of interfering materials such as sulphate, phosphate, aluminium, etc. it
seems that relatively non-volatile chemical compounds are formed in the liquid droplet,
and not by combination of the atoms in the flame itself. H, for instance, a solution contain-
ing both calcium and phosphate is sprayed into a flame, there is little emission from cal-
cium atoms; but if the calcium and phosphate solutions are introduced into the flame
through separate nebulizers, there is no interference with the calcium emission. Similar
results have been obtained for the interference of sulphate, borate, and aluminium with
calcium emission [10,164]. The compounds formed in the flame have in some cases been
identified, e.g., there is strong evidence that calcium pyrophosphate is formed when a so-
lution containing calcium and phosphoric acid is sprayed into an oxygen-hydrogen flame
[159], while particles of spinel (MgO. Alz0 3 ) have been isolated from the products of
combustion when a solution containing magnesium and aluminium salts is sprayed into
an air-acetylene flame [160].
In some instances the depression of absorption reaches a constant level above a certain
concentration of interfering ion, and a possible method for dealing with such interferences
is to add the interfering element in excess to both sample and standard solutions. However,
this method is frequently unsatisfactory because of the great loss of sensitivity entailed,
particularly when a low-temperature flame is used.
A method of general utility in overcoming interference in both emission and absorption
methods is to add a large excess of a metal which can compete with the metal being deter-
mined for combination with the interfering element. For instance, in the determination of
calcium in the presence of phosphorus, addition of an excess of a salt of strontium or
lanthanum is effective in removing the suppression of calcium radiation in both emission
[165, 166] and absorption [92, 167]. In removing the interference of aluminium in the
determination of magnesium, addition of salts of calcium, strontium, barium or lanthanum
is effective [165, 168]. Mansell has shown [168], from consideration of thermodynamic
data, that the formation of magnesium aluminate is favoured over that of the individual
oxides of magnesium and aluminium, and since calcium, strontium, barium, and lantha-
num aluminates are more stable than magnesium aluminate the former compounds will
tend to be formed preferentially, leaving magnesium atoms free.
A second method of overcoming many interferences is by adding a high concentration
of a chelating agent such as 8-hydroxyquinoline [109, 160, 169] or the sodium salt of
ethylenediamine tetracetic acid [167, 170, 171]. The mechanism of this effect is not fUlly
understood; it has been thought that chelate compounds are formed, but this explanation
cannot be fully accepted because several organic molecules without chelating prOI erties
have been found almost as effective. It is probable that oxine and other organi,: com-
pounds hinder the formation of metal oxides either by forming chelates during e /apora-
tion of the water droplets or simply by their reducing properties after the salt particles
have dried out in the flame [109, 160, 171a].
Use of a combination of both methods has been found advantageous by some workers
[158,163].
When using hotter flames such as nitrous oxide-acetylene or plasma jet, chemical inter-
ferences of the type just described are greatly reduced or even completely eliminated [18,
71, 172], and strangely enough it has been found that with these methods of atomization
the presence of a relatively high concentration of other materials sometimes enhances the
absorption of the metal being determined. Phosphoric acid, for instance, very slightly
enhances the absorption of calcium, and this seems to be due, not to a change in the cal-
cium atom-ion equilibrium, but to improved efficiency of atomization in the flame. Such
effects are also found with metals such as titanium [172] and vanadium [173] which are
probably not completely atomized even in the nitrous oxide-acetylene flame. A particu-
larly striking and important enhancement is that caused by traces of fluoride ion, parti-
cularly in the presence of iron, on the absorption of several metals, notably hafnium,
zirconium, tantalum, and titanium [18].
In cooler flames, however, the presence of high salt concentrations (1 % or more) al-
most invariably reduces slightly the absorbance of the metal being determined. The effect
is non-specific and probably arises from changes in the drop size of the aerosol entering
the flame. It can be corrected for by matching roughly the sample and standard solutions
with regard to their major constituents.
A short but excellent summary ofthe different types of chemical interference experienced
-n emission and absorption flame work has been given recently by Alkemade [174].
10.4.4.5 Background effects
In Section 10.4.4.1, brief mention was made of the occurrence in flame photometry of
spectral interference by the background emission of the flame. Although this form of
interference does not occur in atomic absorption work, there is a small, but in some cases
analytically significant, effect due apparently to absorption or scattering of light from the
sharp-line source by the solid particles of material aspirated into the flame. This effect,
which of course results in higher apparent absorption, is only detectable when trace
quantities of a metal are determined in the presence of relatively large concentrations of
other salts.
The effect is greatest in low-temperature flames and is particularly pronounced when
using the long-tube technique [81, 175] or when solutions of metals such as titanium, haf-
nium, and zirconium are sprayed [10]. In general, calcium and magnesium show the effect
to a greater extent than do the alkali metals [176], and the effect increases at shorter
wavelengths, as shown in Fig. 10.16.
Correction can be made if necessary by measuring the loss of light at a non-absorbing
line close to the resonance line [14, 177, 178], by using a continuous light source [81, 176],
or in special cases by altering the flame type so that the metal being determined is oxidized
and so does not absorb [127].
The effect was at first assumed to be due to light scattering by solid particles in the flame
w
zV
< 0-02
ID
a: - - - 51, NaCI
5lID ------- 51, K 2 SO.
<
I-
- - - - - 51 CaCI 2
zw
a:
if
Il.
< 0-01
0-00 '--_ _ _ _ _~_ _ _____>..

_ _-~-:-=-~---___::_::':_
zpoo 3,000 4.,000 5,000
Wt.VELENC.TH, A
Fig. 10.16. Apparent absorbance due to loss of light by molecular absorption or scattering [14].
[10, 14, 176], but Koirtyohann and Pickett [81, 175, 179] have recently shown that in
some cases, at any rate, it is due to absorption of light by salt molecules in the vapour
phase. An approximate calculation using the theory of Mie and of Van de Hulst [180]
suggests that the magnitude of the scattering should be much less than the light loss actual-
ly observed and should be largely independent of wavelength.
10.5 The technique of atomic absorption spectrometry
10.5.1 SELECTION OF OPTIMUM EXPERIMENTAL CONDmONS
The combination of sharp-line source, monochromator, photomultiplier, and amplifier

constitutes an optical-electronic system of which several variables can be altered.
10.5.1.1 Choice of lamp current
The current at which the sharp-line source is operated determines not only the intensity of
the spectral lines produced but also their width. In order to obtain the highest sensitivity
in absorption and a straight absorbance-concentration curve, it is essential that the line
whose absorption is to be measured should not exhibit self-reversal or self-absorption.
(These effects, which have the effect of broadening the line, are caused by partial reabsorp-
tion of the emitted light by the metal vapour in the lamp itself.) For the alkali metals and
others such as silver, zinc, and cadmium, which sputter profusely, this can only be achiev-
10.5] TECHNIQUE OF ATOMIC ABSORPTION SPECTROMETRY 559
ed by running the lamp on very low currents (sometimes as low as 2 rnA for zinc and cad-
mium hollow-cathode lamps).
When the sharp-line source is run under such conditions, however, the discharge may
become relatively unsteady and the signal-to-noise ratio be reduced to such a level that
the advantage of high sensitivity is offset by the uncertainty in reading a fluctuating meter.
In such cases it is frequently better to sacrifice some sensitivity in order to achieve high-
er stability and hence more accurate reading of the output meter. Fig. 10.17 shows the
effect of hollow-cathode current on the calibration curve and signal stability for zinc,
and illustrates this point. Similarly, in the determination of copper, the best results are
often achieved by running the hollow-cathode lamp at a current sufficiently high to result
in some self-absorption, but one which gives such a stable signal that the absorption may
usefully be magnified several-fold by use of scale expansion (Section 10.5.2.2).
'·0
0'8
I
0·6
-<
0·4
0·2
o 2 3 4
Zn.~g/mL
Fig. 10.17. Calibration curves for zinc, using an argon-filled hollow-cathode lamp run at differ-
ent currents [19].
The light emitted by the nitrous oxide-acetylene or other high-temperature flame is fre-
quently sufficient to give rise to appreciable noise at the photomultiplier, and it is then
desirable to run the sharp-line source at a fairly high current to ensure the best possible
signal-to-noise ratio. Fortunately, most of the metals for which the use of such a flame is
required are not very subject to self-reversal or self-absorption phenomena.
10.5.1.2 Choice of slit width
If it is desired to achieve maximum sensitivity for a metal which has a complex spectrum,
the use of low hollow-cathode current and narrow slit width may be required. In such a
case the high tension applied to the photomultiplier and the gain of the amplifier must
be increased. This may introduce noise from the electronic system. Here again the best
conditions of operation must be found by compromise. Use of a high-intensity lamp is
often beneficial in such cases.
Where no background emission or interfering line occurs, a fairly wide slit width is
desirable.
10.5.1.3 Choice of absorbing line
The choice of absorbing line may depend on the strength and stability of the emission
of different lines by the hollow-cathode lamp and in some cases on the presence of adja-
cent lines or continuum. For instance, with nickel it is often better to use the 3414.8 A
line instead of the more sensitive 2320.0 A one when absorbances above 0.4 are to be
measured, owing to the strong curvature in the absorbance-concentration curve when
the latter line is used. This curvature, which occurs with several metals having complex
1'0
0'8
HIGH-INTENSITY
LAMP
0·6
4THODE
/ LAMP
0·4
0·2 Y
o 5 10 15 20
Ni, ~9/ml.
Fig. 10.IS. Calibration curves for nickel using the nickel line at 2320.03 A emitted by conventio-
nal and high-intensity hollow-cathode lamps [39J. Courtesy Spectrochimica Acta.
1-4
1-2
1-0
r: 0-4
HIGH-INTENSITY LAMP
HOLLOW-CATHODE LAMP
0-2
10 20 30 40 50
Co, ~g/m'_
Fig. 10.19. Calibration curves for cobalt using the cobalt line at 2407.25 A emitted by conventio-
nal and high-intensity hollow-cathode lamps [39]. Courtesy Spectrochimica Acta.
spectra, is due to the presence of a non-absorbing line too close to the 2320.0 A line to be
separated by the monochromator. Similar effects have been found for the 2175.9 A line
of antimony and 2407.25 A line of cobalt [22].
Here again high-intensity lamps are valuable, and Figs. 10.18 and 10.19 show the bene-
fits to be gained by using these lamps in the determination of nickel and cobalt [39].
The choice of a suitable absorbing line from a complex spectrum according to the
sensitivity desired has been discussed by Margoshes [180a].
10.5.1.4 Choice o/flame conditions
Choice of optimum flame conditions has already been discussed (Section 10.4.2).
10.5.2 METHODS OF INCREASING SENSITIVITY
10.5.2.1 Optical means
Russell, Shelton, and Walsh [28], who used a Meker-type air-coal gas flame of circular
cross section, achieved an increase in absorption intensity by passing the light beam back-
wards and forwards through the flame, using an optical system based on that of White
[181]. The calibration curves shown in Fig. 10.20 show the effect of increasing path length
on the sensitivity for iron. Other workers [36,49, 109] have also used multiple-pass sy-
stems.
0'10
0'08
I
w
0·04
002
o JOO 150 200

Fe,fl9/ml.
Fig. 10.20. Calibration curves for iron using the 3719.9 A line and multiple traversals of an
air-coal gas flame burning at a Meker burner [28]. Courtesy Spectrochimica Acta.
With a long flame it is difficult to achieve effective multiple passes, particularly when
determining metals for which the atomic concentration varies considerably from one
part of the flame to another. It will be noticed that in Fig. 10.20 a gain of only about six-
fold in absorption was obtained by using 12 passes through the flame, and it is commonly
found that the increase in sensitivity attained by multiple passages through the flame is
partly offset by the light losses on reflexion and by the aberrations involved in off-axis
optical systems. Furthermore, it is not usually possible for each passage of light to traverse
the part of the flame where the concentration of atoms is highest. The author feels that,
except in specialized applications, the additional complexity of a mUltipass system is pro-
bably not justified by the increase in sensitivity obtained.
10.5.2.2 Electronic means
In modem instruments the limit of detection is normally set by the stability of the sharp-
line source with respect to drift and noise, though, when using a high-temperature flame
the noise level due to flame emission may be more important. The instability of atomi-
zation is usually small at very low concentrations of the metal being determined. For a
number of metals scale expansion can profitably be employed, the zero of the meter being
displaced off the scale by means of an electric current, and most commercial instruments
now have facilities for doing this. Use of a recorder is frequently advantageous when em-
ploying scale expansion.
Some workers have minimized the effect of hollow-cathode noise by integrating the
signal over a period of time, but the usefulness of this technique is limited by drift in the
signal from the hollow-cathode tube over the time required for the two readings necessary
to establish the absorption of the sample. Here again, use of a recorder is helpful.
Both noise and drift in the emission of the sharp-line source should be avoidable by use
of a double-beam system, such as the homo dyne amplification technique used by Russell
et al. [28] and by Baker and Garton [109] or the systems used in some of the commercial
instruments. The stability of the electronics will, however, limit the degree of scale expan-
sion that can be usefully attained.
10.5.2.3 Chemical means
The physical aspects of the use of organic solvents were discussed in Section 10.4.3.3, and
it was shown that with the type of nebulizer-burner system generally used for atomic ab-
sorption work an enhancement of about three- or fivefold may normally be expected in
going from a solution in water to a solution in a suitable organic solvent. The advantages
of this increase in absorption may sometimes be offset by increased unsteadiness of the
flame and by correspondingly decreased accuracy of reading the absorption intensity.
The most comprehensive study of the use of organic solvents is that of Allan [143], who,
using an air-acetylene flame, studied the enhancement of absorption intensity of solutions
of several metals in various organic solvents. He concluded that in practical analytical
work the small increases of intensity which can be obtained by using mixtures of water
with miscible solvents such as alcohol or acetone would be more than counterbalanced
by the extra dilution incurred by adding the organic solvent, though he suggested that
dilution with an isobutyl alcohol-acetone mixture would be helpful if the volume of the
original sample were too small to spray.
Dilution of oil specimens with an organic solvent such as p-xylene also leads to useful
enhancement of absorption relative to that obtainable in aqueous solutions of the same
metal concentration [182].
Allan also investigated the use of solvent extraction in atomic absorption work. This
valuable technique, which has been extensively applied to flame photometry by Dean and
his co-workers [73], is of equal use in atomic absorption spectroscopy, particularly for
the determination of trace quantities of heavy metals in agricultural and biological ma-
terials [122, 183]. Allan found the quantitative extraction of such metals from aqueous
solution into a non-miscible ester or ketone by means of a suitable chelating agent could
yield concentration factors of l00-fold or more, and of course the sensitivity of the method
was increased even further by the enhancement of absorption caused by spraying organic
solvent instead of water.
The power of the solvent extraction technique is well illustrated in the methods develop-
ed by the author for the determination of traces of heavy metals in urine. Although the
sensitivity for lead in aqueous solution is about 0.5 ppm, the extraction of this metal
into 2-methyl-4-pentanone enables its determination at the 0.01 ppm level in urine
with a standard deviation of 0.002 ppm [183].
The chelating agent used by both Allan and the author was ammonium pyrrolidine
dithiocarbamate, which is easily prepared from pyrrolidine, carbon bisulfide, and ammo-
nia [184-186], and is commercially available. It chelates with some 30 heavy metals and
can be used at pH values as low as 2, though for extraction from very acid solutions
other chelating agents may be superior, e.g., the substituted dithiocarbamidates described
by Bode and Neumann [187]. Since mutual interference between heavy metals is not
normally found in atomic absorption spectroscopy, there is usually no advantage in
using more specific chelating agents such as prove desirable in colorimetric work.
One advantage of the extraction technique is that sodium and other light metals are
left behind in the aqueous phase. In the analysis of materials which may contain relatively
high concentrations of sodium or calcium, errors due to the background absorption
effect (Section 10.4.4.5) may thereby be avoided.
Another method of concentrating small amounts of heavy metals from large volumes of
solution is by absorption on a chelating resin, followed by elution with acid [188].
10.5.3 PREPARATION AND HANDLING OF SAMPLES
Liquids may frequently be sprayed directly, or after dilution with water or other suitable
solvent. Oils for instance are usually diluted with 2-methyl-4-pentanone, kerosene, or
xylene [182, 189, 190]. Protein-containing fluids, such as blood serum, are often diluted
with trichloracetic acid solution to precipitate the protein. For determination of trace me-
tals in liquids such as urine, extraction into a non-miscible organic solvent is employed
(Section 10.5.2). The usual microchemical precautions against contamination must of
course be observed.
Biological material such as animal or plant tissue may be ashed by a suitable dry- or
wet-ashing technique. Care must be taken if quantitative recovery of volatile metals
such as mercury, arsenic, and selenium is required [191, 192], and use oflow-temperature
ashing in electronically excited oxygen may be advantageous in such cases [193].
Metals and ores are usually dissolved in suitable acids, while for rocks a hydrofluoric
acid treatment or fusion with lithium metaborate is usually necessary [172, 194].
10.5.4 CALIBRATION AND MEASURING TECHNIQUES
Standard solutions containing 100-1000 [Lgjml of the metal to be determined may be

prepared from weighed quantities of the metal or of an appropriate stoichiometric salt,
and acidified with hydrochloric acid if necessary to prevent hydrolysis. Working stan-
dards are made up by dilution as required, and should not be stored longer than a few
days, as adsorption of metal ions from very dilute solutions onto the walls of the con-
taining vessel is not uncommon. These working standards will, of course, have added to
them any interference-controlling material which has been added to the sample solutions.
Since the concentrations of metals normally measured in atomic absorption work are
very low (usually in the [Lgjml range), the precautions to be observed in handling samples
and standards are similar to those required with other methods of trace-element analysis,
e.g., flame photometry or colorimetry. All glassware should be of Pyrex or other borosili-
cate glass, and should be acid-washed, particularly when traces of heavy metals are to be
determined. Only de-ionized water or distilled water from a borosilicate glass still should
be used. Solutions for measurement are conveniently held in polythene cups, which
should be covered except when the solutions are actually being sprayed.
For most work it is usual to make up about four working standards covering the con-
centration range expected in the sample solutions and to measure the solutions in the
order standards, samples, standards, samples, standards. The three measured absorban-
ces for each standard solution are averaged and plotted against concentration to give a
calibration curve, and the concentration of each sample is read off by interpolating on this
graph the mean of its two measured absorbances. For optimum precision the absorbance
of the sample solution should lie in the range 0.1-0.7.
The absorbance-concentration curve in many cases will either be a straight line or have
at the most a slight curvature towards the concentration axis. Any errors in making up
the working standards will be readily detected from points lying off this line. The degree
of curvature will also tell the experienced worker whether the operating conditions of
the hollow-cathode tube and monochromator are correct (Section 10.5.1). Some causes
of curvature in concentration-absorbance graphs have been discussed by various authors
[195,196].
Some authors [85] plot percentage absorption against concentration, which is satisfacto-
ry for most routine work. However, since this method necessarily yields a curve which
approximates to a straight line only at very low absorptions, it is less easy to detect any
errors in the concentrations of the working standards and to assess the performance of
the sharp-line source and monochromator. With scale-expansion methods, where the ab-
sorption to be measured is usually not more than 10-15 %, it is usual to plot the scale read-
ing directly against the concentration, which results in a calibration curve very close to a
straight line.
In some types of experiment it is necessary to measure as accurately as possible the
differences between the concentrations of a number of solutions all of approximately the
same strength. This can best be done by first verifying that the absorbance-concentration
curve is sensibly a straight line over the concentration range covered by the solutions
and then preparing a standard of about the same concentration. The sample solutions are
measured alternately with the standard and their concentrations calculated directly from
the ratio of the absorbances. Alternatively each sample may be "bracketed" between
two standard solutions.
In some analyses where interferences cannot be fully controlled, as in the determination
of strontium in the air-acetylene flame [197], or where the viscosity of the sample and stan-
dard solutions would differ markedly, the standard addition method may be used. If
the absorbance-concentration curve is known to be a straight line, and if the absorbance
of the sample solution of concentration x is Dl and that of a similar solution to which a
known concentration a of the metal has been added is D 2 , then x can be calculated from
the relation
(6)
It is advisable to check the result by measuring also the absorbance D3 of a similar solu-
tion with a different added concentration of metal h. If the assumption of linearity holds,
the two values of x should agree, and if not, an approximate figure for x may be derived
from the three measurements [198,199].
A method of wider application in the determination of metals where interferences
cannot be fully controlled and where the calibration curve is not a straight line has been
described by Bowman and Willis [172]. A calibration curve is drawn, and relative to this
are measured the concen trations of metal in a sample solution without and with the
addition of a known concentration of the metal. The percentage recovery of the added
metal found in the second measurement indicates the correction to be applied to the re-
sults of the first measurement to correct for interference.
The author feels that the standard addition method is useful as a check on other me-
thods but should be used with great caution if the causes of interference cannot be found
and corrected for. The method is based on the assumption that the interfering material
alters the absorbance of the added metal to the same extent as it does that of the metal
in the original sample. This may not always be so, particularly when only a small amount
of interfering material is present, and consideration of the shape of the curves relating
absorbance to concentration of interfering material (Section 10.4.4.4) explains why.
10.5.5 DEVELOPMENT AND ASSESSMENT OF SPECIFIC ANALYTICAL PROCEDURES
When developing a specific procedure for the determination of a given metal in a particu-
lar type of material, likely causes of interference should be investigated and if possible
corrected for by techniques of the type discussed in Section 10.4.4. Finally, the proposed
procedure should be assessed with regard to its accuracy and reliability. The following
criteria are suggested for this purpose:
1. The results obtained by atomic absorption spectrometry should agree, over the widest
possible range of sample composition, with those of a reliable and well-tested alternative
method.
2. Different variations of the atomic absorption technique should give the same results.
3. Measurements on different quantities of the sample should yield the same final result
in terms of concentration.
4. Known quantities of metal added to the sample should be quantitatively recoverable.
5. The standard deviation of the method should be satisfactory for the purposes for
which the analysis is required.
Criterion 1 is unfortunately difficult to fulfill in many instances, as in many determina-
tions the atomic absorption technique is likely to yield results which are more accurate
than those obtainable by any other convenient method. Frequently. too, study of con-
ventional methods shows that they leave much to be desired in the matter of absolute
accuracy even if their reproducibility is satisfactory. In the development of an atomic ab-
sorption method for determining calcium and magnesium in blood serum, for instance, it
was found that the existing methods of analysis gave discrepant results (Table lO.VIII).
TABLE 10.VIII
MEAN CALCIUM AND MAGNESIUM CONTENT OF NORMAL SERA (a)
Method No. of sera Ca, mg./ Mg, mg./

measured 100ml 100m!.
Spectrographic 86 8.6 1.90

Removal of Ca and protein followed by colo-
rimetry with Eriochrome Black T 24 - 2.10
Direct titration with EDTA 710 9.7 -
Precipitation with oxalate followed by KMn04
titration 712 10.5 -
Flame photometry 22 10.8 -
Removal of protein followed by colorimetry
with murexide and Eriochrome Black T 34 9.S 2.02
a Data reproduced, by permission of Nature, from reference [200].

10.6] APPLICATION TO INDIVIDUAL ELEMENTS 567
Furthermore, the most widely accepted standard method for the determination of cal-
cium (precipitation with oxalate followed by potassium permanganate titration) was
known to depend for its accuracy on the cancellation of opposing errors, and the results
obtained would therefore be influenced by small variations in technique.
Criterion 2 is particularly useful when dealing with biological fluids. In the author's
work on the determination of magnesium in blood serum [201], consistent results were
obtained using four variations oftechnique: (1) measurement of directly diluted serum with
addition of EDTA to control protein interference; (2) measurement of directly diluted
serum using strontium chloride for the same purpose; (3) prior removal of organic ma-
terial by dry ashing; and (4) prior precipitation of proteins by addition of trichloroacetic
acid.
Criterion 3 is a rapid means of testing simple methods, particularly those which depend
on direct dilution of the sample with water, as interferences normally decrease with dilu-
tion. In the author's work on the determination of potassium in blood serum [155], it was
the apparent variation of the potassium content of the serum found by measuring solu-
tions of different dilution that led to the discovery of the interference caused by the pre-
sence of sodium.
Criterion 4 is very commonly applied in the development of all types of analytical
methods. Fulfillment of this test is a necessary but not sufficient condition for the reliabili-
ty of the proposed procedure. For instance, in an atomic absorption method where there
is loss of light by background absorption (Section 10.4.4.5), quantitative recovery of added
metal could well be obtained even though the method gave high results for the metal pre-
sent originally.
Criterion 5 should be applied by carrying out a number of parallel determinations
(usually not fewer than six, and ideally at least sixteen [201a]), starting with the original
sample in each case. In this way the whole analytical procedure is tested, and not merely
the accuracy of measurement of the absorption of the solution. With a single-beam in-
strument the relative standard deviation in reading the absorbance is usually about 0.2-1 %
even when a very stable sharp-line source is being used, and this variation seems due to
fluctuations in the rate of atomization of the sample. Relative standard deviations of
about 0.6 %-0.9 % have been quoted for repetitive measurements on one solution in the de-
termination of a major constituent with a modern single-beam instrument [172], and
these figures can probably be improved slightly by use ofa double-beam instrument [202].
10.6 Application to individual elements
Table 10.II shows the approximate sensitivities for nearly seventy metals which have been
investigated in atomic absorption using an appropriate flame to atomize the metal. Not
all these metals, however, have been investigated in practical analytical situations, so that
much work remains to be done on the choice of absorbing line under different conditions,
types of interference to be expected, etc.
In the detailed description of the applications of atomic absorption spectrometry which
follows no attempt has been made to give an exhaustive coverage of the literature, parti-
cularly regarding applications of the technique to the analysis of specific materials. Several
of the manufacturers of atomic absorption equipment issue books of analytical methods,
and these may be consulted for details.
10.6.1 ALUMINIUM
Aluminium is not appreciably atomized in low temperature flames, and has served as the
prototype element in the development of methods for the determination of metals that form
refractory oxides. Robinson [78] obtained fair sensitivity by spraying a solution of an
aluminium salt into a spark discharge, and several workers [49, 129, 130] successfully
atomized this metal by spraying solutions in organic solvents into a turbulent oxygen-ace-
tylene flame. Aluminium can be determined both in oxygen-nitrogen-acetylene and in ni-
trous oxide-acetylene flames [18, 131]. There are several suitable absorption lines, the
most useful one lying at 3092.7 A. Atomic absorption methods have been described for
the determination of aluminium in alloys [131,203] and in bauxite [172].
10.6.2 ANTIMONY
This metal is satisfactorily atomized in an air-coal gas flame and is not subject to chemical
interferences. Mostyn and Cunningham [204] have discussed the relative merits of
different absorbing lines and have described methods for the determination of antimony
in lead and other alloys.
10.6.3 ARSENIC
Allan [20] showed that the most sensitive resonance line of this element, at 1890 A, was
less suitable than that at 1937 A for use in analysis because of excessive absorption by the
flame gases, and this has been confirmed by later workers [205, 206]. An air-acetylene
[205, 206] or air-hydrogen [21] flame is recommended, and methods have been described
for determining arsenic in copper-arsenic alloys [206] and in glass [205].
10.6.4 BARIUM
This metal is incompletely atomized in the air-acetylene flame, even when an excess of ace-
tylene is used, and is also subject to serious interferences. In the nitrous oxide-acetylene
flame, however, good sensitivity is shown, though it is necessary to suppress ionization
by addition ofa high concentration ofa salt of potassium or cesium [18, 172]. The deter-
mination of barium in lubricating oils, frequently carried out by flame photometry [207],
using the air-acetylene flame has been described [182], though this analysis may be carried
out more efficiently with the help of the nitrous oxide-acetylene flame [208]. Barium at
the 100-1000 ppm level in silicate rocks may also be determined using the latter flame
[172].
10.6.5 BERYLUUM
Beryllium is only very slightly atomized in the air-acetylene flame [48, 209], but if the air
is enriched to contain 30% oxygen the metal can be determined with good sensitivity, and
with the nitrous oxide-acetylene flame a sensitivity of 0.02 Ilg/ml for 1 % absorption is
found [18]. A method has recently been described for the determination of beryllium in
process liquors using this flame [210].
10.6.6 BISMUTH
Bismuth is atomized satisfactorily in low-temperature flames and seems free of interfe-

rences. There are several absorbing lines of about the same sensitivity [48], but the one
at 3067.7 A originally recommended [22] lies in the middle of an absorption band due
to the OR-radical and hence is subject to flame noise; the line at 2230.6 A is preferable.
There is little published work on this metal except a method for its determination in urine
using an extractive technique [183], and its absorption characteristics in a turbulent
oxygen-acetylene flame [21Oa].
10.6.7 BORON
This element requires a fuel-rich nitrous oxide-acetylene flame for adequate atomization,
and even then the sensitivity is only about 50 [Lg/ml for 1 % absorption [18]. The degree
of atomization depends on the boron compound used; sodium tetra borate, for instance
shows 10-15 % higher sensitivity than does boric acid [19]. There are two resonance
lines lying only 0.9 A apart, whose oscillator strengths differ by a factor of two, so that
for optimum sensitivity a narrow slit width is necessary. The determination of boron in
biological materials has been described [210b].
10.6.8 CADMIUM
Cadmium is atomized in low-temperature flames, andisnot subject to interferences. The

resonance line at 2288.0 A shows very high sensitivity; that at 3261.1 A, which is due to a
forbidden singlet-triplet transition, shows less sensitivity and may be useful when deter-
mining high concentrations of the metal. The high stability of the emission of the cadmium
hollow-cathode lamp allows the use of scale expansion to improve the limit of detection.
The high sensitivity required for biological and toxicological work can be obtained by
use of the long-tube technique [211, 212] or by extraction into an organic solvent [183].
Other applications of the atomic absorption technique to the determination of cadmium
are in the analysis of steel [213], zinc ores [214], and uranium metal and its salts [215].
Dagnall, West, and Young [216] have recently compared the merits of atomic absorption
and atomic fluorescence spectroscopy in the determination of cadmium and found the
latter technique to be more sensitive.
10.6.9 CALCIUM
Calcium was one of the first metals to be studied by atomic absorption methods, and is
of particular interest because of its importance in many branches of agriculture, biology,
and medicine. It is very incompletely atomized and subject to severe chemical interferen-
ces in air-coal gas or air-propane flames, but an air-acetylene flame is satisfactory in most
applications, the sensitivity being best in a moderately fuel-rich flame [217] and the con-
centration of calcium atoms being somewhat localized in the flame. Interferences occur
from aluminium, which forms refractory calcium aluminates [160], and from anions
such as phosphate, sulphate and silicate [218]. Slight ionization interference is also found.
In a turbulent-flow oxygen-hydrogen flame [163] interferences are worse than in the pre-
mixed air-acetylene flame used by most workers. These interferences can usually be over-
come in the presence of salts of strontium, lanthanum or of EDTA as discussed in Section
10.4.4.4. Hinson [219] has found it possible to determine calcium in plant materials using
an air-coal gas flame providing anions are first removed by an ion-exchange treatment.
The sensitivity for calcium can be improved, and the interferences removed, by use of
the nitrous oxide-acetylene flame, though it is desirable to suppress ionization of the
metal by addition of a potassium salt [18, 125].
The atomic absorption method has been applied to the determination of calcium in
many materials; among them may be mentioned blood serum [167, 220, 221], urine [92],
saliva [222], soils [223], plant materials [126,219], cerebro-spinal fluid [224], glass [225],
and cement [202,226].
A thermal-type resonance detector (Section 10.3.3.2) may be used in calcium determina-
tions, and the performance of such an instrument in the determination of calcium in coal
ash [227] and in blood serum [95] has recently been described.
10.6.10 CERIUM
Neither Mossotti and Fassel [50] using an oxygen-acetylene flame and solutions in or-
ganic solvents, nor Amos and Willis [18] using a nitrous oxide-acetylene flame and aqueous
solutions, were able to detect atomic absorption for this metal. Ramirez-Munoz and
Roth [23], however, using the latter flame and a heated spray chamber, were able to detect
cerium with a sensitivity of 83 [Lg/ml for 1 % absorption, and this figure could be improv-
ed somewhat by using three passages of light through the flame. Since the cerium spec-
trum has not yet been fully analyzed it is possible that there may be a more sensitive
line than the one at 5200 A used by these workers.
10.6.11 CESIUM
The cesium resonance line at 8521.1 A lies further in the red than that of any other metal,
and use of a special red-sensitive photomultiplier and a filter to remove stray light is ad-
visable with some instruments. Cesium is atomized in air-coal gas or in air-propane
flames; since it is highly ionized (Fig. 10.12) the addition of an excess of a salt of another
easily ionized metal [228] is necessary.
A less sensitive line lies at 4555.4 A [22].
10.6.12 CHLORINE
Although as mentioned in Section 10.4.1 this element cannot be measured directly using a
flame to atomize the sample, an indirect method for the determination of chloride ion in
metal oxides has been described [229]. The sample is dissolved in nitric acid and the chlo-
ride precipitated as silver chloride, which is then dissolved in ammonia and sprayed into
the flame for the determination of silver.
10.6.13 CHROMIUM
Chromium is sufficiently well atomized in an air-acetylene flame to enable useful atomic

absorption measurements to be carried out, but the degree of atomization is far from com-
plete and interferences, particularly from iron and nickel, occur. The sensitivity is greatest
in a fuel-rich flame, but the interferences also are greater in this flame than in a leaner one
[230]; these interferences may be greatly reduced by the addition of ammonium chloride
[231]. Use of the nitrous oxide-acetylene flame would probably be advantageous for this
element.
The most sensitive chromium resonance line lies at 3578.7 A which in some argon-filled
hollow-cathode lamps may be partially obscured by the argon lines at 3576.6 A and
3582.3 A. A neon-filled hollow-cathode lamp is advantageous, or the 3593.5 A line may
be used instead [232].
Chromium in the hexavalent form may be quantitatively extracted from acid solution
by 2-methyl-4-pentanone and this solution sprayed into the flame for atomic absorption
measurement [233].
Application of the atomic absorption technique has been made to the determination of
chromium in blood and urine [234, 235], faeces [236], lubricating oils [189, 190, 237],
steels [232], aluminium alloys [237a], and biological materials [237b].
10.6.14 COBALT
Cobalt is atomized in an air-acetylene flame, and it is not subject to any significant inter-
ferences.
The most sensitive line in absorption, though not the strongest in emission, is at 2407.3
A [238]; the presence of an ionized cobalt line at 2407.7 A produces strong curvature in
the calibration graph (Section 10.5.1.3). Harrison [239] has discussed the factors involved
in choice of the best cobalt absorption line under different conditions.
The determination of cobalt in steels [240, 241], alloys [242], glass [225], natural
waters [243], and soil extracts [243a] has been described.
10.6.15 COPPER
Copper is efficiently atomized even in an air-coal gas or air-propane flame, its determina-
tion by atomic absorption spectroscopy is remarkably easy, and no significant interferen-
ces have been reported. There is a considerable choice of absorbing lines [122], but most
workers use the most sensitive one, which lies at 3247.5 A. The precision of the method
has been examined by Khalifa et al. [244].
Among the many published determinations of copper by the atomic absorption techni-
que mention may be made of the analysis of plants, soils and fertilizers [85, 122,245,246],
wines [36], butter [177, 247], blood and urine [248-250], lubricating oils [188, 189], ores
[107], electroplating solutions [251], silicate rocks [252], steels [253] and other metals
[139, 254], and sea water [255,256].
The performance of a resonance monochromator in the determination of copper in

ores has recently been described [257].
10.6.16 DYSPROSIUM
This metal requires an oxygen-acetylene [50, 53] or nitrous oxide-acetylene [18, 24] flame
for adequate atomization, and ionization should be suppressed by the addition of an
excess of potassium chloride. The presence of sulphuric or phosphoric acids, surprisingly
enough, slightly enhances the absorption of dysprosium in the nitrous oxide-acetylene
flame [18].
A comparison has been made of the nitrous oxide-acetylene and oxygen-acetylene
flames in the determination of this and other rare-earth metals [257a].
10.6.17 ERBWM
This metal behaves very similarly to dysprosium, and has been studied by the same
workers.
10.6.18 EUROPIUM
This metal also behaves very similarly to dysprosium and has been studied by the same
authors. It has also been investigated by Skogerboe and Woodriff [43], who sprayed a
europium salt solution into an oxygen-hydrogen flame as a source of line emission and
used an oxygen-acetylene flame to atomize the sample solution, which was made up in
ethanol. The determination of europium in phosphate rock has been briefly described by
Kinnunen and Lindsj6 [258].
10.6.19 FLUORINE
Although, as mentioned in Section 10.4.1, fluorine cannot be measured directly by using a

flame to atomize the sample, indirect methods have been developed for its determination
by atomic absorption spectroscopy. In the absence of other interfering anions such as
phosphate, fluoride ion may be determined at concentrations as low as 0.2 fLg/ml by its
very marked interference with the absorption of magnesium in the air-coal gas flame.
At somewhat higher levels, and in the presence of other anions, the enhancing effect of
fluoride ion on zirconium absorption may be used instead [259, 260].
10.6.20 GADOLINIUM
This metal behaves very similarly to dysprosium and has been studied by the same authors.
10.6.21 GALLWM
Gallium can be atomized without difficulty in low-temperature flames, and there are
10.6] APPUCATION TO INDIVIDUAL ELEMENTS 573
several suitable lines with good sensitivities in absorption [22]. Mulford [261] has in-
vestigated the experimental conditions in the determination of this metal and shown that
there is relatively little interference from metals such as aluminium, magnesium, and
copper in an air-acetylene flame.
10.6.22 GERMANIUM
This metal shows slight absorption in a rich air-acetylene flame (sensitivity ca. 120 (.Lg/ml
for 1 % absorption) and somewhat greater sensitivity in an air-hydrogen one, but use of a
high-temperature flame is necessary to achieve adequate sensitivity for analytical pur-
poses [18]. The choice of absorption line has been discussed by Manning [262] and the
choice of flame conditions by Popham and Schrenk [262a].
10.6.23 GOLD
Gold is satisfactorily atomized in an air-coal gas or air-propane flame. It was reported

by Lockyer and Hames [l05] that the absorption due to this metal decreased as the burner
warmed up, and that the effect was minimized by using a water-cooled burner. This effect,
which was apparently connected with the decomposition of gold salts by the brass of the
burner, has not been found by later workers [22,263]. Interferences are not encountered
to any great extent [263, 264], and the precision of the determination has been studied
by Khalifa, Svehla, and Erdey [244].
The chief interest in the application of the atomic absorption technique is in the analysis
of ores after extraction with cyanide solution [265, 266] or aqua regia [267], and in the
analysis of mill liquors [268, 269]. Gold in the trivalent form is readily concentrated by
extraction into methyl isobutyl ketone [270], or as an iron-phenanthroline complex
into chloroform [270a]. In the monovalent form it may be extracted from cyanide
solution into di-isobutyl ketone with the help of a quaternary ammonium salt [270b].
10.6.24 HAFNIUM
Amos and Willis [18] demonstrated that this metal is atomized in the nitrous oxide-
acetylene flame and shows reasonable absorption at several wavelengths. The sensitivity is
enhanced considerably in the presence of hydrofluoric acid and of high concentrations of
iron.
10.6.25 HOLMIUM
This metal behaves similarly to dysprosium, and has been studied by the same authors.
10.6.26 INDIUM
Indium is atomized in low-temperature flames [48], and there are several suitable wave-
lengths for measurement of its absorption. The choice of experimental conditions has
been studied by Mulford [271], who has shown that in the air-acetylene flame there is little
interference from moderate concentrations of aluminium, magnesium, copper, or com-
mon anions.
10.6.27 IRIDIUM
Iridium is atomized satisfactorily in the air-acetylene flame, and absorbs at several wave-
lengths, of which the most sensitive is 2088.8 A [19] although at this wavelength a narrow
slit is required to prevent passage of neighbouring non-absorbing lines. Use of the 2639.7
A line is recommended for most purposes [272].
10.6.28 IRON
Iron is atomized satisfactorily in the air-acetylene flame and is singularly free from inter-
ference except by silica, whose effect can be eliminated by the addition of calcium chlo-
ride [273].
Iron has a number of suitable absorption lines, the most sensitive of which lies at
2483.3 A [274] though since the iron spectrum is fairly complex in this neighbourhood
most effective use of this line requires a monochromator with good resolution.
Typical applications of the absorption technique are to the determination of iron in the
following materials:
Blood serum and urine [276-278], plants [85, 274], fertilizers [246], lubricating oils
[189, 190,237], alloys [275, 279], coal ash [280] and waters [188,273,281].
10.6.29 LANTHANUM
This metal behaves very similarly to dysprosium and has been studied by the same au-
thors.
10.6.30 LEAD
A low-temperature flame is adequate for the atomization of this metal, and there is little
interference from other metals, particularly if an air-acetylene rather than an air-propane
or air-coal gas flame is used. Chakrabarti, Robinson, and West [282], using a turbulent
flow oxygen-hydrogen flame, found no interferences from cations, but some from common
anions; these effects could be overcome by the addition of EDTA. Low levels of lead in
liquid samples can be concentrated where necessary by an extraction technique [183],
or by co-precipitation with bismuth nitrate [283].
Atomic absorption methods have been developed for the determination of lead in
blood and urine [183,234,283-285], metals and alloys [279,286-288], gasoline [289-291],
worn lubricating oil [189, 237], electroplating solutions [292], wines [36], glass [225]
and air [292a].
10.6.31 LITIUUM
This metal shows great sensitivity in emission and the flame photometric technique has
been widely used in its determination. An air-coal gas flame atomizes lithium satisfac-
torily, and the loss of neutral atoms by ionization is less than for the other alkali metals
(Section 10.4.4.3). Little work has been published on the determination of lithium using
the atomic absorption method, though Patassy [293] has described the analysis of waters
and plant materials. Bowman [294] has determined lithium in blood serum and has com-
pared the results obtained with conventional and resonance monochromators.
The lithium resonance line at 6707.8 A is actually a doublet with a separation of about
0.15 A, and since the isotope shift between 6Li and 7Li is also 0.15 A one line of 6Li is
superimposed on one line of 7Li. In spite of this Zaidel' and Korennoi [27] and Manning
and Slavin [42] demonstrated the possibility of isotope analysis of lithium using a flame
to vaporize the material. Goleb and Yokoyama [60] extended this technique, using a
sputtering cell to vaporize the sample of lithium metal. Efforts to measure the lOB/llB
isotopic ratio, however, were not so successful, as the half-widths of the absorption lines
appear to be greater than the isotopic separation [295].
10.6.32 LUTETIUM
This metal behaves very similarly to dysprosium and has been studied by the same
authors. It has also been studied by Fernandez and Manning [295a].
10.6.33 MAGNESIUM
The determination of magnesium in agricultural materials was the first practical analysis
to which the atomic absorption technique was applied [84] and it remains the most sensi-
tive of all the analyses. Magnesium is difficult and tedious to determine by other means,
and atomic absorption is almost always the method of choice. The determination is very
easy and subject to few interferences, and several dozen papers have been published on the
application to different materials. For determination of higher concentrations of the metal,
the line at 2025.8 A may be used instead of the usual 2852.1 A line [296].
Although magnesium is atomized fairly well in the air-coal gas or air-propane flame, the
absorption depends on the exact composition of the gas used and the part of the flame
at which the absorption is measured [297]. Numerous chemical interferences, both from
cations and anions, are encountered in such flames [159-162,298] and also in turbulent-
flow oxygen-hydrogen flames [163]. Some of these interferences can be overcome by the
addition of materials such as 8-hydroxyquinoline or EDTA. The theory of these inter-
ferences and of the means of overcoming them has been discussed in Section 10.4.4.4.
A useful summary of the interferences found by different workers has recently been given
by Fleming and Stewart [299 J.
In the air-acetylene flame, which is now recognized as being far more satisfactory than
the air-coal gas or air-propane flame for the determination of magnesium, the only
common interfering material is aluminium, though high concentrations of phosphate and
of protein may have a slight effect on the absorbance of magnesium. These interferences
can be overcome by the methods discussed in Section 10.4.4.4.
Use of the nitrous oxide-acetylene flame eliminates interferences in the determination

of magnesium [18, 19] and even a flame burning acetylene with a 1:3 nitrous oxide-air
mixture is sufficiently hot to achieve this freedom from interference [300].
The atomic absorption method has been applied to the determination of magnesium in
a large number of biological materials, of which it will suffice to mention blood serum
[201,301-304], urine [92,301,303], and tissues [305]. There has been considerable study
of the relative merits of different methods for the determination of magnesium in blood
serum [306-308] and although it is not yet possible to reconcile all the data, it seems that
the atomic absorption technique is the method of choice.
In the agricultural field the determination of magnesium has been described in plant
materials [84, 85, 245, 309], soils and soil extracts [223, 310], and fertilizers [246].
Iron [311], uranium [312] and other metals [169,298,313] have been successfully ana-
lysed for magnesium, and the method has also been applied to materials such as silicate
rocks [314], cement [226] and coal ash [280]. Sullivan and Boar [315] have compared
the performance of conventional and resonance monochromators in this last analysis.
10.6.34 MANGANESE
Manganese is atomized satisfactorily in the air-coal gas flame, though the air-acetylene one
is more generally used. Allan [274] early studied the determination of this metal in the
latter flame, and found absorption at several wavelengths, of which 2794.8 A is the most
sensitive. Apart from silicon, interfering elements are few, and the effect of this element
can be overcome by measuring the absorption in the middle of the flame only [316] or by
adding an excess of calcium chloride [273]. Manganese can be concentrated by extraction
from aqueous solution into an organic solvent using 8-hydroxyquinoline, though more
care is required to achieve complete separation than is usual with other metals [317, 318].
Materials in which manganese has been determined include soils and plant materials
[274], fertilizers [246], iron, steel, and other metals [316, 319], cement [226], glass [225]
and natural waters [273].
10.6.35 MERCURY
Mercury is atomized readily even in low-temperature flames, but the efficiency of atomi-
zation seems to depend very much on the valency state, the absorption due to Hg+ being
about three times that due to Hg++ [320]. The absorption is considerably increased by
introducing a reducing agent such as stannous chloride at the point of nebulization [320]
or by spraying a solution of this material immediately before spraying the mercury solu-
tion [19]. The presence of stannous chloride reduces the Hg+ and Hg+ + salts to the metal,
whose vapour then passes into the flame; this is confirmed by the fact that absorption
is obtained under these circumstances even if no flame is used [321]. The sensitivity of
the determination can be greatly improved by use of the long-tube technique.
The spectral line generally used is the well-known one at 2536.5 A. This line, however, is
due to a forbidden singlet-triplet transition and in principle the true resonance line at
1849 A should give fifty times greater sensitivity. This wavelength, however, lies just
beyond the point where flame and atmospheric absorption become prohibitive. It is
possible that mercury determinations could be carried out at 1849 Awith a suitable choice
of flame and the use of a vacuum or nitrogen-purged monochromator, but so far no work
at this wavelength has been reported.
The only published work on the determination of mercury by atomic absorption using
a flame seems to be that of the author on the determination of traces of the metal in
urine, using an extraction technique [183].
Although, strictly speaking, lying outside the scope of Analytical Flame Spectroscopy,
several interesting techniques have been described for the determination of traces of mer-
cury in soils and in organic materials. The metal is liberated from the material by heating
in a flame [322] or a furnace and the vapour collected in a long absorption tube where the
absorption of the 2536.5 A line is measured. The principal difficulty is the fact that so
many organic vapours absorb strongly in this region, and some means has to be provided
to overcome this interference. Methods which have been used include double-beam sy-
stems in which one beam traverses untreated vapour and the other traverses vapour from
which the mercury has been removed by absorption in palladous chloride solution [323]
or gold [324]. An elegant method has recently been developed by Ling [325] in which the
sharp-line absorption by mercury atoms at 2536.5 A, though not molecular absorption at
this wavelength, is suppressed by admission of nitrogen to one of the absorption cells
of the double-beam system.
10.6.36 MOLYBDENUM
This metal is sufficiently atomized in a rich air-acetylene flame for useful measurements to
be possible but the absorption is highly dependent on the gas mixture used and the height
above the burner at which the light beam traverses the flame, as shown in Fig. 10.10.
Early work [127] suggested that the interfering effects could be overcome by the addition
of an excess of aluminium chloride, but later ammonium chloride was found to be
more satisfactory [326]. Use of the nitrous oxide-acetylene flame leads to better atomiza-
tion of molybdenum and the absorption is not so dependent on flame conditions as it is
in the air-acetylene flame [18].
Using the air-acetylene flame, methods have been described for the determination of
molybdenum in fertilizers [127], in steels [127, 326] and in natural waters using an ex-
traction technique [327]. The analysis of steels and of niobium and tantalum metals for
molybdenum is improved by the use of the nitrous oxide-acetylene flame [328, 329].
10.6.37 NEODYMIUM
This metal behaves very similarly to dysprosium, and has been studied by the same authors·
The determination of neodymium in phosphate rocks has been discussed briefly by Kinnu-
nen and Lindsjo [258].
10.6.38 NICKEL
Nickel is atomized satisfactorily in an air-coal gas or air-acetylene flame and few inter-
ferences have been reported.
The line at 2320.0 A, while not the strongest in emission, is the most strongly absorbed
line [238], though it suffers from the drawback of being close to the Ni+ line at 2319.9 A
SO that use of a high-intensity hollow-cathode lamp (Section 10.3.1.3) is generally neces-

sary if a straight calibration graph is desired. The line at 3414.8 A, while somewhatless
sensitive than that at 2320.0 A, does not suffer from this disadvantage.
The atomic absorption technique has been applied to the determination of nickel in
such materials as blood and urine [234, 330-332], steel [333], alloys [279], worn lubri-
cating oils [190,237], crude petroleum [334], and waters [188].
An interesting application of the determination of nickel has been described by
Densham, Beale, and Palmer [335] who determined nickel and iron carbonyls in coal gas
by burning the sample with air at the burner of an ordinary atomic absorption instru-
ment. Using the 2320.0 A line, a detection limit of 0.002 ppm (v/v) of nickel carbonyl
was obtained.
Sullivan, Timms and Young [336] have compared the performance of conventional
and resonance monochromators in the analysis of ores for nickel.
10.6.39 NIOBIUM
This metal requires the oxygen-acetylene [49] or nitrous oxide-acetylene flame [18] for
atomization.
Recent work by Manning [262] suggests that the 3343.7 A line is slightly more sensitive
than the one at 3349.1 A shown in Table 10.II.
Niobium may also be determined indirectly by conversion to molybdeniobiphosphoric
acid, which is extracted into isobutyl acetate and measured by atomic absorption for
molybdenum [337].
10.6.40 OSMIUM
This metal is partially atomized in an air-acetylene flame but shows higher sensitivity in a
nitrous oxide-acetylene one. There are a number of absorbing lines, of which the most
sensitive is that at 2909.1 A [19, 337a].
10.6.41 PALLADIUM
Palladium is atomized satisfactorily in air-coal gas or air-propane flames, and apart from
strong acids [263, 338] and iron [339] no significant interferences have been noted. The
2476.4 A line is normally used though according to Erinc and Magee [338] that at 2447.9
A is slightly more sensitive. Strasheim and Wessels [263] claimed that the 3403.6 A
line was far more sensitive than the 2476.4 A one, but this was probably because their
hollow-cathode lamp had high background emission in the region of the latter line [340].
Use of ethanol or other alcohols as solvents instead of water improves the sensitivity for
palladium by as much as sevenfold [338].
Methods have been described for the determination of traces of palladium in gold [139]
and in copper [264].
10.6.42 PHOSPHORUS
Althouih as mentioned in Section 10.4.1 this element cannot be measured directly using a
10.6] APPUCATION TO INDIVIDUAL ELEMENTS 579
flame to atomize the sample, an indirect method for the determination of inorganic
phosphate has been described [341]. Ammonium molybdate is added to the sample
solution, the phosphomolybdic acid formed is extracted into 2-octanol, and the extract
is sprayed into the air-acetylene flame for determination of molybdenum.
10.6.43 PLATINUM
Atomization of this metal is sufficient in the air-coal gas or air-propane flame to enable
measurements to be carried out [105, 263, 264], but various interferences, both from acids
and from other cations, are encountered. These interferences are not completely removed
by use of the air-acetylene flame, but may often be minimized by adding a high con-
centration of copper to the solution to be analysed [263]; they seem to be reduced still
further in the nitrous oxide-acetylene flame [19].
No applications of the atomic absorption technique to actual analysis have been pub-
lished, though it is possible to determine platinum in jeweller'S waste with sufficient ac-
curacy for many purposes [19].
10.6.44 POTASSIUM
Low-temperature flames, especially if slightly fuel-rich, are adequate to achieve atomiza-

tion ofthis metal. Interferences are few [223], apart from the suppression of the ionization
of potassium by other alkali metals (Section 10.4.4.3), which is more marked in the air-
acetylene than in the air-coal gas flame. This type of interference can be removed by
addition of excess of a sodium salt, and Sanui and Pace [342] have shown that the ab-
sorption of potassium is not affected by varying amounts of sodium provided that excess
cesium is added.
The most sensitive line lies at 7664.9 A; a less sensitive one is found at 4044.1 A.
Methods have been described for the determination of potassium in blood serum [155,
343], plant materials and soils [223], cement [226], glass [225] and fuel ash [280].
Sullivan and Walsh [95] have shown that a thermal-type resonance monochromator
can replace the conventional monochromator in the determination of potassium in blood
serum.
10.6.45 PRASEODYMIUM
This metal behaves very similarly to dysprosium, and has been studied by the same au-
thors.
10.6.46 RHENIUM
The atomization of this element requires the use of an oxygen-acetylene [49] or nitrous
oxide-acetylene [18] flame. Schrenk, Lehman and Neufeld [344] have investigated the
distribution of rhenium in a turbulent-flow oxygen-acetylene flame and have found the
absorption to be affected by the presence of several cations, in particular calcium, manga-
nese, aluminium, and irDn.
10.6.47 RHODIUM
Although Lockyer and Hames [105] reported that rhodium can be satisfactorily atomized
in a low-temperature flame, other workers [263, 264] have found serious interferences,
particularly from sulphuric acid and from a number of cations. Heneage [345] has found
a lean air-acetylene flame to be best for rhodium, and has measured the sensitivities for a
number of spectral lines.
10.6.48 RUBIDIUM
The flame conditions required for atomization of this metal are very similar to those
needed for potassium, and once again, presence of excess of another alkali metal is ne-
cessary to ensure suppression of ionization. Slavin, Trent, and Sprague [346] have studied
the optimum choice of light source and flame for rubidium.
The most sensitive line lies at 7800.2 A, and there is a less sensitive one at 4201.8 A.
Few applications of the atomic absorptIon technique to the determination of rubidium
have been described, but mention may be made of Stupar's work on the analysis of agri-
cultural materiah. [347] and of the determination of rubidium in rocks and ores [348,
349] and in sea water [281].
10.6.49 RUTHENIUM
This metal is atomized in a fuel-rich air-acetylene flame and shows good sensitivity in
absorption [19,48], but no further work seems to have been published on it.
10.6.50 SAMARIUM
This metal behaves very similarly to dysprosium, and has been studied by the same
authors.
10.6.51 SCANDIUM
This metal requires an oxygen-acetylene [49] or nitrous oxide-acetylene [18, 24, 349a]
flame, but no applications have as yet been reported.
10.6.52 SELENIUM
Selenium is apparently best atomized in an air-hydrogen flame [20, 21] though the air-
acetylene flame is quite satisfactory and interferences do not seem to occur. The absorp-
tion of radiation by the flame gases, however, is considerable at the wavelength of the
most sensitive selenium resonance line (1960 A). The distribution of selenium atoms in the
air-acetylene flame has been studied by Rann and Hambly [128], who have also describ-
ed the determination of this element in wheat and in galena [44]. The determination of
10.6] APPLICATION TO INDNIDUAL ELEMENTS 581
selenium in copper and its alloys has also been described [350]. A study of absorption
of selenium in different flames has been made by Chakrabarti [350a].
10.6.53 SILICON
Silicon requires a fairly rich nitrous oxide-acetylene flame for effective atomization [18,
19], and its absorption is enhanced slightly by the presence of high concentrations of such
materials as aluminium, sodium hydroxide, and sodium borate [172]. Owing to high
emission from the flame, it is probably desirable to use a high-intensity hollow-cathode
lamp when the highest sensitivity is required in the determination of this element.
Silicon may also be determined by conversion to silicomolybdic acid, which is then
extracted into butanol and sprayed into the flame for measurement of the molybdenum
content [350b].
The determination of silicon has been described in bauxite [172], steels and alloys
[35Oc], cement [35Oc, 350d] and organic materials [350e].
10.6.54 SILVER
Silver is a particularly easy metal to determine by atomic absorption measurement, as it

is atomized satisfactorily in an air-coal gas or air-propane flame, shows high sensitivity,
and is not subject to interferences [105, 351-353].
The determination of silver in a number of materials has been described; these include
aluminium alloys [353], gold [139], lead, zinc and copper [264], lead concentrates [351],
ores [267], worn lubricating oil [189, 237], photographic film [354] and fine bullion
[354a].
10.6.55 SODIUM
Sodium is satisfactorily atomized in an air-coal gas or air-propane flame, and few inter-
ferences are encountered [76, 155,355,356], though large excesses of other alkali metals
will enhance the absorption of sodium, particularly in the air-acetylene flame (Section
10.4.4.3).
The most sensitive line is that at 5890.0 A .With a grating instrument this can normally
be resolved from the 5895.9 A component of the D-doublet, but most prism instruments
pass both lines, so that the calibration graph is curved in consequence of the lower sensitivi-
ty of the 5895.9 A component. A less sensitive line (again a doublet) is available at 3303 A.
Though the atomic absorption method is less sensitive than flame photometry for the
determination of sodium, it has the merit of not being subject to interferences from mole-
cular emission (Section 10.4.4.1). Applications have been found in the analysis of blood
serum [155, 343], soil extracts [223], rocks [357, 358], petroleum [76], glass [225], coal
ash [280], cement [226], and lamp phosphors [359].
Sullivan and Walsh [95] have compared the performance of conventional and resonan-
ce monochromators for the determination of sodium in blood serum.
10.6.56 STRONTIUM
Strontium is sufficiently well atomized in the air-acetylene flame to enable useful measure-
ments to be made, but it is subject to chemical interferences from cations such as alumi-
nium and from many anions; these interferences can be largely suppressed by the addi-
tion of excess lanthanum [360] though it is sometimes necessary to remove interfering
anions by ion-exchange [197]. A detailed study of interferences in both the air-propane
and air-acetylene flames has recently been made [360a].
In the absence of an excess of alkali metal, strontium is appreciably ionized in an air-
acetylene flame; the extent of the ionization may be as much as 20% in an oxidizing and
7 % in a reducing flame [360]. In the nitrous oxide-acetylene flame ionization is even more
marked, but if it is suppressed by the addition of an excess of alkali metal the determina-
tion of strontium with this flame is practically free of interferences, and the sensitivity is
better than that achieved with the air-acetylene flame [18, 172].
Methods have been described for determining strontium in soils and plant materials
[197], biological samples [360], coal ash [361], sea water [281], and rocks [172, 362].
10.6.57 SULPHUR
Although as mentioned in Section 10.4.1 sulphur cannot be measured directly using a

flame to atomize the sample, an indirect method for its determination in biological ma-
terials has been described [363]. The sample is oxidized to convert the sulphur to sul-
phate, which is precipitated as barium sulphate, and after solution in EDTA is sprayed
into the air-acetylene flame for determination of barium.
10.6.58 TANTALUM
Tantalum requires a nitrous oxide-acetylene flame for its atomization, and its degree of
atomization is improved considerably in the presence of iron and of hydrofluoric acid [18].
It may be determined indirectly in the same way as niobium [337].
10.6.59 TELLURIUM
Tellurium is atomized satisfactorily in a low-temperature flame, and no interferences have

been reported [363a, 363b]. Methods have been described for the determination of this
element in copper and copper-base alloys [350], in ashed biological material [364]
and in iron and steel [364a].
10.6.60 TERBIUM
This element requires an oxygen-acetylene [50, 53] or a nitrous oxide-acetylene [19,24]

flame for adequate atomization. Its behaviour is very similar to that of the other rare-
earth metals.
10.6] APPLICATION TO INDNIDUAL ELEMENTS 583
10.6.61 THALLIUM
Thallium is atomized satisfactorily in an air-coal gas flame and has several absorbing
lines, the most sensitive being that at 2767.9 A. Its determination in urine has been re-
ported (234).
10.6.62 THORIUM
Amos and Willis, using a nitrous oxide-acetylene flame, were unable to detect atomic ab-
sorption for thorium. Ramirez-Munoz and Roth [23], using this flame and a heated spray
chamber, were able to detect thorium absorption at the 3245.8 A line, but only with a
sensitivity of 850 [Lg/ml for 1 % absorption.
10.6.63 THULIUM
This element requires an oxygen-acetylene [50,53] or nitrous oxide-acetylene flame [19,

295a] for adequate atomization. Its behaviour is very similar to that of the other rare-
earth metals. Skogerboe and Woodriff [43] used as line source an oxygen-hydrogen
flame fed with a solution of a thulium salt, but a hollow-cathode lamp gives better
sensitivity and stability.
10.6.64 TIN
Tin is appreciably atomized in a rich air-acetylene flame, but rather better in an air-hy-
drogen flame [20, 21]. Capacho-Delgado and Manning [125] and Amos and Willis [18]
compared the sensitivities in these two flames, and found that interferences are rather
worse in the air-hydrogen flame. With regard to sensitivity the nitrous oxide-acetylene
flame lies between the other two, but interferences are less than in either [18, 19].
The optimum sensitivity is obtained by using the 2246.1 A line with the air-hydrogen or
air-acetylene flame and the 2354.8 A line with the nitrous oxide-acetylene flame. The rea-
son for this behaviour lies in the temperature-dependence of the populations of low-lying
states of the tin atom [18].
The determination of tin in alloys [125] and in hydrogen peroxide [365] has been des-
cribed. In the latter determination high sensitivity was obtained by use of a turbulent-
flow oxygen-hydrogen burner and the long-tube technique (Section 10.3.2.2). Tin has
been determined in cassiterite ores by heating with ammonium iodide and determining
tin on a solution of the sublimed stannic iodide [365a, 365b].
10.6.65 TITANIUM
This metal requires the use of an oxygen-acetylene [49, 129] or nitrous oxide-acetylene
[18] flame to achieve adequate atomization. Even in such flames atomization seems in-
complete, as the absorption is enhanced in the presence of hydrofluoric acid, iron and
aluminium [18, 172,366]. There is a considerable choice oflines showing absorption.
The atomic absorption method, using the nitrous oxide-acetylene flame, has been
applied to the determination of titanium in steels [172, 366, 367], cement [350d], and
bauxite [172].
10.6.66 TUNGSTEN
Tungsten requires the use of the nitrous oxide-acetylene flame for atomization [18], and
Manning [24] has measured the sensitivity at some of the numerous lines which show ab-
sorption.
10.6.67 URANIUM
Uranium requires use of the nitrous oxide-acetylene flame for atomization, and Manning
[24] has measured the sensitivity at some of the numerous lines which show absorption.
He reports that uranium is ionized to the extent of about 45 % in the flame, and that this
ionization can be suppressed by addition of an excess of an alkali metal salt.
Goleb [61], atomizing his samples in a sputtering cell, has determined the 235Uj238U
ratio of uranium metal by atomic absorption measurements. He used lines at 4153 A
and 5027 A, since these have isotope shifts approaching 0.1 A and show little hyperfine
structure.
10.6.68 VANADIUM
Vanadium is not appreciably atomized in the air-acetylene flame, but has been detected
using the oxygen-cyanogen [77], oxygen-acetylene [49, 129, 368] and nitrous oxide-
acetylene [18] flames.
Sachdev, Robinson, and West [369] have found that a number of cations, acids, and
detergents enhance vanadium absorption by 10-25 %, and show that these interferences
can be overcome by addition of an excess of aluminium to both sample and standard
solutions. Extraction by means of cupferron into an organic solvent was suggested by the
same authors [142] in order to improve the sensitivity of the determination when using a
turbulent-flow oxygen-acetylene flame.
The spectral line quoted in Table lO.n as lying at 3184.0 A actually consists of a group
of three lines (3183.4, 3184.0, and 3185.4 A) having about the same absorption intensity,
and which it is scarcely worthwhile trying to resolve.
Methods have been described for the determination of vanadium in steels [173], gas
oils [173], and fuel oils [172].
10.6.69 YTTRIUM
This metal requires the use of an oxygen-acetylene [53] or nitrous oxide-acetylene [18]
flame for effective atomization, and it is ionized to the extent of about 25 % in such a
flame [24].
REFERENCES 585
A method has been briefly described for the determination of this metal in phosphate
rock [258].
10.6.70 YTTERBIUM
This metal is appreciably atomized in the air-acetylene flame [19] but the use of the fuel-
rich oxygen-acetylene [43, 50] or the nitrous oxide-acetylene [18,24] flame is necessary to
obtain satisfactory sensitivity. Like the other rare earths it is partially ionized in such
flames.
10.6.71 ZINC
Zinc is atomized in an air-coal gas or air-acetylene flame and is not subject to any signifi-
cant interferences; the alleged effect of halogen acids on the determination of this metal
[113] was later shown [370] to be due to corrosion of the brass burners employed at that
time.
The high sensitivity and freedom from interferences of the atomic absorption method
have made it the method of choice for zinc in many fields of analysis. However, owing to
the fact that molecular absorption and scattering (Section 10.4.4.5) are appreciable at the
wavelength of the resonance line, 2138.6 A, a small correction may be needed when
measuring traces of zinc in the presence of large concentrations of other material.
Applications of the atomic absorption technique have been described to the determi-
nation of zinc in numerous materials, e.g., blood serum [275,371,372], urine [183], bio-
logical materials [250, 373], plant materials [85, 245, 374], fertilizers [246], wines [36],
silicate rocks [252,375], metals [113,319,376], glass [225], waters [188, 255, 273], and
electroplating solutions [251].
10.6.72 ZIRCONIUM
Zirconium requires the nitrous oxide-acetylene flame for satisfactory atomization [18, 24]
and the absorption is enhanced in the presence of iron, hydrofluoric acid and a number of
nitrogen-containing compounds [18, 260]. A brief note has recently appeared describing
the determination of this metal in thorium oxide samples [377], and a method has been
developed for determination of zirconium in aluminium alloys [237a].
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364. R. E. KINSER, Am. Ind. Hyg. Assoc. J. 27, 260 (1966).
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380. C. T. J. ALKEMADE, Appl. Optics 7, 1261 (1968).
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384. C. S. RANN, Spectrochim. Acta 238, 245 (1968).
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388. R. M. DAGNALL and T. S. WEST, Appl. Optics 7, 1287 (1968).
389. R. M. DAGNALL, K. C. THOMPSON and T. S. WEST, Talanta 14, 551 (1967).
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394. R. WOODRIFF and G. RAMELOW, Spectrochim. Acta 238,665 (1968).
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(1968).
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204 (1966).
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415. R. SMITH, C. M. STAFFORD and J. D. WINEFORDNER, Anal. Chim. Acta 42, 523 (1968).
416. H. L. KAHN and J. E. SCHALLIS, Atomic Absorption Newsletter 7, 5 (1968).
417. J. B. WILLIS, Appl. Optics 7, 1295 (1968).
418. J. A. FIORINO, R. N. KNISELEY and V. A. FASSEL, Spectrochim. Acta 238,413 (1968).
419. R. M. DAGNALL and K. C. THOMPSON, Analyst 93, 153 (1968).
420. E. E. PICKETT and S. R. KOIRTYOHANN, Spectrochim. Acta 238, 235, 673 (1968).
421. D. N. HINGLE, G. F. KIRKBRIGHT and T. S. WEST, Analyst 93, 522 (1968).
422. J. W. ROBINSON and C. J. Hsu, Anal. Chim. Acta 43, 109 (1968).
423. A. FULTON and L. R. P. BUTLER, Spectrosc. Letters 1, 317 (1968).
424. V. A. FASSEL, J. O. RASMUSON and T. G. COWLEY, Spectrochim. Acta 238, 579 (1968).
425. D. C. MANNING and F. FERNANDEZ, Atomic Absorption Newsletter 7, 24 (1968).
426. S. SLAVIN and T. W. SATTUR, Atomic Absorption Newsletter 7,99 (1968).
427. W. G. SCHRENK, C. E. MELOAN and C. W. FRANK, Spectrosc. Letters 1,237 (1968).
428. D. C. MANNING, Atomic Absorption Newsletter 6, 75 (1967).
429. J. SCHNEIDER and F. W. HOFMANN, Phys. Rev. 116, 244 (1959).
ADDENDUM 595
ADDENDUM TO CHAPTER 10
ATOMIC ABSORPTION SPECTROMETRY

by J. B. Willis
During the period of more than eighteen months that has elapsed since writing this
chapter there has been a steady stream of publications in the field of atomic absorption
spectroscopy. It is not possible to discuss here those dealing with applications of the
technique to specific analyses, but some papers dealing with topics of fundamental
importance will be briefly reviewed.
Two more books on atomic absorption spectroscopy have appeared [378, 379], and
one issue of Applied Optics (July 1968) was devoted almost entirely to invited papers
on the subject. Of particular interest is the contribution by Alkemade [380], which dis-
cusses critically several assertions which are frequently made about the relative merits of
atomic emission and absorption spectroscopy, and about the shape of calibration graphs.
Instrumental
LIGHT SOURCES
Improvements in the design of conventional, high-intensity, and selectively-modulated

hollow-cathode lamps have been described [381-383].
A theoretical and experimental study of the flame as a light source for atomic absorp-
tion measurements has been made by Rann [384], who showed that this source results
in about half the sensitivity obtainable with a hollow-cathode lamp, and also produces
quite strong curvature of the calibration graph.
Following their successful application in atomic fluorescence spectroscopy [385, 386]
microwave-excited electrodeless discharge lamps have been used by several groups of
workers as sources for atomic absorption measurements [387-389], and are claimed to
be much more intense and to warm up more quickly than hollow-cathode lamps. Insta-
bility of the discharge may however present problems [390].
AUTOMIZATION OF THE SAMPLE
Non-flame methods of atomization
Since the problem of atomizing the sample is fundamental to the whole atomic absorp-
tion technique it is hardly surprising that a number of non-flame methods of atomization
have been investigated. Massmann [391] and Woodriff [392-394] have shown that many
metals can be determined with a detection limit of as little as 10- 11 g by atomic absorp-
tion measurements made on the sample carried in a stream of argon through a graphite
tube heated electrically to a temperature between 1000 °C and 3000 0c. The precision
and accuracy of this technique, though promising, are not yet equal to those obtainable
in flame methods of atomization, and matrix and memory effects occur to some extent.
Mossotti, Laqua and Hagenah [395] used a Q-switched ruby laser beam to vaporize
small volumes of solid metals. They found that the atomization efficiency was critically
dependent on the nature of the target material, and that even for a given material the
absorption of the vapour produced varied widely from one pulse to another.
A critical evaluation of the induction-coupled radio-frequency plasma torch fed with a
dry aerosol has been made by Veillon and Margoshes [396]. These authors found useful
emission signals for metals such as barium, tantalum and titanium, which are difficult
to excite in chemical flames, but that to be of value in atomic absorption the plasma
torch had to be used in conjunction with a high-intensity line source. Intermetal inter-
ference effects, due possibly to the departure of the plasma from thermal equilibrium,
occurred to a considerable extent, particularly in emission.
Flames
There has been considerable interest in the development of alternatives to the pneumatic
nebulizer for introducing the sample into the flame.
For some determinations the "sampling boat" technique of Kahn, Peterson and
Schallis [397] is useful. A measured volume (l m1 or less) of solution is evaporated to
dryness in a tantalum boat, which is then introduced into the flame. The method is
limited to readily atomizable metals such as lead, zinc, arsenic, etc., and is prone to
matrix effects.
Ultrasonic nebulization, which has frequently been used to introduce solutions into
plasma discharges, has been tried also with flames [398-401]. The mean drop size of the
spray decreases with increase in the frequency of the ultrasound used, and it is desirable
to use frequencies of at least 500-1000 kHz. The fraction of aerosol actually carried into
the flame is several times greater than with a pneumatic nebulizer, and the volume of
carrier gas required (normally the combustion-supporting gas for the flame) can be very
much less than that needed to operate a pneumatic nebulizer. The drawbacks of the ultra-
sonic technique lie chiefly in the difficulty of achieving a steady rate of nebulization and
in the lack of simple and rapid means of changing sample solutions. Some progress,
however, has recently been made in these directions [402, 403].
DETECTORS, AMPLIFIERS AND READOUT SYSTEMS
Larkins et al. [404] have recently demonstrated that the characteristics of solar-blind
photomultipliers make them suitable for use without a monochromator for measure-
ments of both atomic absorption and atomic fluorescence when using resonance lines
below about 3100 A.
Methods of simultaneous multi-element analysis have been discussed by Walsh [405],
and other instruments for this type of measurement have been described by various
authors [406-408].
ADDENDUM 597
Atomic absorption spectrometry and flame photometry
USE OF DIFFERENT FLAME TYPES
General considerations
There has been considerable interest in the investigation of different flame types in atomic
absorption spectroscopy, and it has become apparent that the temperature of the flame
is not the only factor in the atomization of metals. The composition of the flame gases
and the presence of reducing radicals seem to be the most important influences in the
atomization process.
The very elegant work of Hieftje and Malmstadt [409], in which stroboscopic techni-
ques were used to follow the fate of droplets of controlled size introduced into a flame,
has given for the first time a direct picture of the evaporation and vaporization processes
involved in the production of metal atoms for measurement in flame spectroscopy. On
the theoretical side, de Galan and Winefordner [410] have calculated the influence of
flame temperature on the signals obtained in the absorption and emission methods, taking
into account incompleteness of atomization and possible ionization effects.
Low and medium-temperature flames
Separation of the interconal zone of a flame such as that of air-acetylene, by means of a

separator tube or a sheath of nitrogen around the flame, results in less background
emission or absorption. This may lead to improved detection limits for those metals
whose resonance lines lie in regions of flame emission [411]. The chief benefits of flame
separation, however, lie in the fields of emission and fluorescence spectroscopy [412].
The success of the hydrogen-argon-entrained air mixture in providing a low-tempera-
ture flame with little background emission for atomic fluorescence [413-415] led Kahn
and Schallis [416] to investigate the usefulness of this flame in atomic absorption. They
achieved better sensitivities and limits of detection than with the air-acetylene flame for
several easily atomized metals such as arsenic, selenium and cadmium. However, chemical
interferences are likely to limit usefulness of this flame in many analyses, as has been
shown to happen in emission [415].
High-temperature flames
There has been continued interest in high-temperature flames for the atomization of
metals which form refractory oxides, and a review of the subject has appeared [417].
A successful slot burner for the premixed oxygen-acetylene flame has been described
by Fiorino, Kniseley and Fassel [418]. The limits of detection for metals in this flame were
found to be very similar to those obtained using nitrous oxide-acetylene mixtures with
the same burner.
The nitrous oxide-hydrogen flame, which because of its high temperature and relatively
low background emission looks attractive as a means of atomizing metals forming
refractory oxides, has been studied by two groups of workers [124a, 419] but found to
be much less efficient for this purpose than the nitrous oxide-acetylene flame.
Temperature profiles of the fuel-rich nitrous oxide-acetylene flames used in atomic
absorption and emission spectroscopy have been measured [123a, 124b, 124c] and the
red interconal zone found to be at least 300 °C cooler than had hitherto been thought.
The usefulness of the nitrous oxide-acetylene flame in practical analysis by atomic
absorption is demonstrated by the number of papers describing its use [417], and recent
work has shown this flame to be valuable also in emission [420] and fluorescence [421,
422].
Butler and Fulton [123a, 423] have investigated the nitrous oxide-propane-butane flame,
and found it sufficiently hot to overcome several types of chemical interference though
not to atomize effectively metals forming refractory oxides.
INTERFERENCES
Spectral or radiation interference
Since the half-width of the resonance lines of metal atoms in flames may be 0.05 A or
more [25], and since the wings of a line may extend some distance further than this from
the centre, it is possible for appreciable interference to occur between metals if they have
absorbing lines within about 0.3 A of each other. Fassel, Rasmuson and Cowley [424]
have discussed the problem and have described several cases in. which this type of inter-
ference might affect analysis. For instance, the absorption of silicon at 2506.899 A is
enhanced by the presence of high concentrations of vanadium, owing to an absorbing
line of the latter at 2506.905 A. Fortunately such difficulties can usually be avoided quite
simply by choice of another absorbing line.
Other examples of the overlap of absorption lines have been given [425, 426], and in
some cases advantage may be taken of this phenomenon to determine several metals,
though usually with poor sensitivity, by the use of lines from one hollow-cathode lamp
[33, 427, 428].
Ionization interference
Even in the absence of added metal, hydrocarbon flames contain appreciable concen-
trations of free electrons [429], which according to Eq. (3) will tend to suppress the ioniza-
tion of metals introduced into the flame. For the purpose of calculating the degrees of
metal ionization shown in Table 10.VI and Fig. 12 the value of P, the total partial pres-
sure of electrons, metal atoms, and metal ions, was taken as 10- 6 atmospheres. Recent
measurements of metal concentrations in flames under the conditions normally used in
atomic absorption spectroscopy show that P is likely to be closer to 10- 8 than 10- 6
atmospheres [150c], and the temperature of the nitrous oxide-acetylene flame is now
known to be several hundred degrees less than the figure used for the calculations. Thus
the good agreement between the. calculated and observed degrees of ionization for this
flame must be regarded as due to a happy but fortuitous compensation of opposing errors.
CHAPTER 11
ATOMIC FLUORESCENCE FLAME SPECTROMETRY
J. D. Winefordner
R. Smith
Fluorescence flame spectrometry is based upon the absorption of radiation by an atomic

vapor to produce excited atoms, and the measurement of the radiation emitted when a
fraction of these excited atoms lose their energy by a radiational process or processes
called atomic fluorescence. Mitchell and Zemansky [1] and Pringsheim [2] have discussed
much of the original research on the fluorescence of atomic vapors in quartz containers.
However, the first reference to the fluorescence of atomic vapors in flames was reported
in 1924 by Nichols and Howes L3] who observed the atomic fluorescence of calcium,
strontium, barium, lithium, and sodium in a Bunsen burner flame. In 1927, Badger [4]
published a classic paper on the atomic fluorescence of thallium, mercury, magnesium,
copper, silver, cadmium, and sodium in an ordinary Bunsen burner flame as well as in a
separated flame. Few references to flame fluorescence can be found between the years
1927 and 1962. However, in 1962, Alkemade [5] discussed the principles of atomic fluo-
rescence flame spectrometry, particularly with regard to the measurement of quantum
efficiencies. In 1964, Winefordner and Vickers [6] published the first paper on atomic
fluorescence flame spectrometry as an analytical method. Since then, numerous manu-
scripts concerning the basis [7-9], the instrumentation [10-20], and the possible uses and
advantages [21-35] of atomic fluorescence flame spectrometry have been published. In this
chapter, the basis, instrumentation, and current and possible future uses of flame fluo-
rescence spectrometry will be discussed.
11.1 Theoretical considerations
11.1.1 MECHANISM OF ATOMIC FLUORESCENCE [1,2]
In atomic fluorescence, an atom is radiationally excited, and the radiation emitted when a
fraction of these excited atoms undergoes radiational deactivation is called atomic fluo-
rescence. In Fig. 11.1, several fluorescence processes are indicated. The fluorescence
which proves of greatest analytical interest is the first resonance transition (l -+- 0). This
transition is primarily a result of the first resonance absorption transition (0 -+- 1),
although activation of higher levels (2,3, ... ) and stepwise deactivation of the atom to the
first excited level (l) can also result in the first resonance fluorescence transition. The latter
600 ATOMIC FLUORESCENCE FLAME SPECTROMETRY [11
2 i
I
I
I
I
I C
I
I
I
i
I
I
I
I
a b
I
I
I
I
o
I
Fig. 11.1 Schematic diagram representing mechanisms of activation and deactivation of atoms.
Processes: (a) Resonance absorption - Resonance fluorescence; (b) Stepwise line fluorescence;
(c) Direct-line fluorescence (Dotted lines represent radiationless deactivation and solid lines
represent radiational processes).
processes of activation of the first excited level of an atom are usually unimportant com-
pared with the first resonance absorption transition, because the intensity of most exci-
tation sources is much lower at wavelengths corresponding to the second and higher
absorption transition; moreover, the efficiency of population of the first excited state due
to stepwise deactivation processes is very small [8].
Stepwise line atomic fluorescence results when an atom is excited by the second or higher
resonance absorption transition and the first resonance fluorescence transition is measur-
ed. For example, stepwise line fluorescence is represented by the Na-5890.6 A emission
after excitation of Na-atoms by the Na 3302 A doublet. Up to now, stepwise line fluores-
cence has been of little analytical use, as would be expected from the reasons given in the
above paragraph.
Direct line fluorescence, which is of analytical use, results when an atom is excited to a
state which radiationally deactivates to a metastable state above the ground state. For
example, direct line fluorescence occurs in the case of thallium when TI is excited by 3776
A radiation and fluoresces at 5350 A.
Energy transfer (sensitized) atomic fluorescence occurs when an excited species (donor)
transfers energy to another atomic species (acceptor) and radiational deactivation (fluo-
rescence) of the acceptor results. This process has no analytical use in flames because colli-
sional deactivation of excited donors is quite efficient and also because of the difficulty
of producing a sufficiently high concentration of efficient donors in the flame.
11.1.2 INTENSITY OF ATOMIC FLUORESCENCE [7, 36]
The intensity of atomic fluorescence in ergs sec- 1 cm- 2 is given by:

L.m QF
IF =IA-Y!'/.- (1)
1 4:n;
11.1] THEORETICAL CONSIDERATIONS 601
if it is assumed that: (i) only a single, isolated resonance line is being studied; (ii) that
the absorption and fluorescence lines are broadened only by Doppler and Lorentz
broadening; (iii) that the flame has a uniform temperature and atomic concentration of
absorbers in the volume increment of importance at the height of observation and is in
thermal equilibrium; (iv) that the flame region being studied is uniformly illuminated by
the light source; and (v) that the fluorescence over the entire flame (flame has a length 1
in the excitation direction and a length L in the emission (measurement) direction) and
in the direction of the detector is imaged on to the monochromator entrance slit. The
terms in equation (1) are defined as: l,t is the integrated radiant power (per unit area)
absorbed from the source - units of ergs sec- 1 cm- 2 ; (/J is the fluorescence power
efficiency (ratio of radiant fluorescence power to radiant power absorbed) and is identical
to the fluorescence quantum efficiency, (/J, if only the resonance absorption-fluorescence
transition is considered as in this case; Is is the dimensionless self-absorption factor
accounting for the decrease in fluorescence due to self-absorption by similar atoms; and
DF/4n is the fraction of fluorescence radiation measured by the instrument within the
solid angle of observation, D F , in ster.
The absorbed radiant power per unit area, l,t, is given by:
(2)
where I A is the source intensity at wavelength, A, [J,./41t is the fractional solid angle of
radiation collected by the excitation source and incident upon the flame, kA is the atomic
absorption coefficient of the absorbing species at A, and the integration is over the wave-
length interval over which radiation is absorbed. The self-absorption factor, Is is given by:
t. = ( V 2 Vln2 ) f [1 - exp(-kJ.L)]dA. (3)

n koLLIAD
where ko is the peak absorption coefficient at wavelength, Ao, for pure Doppler broaden-
ing, LlAD is the Doppler half-width, in A, and the integration is over the entire width
of the fluorescence line.
When using a continuum source for excitation:
(4)
where loc is the spectral intensity of a continuum source at the peak absorption wavelength,
Ao, in ergs sec- 1cm- 2 A-I. If the optical density kAt, is low at all wavelengths (dilute
atomic gas), then:
(5)
where:
ko = 2 ViD2 V3te2 A02 Nol (6)
me2 LlAD
where No is the atomic concentration of the ground state of the absorbing atom,lis the
oscillator strength for radiative transition, m and e are the mass and charge of the electron,
and e is the speed of light. The self-absorption factor for low optical densities is unity.
Therefore for a continuum source and a dilute atomic gas:
IF = e 2 Q F LAo2 No!(/) IoeDA
(7)
6,,4 me2
At high optical densities (high atomic concentrations), I A varies with VNo and!. with
l/VNo and so IF is independent of No, whereas at low optical densities IF is proportional
to No.
When using a narrow line source for excitation:
DA -
IA = - h [1- exp(-kl)] (8)
4"
where h is the integrated radiant power for the exciting line per unit area - units of
ergs sec- 1cm- 2 and k is the average atomic absorption coefficient over the source line
half-width and is defined as k = koCJ, where CJ is a correction factor accounting for the
relative widths of the source and absorption lines, is approximately independent of No
and can be evaluated from standard tables [37]. For a dilute atomic vapor:
DA -
I A = -klh (9)
4"
Because!. is unity at low atomic concentrations:
IF = 2 ViD2e 2 QF LA o2NoICJ(/)ILD...
(10)
6" Vn me 2 LlAD
At high optical densities, IA is independent of No and!. depends on l/VNo, and so IF
is proportional to l/VNo, whereas again for dilute atomic gases, IF is proportional to No.
11.1.3 VARIATION OF ATOMIC CONCENTRATION IN FLAME, AND SOLUTION CONCENTRATION [38]
The atomic concentration in the ground electronic state, No, is related to the concentration
of atoms in all electronic states, N, by the Boltzmann distribution, and so:
N =K1N (11)
o B(T)
where B(T) is the electronic partition function of the atom and is given by:
B(T) = gl + gm e-EmlkT + gn e-EnlkT ••• (12)
where the g's are statistical weights of the energy levels /, m, n, ... having energies EI = 0,
Em, En, ... , and T is the absolute temperature of the hot gas. For atoms having simple
atomic spectra, i.e., no low lying levels, B(T) c:::. gl, whereas for atoms with complex spectra,
B(T) > gl, and so B(T) is then dependent on the gas temperature.
The relationship between the total atomic concentration in all electronic states, N, and
the solution concentration, C, in moles [-I (aspirated), is given by:
(13)
where F is the sample solution transport rate into the flame gases, in cm 3 min -1, ef is the
flame gas expansion factor (no units), given by:
(14)
(where nT and nR are the number of moles of flame gas products at the flame temperature
T and room temperature, TR , respectively). Q is the flow rate of gases into the flame,
cm 3 sec-I. e is the efficiency of sample aspiration [39,40] and it is defined as the number of
truly nebulized salt particles actually present in the flame gases to the total number of
salt particles transported into the flame gases. e accounts for both incomplete solvent
and solute evaporation when using total-consumption aspirator-burners and also for low
transfer yield when using chamber-type aspirator-burners. p is the efficiency of atom-
ization [38,41] which is defined as the number of species present as atoms to the number
of species present in all gaseous forms, e.g., compounds, ions, etc. The efficiency of
aspiration, e, depends on such factors as solution transport (flow) rate, solvent, solute,
flame, aspirator-burner characteristics, and should be a constant for any given series of
sample solutions, as long as the solvent and aspirator-burner system remain the same,
and as long as the sample concentration is sufficiently low that the solution viscosity does
not change. The efficiency of atomization, p, is critically dependent on the element, the
salt, the solvent and other ions in the solution, and also on the flame gas composition
and temperature [42].
If equations (11) and (13) are combined, the variation of No with C can be found:
N = 1019 gl FePC
(15)
o ef Q B(T)
As long as F, e, p, and ef do not depend on sample solution concentration, C (of course,

Q and B(T) are independent of C), No is directly proportional to C and thus IF varies
linearly with C provided that C is relatively small. Unless the sample solution is extremely
concentrated (C > 1000 ppm), F, ef and e should not be greatly influenced by C. How-
ever, p may ,veIl be a sensitive function of C, because ionization in flames is often signi-
ficant at low concentrations, and this results in a decrease in p.
11.1.4 FLUORESCENCE POWER EFFICIENCY [S, 9, 43, 44]
The fluorescence power efficiency, CP, is related to the fluorescence quantum efficiency,
T, by:
(16)
where 'IIF and'll A are the peak frequencies of the fluorescence and absorption lines, assum-
ing only one absorption line results in one fluorescence line. T is the fluorescence quan-
tum efficiency, i.e., the number of quanta emitted as fluorescence to the number of quanta
absorbed causing the fluorescence. The quantum (and power) efficiency is very sensitive
to flame gas composition [S, 9] and for the simplest case of a single collisional deactiva-
tion of the fluorescence state it is given by:
cP = A 10 Sn 2 e2 gd
(17)
AlO + kQNQ Sn 2 e2 gd + me 1.0 2 go kQNQ
where kQ is the second-order rate constant in units of deactivation transitions per second
per unit concentration of quencher, Q. N Q is the concentration of quencher. Of course, if
species other than Q can cause deactivation of the excited species, terms similar to kQNQ
can be added to the denominator of equation (17) (i.e. replace kQNQ by L.kQ/ NQi' where
the summation is over all collisional quenching species). kQNQ is a pseudo first order rate
constant representing the number of radiationless deactivations per second, whereas AUI
is the first order rate constant representing the number of radiational deactivations per
second. It should be stressed that flame gas composition influences the magnitude of N Q ,
and the flame temperature affects k Q • This demonstrates the great importance of selecting
optimum flame conditions for analysis. Of course, flame composition and temperature
also influence the degree of atomization, {J. The influence of flame gas composition and
temperature on {J and T (or (/J) is much greater with laminar (pre-mixed) flames than with
turbulent (un-pre-mixed) flames because the latter are effectively normalized over the
whole of the flame height due to turbulence and air-entrainment [9,45].
11.1.5 SHAPE OF ANALYTICAL CURVES [46]
An analytical curve is a plot of photodetector signal due to fluorescence, iF, against sample
concentration, C, for the element of interest. The photodetector signal, iF, is directly
proportional to the intensity of fluorescence, IF,
(IS)
where m is a factor accounting for light losses due to the use of a mechanical chopper
(m = 1 if no chopper is used, and m = 1/2 if a standard chopper is used). U is given by
W/(W + W), where W is the monochromator slit width, We is the minimum resolving
power slit width of the monochromator and is essentially the slit widening due to diffrac-
tion, coma, etc., k m is a constant characteristic of the monochromator-detector-amplifier-
readout system and is determined by the slit height, the monochromator transmission
and the detector-amplifier-readout sensitivity. For a given instrumental apparatus, k m is
generally a constant. The concentration, N, of atomic species in the flame gases is also
directly proportional to e, as can be seen from equation (13) by assuming that {3 is inde-
pendent of concentration. The analytical curve of log iF vs.log e should, therefore, have
a slope of unity except at very low concentrations, where {3 decreases due to ionization
of the atomic species in the flame, and at high concentrations, when self-absorption
effects become significant. The slope will also deviate from the theoretical at the point
where P, ef and e begin to be influenced by the variation in sample concentration.
11.1.6 LIMITS OF DETECTION [46-48]
The limit of detection in any spectrochemical method can be evaluated from a statistical
approach [48] if the noise is truly random. This is essentially the case in flame fluores-
cence where the major source of noise is phototube shot noise and flame background
flicker noise. The limit of detection can therefore be defined [48] as that sample con-
centration emin' in moles [-1, resulting in a signal-to-noise ratio, sin, of:
(19)
where t is the Student "t" for a given confidence level, e.g., 99.5 % and a given number of
degrees of freedom, i.e., 2p - 2, if p is the effective number of combined measurements of
the sample and blank. A value ofp = 1 would involve a measurement ofthe sample signal
for a time period equal to about ten time constants and a measurement of the blank signal
for the same length of time. (The signal s is the difference between the sample and blank
signals.) The time constant, 't, is the amplifier readout time constant and a time of at
least 5 't's is needed to assume that the readout is recording a reliable value of s; a time
of 5 more 't's is needed to record the measurement of significant noise components (n is
r.m.s. noise which is approximately the peak-to-peak noise divided by 5) [48]. Several
experimental factors, however, should be mentioned. First, it is better to make many
successive sample-blank measurements to avoid drift rather than one long sample and
one long blank measurement. Second, a convenient definition for emin is to use a 99.5 %
confidence level and a value of p = 3 which gives a tV2IV3 ~ 5, and so the limit of
detection is simply that concentration (for p = 3) resulting in a signal, S, identical to
the peak-to-peak noise. The above definition for emin is statistically valid and therefore
has meaning when reported in the literature. This limiting signal-to-noise ratio of 1 has
also been used empirically by several workers in the various branches of flame analysis.
11.1.7 OPTIMIZATION OF EXPERIMENTAL CONDITIONS
Equations for N mln , the minimum detectable atomic concentration in the flame, in terms
of instrumental, spectral, and flame compositional parameters, have been derived by
Winefordner and co-workers [46,47] where N mln is related to Gmln by equation (13).
From plots of N mln vs. monochromator slit width (the one parameter which can be varied
continuously) at constant values of other instrumental, spectral, and flame compositional
parameters; optimum values of a number of other parameters can be estimated. For
example the major sources of noise in flame fluorescence studies are flame background
flicker, FF, source scattering flicker noise, SS, due to scatter of source radiation by
particles in the flame gases, and phototube shot noise, PS. For small slit widths, PS will
predominate whether a line or a continuous source is used. For large slit widths, FF will
generally predominate when using a line source, although with a continuous source, FF
and SS will increase at the same rate when W is increased. Plots of N min vs. W for a line
source will, therefore, have a distinct minimum when flame flicker noise becomes the
major noise for larger slit widths. On the other hand, N min vs. W will be flat when using
a line source if source scatter is the predominant type of noise. For a continuous source,
plots of N min vs. W will have a distinct minimum at medium slit widths if FF or SS are
the major noises.
In most practical instrumental systems used for atomic fluorescence studies, N mln is
not a critical function of monochromator slit width, whereas an increase in source in-
tensity results in an almost linear decrease in Nmln •
From signal-to-noise ratio expressions, it is also possible to estimate values of N mln for
any line of any element for the instrumental system concerned (assuming that reliable esti-
mates of instrumental, spectral, and flame compositional parameters are known). If good
estimates of e, ef and fJ are known, then Gmln can also be estimated. Such calculations
can be of great assistance in designing a new instrumental system or in comparing
atomic fluorescence flame spectrometry with other methods of analysis for the same ele-
ment.
11.2 Basic instrumentation
At the time of writing, there is no commercial instrumentation available which has been
designed specifically for atomic fluorescence spectroscopy, altbough good results have
been obtained using modified flame emission spectrophotometers [17,18, 28, 31-35]. How-
ever, all the work to date has been performed using apparatus which can be schematically
represented by the simple block diagram shown in Fig. 11.2. The basic system consists
of an intense source of focussed-radiation which is incident upon a flame cell containing
the analyte species. The fluorescence and scattered radiation, emitted in all directions, is
measured at an angle of 90° to the excitation beam, using a second lens to focus the
fluorescence on the slit of a monochromating device. The signal is then measured using
a photomultiplier tube, amplifier and readout system.
11.2.1 OPTICS AND MONOCHROMATOR
Although the optical arrangements for atomic fluorescence have covered a wide range of
11.2] BASIC INSTRUMENTATION 607
Monochromator
Detector
"Chopper
Source
Amplifier- Readout
Fig. 11.2. Block diagram of an atomic fluorescence spectrometer.
refinement, some good results have been achieved with relatively unsophisticated appa-
ratus [10,11,26]. In these systems, no focussing lenses were used. In other setups, multiple
pass optics [27] and ellipsoidal mirrors for collecting and focussing the fluorescence ra-
diation [28] have been employed. Baffle systems and slits have also been used to minimize
the effects of scattered and stray radiation [12, 13,28]: this is necessitated by the use of
slit widths of the order of 1-4 mm. The major requirements of the optical system are to
collect and impinge on the flame the maximum power of exciting radiation, and to collect
and impinge on the detector the maximum power of resolved line fluorescence, i.e., to
have the largest possible k m factor in equation (16).
The monochromating devices employed have been either grating or prism [26, 28]
designs, although one author has used a spectrograph as a monochromator [25]. From
the point of view of sensitivity, the most suitable monochromators are low resolution,
short path length, grating designs which view a large solid angle (i.e., large k m factor).
Short path lengths are particularly desirable for wavelengths around 1800-2000 A be-
cause of partial atmospheric absorbance.
West [29] has suggested a system in which an additional monochromator is placed be-
tween the source of radiation and the flame. Although this would appear at first sight to
be a redundant addition, it may prove useful by enabling a more rigorous examination
of stepwise-line and direct-line fluorescence to be made.
Recently, Knapp and Winefordner [49] have examined an instrument employing no
monochromator. The system derives its selectivity from the sharp line emission of elec-
trodeless discharge tube light sources. The apparatus is particularly useful for those ele-
ments which have simple spectra and whose fluorescence can be measured high above the
flame. This latter factor is essential to prevent overloading of the photomultiplier tube due
to flame background radiation. Some difficulty is still being experienced with scattered
visible radiation, but despite this, the apparatus is very sensitive, inexpensive, and because
of small optical distances it is particularly applicable to the 1800-2000 A spectral region
where atmospheric absorption of radiation becomes increasingly important. The feasibi-
lity of this type of instrument is obviously much greater for atomic fluorescence than for
atomic absorption flame spectrometry.
11.2.2 DETECTOR/AMPLIFIER SYSTEMS
Photomultiplier tubes have been used almost exclusively in atomic fluorescence studies as
radiation detectors, the more frequently used types being the RCA IP28, EMI 6255B [16]
and EMI 960lB [17]. Several types of amplifiers have been used in conjunction with
these detectors.
The DC Electrometer-Amplifier is potentially the least expensive and most sensitive
amplifier (no signal is eliminated due to use of a mechanical chopper). It is used mainly
for measurements in the ultraviolet region where thermally excited emission is less. How-
ever, thermally excited emission of the analyte, flame background, scatter, etc., can all
increase the measured fluorescence signal. Some device to suppress this blank signal
is generally used, particularly for work in the visible region.
The AC Amplifier has also been used in several systems. In this case, the exciting radia-
tion is chopped mechanically [25, 27] or modulated electronically [17], and the amplifier
is tuned to the same frequency of modulation 10. The amplifier will, therefore, only
measure phototube signals which are modulating at this characteristic frequency, and
within the frequency response bandwidth, Llf, of the measurement system. That is, the
measured signals will cover the frequency range of (fa + LlI/2) to (fa - LlI/2), and so
the measured signal will be primarily due to atomic fluorescence plus a noise signal which
depends upon V4f [46]. Such factors as thermal emission of the analyte, flame back-
ground emission, etc., which are constant, do not contribute to the signal although they
do contribute to the noise. Typical frequency response bandwidths (Llf) of AC amplifiers
used in flame spectrometry are of the order of 50-100 Hz and the amplifier frequency
should be of the order of 300 Hz in order to reduce the 1/1 noise of the system to a
minimum.
AC Phase Sensitive (Lock-in) Amplifiers [13, 16, 19,50] are similar in concept to the AC
amplifiers described above but are characterized by a very narrow frequency bandwidth
(about 1 Hz or less). Because of this, a reference signal modulated at the same frequency
as the fluorescence signal and of the proper phase is normally provided to allow the
amplifier to compensate for variation in the chopping frequency. A much more favorable
signal-to-noise ratio is possible than with a typical AC amplifier, since many experimental
sources of noise are proportional to VLli [46].
AC Galvanometers have been used as a direct means of photocurrent measurement. A
moving-coil galvanometer is supplied with a magnetic field which alternates at the same
frequency and with the same phase as the amplified signal current passing through the
coil; the signal current is amplified using a wide band AC amplifier. The deflection of the
coil is, therefore, only proportional to the alternating signal and any DC component, due
to thermal emission etc., is not measured. This instrument has been used for atomic fluo-
rescence flame spectrometry [51] and has been fully described elsewhere [52, 53]. The
frequency bandwidth depends on the free period of the moving coil Lli = l/T and is
usually of the order of 1 Hz.
11.3 Sources of excitation
One of the major fields of research in atomic fluorescence has been, and will continue to
be for some time, the examination of light sources which are suitable for excitation pur-
poses. Fortunately, there has been a similar, previous search by physicists for intense
11.3] SOURCES OF EXCITATION 609
sources for use in optical pumping and related experiments and the analytical spectrosco-
pist has derived considerable benefit from this. The general requirements for a light source
for atomic fluorescence are:
(a) High intensity of radiation at the line center, because the fluorescence intensity and
resultant photodetector signal is directly proportional to the source intensity, r (see
Section 11.1). Self-absorption should be a minimum, and the output should be around
10 15 _10 18 photons/sec (or 1 mW-l W for ultraviolet radiation). Although the effects of
self-absorption are not quite so critical as in atomic absorption, this is quite an important
factor in determining signal-to-scatter ratios.
(b) Good stability. Short term stability should be better than 1 part in 10 3 and long term
stability better than 1 part in 10 2 •
(c) Availability for a large number of elements.
(d) Long running-life and long shelf-life.
(e) Small sample content is desirable for the production of precious metal lamps and
also isotope lamps.
(f) Practical considerations which include short warm-up time, ability to be used by
unskilled personnel, ease of manipulation, cost of lamps and associated power supplies,
etc.
The following is a list of excitation sources which have been used for atomic fluorescence
flame spectrometric studies.
11.3.1 METAL VAPOUR ARC LAMPS
The lamps which have been used have been mainly Osram and Philips lamps; these were
in fact the only ones employed in the early analytical studies on atomic fluorescence flame
spectrometry [10] and have been used since by several authors [11, 12, 17,25,26,28].
These lamps have high output intensities but exhibit serious self-absorption and as a re-
sult can only be used satisfactorily for zinc, cadmium, and thallium [10, 11, 12,26,28].
Other metal vapour arc lamps, for instance indium and gallium [12], show high self-
absorption and are practically unusable, while mercury and alkali metal lamps were
found to be almost completely self-reversed [11]. In practice, vapour arc lamps are usually
run at currents far below those specified by the manufacturers [12]. This reduces the va-
pour pressure of the metal and consequently reduces self-absorption. Dagnall, et al. [28]
used a stream of cold air to the same effect but noted that extreme cooling caused conden-
sation of metal on the lamp walls and a serious decrease in the atomic fluorescence signal.
11.3.2 HOLLOW CATHODE DISCHARGE LAMPS
Most of the hollow cathode discharge lamps used today in atomic absorption flame spec-
trometry are modifications of the design of Walsh [54,55]. Because oftheir low intensity,
these lamps cannot be used in atomic fluorescence flame spectrometry. The use of higher
operating currents gives rise to high self-absorption due to increased sputtering action at
the cathode and also results in reduction of the useful life of the lamp.
Shielded-hollow cathode lamps [56] are now available which are only slightly less in-
tense than the "high-intensity" hollow cathode lamps described below. Bismuth [57-59],
tin [60], lead [59], nickel [59], germanium [59], and titanium [59] lamps are described in
which the cathode is a hollow cup, covered by a white cylindrical ceramic shield. Emitted
radiation travels through an aperture in the shield which prevents diffusion of the metallic
vapour. The metal in the cathode is molten during the operation of several of these lamps.
Another approach to the problem of excess sputtering at high currents has been the
pulsed operation of hollow cathode lamps [61] using a low direct current to maintain the
discharge and superimposed 15 microsecond pulses of several hundred milliamps at a
frequency of 300 times per second. In addition to several hundredfold gain in intensity,
the authors found rapid warm-up, longer lamp life, and even rejuvenation of old lamps.
Although not examined thus far for atomic fluorescence studies, this new development is
sure to receive some attention in the near future.
High-intensity hollow cathode lamps were introduced by Sullivan and Walsh [62]as a
means of overcoming the inherent disadvantages of operation of hollow cathode lamps at
high power levels. The lamps are basically two sets of electrodes of which the first set
provides the sputtering action and the second increases excitation. Two power supplies
are needed because the sets of electrodes are operated independently; this would appear
to be a major disadvantage. However, Armentrout [27] has successfully used these lamps
in the determination of nickel; and Mulford, et al. [63] have obtained very low limits of
detection for lead, iron, nickel, cobalt, and copper with modulated high-intensity hollow
cathode lamps.
The design and use of hot hollow cathode lamps has been reviewed [64] with respect to
the uses ofthese lamps in emission spectrography. Dinnin and Helz [19,20] have describ-
ed the use of a demountable hot hollow cathode lamp for atomic fluorescence flame spec-
trometry. About 50 mg of metal turnings or powder is packed into a cylindrical graphite
cathode and the lamp is run at several hundred milliamps with low pressure helium or argon
fill gases. The lamp is water cooled during operation and gives an output intensity as good
as that of a high-intensity hollow cathode. Results are quoted for eighteen elements, and
in many cases, much lower limits of detection were obtained despite incomplete experi-
mental optimization.
11.3.3 ELECTRODELESS DISCHARGE TUBES
These sources were first used by Jackson [65] in 1928; electrodeless lamps have been devel-
oped for many applications where high intensity and extreme stability were not required.
Renewed interest in this type of lamp [66-74] resulted in lamps having high intensities,
low self-absorption and sharp spectral lines in addition to low cost, ease of manufacture,
ease of manipulation, and, in most cases, long life. Electrodeless discharge tubes are
therefore being recognized as probably the most suitable sources for atomic fluorescence
flame spectrometry, and will therefore be discussed in more detail than other lamps. Their
uses in atomic absorption flame spectrometry have been reviewed [75, 76].
The lamps consist of quartz cylinders of about 5-10 mm bore, containing a few milli-
grams ofthe element (or one of its compounds) and an inert gas at a pressure of 1-5 Torr.
The discharge is maintained by coupling with a 2450 MHz microwave power generator
(up to 125 watts); the discharge is generally initiated by a Tesla coil. The lamps frequently
exhibit an inert gas discharge initially; the principal element emission only appears after
a short warm-up period of a few minutes.
11.3] SOURCES OF EXCITATION 611
11.3.3.1 Types of electrodeless discharge tubes
The following types of electrodeless discharge tubes have been prepared although not all
have been employed in atomic fluorescence flame spectrometry.
Pure element lamps - These include isotopic lamps [66,77-80] and are mostly used for
the softer metals such as mercury, zinc, cadmium [81], selenium [18], etc. Less volatile
metals can be used, but the lamps require a higher operating temperature [81].
Metal compound lamps - The metal iodides [15,70,80] and chlorides [72] have been used
almost exclusively in order to obtain higher element vapour pressures.
Metal amalgam lamps - Vf!ry little work has been done using these lamps, although
some promising results have been obtained with a few elements [15]. Confined discharges
were found with some heavy metal amalgams.
Metal halide amalgam lamps - Metal iodide amalgam arc discharges have shown in-
teresting features [83-86] and recently a cuprous chloride amalgam tube [82] and metal
iodide amalgam tubes have been described as potential sources of radiation for atomic
fluorescence flame spectrometry.
Foreign element lamps- The use of a lamp of one element to excite the atomic fluorescen-
ce of another has been reported by Dagnall, et al. [34] who used an iodine lamp for the
excitation of bismuth.
11.3.3.2 Power requirements
Although radio-frequency (10-100 MHz) fields have been used in conjunction with elec-
trodeless lamps [88-91], these have only been used in atomic fluorescence experiments
by physicists [83, 87]. Operation of electrodeless discharge tubes for analytical atomic
fluorescence studies has been confined to microwave (2450 MHz) excitation which has
been provided in all cases by magnetron units designed primarily for medical diathermy
[10--15, 18, 22, 25, 31-35]. The use of microwave frequencies is reported [71, 73] to
result in more efficient power coupling and longer lamp life [73, 94] than with radio-
frequency operation.
The design of six microwave cavities has been reviewed [92, 93] and their operating
characteristics compared for helium and hydrogen lamps. Mansfield [94] has evaluated
the performance of two types of antenna and three types of cavity in conjunction with
atomic fluorescence studies and has confirmed the success of the "A" type antenna [70,
72, 74] used by other workers (see Fig. 11.3). The "C" type antenna was found [94] to be
unsuitable for use in atomic fluorescence flame spectrometry, while 3/4-wave foreshorten-
ed coaxial or Broida (see Fig. 11.4) and 1/4-wave foreshortened coaxial or Evenson (see
Fig. 11.5) cavities were found [94] to be inferior to the "A" antenna due to development
of "hot spots" on the discharge tube and the necessity of tuning these cavities for each
tube.
Dagnall, et al. [18,31-35] have used the Evenson type cavity with success but have re-
ported localized heating effects in some applications.
The tapered rectangular cavity (Fig. 11.6) [94] has performed well although it has a low
coupling efficiency; it does not require tuning and is large enough to act as a heat sink so
that cooling is unnecessary. Some results obtained using this cavity have been reported [14].
F.";=;==yElec1rodeless Lamp
Electrodeless ToV~
Lamps
In dow
Coaxia I Conn.
Coupler
(a) (b)
Fig. 11.3. Schematic diagrams of the "A" Fig. 11.4. Schematic diagram of the Broida
antenna with (a) quartz shield and with (b) cavity.
evacuated jacket.
Coaxial
--=__ I~vuonnector
Electrodeless Lamp
!.
Coupling Adjustment
Fig. 11.5. Schematic diagram of the Even- Fig. 11.6. Schematic diagram of the tapered
son cavity. rectangular cavity.
11.4] FLAME CELLS 613
11.3.3.3 Stabilization of electrodeless discharge tubes
Microwave heating effects, extraneous draughts, etc., contribute to the erratic operation
of electrodeless discharge tubes. Whenever these sources have been used in atomic fluores-
cence flame spectrometry, full optimization of the operating temperature has not been
achieved. Cooling of tubes has been effected by direct blowing of cold air [15, 18] and
has been remarkably satisfactory. Heating has been necessary to volatilise many of the
transition elements and this has been achieved by building a furnace round the source
[72, 74], or by surrounding the tube with a quartz jacket containing quartz wool to act
as a thermal insulator (see Fig. 11.3a). This latter arrangement relies on microwave heat-
ing of the discharge tube and is satisfactory for low-level heating [15, 94]. Recently a
vacuum jacket (see Fig. 11.3b) has been designed [81] which effectively insulates the dis-
charge tube so that even very involatile compounds can be used in lamps. The jacket also
prevents extraneous drafts and good results have been obtained [81] using this device.
11.3.4 CONTINUOUS SOURCES
In contrast to atomic absorption flame spectrometry, continuous excitation sources can

be used for atomic fluorescence flame spectrometry with a low resolution monochromator
even in the presence of many foreign ions. The main advantages of continuous sources
are their versatility in multi-element analysis; however, the intensity output is generally
low at any wavelength over the half-width of the absorption level(s) compared with a
line source, and the amount of light scatter can be significant. Despite these disadvantages,
continuous sources offer a useful means of excitation for atomic fluorescence analysis.
The theory of their use has been discussed [7], and limits of detection have been reported
[13, 17] for 150 watt high pressure xenon arc lamps. Ellis and Demers [16] have obtained
excellent results using a 450 watt xenon arc lamp in conjunction with a medium resolu-
tion Ebert type monochromator. Their limits of detection are at least one order of magni-
tude lower than those obtained [13, 17] using 150 watt lamps and low resolution mono-
chromators.
11.4 Flame cells
The general requirements for a flame for use in atomic fluorescence flame spectrometry
are:
(a) The flame temperature should be sufficiently high to cause complete dissociation of
the sample salt introduced into the flame gases.
(b) The flame temperature should be as low as possible in order to minimize collisional
deactivation of the excited species, thermal excitation, and ionization of the atomic species.
(c) The composition of the flame should be such that a reducing atmosphere is produced
in the combustion zone resulting in a suppression of metal oxide formation, i.e., maximi-
zation of the degree of atomization, fl.
(d) The flame should be steady, have low background emission, contain few particles
which may scatter incident radiation, and be produced by a sufficiently high gas flow rate
so that aspiration of the sample can be effected. The aspiration process should also be
highly efficient.
Most flames used in atomic fluorescence flame spectrometry have been only partially
successful in meeting these requirements [41].
Flame cells used in atomic fluorescence studies have consisted of either laminar flames
using chamber aspirators or turbulent flames with total consumption aspiration. Ellis
and Demers [24] have employed a syringe injection system for introducing sample solu-
tions into a turbulent Hz/entrained air flame.
11.4.1 TURBULENT FLAMES/TOTAL CONSUMPTION BURNERS
Turbulent flames have been used in atomic fluorescence studies far more than have la-
minar flames. Despite their relatively poor droplet size distribution, these burners have
the advantages of being inexpensive, easy to use, and produce a higher atomic concen-
tration in the flame gases than do most laminar burners. Several total consumption
aspirator burners and flame gas compositions have been examined [14, 16]. H 2 /0 2 flames
were found [14] to be noisy and produce low fluorescence signals; H 2 /air flames gave
lower background [14] and also gave reduced thermal emission from some metal species
in the flame. Ellis and Demers [16, 24] have obtained some interesting results using a
H 2 /entrained air turbulent flame. They found that fluorescence line intensities were en-
hanced and scatter was much reduced when compared with a H z/0 2 flame. Excellent
results have also been obtained [14, 15] when using Hz/Argon/entrained air flame with total
consumption burners. Presumably the use of an entrained oxidant tends to maintain a
highly reducing atmosphere in the center of the flame, resulting in a lower degree of oxide
formation i.e., an increase in the p-factor. The use of a noble gas increases the quantum
efficiency for the fluorescence process because of inefficient energy transfer by these gases
when in collision with an activated species [8, 51]. The fuel-rich, turbulent C 2 H 2 /0 2 flame
has been examined [11], but was found to be unsuitable for atomic fluorescence studies
because of high background flicker, i.e., a poor signal-to-noise ratio resulted. Variations
in flame gas composition are not as critical with turbulent as with laminar flames due to
the greater degree of air entrainment which is possible and also to the absence of discrete
well-defined reaction zones.
11.4.2 LAMINAR FLAMES/ASPIRATION CHAMBER BURNERS
Laminar, pre-mixed flames have been used in atomic fluorescence flame spectrometry in
order to minimize light scattering from droplets and particles in the flame, to produce a
larger flame area, and to reduce flame flicker. Unfortunately, some oftheadvantages oftotal
consumption aspirator burners and turbulent flames are not apparent when using cham-
ber type aspirators. Dagnall, et al. [17] have compared propane/air, acetylene/air and
hydrogen/air flames for suitability in atomic fluorescence studies. The acetylene/air flame
exhibited high background emission and severe scattering of incident radiation sLlch that
it was quite unsuitable for atomic fluorescence flame spectrometry. The propane/air flame
was found to possess satisfactory characteristics and has been used successfully in subse-
quent work [31, 32]. The hydrogen/air flame was found [17] to have a slightly lower
background between 2000-3200 A. Because of discrete reaction zone divisions in laminar
flames, factors such as gas composition, height of measurement, and solvent become in-
creasingly important. Laminar flames do have one more advantage in addition to those
specified above, namely that they can be used in conjunction with a Smithells flame sepa-
11.5] COMPARISON WITH OTHER FLAME SPECTROMETRIC METHODS 615
rator [95] which enables considerable reduction in the level of OR radical emission from
the flame. The use of flame separators in flame emission analysis [96] and atomic absorp-
tion [97] has been reported by Kirkbright, et aI., although it is known in the atomic
fluorescence literature [4].
11.4.3 NON-FLAME CELLS
Massmann [98,99] reported the use of a heated graphite tube instead of a flame. The tube
was held vertically and source light was passed along the axis to a focus in the center.
Fluorescence radiation was viewed through vertical slits cut in the graphite wall. Large,
high-current (eg., 250 rnA) hollow cathode discharge tubes were used as sources, and
limits of detection were of the order of 10- 9 _10- 14 gram. The sample was dissolved in an
ethanol-water mixture, the composition of which had been adjusted to minimize evapora-
tion of the graphite tube. Svoboda [100] has used an electrically heated graphite crucible
as the cell and a high current graphite arc as a continuous source. In addition, physicists
have long used heated quartz cells to observe the atomic fluorescence of metal vapors [1,
2].
11.5 Comparison with other flame spectrometric methods
11.5.1 THEORY
Both atomic absorption (AA) and atomic fluorescence (AF) are based necessarily on
absorption of radiation by ground state atoms (actually metastable states above the ground
state for some atoms can be significantly populated and produce appreciable absorption,
but these cases are generally of lesser importance and will be omitted from this discussion).
In AA, the fraction of radiation absorbed is measured. For a dilute atomic gas [37],
the fraction of radiation absorbed depends on the atomic concentration of the ground
state, No. In AF, the fluorescence intensity of a dilute atomic gas again depends on the
atomic concentration of the ground state. In both cases, the effect of flame temperature
on the measured signal is rather small if the variation of the degree of atomization,
fl, with flame temperature is neglected. The half-width of absorption lines increases
linearly with VT which influences the Voigt profile factor, t5, when using a line
source in either AA or AF. When using a continuous source in either AA or AF, flame
temperature should have even less influence. Of course, the power efficiency, lP, is in-
fluenced by flame temperature and composition [8]. In FE, the emission intensity depends
not only on the ground state atomic concentration but also on the Boltzmann factor,
exp(-EJkT), where Eu is the energy of the upper state involved in the resonance emis-
sion transition. Therefore FE is critically dependent on flame temperature for all elements.
It should be stressed, however, that for some elements, a very significant effect of a tem-
perature change is on fl which influences all three methods in the same manner (assuming
that in FE atomic emission is measured).
11.5.2 LIMITS OF DETECTION
The limits of detection, in any spectrochemical method in which the noises (or variations
in results) are random, should be defined by the statistical definition - equation (19) -
previously discussed. Unfortunately, almost as many definitions of limits of detection as
authors of manuscripts have been given. To make matters worse most authors report far
too little information to allow anyone to repeat their unique experiments. Even so, several
general comments concerning limits of detection in the three methods can be given.
Fassel and Golightly [101] have compared flame emission and atomic absorption limits
of detection. Their results and the most recent limits of detection in AF for a number of
elements are given in the Appendix. It should be pointed out that AF and AA appear to
be competitive methods, i.e., elements which have low limits of detection in one method
generally have low ones in the other, if good light sources are available. In fact, since
greater signal-to-noise ratios are obtained for many elements having good sources, con-
siderably lower limits of detection can be obtained in AF than in AA. This can be qualita-
tively explained by use of an old principle, namely, it is easier to measure a small signal
above noise than it is to measure a small difference between two large noisy signals. It
should also be stressed that up to now FE appears as a complementary technique to
AF, to be used in the wavelength region above 3500 A. Since the limit of detection in
AF depends upon source intensity, it would seem that sufficiently intense sources could
ultimately be developed for all elements now measured by AA so that lower limits of
detection would always result when using AF.
11.5.3 ANALYTICAL CURVES
Analytical curves in all flame methods generally are linear from about the limit of detec-
tion up to concentrations (about 10-100 ppm) which would result in self-absorption as in
FE. Since limits of detection for a number of elements in AF are in the 1 ppb or lower range
linear analytical curves will often extend over a 102 to 106-fold range. Of course, abnor-
mal ionization of the species in the flame can result in considerable curvature at low
concentrations. Analytical curves in AA, when absorbance vs. concentration is plotted,
are generally linear over no more than a 102 to 10 3 -fold range. The largest range in
AA is seldom as large as in AF because the best limits of detection obtained are rarely
lower than 1 ppb. The analytical curves obtained in FE, particularly for the alkali metals,
are also generally linear over about a 10 5 -fold concentration range. Of course, most other
elements in FE result in useful analytical curves over a considerably smaller range.
11.5.4 SELECTIVITY AND INTERFERENCES
11.5.4.1 ;S>pectralinterj"erences
This type of interference is most predominant in FE where any thermally excited radiation
emitted from other species in the sample gives a positive interference (if within the spectral
11.5] COMPARISON WITH OTHER FLAME SPECTROMETRIC METHODS 617
bandwidth of the monochromator). In AA and AF this can be entirely eliminated by the

use of a modulated source and detector, although there will be a concomitant noise con-
tribution. Spectral interferences caused by absorption of either emitted or source radia-
tion due to foreign species in the flame will be common to all three methods. This will be
comparable to the filter effect found in molecular spectrofluorimetry and will result in ne-
gative interferences in FE and AF and positive interference (i.e., enhanced signal) in AA.
In AF, this effect will apply to both incident and emitted radiation.
Some other spectral phenomena which are not elemental interferences can also be com-
pared here. In AA, the use of a poorly resolved source line results in extraneous radiation
entering the monochromator. This leads to low absorbance values, since absorbance is a
ratio, and also increases the possibility of spectral interference by other elements in the
flame. It will also give rise to curvature of the analytical working curve. In AF, the source
radiation passes through the flame and is not measured by the detector. The monochro-
mator need only be capable of resolving the fluorescence emission from the element being
determined.
In general, inexpensive, low resolution monochromators are more successful in AF
than AA; in fact, for some applications, monochromators need not be used in AF [49].
In AA and AF, scatter of the incident source radiation by particles in the flame is pos-
sible and results in enhanced signals which can often be compensated for analytically
by the use of suitable blanks. The degree of scatter, however, can be directly measured
in atomic fluorescence by measuring the scatter from a source line of similar wavelength,
if this line does not contribute to fluorescence. The relative intensities of the two lines must
be taken into account when computing the scatter signal. When a continuous source is
used, scatter measurements may be made by scanning the wavelength on either side of
the fluorescence line. The noise components due to scatter can not readily be allowed for.
Quantum efficiency measurements have shown [9] that atomic resonance fluorescence
is unlikely to cause any serious interference in AA.
11.5.4.2 Non-specific interferences
These interferences comprise those factors which influence sample transport rate (F),
efficiency of aspiration (e), and the shape of the flame. Any factor causing a variation in
any of the above items would be expected to give corresponding interferences in all of the
three methods of flame spectroscopy.
11.5.4.3 Specific interferences
These interferences are apparent in the determination of certain elements and include
solute vaporization, dissociation of the analyte, formation of compounds within the flame
and ionization interferences. All three flame methods of analysis are subject to these types
of interference which can be treated as variations in the {J factor (the degree of atomiza-
zation), or I' factor.
The reader is referred to Herrmann and Alkemade [102] for a thorough discussion of
the procedures employed in minimizing interferences. The studies carried out by Dagnall
et al. [28,31-35] and Ellis and Demers [24] have indicated that AA and AF are subject to
essentially the same types of specific and non-specific interference.
11.6 Future studies in atomic fluorescence
Certainly most of the future studies in atomic fluorescence will concern improvements in
instrumentation, particularly on the sources of excitation and on the method of atomiza-
tion. For example, electrodeless discharge tubes operated at radio frequencies have already
been shown to be useful for optical pumping studies of the alkali metals and are likely
to be tried in AF. Dawson and Ellis [61] have already shown that hollow cathode dischar-
ge lamps operated at low dc currents but with superimposed high current pulses, result in
hundredfold gains in intensity of resonance lines with little self-reversal. Pulsed hollow
cathode lamps are certain to be tried in AF. The success in the authors' laboratory of an
evacuated jacket surrounding electrodeless discharge tubes is also to be studied in more
detail [81]. Finally, it is also reasonable to expect lasers, especially the tuneable dye
laser [103], because of their high intensities and simple optical requirements, to be
used for selected elements. Other possible sources of excitation include the continuous
high-intensity Plasmadyne argon torch and modifications of hollow cathode discharge
lamps.
The ideal method of atomization would involve a technique which uses solutions and
which results in 100% atomization of all samples. Obviously flames can not do the latter
for all elements. Massmann [98, 99] and Svoboda [100] have studied interesting non-
flame cells described elsewhere in this chapter. This technique would appear to have
some very desirable characteristics which would justify further research. Badger [4], a
number of years ago, showed the value of the separated flame for measuring the atomic
fluorescence of mercury and thallium. More recently Kirkbright, et al. have used a se-
parated air-acetylene flame in flame emission [96] and atomic absorption [97] spectrosco-
py. The advantages of a flame separation include shielding of the flame from the atmosphe-
re, a lowering in flame background with little apparent effect on atomization efficiency,
and therefore an improvement in signal-to-noise ratio for some elements. This technique
will also certainly be tried in atomic fluorescence work. The flame is the simplest and pro-
bably the most precise means of producing an atomic vapor; therefore, more research on
flame types and burner systems is expected to be forthcoming.
Because of the lack of spectral interferences from the source of excitation in AF, it should
be possible to improve the monochromatorless system developed in the authors' labora-
tory [49]. Also because of the efficiency of energy transfer between excited mercury atoms
and other atoms in heated quartz containers, it should also be possible to develop a simple
system with a single source to excite the sensitized atomic fluorescence of a variety of im-
purity metals in mercury. Such research is also in progress in the authors' laboratory.
Finally, the signal-to-noise ratio can be improved and limits of detection decreased by
use of photon counting techniques rather than use of dc or tuned ac amplifier-readout
systems. If a bidirectional counter is used, it should be possible to eliminate flame emission
and to minimize all random noises.
We feel that atomic fluorescence spectrometry will prove to be a versatile, sensitive and
widely used technique, and look forward to the publication of some practical applications
for the analysis of real samples in the near future.
Acknowledgement
This work was supported in part by AFOSR(SRC)-OAR, U.S.A.F. Grant No. AF-
AFOSR-I033-67.
REFERENCES 619
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APPENDIX 621
Atomic Absorption, Prague, August, 1967.

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Appendix
Comparison of Limits of Detection in Flame Emission (FE), Atomic Absorption (AA), and
Atomic Fluorescence (AF) Flame Spectrometry
Element FE AA AF
Ag 0.3 0.01 0.0001

Al 0.2 0.1 25
As 50 0.5 0.1
Au 4 0.1 0.01
B 30 15 b
Ba 0.03 0.1 b
Be 1 0.003 b
Bi 40 0.02 0.1
Ca 0.005 0.003 0.02
Cd 6 O.ol 0.000001
Ce 10 b b
Co 0.007 0.04
Cr 0.005 b
Cs 0.005 0.05 b
Cu 0.1 0.01 0.001
Dy 0.1 0.2 b
Er 0.3 0.2 b
Eu 0.003 0.2 b
Fe 0.7 0.01 0.1
Ga 0.07 0.07 1
Gd 2 4 b
Ge 0.6 2 15
Hf 75 15 b
Hg 40 0.2 0.1
Ho 0.1 0.3 b
In 0.03 0.05 0.1
Ir 100 4 b
Element FE AA AF
K 0.003 0.005 b
La 80 b
Li 0.000003 0.005 b
Lu 0.2 50 b
Mg 0.2 0.0005 0.004
Mn 0.1 0.005 0.006
Mo 0,03 0.1 b
Na 0.0001 0.005 100
Nb 20 b
Nd 2 b
Ni 0.6 0.01 0.003
Os 10 b b
Pb 3 O.ot 0.02
Pd 0.5 0.5
Pr 2 6 b
Pt 40 0.5 b
Rb 0.002 0.005 b
Re 1 1.5 b
Rh 0.3 0,03 b
Ru 0.3 0.3 b
Sb 20 0.2 0.05
Sc 0.07 0.2 b
Se b 0.15
Si 5 0.2 b
Sm 0.6 5 b
Sn 4 0.1 b
Sr 0.004 0.01 0.1
Ta 18 6 b
Tb 2 b
Te 200 0.3 0.05
Th 150 b b
Ti 0.5 0.1 b
Tl 0.09 0.2 0.008
Tm 0.2 0.1 b
U 10 12 b
V 0.3 0.1 b
W 4 3 b
Y 0.3 0.3 b
APPENDIX 623
Element FE I AA AF
Yb 0.05 0.04 b
Zn 50 0.002 0.00004
Zr 50 5 b
a. The limits of detection in AA and FE are the reported values tabulated by Fassel and Golightly
[101 J. The limits of detection in AF are the lowest reported values and in several instances re-
present unpublished data from the authors' laboratory. No attempt has been made to reference
each result but rather the data is given only for gross comparison.
b. No reported value.
CHAPTER 12
HOLLOW CATHODE DISCHARGE DEVICES
J. C. Burger, W. Gillies
and G. K. Yamasaki
12.1 Introduction
Many types of devices have been used as fine-line sources for spectroscopic investigation.
Arcs, Geissler tubes, radio-frequency electrodeless discharge tubes, high pressure dischar-
ge devices, atomic beams and hollow cathode devices have all been used to study hyper-
fine line structure. However, no other source has been used as extensively as the hollow
cathode for this purpose. Atomic beams and some laser sources can give spectral lines
of the required narrow widths but, as reported by Tolansky [1] " ... No other source
gives the same all-round brilliance over an entire spectrum with the same degree of line
sharpness... " as a hollow cathode.
This source offers a number of advantages for spectral studies where a fine-line source
is needed. These advantages are: (1) there are a large number of lines emitted from the
hollow cathode covering the range from the vacuum ultraviolet to the infra-red region,
(2) by properly altering construction and/or operating parameters, one can obtain either
primarily arc or spark spectra, (3) for the amount of electrical current employed, they
provide very intense spectra, (4) hollow cathodes emit very sharp lines, approaching
0.01 cm- 1 or, for example, 0.002 A for the 3247 A line emitted from a cooled copper
cathode, (5) they require simple and inexpensive power supplies, (6) the device is relatively
simple to construct and operate, and (7) they have a stable output over long periods of
time. For these reasons, the hollow cathode has been extensively used for the study of
hyper-fine line structure, for other spectral investigations, and recently, as a source for
atomic absorption spectroscopy.
12.2 Early history
In a discussion of the history of devices such as hollow cathodes, we can only hope to
cover the most important contributions. The hollow cathode glow was first discovered in
1916 by Paschen [2], who recognized the potential of the device as a fine-line source. To-
lansky [3], in a later design, attempted to overcome the outgassing problems experienced
by Paschen by providing for cooling of the anode and the cathode support structure. This
design still permitted the cathode to run hot because of the limited heat conduction path
between the cathode and the cathode support structure. It should be noted that this is the
first reported device with the capability of quickly changing the cathode. Tolanksy (4)
626 HOLLOW CAmODE DISCHARGE DEVICES [12
also proposed a slit-type hollow cathode which would match the geometry of the cathode
discharge to that of the entrance slit of a spectrograph and thereby give better utilization
ofthe light.
The next important contribution to the hollow cathode was by SchUler [5, 6]. He
constructed the tube such that the cathode was part of the outer wall of the device, and
hence could be cooled with water or liquid air. Cooling the cathode reduced the Doppler
width of the spectral lines and also lowered the vapor pressure of the cathode material,
thus reducing the effect of resonance broadening. He investigated in some detail the pro-
perties of his devices as a convenient source for the study of line spectra and the hollow
cathode tube is still spoken of as a "SchUler tube." His contributions were extremely im-
portant because they permitted the observation and study of much narrower lines than
had been observed with the hot hollow cathodes previously employed.
SchUler and Schmidt [7] have described a tube where both the anode and cathode were
liquid-air cooled. With a voltage drop of 250 volts and a tube current of 60 milliamperes,
they were able to excite the stronger lines in a spectrum, but encountered some difficulties
in exciting the weaker lines at this current.
Richter [8] reported on the electrical discharge characteristics of a hollow cathode de-
vice in the first detailed study of the gas plasma. He used an oxide-coated, nickel, hot
hollow cathode that was indirectly heated by a double spiral of tungsten. Approximately
1200 measurements were made using a Langmuir probe. The electron temperature,
electron current, and the potential distributions were determined at various values of anode
current, cathode heating voltage, gas pressure, geometrical constants of the cathode and
for different fill gases.
Van Voorhis and Shenstone [9] described some characteristics of uncoated nickel, hol-
low cathode devices. They determined the minimum pressure necessary to start and main-
tain the hollow cathode discharge as a function of cathode dimensions for gas fills of he-
lium, neon, and argon.
12.3 Development of sealed-off devices
The first successful sealed-off hollow cathode was constructed and reported by
Crosswhite, Dieke and Legagneur [10] for use as a wavelength standard. Previously, it
had not been feasible to construct such devices because outgassing of the various compo-
nents after seal-off would give extraneous spectral radiation and/or would interfere with
the desired transitions. Their use of activated uranium as a getter material resulted in a
tube which could be operated for much longer periods of time without the problems caus-
ed by outgassing of the parts. An iron cathode about 50 mm in length and 10 mm in dia-
meter was used, with a hole 8 mm in diameter drilled almost the entire length. Gas fillings
of helium, neon, argon, krypton and some mixtures of these gases were investigated and
it was found that, for a given current, neon gave the strongest iron spectrum. Their work al-
so indicated that with properly regulated power supplies the tubes gave stable outputs for
hours or even days. Sufficient data were accumulated to construct a graph showing the
intensity of the discharge as a function of current for the four gases mentioned. For their
cathode geometry, they found the intensity of the iron lines to be a maximum near 3 Torr
pressure of neon. A study was also made of the intensity ratios of a number of iron lines
as a function of neon fill pressure. As an extension of the above work, Stanley and Dieke
12.4] DESIGN PARAMETERS 627
[11] made precise wavelength measurements on 189 iron lines from 3570 to 5709 A, using
a hollow cathode device.
In 1955, Walsh [12] and Alkemade and Milatz [13, 14] concurrently proposed atomic
absorption as an analytical tool. Walsh also reported the construction of sealed-off hollow
cathode devices in his laboratory.
Adams and Bums [15] investigated the use of sealed-off hollow cathodes for the trace
detection of impurities in high purity materials by emission techniques. Jones and Walsh
[16] reported the satisfactory use of sealed-off hollow cathode "lamps" (which did not
require a uranium getter) as sources for atomic absorption spectroscopy. They gave detail-
ed instructions for the processing of such tubes and reported lifetimes of up to 30 ampere-
hours. An extensive spectroscopic study of hollow cathode tubes was made by Mitchell
[17]. The ionization and excitation of iron and uranium atoms was studied with respect
to fill gas, fill gas pressure, discharge current and cathode geometry. Berezin [18] made a
study of the intensity distribution of the spectral lines in a cross section and a longitudinal
section of the hollow cathode. Measurements along both axes were made for He, Hg, Na,
H, Fe and CH lines and/or bands.
The above discussion summarizes the more important contributions to the design or
understanding of the hollow cathode leading to the first successful sealed-off devices.
Recent developments in hollow cathode devices relative to atomic absorption spectroscopy
will be discussed later in this chapter.
12.4 Design parameters
12.4.1 WINDOW TYPE AND ENVELOPE STRUCTURE
Early hollow cathode devices were produced in a great variety of shapes and sizes. Sealed-
off types were generally constructed with an appendage containing a gettering powder,
such as uranium or titanium, behind a porous retaining plug. In addition, large volume
devices were thought to be necessary to prevent tube failure due to loss of fill gas by ion
bombardment. See Fig. 12.1.
Further developments and improvements in electronic design, parts fabrication, and
tube processing have shown these extraordinary precautions to be unnecessary. Most pre-
sently manufactured hollow cathode sources are much smaller in size, being about 4-5 cm
in diameter and about 16 cm in total length. They employ end-on optically transmissive
windows (see Fig. 12.2). The envelope is usually made of electronic grade glass that
matches the thermal expansion characteristics of electrically conductive leads to provide
a vacuum seal.
The window material is selected to transmit the spectral radiation of interest for atomic
absorption spectroscopy which falls in the region from 1900 A to 8600 A. Transmission
data for some commercial glasses that cover the range are shown in Fig. 12.3. The most
versatile window material is quartz, which provides good transmission down to about
1900 A; however, to match quartz to electronic grade glass a graded seal is necessary to
reduce sealing strain resulting from large differences in thermal coefficients of expansion
between the two materials. Some devices eliminate the graded seal by cementing the win-
dow directly to the bulb. Subsequent performance often suffers in this type of con-
struction because of limitations imposed on the processing schedule by the thermally
628 HOLLOW CATHODE DISCHARGE DEVICES [12
l"!"i"'ii''''/'''jI''''''1'''I'W''''Y''1 i'lIif'llr.illi',1t'I"i"I'iil"I"I"I
'ifPlf'\Iii"'I'jIl:fP'1"\\f\"f'~
Fig. 12.1. Two types of early sealed-off hollow cathode devices.
decomposable nature of cements. Ultraviolet transmissive glasses such as Corning 9741

are used by some manufacturers to replace the quartz window and graded seal, with a
resultant decrease in transmission below 2400 A (see Fig. 12.3). For wavelengths above
3000 A the transmission of Pyrex 7740 glass is satisfactory adequately to cover the upper
range of immediate interest in atomic absorption. It has the added advantage of being
easy to seal to other glasses used in glass-to-metal vacuum seals. For these reasons, there
is an increasing tendency to use quartz for all wavelengths from 1800 to 3000 A and Pyrex
for wavelengths greater than 3000 A.
12.4.2 CATHODES
As the name hollow cathode implies, the cathode is shaped in a hollow configuration with-
in which light production occurs. From an electrical discharge point of view, the most
efficient cathode is a spherical cavity with a small opening [19]. In most commercially
available devices, designed for optimum light output, the cavity is cylindrical in shape.
For either shape, when the cathode dimensions and fill gas pressure are such that the
hollow diameter is less than twice the thickness of the cathode dark space, a unique dis-
charge process occurs in which intense ionization and excitation become concentrated in
the center of the hollow. The values of diameter and gas fill pressure approximate the re-
lationship d = c/p where d is the hollow diameter in em, p is the fill gas pressure in Torr,
and c varies in value from about 0.5 to 10 depending on the type of gas, temperature,
shape of hollow and cathode material. The degree of ionization inside the cathode is
strongly affected by the hollow geometry [17]. The ratio of ion line to ground state line
intensities becomes greater as the hollow diameter and fill gas pressure are increased, as
Fig. 12.2 Hollow-cathode tubes of recent manu-

facture:
a. Fabbrica Italiana Valvole Radio Elettriche
(FIVRE),
b. The Perkin-Elmer Corp.,
c. Cary Instruments,
c d d. Westinghouse Electric Corp.
w
~ 80
~
!:::
1:5 60
z
«
0::
I- 40
~
l':l
[520
a.
O~~~~~~~~~~---L--~~ __-L~
160 180 200 220 240 260 280 300 320 340 360 380
WAVELENGTH IN MILLIMICRONS
Fig. 12.3. Transmittance of several commercial glasses.
10.0
5.0
If
"-
1=1
~
0
I"
i=
«
0::
1.0 "8
>-
I-
u;
~ 0.5
I-
:::
0.1 0 2 4 6 8 10 12 14 16 18
PRESSURE (mm Hg)
Fig. 12.4. Intensity ratio Fe II 2749.324/Fe I 2733.581 vs neon pressure for different cathode
bore diameters. Cathode bore length was 1 5/8 in. and discharge current 160 rnA.
(This figure reproduced from K. B. Mitchell, J. Opt. Soc. Am., 51, 846 (1961) by permission of
the Journal of the Optical Society of America.)
may be seen in Fig. 12.4. The ratio also becomes greater as the depth of the hollow is
decreased, as shown in Fig. 12.5.
The cathode material itself should be a reasonably good electrical conductor. However,
wi th proper alloying, the spectra of even poor conductors such as phosphorus, sulfur and
boron may be produced.
10.0 r-r-r-r-r-r-r-r-r-r-r-r-r-r-r-r-r-r-"
...
.t
.....
1::1
If
o
Ei
0:'
10
>-
I-
iii
~ 0.5
I-
!:
ru o 2 4 6 8 ~ ~ ~ ~ ~
PRESSURE (mm Hg)
Fig. 12.5. Intensity ratio Fe II 2749.324/Fe I 2733.581 vs neon pressure for different cathode bore
lengths. Cathode bore diameter was 1/4 in. and discharge current 160 mAo
(This figure reproduced from K. B. Mitchell, J. Opt. Soc. Am., 51, 846 (1961) by permission of
the Journal of the Optical Society of America.)
As is the case in any electrical device, heat is a major problem associated with current
flow; therefore, at an operating current of about 30 milliamperes (rnA), the cathode tem-
perature can reach 400-500 °C depending largely on gas fill and cathode fall (potential
gradient close to the surface) which varies for different materials. The gas fill not only
affects the value of the cathode fall to some extent, but is also the major vehicle by which
heat is dissipated by convection and conduction. The cathode fall voltage multiplied by
the cathode current approximates the cathode heating power resulting from ion bom-
bardment. The cathode material must be capable of withstanding this heat without melting
and deforming and it must also have a low enough vapor pressure so as not to sublime or
rapidly evaporate over the interior of the device. Some elements such as Ga, Pb and Sn
can actually be operated in the molten state when they are made to properly "coat" the
surface of a carrier cup fabricated from iron or copper. This is made possible because
they have low vapor pressures even in the liquid state. Devices using high vapor pressure
cathode materials must be operated at lower currents, provided with external cooling, or
have the elements rendered more stable by alloying.
The best and simplest method of manufacturing a cathode is by machining it from pure
elemental rod stock; however, physical characteristics and cost often necessitate other
means of fabrication. Some of these are powder metallurgy, alloying, plating, and eva-
poration of salt solutions in the hollow.
Fluctuations and gradual reduction in spectral line intensities are usually noticed when
non-homogeneous methods such as salt coatings and thin platings are employed. Since
the spectra are produced by the continual sputtering and erosion of the hollow surface, a
thin plating or coating becomes rapidly depleted, thus exposing the supporting base metal.
Multi-element cathodes are usually fabricated by powder metallurgy or alloying techni-
ques. Elements with high melting points such as tungsten, boron and osmium present
some problems in producing structurally strong compacts by powder metallurgy unless
extra high pressures, sintering temperatures and special techniques are used. However,
this difficulty can be circumvented by mixing these elements with a lower melting point
"bonding" powder of copper or aluminium. Generally, a large variety of elemental pow-
der mixes can be pressed and sintered together with somewhat less concern with critical
parameters such as stoichiometric compound and eutectic formations, elemental solubilities
and phase diagrams which must be adhered to in the casting of alloys. It is, however, im-
portant to keep in mind that the probability of elemental spectral line interferences can
become large as the number of combined elements is increased. Elements with relatively
simple sPectra such as AI, Au, Ge, and Mg and elements with very intense absorbing lines
such as Ag, Cu, Cr, and Zn can be much more easily combined to make an acceptable
multi-element cathode than elements with a large number of relatively weak lines such as
U, Th, Fe, Ru, and Ni.
Another means of fabricating multi-element devices is by incorporating two or more
cathodes side by side in one envelope [20] or by stacking a series of washers of different
elements to form a single cathode [21,22]. By judicious selection of elements with regard
to their sputtering rates, a fairly stable device is possible. Another method is to employ
a series of tandem cathodes of cylindrical shapes mounted along a single axis so that the
light emitted from the rear cathode can radiate through the cylindrical cathode in front.
With proper construction, the current to each cathode may be independently controlled
12.4.3 GAS FILL AND PRESSURE
All hollow cathode spectral light sources used in atomic absorption spectroscopy are inert
gas filled devices with the most commonly used fill being neon or argon. Usually, the
neon fill is preferred because it permits production of greater spectral line intensities, but
argon is used when interfering neon lines are found to be located closer to the desired
elemental absorbing line than the isolating ability of the instrumentation.
For the emission of sharp spectral lines, two major processes must occur in the cathode
hollow: the liberation of free atoms of the cathode material, and their subsequent excita-
tion and de-excitation with the emission of spectral Hght.
Free atom formation is accomplished by the physical collision and "sputtering" of the
cathode material by the impact of gas ions which have been accelerated by an electrical
potential applied between the anode and cathode. The effectiveness of the bombarding
gas ions is largely dependent on their masses and velocity. For high energy ions of about
1000 electron volts or greater, the gas ion with the higher mass is more efficient for free
atom formation. For lower energy ions up to several hundred electron volts, as found in
the hollow cathode discharge, the most efficient sputtering ions are those of argon; how-
ever, there is considerable overlapping among the gases depending on the crystalline
structure, atomic mass, and temperature of the cathode and dimensions of the hollow.
Theoretically, helium, with ionization and excitation potentials of 24.6 volts and 19.7
volts respectively has ample voltage to effect excitation of most arc and spark spectra, but
it is actually much inferior to neon and argon for excitation because of its low mass and
12.5] OPERATION OF HOLLOW CATHODE DEVICES 633
inferior sputtering ability. On the other hand, krypton and xenon have sufficient masses
for sputtering, but have low ionization and excitation potentials. Neon has an ionization
potential of 21.6 volts which is somewhat less than the value found for helium, but at the
same time it has the added advantage of having sufficient atomic mass for effective sput-
tering. Therefore, neon produces the most intense emission of the ground state lines [10,
17] which are used for atomic absorption analysis. Xenon gives the least with helium,
krypton, and argon falling in between in ascending order.
A discharge useful for efficient production of atomic spectra in a hollow cathode occurs
only within a certain range of gas pressures, and within this range there exists an opti-
mum pressure for production of maximum spectral line intensity. For neon, this is attain-
ed with a fill pressure of about 2 Torr while for helium, argon and xenon the values are
about 1.5, 4.0 and 0.5 Torr, respectively, for a cathode with a 3/8" diameter hollow.
The ratio of nonabsorbing ion line to absorbing ground state line is usually greatest for
xenon and least for argon with neon about halfway in between.
The spectral lines of the fill gas are also produced in the hollow cathode discharge,
which may lead to interferences with the lines of interest. The hollow cathode spectra of
helium is almost exclusively He (I). For neon and argon in the ultraviolet and shorter
visible region, the arc (I) lines are weaker and the ion (II) lines dominate, while for Kr and
Xe, the gas spectrum consists almost exclusively of ion (II) lines.
Van Voorhis and Shenstone [9] have shown that anode to cathode distances have a
marked effect on the minimum fill gas pressure necessary for stable operation only
when the distance becomes less than 1.5-2 cm. In a low pressure gas filled device, most
of the voltage gradient between two electrodes is located in rather well defined narrow
region snear the cathode and anode. These two regions are connected by a region of rel-
atively low potential gradation called "the positive column." The length of this column can
vary considerably depending on the cathode to anode distance while having only a slight
effect on the discharge voltage. It is apparent that as long as sufficient distance is main-
tained to include the critical regions near the cathode and anode where most of the volt-
age variations occur, moderate changes in anode to cathode distances will have only
slight effect on the operational voltage. Likewise, spectral emission will also not be affect-
ed to any extent.
12.5 Operation of hollow cathode devices
12.5.1 VOLT-AMPERE CHARACTERISTICS
The hollow cathode operates in the glow discharge region where the operating voltage is
mainly dependent on cathode material and gas fill and is relatively independent of tube
current. A device operating in this mode tends to have very stable characteristics once the
discharge is struck. The hollow also permits better utilization of the positive ions, meta-
stables and photons [23] in producing further excitation, ionization and liberation of
electrons. The result is a higher current density for the same amount of cathode area, a
higher positive ion density, and an increased number of sputtered and excited atoms for
spectral light emission.
Fig. 12.6 shows typical voltage - current (ampere) curves for various hollow cathode
devices, with the voltage measured directly across the electrodes of the device. The start-
70r-------------------------,
60 Fe Mn
.....ffi 50
....
!1i
::;
40
i
" 30
z
iiII:
~ 20
Y
o
10
o-c OPERATING VOLTS

Fig. 12.6. Typical operating characteristics for various hollow cathode devices.
ing voltage is primarily dependent on the type of gas fill, its pressure, and the cathode
material, and may vary from a few to over 150 volts above the discharge sustaining volt-
age. Therefore, a high initial surge current may pass through the device unless a protective
load resistor is connected in series. For the usual operating current values up to about
50 milliamperes, a resistor on the order of 5,000-50,000 ohms and 25 watts should suffice
depending on the voltage drop across the hollow cathode and the voltage capability of the
power supply.
12.5.2 POWER SUPPLY
Basically, the hollow cathode operates as a diode and it is usually connected in series
with a load resistor to a power supply. The choice of a power supply will depend to a great
extent on the desired detectability and accuracy of the analytical determinations. It will al-
so be dependent on the type of detection instrumentation used for atomic absorption
spectroscopy. In general, a regulated voltage output is desirable. For most general in-
vestigations with single beam instrumentation the regulation should be of the order of
1 %. For precise or low level, single-beam measurements, a well-regulated constant cur-
rent supply providing 0.1 % (or better) current regulation would be desirable.
The spectral output from a hollow cathode is closely dependent on device current, there-
fore any fluctuations present in current would become immediately noticeable in the in-
tensities of the emitted spectral lines. This in turn will affect the precision and limit of de-
tection of the analytical determination when the device is employed as a line source for
atomic absorption spectroscopy. Within its operating limits, a pure single element hollow
cathode device exhibits stability of current and spectral output over long periods of time.
When double beam instrumentation is available, the requirements placed on the supply
are less stringent and a regulated 1 % supply should be adequate for most purposes. The
reason is that the effects of variations in hollow cathode current or voltage are consider-
ably reduced when the ratio of the radiation through the flame to the reference beam can
be concurrently measured.
Most commercially available hollow cathode devices have starting voltages that are
reasonably low and, with the proper series load resistor, the power supply requirements are
reduced and high surge currents at starting are minimized. In general, a 500 volt power
supply will be adequate for most applications; however, a power supply with higher out-
put voltage does offer definite advantages. With reference to Fig. 12.7, it can be seen that
the use of a supply of voltage VI to attain an operating point Vo, 10 would require a value
of resistance of VIllI, which would be considerably higher than the resistance required if
a supply of voltage V2 were used (R 2 = V2 II2 ). The effect of the increased voltage and
resistance is to minimize the effect of variations in the voltage-current characteristic of the
hollow cathode source. This may be seen in the detailed inset of Fig. 12.7 which illustrates
the effect of variations in the sustaining voltage which is the characteristic most likely to
change. For purposes of illustration, the variation has been highly exaggerated as most
devices will remain relatively stable over long periods.
Typical Hollow Current Variation of

Cat hade
I- Characteristic
Z
W
a:::
a:::
:::>
u
<.9
Z
(f) Current
« Variatian
w With Supply
a::: Of V2 Valls
u
z R I = V, = V, - Vo
I, 10
INCREASING VOLTAGE
Fig. 12.7. Effect of different supply voltages on the voltage-current characteristic of a hollow
cathode device.
12.5.3 CURRENT LIMITS
The maximum current rating of present sealed-off hollow cathodes for atomic absorption
is about 40 milliamperes and it is doubtful that values in excess of this will be required
in the near future except for specialized experiments.
Each manufacturer should designate the maximum current to be used for a particular
device and this value should not be exceeded. A resistor of sufficient value should be pre-
sent to limit the current to this value or lower at all times. Operation with excessive cur-
rents may cause an acceleration in "clean-up" ofthe fill gas (reduction in pressure) with sub-
636 HOLWW CATHODE DISCHARGE DEVICES [12
sequent unstable operation, or in severe situations it may result in melting of the cathode.
The user may readily calculate the minimum value of series resistance which should be
used once the supply voltage and the electrical characteristics of the devices to be used are
known. It is suggested that the series resistance consists of a fixed resistor plus a continu-
ously variable resistance. The former should be sufficient to limit the current to a safe
value for the power supply; the latter may serve to set the current to the precise, required
value.
Maximum life will be achieved when the operating current is the lowest value which
will give a satisfactory signal-to-background ratio in the instrument under consideration.
12.5.4 WARM-UP AND LIFE
During its life, many changes occur in the hollow cathode device. Since spectral light is
emitted by free excited atoms in the cathode hollow, sputtering or vaporization of the
cathode element must take place. This naturally tends to alter the geometry of the hollow,
and as a result, the intensity of the spectral output. Gas clean-up occurs constantly with
a subsequent gradual reduction in gas pressure. Since this has a direct effect on the
electrical discharge, the intensity and also the relative intensities of one elemental line
to another may also change. The spectral output is also dependent on the temperature
of the cathode which is related to the cooling effect of the gas present and the heat
reflecting, absorbing, and radiating properties of all the surfaces present in the device.
Furthermore, different elements in an alloy or multi-element cathode may diffuse and
sputter from the cathode surface at different rates. The net result of all this is a gradual
change in spectral output of the device during its life (Figs. 12.8, 12.9, 12.10). However, it
must be noted that even though large variations may occur over the life of a device, these
changes are occurring over many hours of operation. For normal atomic absorption
usage, which usually spans only several hours, these long term variations are rarely
noticeable.
The greatest change in spectral intensity occurs in the first few minutes of operation,
with this warm-up drift period lasting from about 2 minutes to over an hour in extreme
cases. All devices exhibit this initial drift until thermal, electrical, and atomic vapor
population equilibrium is reached.
>-
!:::I2
(f)
z
W
I-
~
w
~8 END OF LIFE I
I- (GAS CLEAN-UP)
<! 1590 HOURS
Q61
0:
O~--~----~--~~---L----~--~~
o 500 1000 1500
TUBE LIFE IN HOURS
Fig. 12.8. Variation in intensity of a lead line during life. (pb 2170 A, 15 rnA current, argon fill.)
12.5] OPERATION OF HOLLOW CA1HODE DEVICES 637
26
>-
I-
~22
w
I-
Z
- 18
w
>
~ 14
....J
w
II:
10
o 1000 2000
TUBE LIFE IN HOURS
Fig. 12.9. Variation in intensity of a zinc line during life. (Zn 2139 A, 15 rnA current, neon fill.)
>- 20
!::
~ 16
ILl
I-
z 12
ILl
> 8
~
W
II:
1000 2000 3000 4000

TUBE LIFE IN HOURS
Fig. 12.10. Variation in intensity of a tin line during life. (Sn 2863 A, 15 rnA current, argon fill.)
Many instrument manufacturers provide a warm-up supply to keep a set of devices in a

ready to use condition, but unless the warm-up current is exactly the same as the opera-
tional current, a certain amount of drift in output will be noticed when any change is
made in the cathode current.
Typical warm-up curves for various cathode types are shown in Fig. 12.11. Curve "A"
shows a cathode in which free and excited atom population is highly dependent on tem-
perature such as would be the case for Cd or Pb.
Curve "B" shows the most common type of warm-up curve followed by a hollow
cathode device. "C" represents the type of curve usually obtained with pure cathodes such
as W, Re, Ta and V which are relatively insensitive to temperature changes. Curve "D"
shows how some of the very volatile elements in a multi-element or alloyed cathode reach
>-
I-
enz
lJJ
I-
z
o 5 10 15 ZO 25 30
TIME IN MINUTES
Fig. 12.11. Typical warm-up curves for various cathode types.
stabilization. After the previous operation, while the cathode is cooling, some of the
more volatile elements recondense on the surface of the hollow. As a result, when the
device is first restarted, most of the atoms present in the hollow will be of this type until
the normal cathode surface becomes exposed again.
12.5.5 PULSED OR A-C OPERATION
Pulsed or alternating current operation of hollow cathode devices offers certain obvious
advantages. For example, the mechanical chopper is eliminated when modulation of the
light source is provided. Modulation also reduces the signal noise due to the flame and per-
mits the use of alternating current amplifiers which are much easier to stabilize.
Considerable caution should be used when contemplating pulsed or a-c operation.
Fig. 12.12 shows a typical tube operating from a 220 volt line. In the extreme case chosen,
(1) the device will fire at the peak of the forward cycle, (2) the voltage across the electrodes
will drop to a value dependent on the cathode and the amount of current being drawn,
(3) the voltage will remain relatively constant until the discharge is extinguished and then
will assume the waveform of the supply voltage. Looking at the current, it will increase
immediately to a value dependent on the line voltage, the tube voltage drop, and the
series impedance. As the cycle goes on, the value of current will be dependent on the
SUPPLY WLTAGE
'j . :
,
,
,\
\
,
,I
,I
I
',~'
AVERAGE CURRENT REQUIRED

FOR SAME SPECTRAL OUTPUT
WITH D-C EXCITATION AND ISOO
MECHANICAL CHOPPER
Fig. 12.12. Alternating current operation compared with direct current operation and mechanical
chopping.
instantaneous value of the supply voltage minus the voltage drop, and the series impe-
dance. Finally, when the voltage is too low to support the discharge, the current will
drop to a low value. Under the conditions chosen, the average output current (and thus
the spectral output) can be represented by a continuous level as shown by the dashed-line.
The ratio of the peak-to-average current for this case is about 10 : 1. If 10 rnA average
were required for sufficient light output, the peak current would have to be 100 rnA! This
would require a higher level of ionization in the device and increase the probability of
loss of gas by "clean-up."
As a comparison, if the source were operating on d-c with a mechanical chopper provid-
ing 180 0 of output, the required d-c current would be as shown by the solid line. This is
twice the average current required under a-c operation, but the peak current level is only
1/5 as large. A copper device operated close to the a-c conditions shown, but firing some-
what earlier in the cycle so that the peak-to-average ratio was 7 : 1 with a peak current
of 100 milliamperes failed after about 20 hours of operation. Copper devices with equi-
valent output operating on direct current have given lives of over 1000 hours.
The condition shown is an extreme case; the situation is improved if the voltage is
increased to about 500 volts so that the source fires earlier in the cycle and the peak
to average ratio is decreased to a minimum. In order to avoid application of reverse
voltage to the device, it is recommended that a series diode be used.
The output of a typical device increases in a non-linear manner with current, as may
be seen in Fig. 12.13. If the excitation of the sputtered metal atoms was caused only by
primary electrons from the cathode, the intensity would be proportional to current, but
since other means of excitation are present, non-linearity occurs. This is one reason why
operation under pulsed conditions will give a more intense light output than when
operated on direct current. Since a source being pulsed must pass a much higher current
during its peak conduction time in order to give the same average direct current to a
given value, it will be operating in the more efficient upper region of the curve.
120
100 CATHOOE - COPPER

GAS -NEON
WINDOW - PYREX (7740)
LINE - 3247A
80
,.
Iiiz 60
'"....
~
'"
>
40
S1.J
II!
20
v+----r--~----+_--_+----~~
o 10 20 30 40 SO 60
CURRENT IN MILUAMPERES (D.C.)
Fig. 12.13. Relative intensity of a hollow cathode device as a function of operating current.
For certain elements which inherently emit very bright spectral lines such as Cu, Mg, Ag,
and Cr, alternating current operation may actually prove to be deleterious to the analyti-
cal procedure because of photomultiplier saturation unless proper filtering or slit adjust-
ments are made. This will be more fully discussed later.
12.5.6 DEVICE LIFE
Under normal operating conditions, within specified current limits, two factors seriously
affect the overall life of any inert gas filled discharge device such as a hollow cathode.
The first is gas clean-up, or the loss of gas fill due to sorption by sputtered material, with
the rate of depletion depending mainly on the operating current and electrical configura-
tion of the device. The second factor is the extent to which the manufacturer can and does
outgas and process the device before sealing it off from the vacuum exhaust system. The
various parts, and especially the relatively thick cathode, require extended pumping at
high temperature under stringent conditions to produce a satisfactory sealed- off device.
This is usually accomplished either by processing at a high current, or by using an external
heating device such as an oven, and radio frequency induction heating. Failure to do so
will result in devices which become gassy and inoperative after prolonged idle standing
and often require periodic operating at rated current to protect the device from deterio-
ration.
A typical exhaust schedule for an iron hollow cathode device involves an initial en-
velope bake at about 400 °C for several hours and then an actual operation of the device
at currents in excess of 100 milliamperes until the cathode becomes heated to over 800 °C
by ion bombardment. The fill gas is then pumped out until the cathode has cooled to be-
low visible heat and evacuated below 10- 5 Torr pressure. The procedure is repeated several
times until a clean discharge is attained. The device is finally cooled and pumped to below
10- 5 Torr pressure, refilled to about 5 Torr of neon or argon and tipped off.
The life is rated in ampere-hours which is the number of hours a device is run multiplied
by its operating current. For example, if a device operated at 10 milliamperes fails after
1000 hours, it is said to have run 10,000 milliampere-hours or 10 ampere-hours. Normally,
this value varies from about 5 A-hr. up to as much as 40-50 A-hr, depending primarily
on cathode type, with the overall average being in the neighbourhood of 10 to 15 ampere-
hours.
12.6 Application of hollow cathode devices to atomic absorption spectroscopy
12.6.1 LINE BROADENING
Best results are obtained in atomic absorption spectroscopy when the half-width of the
line emitted by the source is much less than that ofthe absorbing system. Line widths pro-
duced by most uncooled hollow cathodes appear to be in the range of 0.01 to 0.04 A,
depending on the nature of the spectral line and tube operational conditions. The natural
width for resonance lines is approximately 0.0001 A, but various broadening effects tend
to increase this value. Contributing factors are 1) Doppler broadening resulting from the
different vector velocities of the emitting atoms along the direction of observation, 2)
12.6] APPLICATION TO ATOMIC ABSORPTION SPECTROSCOPY 641
pressure broadening, caused by interaction of the emitting atoms with foreign atoms, 3)
resonance broadening in which the emitting atoms interact with their own kind, 4) self-
absorption broadening which is caused by reabsorption of emitted photons by atoms of
the same kind, resulting in a loss of peak intensity, 5) Zeeman broadening due to magnetic
fields resulting from current flow, and 6) Stark broadening due to the high electrical field
concentrated near the surface of the cathode. The first four effects are the most important
factors in hollow cathodes. Since all four of these broadenings are related in one way
or another to kinetic energy or temperature, and atomic vapor pressure, increasing the
tube current will tend to increase the width of the resonance line radiating from the
hollow cathode.
100 ,-----.,-----.,-----,----,
CHOPPED D.C. OPERATION
0.16A BANDPASS
~ 80 3247 A-Cu
i=
Q.
0::
~ 60
CD
<
I- 40
z
ILl
U
ffi
Q.
20 25 PPM
~mA 10 20 30
CURRENT IN mA
40
Fig. 12.14. Fabry-Perot interferometer tra- Fig. 12.15. Effect of line broadening on ab-
ces of the copper 3247 A line at different sorption.
operating currents.
Fig, 12.14 shows Fabry-Perot interferometer traces for the copper 3247 A line in a
copper-neon hollow cathode device at various currents. The Fabry-Perot interferometer
used has a resolution of about 0.003 A, and the fine structure of the 3247 A Cu line
is shown with the half-width of the 8 milliampere (rnA) line being about 0.012 A. At
8 rnA no reversal is seen for the 3247 A doublet, but at 15 rnA it can be readily seen. At
30 rnA the reversal is quite severe. The decrease in absorption with increase in hollow
cathode current for the eu 3247 A line as shown in Fig. 12.15 is due to self-absorption
and line broadening in the hollow cathode. Note that even though reversal is severe at
30 rnA the absorption changes by only a few per cent as compared to the non-reversed
condition at 8 rnA.
12.6.2 LINE INTERFERENCE AND RESOLUTION
One item of interest in sealed-off hollow cathodes is the interference from fill gas lines.
This problem has been met by either changing the fill gas or by using monochromators
with a sufficiently narrow band pass. In the case of interference from second order gas
lines when using a grating monochromator, a cut-off filter may be used as shown in
Fig. 12.16. This figure shows that second order neon interference on the Li 6708 A line
Li-6708
Li-6708
Ne2nd Ne 2nd
Order Order
With CS2-60
Filter
Without
Filter
Ne
N
Fig. 12.16. Spectra in the region of the Li 6708 A line with and without filter to remove second
order interference.
may be eliminated without significant reduction in Li intensity by use of a filter such as

the Coming CS2-60.
An example of first order gas line interference occurs with the sodium 3302/3 A doublet
used for the determination of sodium at higher concentrations. Both argon and neon have
numerous lines near this wavelength. It is interesting to look at the spectra taken as a
function of bandpass for a sodium-argon hollow cathode device in the region of the
3302/3 A sodium lines as shown in Fig. 12.17. The sodium doublet is unresolved in all
these spectra. Ata 0.4 A bandpass note that the line-to-background ratio is about 15 to 1
and the actual background is low. The instrumental zero is shown by the index marks on
the vertical sides of the box. The spectra taken at a 1.6 A bandpass show a degradation of
the line-to-background ratio to a value of 6.5 to 1 because the apparent background has
increased at a faster rate than the line intensity. At an 8.0 A bandpass, the complete
character of the 3302/3 A line has been lost except that a peak in the curve occurs at or
near this wavelength.
O.4A 1.6A
No-3302 Na-3302 No-3302

~
1 1
II ~
r-,
, ,
~40A--l
Fig. 12.17. Degradation ofline-to-background ratio as monochromator bandpass is increased.
Ni-3415
Ni-2320
Ni
Ni
Ne
Fig. 12.18. Spectra showing other nickel lines in the region of the most commonly used Ni 2320 A
and Ni 3415 A absorbing lines.
0.6,---------,
0.5
~ 0.4
z
«
~ 0.3
§
« 0.2
0.1
40 60 80 100
CONCENTRATION. ppm Ni
Fig. 12.19. Absorbance vs concentration at various bandwidths. (Ni 2320 A line, neon fill, 5.0 rnA
operating current.)
Fig. 12.18 shows the nickel 2320 and 3415 A lines. Of particular note is the fact that the
more sensitive 2320 A line is surrounded by numerous non-absorbing and poorly ab-
sorbing Ni lines. One way adequately to isolate this line to gain sensitivity and linearity
is to use a narrow bandpass monochromator. The effect of bandpass variation on the
working curve for the 2320 A Ni line may be seen in Fig. 12.19. The curve established at a
bandpass of 0.16 A is a straight line over the indicated concentration range. Some bending
of the curve occurs up to a 1.6 A bandpass, and then between a 1.6 and 8.0 A bandpass
a serious deterioration of the working curve occurs, primarily because the light from the
extraneous nickel lines is entering the monochromator.
12.6.3 FACTORS AFFECTING SIGNAL-TO-NOISE RATIO
Most major problems in atomic absorption spectroscopy involving low signal-to-noise

ratios are encountered outside the range of 2000 to 6000 A. Some of the factors contribut-
ing to reduced system performance outside this range are atomic absorption components
other than the hollow cathode source. In addition to the optical transmission of the win-
dow of the hollow cathode device, consideration should be given to the combined thick-
ness and type of fused quartz incorporated in the transmission optics, the condition of re-
flecting surfaces, and the relative efficiency of the total optical system. Serious detection
and sensitivity problems can arise, especially at low wavelengths, if transmission or re-
flection losses are high.
f- 100 All gratings are 590 grooves/mm

z Un polarized Ught
~ 80 f--+--=----+:,_-+~-+---_+_-____j;,.-c-__j-__J
0:
w
a.
z 60 f-+-+-+--+-----'''''-:-t--t--''''-.;;;:--v--+-__j-__J
Data courtesy of
Jarrell·Ash Co.-
4000 6000 8000 ~OOO
WAVELENGTH IN ANGSTROMS
Fig. 12.20. First order efficiency for three gratings blazed at different wavelengths.
The blaze angle of the grating is another factor in determining the region in which the
instrument is going to be most efficient. Fig. 12.20 shows three typical grating efficiency
curves. If an instrument is equipped with a grating such as the one that peaks at 3400 A,
the efficiency will fall off above 6000 A and, in order to maintain a sufficient signal-to-
noise ratio, the slit width will have to be increased. The extent to which this can be done
will be limited by the dispersion characteristics and efficiency of the grating, the design of
the instrument, and the problem under consideration. The grating blazed at about 4500 A
would cause similar problems at wavelengths below 2500 A.
~ IOOf-__j--H~~~4+--+-4--~
f-
:>
i= 80
iii
z
w
~ 6Of-__j~__j+--+-+-+~-+-4--~
w
>
~ 4Of-~-~--+-~-~-4--~
...J
w
0: 20~--H~__j--+--+~-+~4--~
2000 4000 6000 8000

WAVELENGTH IN ANGSTROMS
Fig. 12.21. Typical spectral response of some photomultipliers used in atomic absorption spec·
troscopy.
Another component that can cause some difficulty is the photomultiplier. Many types
are available and response curves for two of these generally used in atomic absorption are
shown in Fig. 12.21. The Hamamatsu R106 has relatively poor response at the higher
wavelengths where a grating blazed at 3000 A is also least efficient. This combination can
lead to serious signal handling problems for elements such as sodium, lithium and potas-
sium. The R136 photomultiplier has a low response below 2500 A and would limit detecta-
bility on such elements as selenium and arsenic. The problem is further complicated be-
cause the curves shown are nominal and one finds relatively wide variations in response
from detector to detector. It is unfortunate that a single inexpensive photomultiplier has
not been developed to cover the entire range of interest in atomic absorption spectroscopy.
The user should be aware of the above limitations and select the various components so as
to optimize his instrument for the region of major interest.
12.6.4 PHOTOMULTIPLIER SATURATION
Some atomic absorption systems, when operated on half-wave rectified alternating current,
have presented difficulties because absorbance-concentration curves did not yield the ex-
pected shape. However, this problem was found to be one of photomultiplier saturation
rather than a hollow cathode problem. The saturation is caused by high peak light
intensities reaching the photomultiplier. These high light intensities generate such high
electron densities in the final multiplier stages that the photomultiplier is incapable of
handling them. When operating a hollow cathode on half-wave rectified alternating
current, the peak currents and also the peak light intensities required to attain the same
average output are about four to six times those reached in normal direct current opera-
tion. Fig. 12.22 shows voltage traces across a 22 megohm resistor across the output of an
R106 photomultiplier. The dashed line represents the voltage imposed on the hollow ca-
thode while the solid lines show the wave form of the photomultiplier pulse for four
40 /~,
w /
/ ' 15mA Avg.
;:::.J
c.!l
I
I
30 I \
~ I
I \
\
I \
l- I \
:J I \
~20 I \
\
:J I \
0 I \
I \
I \
I \
10 I \
I \
I \
I \
I \
\
0
TIME
Fig. 12.22. Photomultiplier saturation resulting when a copper hollow cathode device is operated
under half-wave rectified conditions. The curves show voltage traces across a 22 megohm resis-
tor across the output of an R 106 photomultiplier.
average hollow cathode currents. As indicated, the photomultiplier begins to saturate some-
where between 15 and 20 milliamperes hollow cathode current. The output voltage for
20 rnA on direct current operation would be about 12 volts on this scale. The placement of
a neutral density filter between the hollow cathode and the monochromator slit or a
reduction in hollow cathode device current will correct this problem.
12.6.5 ELECTRONICS
The photomultiplier power supply and amplifier electronics become a major factor in
signal processing in any situation where the signal level is low. When higher photomulti-
plier voltages are required, the noise properties of the high voltage supply become a
major factor in determining how much gain is attainable; i.e., noise injected into the sys-
tem from the supply will be amplified in both the detector and the amplifier. Since the de-
tection limit in atomic absorption spectroscopy is defined as the concentration of the sam-
ple at which the absorption signal is just twice that of the background noise level, it is
highly dependent on such factors as the availability of scale expansion and the general
quality of all the various components which may introduce noise into the system.
12.7 Current status of hollow cathode devices
Fig. 12.23 shows three basic types of hollow cathode structures. The first structure
used extensively for atomic absorption spectroscopy was the open type. However, it was
found to be highly inefficient because of current loss to the outside of the cathode. This
disadvantage was overcome in the shielded structure [24] which made more efficient use
of the total discharge current. As a result improved stability of spectral output and gains
n line intensities of up to about fifteen times that of the open structure were attained.
OPEN SHIELDED
HIGH
INTENSITY *
NJX. AUX.
A C A C AC
* Far E'xample :
A. Walsh • c.s.I.R.O•• Melbourne. Au ••
Fig. 12.23. Various types of hollow cathode structures.
The next improvement in hollow cathode devices was reported by Sullivan and Walsh
[25]. It consisted of an open structure hollow cathode with an additional pair of electrodes
to effect the passage of a high electrical current across the face of the hollow. This second
discharge permitted more efficient use of the available atoms in the discharge space, re-
sulting in greater peak line intensities as measured by a Fabry-Perot interferometer [26].
12.7] CURRENT STATUS OF HOLLOW CATHODE DEVICES 647
Absorption sensitivity measurements show that the resonance lines produced by the
auxiliary discharge are narrower than their counterparts produced in standard hollow
cathodes, and for some elements such as Cu, Cd and Zn, the standard hollow cath-
ode device run at high cathode currents can suffer up to about a 30 %reduction in analyti-
cal absorption sensitivity. However, concurrent improvements in the standard, shielded
device have resulted in light sources with improved resonance-to-ion line ratios and
equally intense outputs without the necessity of auxiliary electrodes and their extra power
supply. Coupled with added problems of life and stability, the high intensity lamps have
found only limited use in atomic absorption spectroscopy.
The advent of these higher intensity hollow cathode devices has made possible the detec-
tion and measurement of the atomic resonance line(s) by resonance detection [27] with-
out the use of a conventional monochromator. The "resonance detector" is used to iso-
late the resonance line of interest from a modulated hollow cathode source. Free atoms
produced by sputtering in the hollow cathode contained in the "resonance detector" are
excited by the resonance lines in the impinging light beam. A detection means placed at
right angles to the "resonance detector" is used to measure the fluorescent resonance
spectra produced by deexcitation of these atoms.
Although other sources, including xenon-argon continuum lamps and radio frequency
discharges, have been used for atomic absorption, the hollow cathode remains the pre-
dominant light source for this purpose. A listing of the many hollow cathode discharge
devices available from various manufacturers is given in Tables 12.1, 12.II and 12.111.
In addition, Table 12.IV gives a list of hollow cathode manufacturers.
(The authors would like to thank Westinghouse Electric Corporation, Elmira, New York,
for permission to use the figures not acknowledged elsewhere in the text.)
TABLE 12.1
SINGLE ELEMENT HOLLOW CATHODE DEVICES CURRENTLY AVAILABLE *
Aluminum Iridium Ruthenium
Antimony Iron Samarium
Arsenic Lanthanum Scandium
Barium Lead Selenium
Beryllium Lithium-Natural Silicon
Bismuth Lithium-6 Silver
Boron Lithium-7 Sodium
Cadmium Lutetium Strontium
Calcium Magnesium Sulfur
Cerium Manganese Tantalum
Cesium Mercury Tellurium
Chromium Molybdenum Terbium
Cobalt Neodymium Thallium
Copper Nickel Thorium
Dysprosium Niobium Thulium
Erbium Osmium Tin
Europium Palladium Titanium
Gadolinium Phosphorous Tungsten
Gallium Platinum Uranium
Germanium Potassium Vanadium
Gold Praesedymium Ytterbium
Hafnium Rhenium Yttrium
Holmium Rhodium Zinc
Indium Rubidium Zirconium
* Narrow line spectra of the inert fill gas are also produced in each device.
TABLE 12.11
HIGH-INTENSITY HOLLOW CATHODE DEVICES CURRENTLY AVAILABLE
Aluminum Lead Tantalum
Antimony Magnesium Tellurium
Beryllium Molybdenum Titanium
Cadmium Niobium Tungsten
Chromium Nickel Uranium
Cobalt Palladium Zinc
Copper Platinum Zirconium
Gold Silicon
Iron Silver
TABLE 12.111
MULTI-ELEMENT HOLLOW CATHODE DEVICES CURRENTLY AVAILABLE
Ag,Au Co, Cr, Ni
Ag, Cd, Pb, Zn Co,Cu
Ag, Cr, Cu, Ni Co, Cu, Mo, Zn
Ag,Cu,Pb,Zn Co, Fe
Ag, In Co, Ni
Ag, Pb, Zn Cr, Cu
AI, Ca, Li, Mg Cu, Fe, Mn
AI, Ca, Mg Cu, Fe, Mn, Ni
As, Bi, Sb Cu, Fe, Mn, Zn
As, Ni Cu, Fe, Mo
As, Se, Te Cu, Fe, Ni, Pb, Zn
Au, Co, Cu, Ni Cu,Ga
Au, Cu, Fe, Ni Cu, Mn
Au, Ni Cu, Mo, Zn
Ba, Ca, Mg, Sr Cu. Ni
Ba, Ca, Sr Cu,Pb,Sn,Zn
Ca, Mg, Zn In, P
Ca,Zn K,Na
Cd, Cu, Pb, Zn Mg,Zn
Co, Cr, Cu, Fe, Mn, Ni Ni, Se
Co, Cr, Cu, Mn, Ni Pt, Ru
TABLE 12.IV
HOLLOW CATHODE DEVICE MANUFACTURERS
1. Atomic Spectral Lamps Pty., Ltd.
23-31 Islington Street
Melbourne N. 5, Victoria, Australia
2. Cathodian, Ltd.
Church Street
Cambridge, U.K.
3. Fabbrica ItaJiana Valvole Radio Elettriche (FIVRE)
Via Panciatichi 70
Firenze-Castello 50127, Italy
4. Hilger and Watts, Ltd.
98, St. Pancras Way
Camden Road
London N.W. 1, U.K.
REFERENCES 649
5. Hitachi, Ltd.
1-4 Marunouchi
Chiyoba-Ku, Tokyo, Japan
6. Dr. Kern and Sprenger Gmbh.
Florenz Sartorius Strasse 5
Postfach 751
3400 Gottingen, Germany
7. Perkin-Elmer Corporation
Instrument Division
Norwalk, Connecticut 06852, U.S.A.
8. Quarzlampen GmbH.
(16) HanaujMain
Hoehensonnenstrasse, Germany
9. Westinghouse Electric Corporation
P. O. Box 284
Elmira, New York 14902, U.S.A.
References
1. S. TOLANSKY, High Resolution Spectroscopy, Methuen and Co., London, 1947, p. 63.
2. F. PASCHEN, Ann. der Physik 50,901 (1916).
3. S. TOLANSKY, op. cit., p. 52.
4. S. TOLANSKY, op. cit., p. 55.
5. H. SCHULER, Z. S. Physik, 35, 323 (1926).
6. H. SCHULER, Z. S. Physik, 59, 149 (1930).
7. H. SCHULER and G. C. SCHMIDT, Z. S. Physik, 96, 485 (1935).
8. E. F. RICHTER, Z. Tech. Physik, 17, 3Q6 (1936).
9. C. C. VAN VOORHIS and A. G. SHENSTONE, Rev. Sci. Instr., 12, 257 (1941).
10. H. M. CROSSWHITE, G. H. DIEKE and C. S. LEGAGNEUR, J. Opt. Soc. Am., 45, 270 (1955).
11. R. W. STANLEY and G. H. DIEKE, J. Opt. Soc. Am., 45, 280 (1955).
12. A. WALSH, Spectrochim. Acta, 7, 108 (1955).
13. C. T. J. ALKEMADE and J. M. W. MILATZ, J. Opt. Soc. Am., 45, 583 (1955).
14. C. T. J. ALKEMADE and J. M. W. MILATZ, Appl. Sci. Res., B4, 289 (1955).
15. K. B. ADAMS and K. BURNS, Westinghouse Electric Corporation Research Memo 6-94602-9-
M37 (1957).
16. W. C. JONES and A. WALSH, Spectrochim. Acta, 16, 249 (1960).
17. K. B. MITCHELL, J. Opt. Soc. Am., 51,846 (1961).
18. I. A. BEREZIN, Opt. Spectry. (USSR) (English Trans1.), 13, 483 (1962).
19. A. D. WHITE, J. Appl. Phys., 30, 711 (1959).
20. A. WALSH ET AL., U.S. Patent 3,089,054.
21. H. MASSMAN, Z. Instrumentenk, 71, 225 (1963).
22. L. R. P. BUTLER and A. STRASHEIM, Pittsburgh Conference on Analytical Chemistry and
Applied Spectroscopy, March 1964.
23. P. F. LITTLE and A. VON ENGEL, Proc. Roy. Soc. (London), 224A, 209 (1954).
24. G. K. YAMASAKI, U. S. Patent No. 3,264,511.
25. J. V. SULLIVAN and A. WALSH, Spectrochim. Acta, 21, 721 (1965).
26. D. K. DAVIES, J. Appl. Phys., 38, 4713 (1967).
27. J. V. SULLIVAN and A. WALSH, Spectrochim. Acta, 21, 727 (1965).
CHAPTER 13
BmLIOGRAPHY ON FLAME SPECTROSCOPY

ANAL YTICAL APPLICATIONS
1966-1968
R. M avrodineanu*
Briarcliff Manor, New York, U.S.A.
This collection of references to works on flame spectroscopy is a continuation of a biblio-

graphy published earlier which covered the period from about 1800 to 1966 with 5113
references. .... The present collection consists of 2156 references to works on flame spec-
troscopy, selected with emphasis toward analytical measurements, and roughly covers the
period from about 1966 to 1968. The references are arbitrarily classified according to the
scheme followed in the previous bibliography:
References collected in
Previous This
Bibliography Bibliography
1. Emission
1.1. Early papers (1800 to 1928) 503 30
1.2. Books on analytical flame spectroscopy 14 4
1.3. Theses 60 11
1.4. Reviews 80 36
1.5. Bibliographies 20 5
1.6. Chapters in books and related material 65 15
1.7. Fundamental papers 1173 480
1.8. Instrumentation 401 133
1.9. Analytical procedures 1987 602
1.10. Less familiar flames 92 30
2. Atomic Absorption
2.1. Atomic absorption spectroscopy 353 553
2.2. Hollow cathodes 87 82
3. Electrical Discharges having the aspect of combustion flames
3.1. RF discharges 154 66
3.2. Plasma arcs 98 103
3.3. Arc-and-spark-in-flame 26 6
*Present address: Analytical Chemistry Division, National Bureau of Standards, Washington

D.C., U.S.A.
**R. MAVRODINEANU, Bibliography on Flame Spectroscopy, Analytical Applications, 1800-1966,
National Bureau of Standards Miscellaneous Publication 281, 1967. For sale by the Superin-
tendent of Documents, U. S. Government Printing Office, Washington, D. c., 20402. Price,
$2.00.
652 BIBLIOGRAPHY ON FLAME SPECTROSCOPY [13
The procedures used in collecting, organizing, and presenting the references are those
used and described in the previous bibliography.
The present collection contains, in addition to references to papers published in 1966
and 1967, a number of earlier references not contained in the first collection. These re-
ferences, which amount to not more than 25 percent of the total number assembled here,
became available to the author at a later date and could not be included at the time the
first collection was completed.
Among the works assembled in this collection, the reader will find a certain number of
references to papers published by U. S. Government organizations. These can be obtained
as follows: National Bureau of Standards Circulars, Monographs, Technical Notes, and
Miscellaneous Publications can be ordered from the Superintendent of Documents,
U. S. Government Printing Office, Washington, D.C., 20402. All other reports carrying
the indication AD with the corresponding number or other identifying numbers can be
ordered from the Clearinghouse for Federal Scientific and Technical Information, Spring-
field, Virginia, 22151.
The reports published by the U. S. Atomic Energy Commission can be obtained from
the USAEC, Division of Technical Information Extension, P.O. Box 62, Oak Ridge,
Tennessee, 37831.
Copies of theses published in the United States can be obtained from the University
Microfilm, Ann Arbor, Michigan, 48103.
Acknowledgement
The author expresses his great appreciation to Miss Marcia Gordon for the capable
assistance in assembling, organizing, and checking the references, and to Mrs. Kathryn
Torgeson for editing and typing the manuscript.
13.1] EMISSION 653
13.1 Emission
13.1.1 EARLY WORKS
Subject Index
Books 21, 23, 24, 27, 30

Flame radiation and reaction; temperature, electrical conductivity, ionization 1, 3, 7, 8, 9,
10, 11, 13, 14, 15, 16, 19, 20, 22, 25, 26, 28, 29
Instrumental 2, 4, 5, 6, 12, 17, 18
Low pressure flames 26
Copper 9
Cyanogen 13
Hydrogen peroxide 20
Magnesium 9
Manganese 9
Ozone 20,25
Potassium 11, 17, 18
Rubidium 11
Sodium 11, 29
References
1. ANDRADE, E. N. DA C. Note on a report by Mr. Herbert Schonborn, On the mobility 0
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654 BIBUOGRAPHY ON FLAME SPJ!CTR.OSCOPY [13
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13.1.2 BOOKS
1. DEAN, J. A., T. C. RAINs (eds.). Flame Emission and Absorption Methods, a Handbook of Practi-
cal Techniques and Procedures. 3 vols. (in preparation) Marcel Dekker, Inc., New York, 1969
(tentative).
2. HERRMANN, R., C. T. J. ALKEMADE. Chemical Anolysis by Flame Photometry. 3rd rev. ed. trans.
by P. T. Gilbert, Jr. (in preparation). Interscience Publishers, a division of J. Wiley and Sons,
New York, 1969 (tentative).
3. MAVRODINEANU, R. (ed.). AlUllytical Flame Spectroscopy, Selected Topics. (in preparation).
Centrex Publishing Company, Eindhoven, The Netherlands, 1970 (tentative).
4. PUNGOR, E. Flame Photometry Theory. 230 pp. Van Nostrand, London, 1967.
13.1.3 THllSES
1. ANDERSEN, N. R. Flame photometric determination of strontium and barium in sea water.

Thesis, Massachusetts Inst. Technol., Cambridge, Mass., September, 1965.
2. ARMENTROUT, D. N. Interference mechanism in analyses by flame spectrometry. 101 pp.
Thesis, Cornell University, Ithaca, N.Y. Dissertation Abstr. 26,5001 (1966); C.A. 65, 1359
(1966).
3. CoWLEY, T. G. A spectroscopic study of the premixed, fuel-rich oxyacetylene flame. 200 pp.
Thesis, Iowa State Univ. of Sci. & Technol., Ames, Iowa. Dissertation Abstr. B 27, 1051
(1966); C.A. 66,51847 (1967).
4. EYMMER, H. J. The flame photometric investigation of Na in the organs of cows. 62 pp. Thesis,
Karl Marx University, Leipzig, 1955.
5. GOLIGHTLY, D. W. Spectral detection sensitivities of the elements in the premixed, fuel-rich,
oxyacetylene flame. 46 pp. Thesis, Iowa State University, Ames, Iowa, 1965.
6. HEINE, W. Contribution to the flame phatometric determination of calcium and sodium in the
serum ofdogs. 31 pp. Thesis, Veterinary School Hannover, 1959.
7. HOFFSTETTER, J. The flame photometric determination of alkalies and alkali earths. 144 pp.
Thesis, Zurich, 1953.
8. KLAus, H. Theflame photometric investigation of Na, K, and Ca content in the serum of healthy,
pregnant, and nursing dogs. 94 pp. Thesis, Karl Marx University, Leipzig, 1955.
9. PARSONS, M. L. Derived expressions to compare atomic fluorescence flame spectrometry with
other flame spectrometric methods. 244 pp. Thesis, Univ. of Florida, Gainesville. Dissertation
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13.1] EMISSION 655
10. REMINGTON, L. D. Factors which influence the signal-to-noise ratio in atomic emission flame
spectrometry. 154 pp. Thesis, Univ. of Florida, Gainesville. Dissertation Abstr. B 27, 1388
(1966); C.A. 66, 72088 (1967).
11. VEILLON, C. Sources of excitation for atomic fluorescence flame spectrometry. 83 pp. Thesis,
Univ. of Florida, Gainesville. Dissertation Abstr. B 27, 1764 (1966); C.A. 66, 121689 (1967).
13.1.4 REVIEWS
1. ADDlNK, N. W. H. Optical and x-ray spectroscopy, pp. 121-148 in W. Wayne Meinke and
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8027 (1955).
6. BACHMAN, R. Z., C. V. BANKS. Nonferrous metallurgy. II. Zirconium, hafnium, vanadium,
niobium, tantalum, chromium, molybdenum, and tungsten. Anal. Chern. 39, IlOR-133R (1967).
7. DEAN, J. A. Developments inflame emission and flame absorption photometry. Develop. Appl.
Spectrosc. 5, 317-332 (1965). C.A. 66, 91266 (1967).
8. DEKALB, E. L., R. N. KNISELEY, V. A. FASSEL. Optical emission spectroscopy as an analytical
tool. Ann. New York Acad. Sci. 137,235-261 (1966).
9. DINGLE, H. A hundred years of spectroscopy. Brit. J. Hist. Sci. 1, 199-216 (1963). C.A. 64,
18366 (1966).
10. FISHMAN, M. J., B. P. ROBINSON, M. R. MIDGETT. Water analysis. Anal. Chern. 39, 261R-294R
(1967).
11. GEHRKE, C. W., J. P. USSARY. Fertilizers. Anal. Chern. 39, 69R-74R (1967).
12. HAMILTON, P. B. Biochemical analysis. Anal. Chern. 38, 19R-31R (1966).
13. HEADRIDGE, J. B., T. B. PIERCE, D. M. W. ANDERSON. Analytical chemistry. Ann. Rept. Progr.
Chern. (Chern. Soc. London) 61, 527-565 (1964). C.A. 64, 8905 (1966).
14. HERRMANN, R. Flame photometry. Z. Chernie f. Labor und Betrieb 3, 401-406 (1952).
15. HERRMANN, R. The practice of flame photometry. Z. Chernie f. Labor und Betrieb 4, 337-347
(1953).
16. HERRMANN, R. Development of modern flame photometry. Z. Chernie f. Labor und Betrieb 4,
586-592 (1953).
17. KAISER, H. On the physics and technology of spectrochemical light sources. Trans. Instrurn.
Meas. Conf., Stockholm (1949) 16-22 (1950). Sci. Abstr. A54, 4326 (1951).
18. KINGSLEY, G. R. Clinical chemistry. Anal. Chern. 39, 22R-41R (1967).
19. LAITINEN, S. Flame photometric analysis of rare earth metals. Kern. Teollisuus 22, 189-192
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20. LAQuA, K. Present status of spectrochemical trace elements determination. Fresenius' Z. Anal.
Chern. 221, 44-68 (1966). C.A. 66, 16167 (1967).
21. MARGOSHES, M. Recent advances in excitation of atomic spectra. Proc. XII Colloq. Spectry.
Intern. Exeter 1965, pp. 26-42. Hilger and Watts Publ., London.
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C.A.65, 1616 (1966).
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82032 (1967).
24. MUTHIAH, P. L., D. RAMASWAMY, Y. NAYUDAMMA. Analytical techniques and their applica-
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25. OLIVER, R. T., E. P. Cox. Nonferrous metallurgy. I. Light metals. Anal. Chern. 39, 102R-IlOR
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27. PUNGOR, E. Flame photometry. Advances of the basic principles and experimental techniques.
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(1959). C.A. 55, 1272 (1961).
28. PUNGOR, E. Development of flame photometry. Magyar Tudomanyos Akad. Kemiai Tudo-
manyok Osztalyanak Kozlemenyei 25, 59-75 (1966). C.A. 64, 18373 (1966).
29. RAMIREZ·Mu"l')oz, J. Flame photometry information. II. Inform. Quim. Anal. (Madrid) 19,
104-106 (1965). C.A. 64, 2730 (1966); C.A. 64, 7346 (1966).
30. RAMlREZ-Mu"l')oz, J. Information on flame photometry. VI. Inform. Quim. Anal. (Madrid) 19,
198-200 (1965). C.A. 66, 82037 (1967).
31. RICH, C. 1. Elemental analysis by flame photometry. Agronomy 9, 849-865 (1965). C.A. 65,
6282 (1966).
32. ROBINSON, J. W. Atomic fluorescence. Develop. Appl. Spectrosc. 5, 255-257 (1966). C.A. 67,
39739 (1967).
33. SCRIBNER, B. F. Advances in excitation sources for spectrochemical analysis. Pure Appl. Chem.
10, 579-594 (1966). C.A. 66, 34453 (1967).
34. SKOUGSTAO, M. W., M. J. FISHMAN. Water analysis. Anal. Chem. 37, 232R-260R (1965).
35. WEST, T. S. Inorganic trace analysis. Chem. Ind. (London) 1966, 1005-1016. C.A. 65, 9713
(1966).
36. WOOTTON, I. D. P. Optical measurements with ultraviolet and visible light applied to clinical
problems. Rec. trav. chim. 74, 467-475 (1955). C.A. 49,16034 (1955).
13.1.5 BIBLIOGRAPHIES
1. MABROOINEANU, R. Bibliography on Flame Spectroscopy, Analytical Applications 1800-1966.

Nat. Bur. Stand. (U.S.), Misc. Publ. No. 281, 155 pp. (1967). C.A. 67, 7627 (1967); C.A. 67,
96596 (1967).
2. SCRIBNER, B. F. Index to the Literature on Spectrochemical Analysis 1956-1960. (in preparation.)
3. SOMEREN, E. H. S. VAN, F. LACHMAN, F. T. BIRKS. Spectrochemical Abstracts. Vol. IX: 1962-
1963.94 pp. Hilger and Watts, London, 1964. C.A. 63,5158 (1965).
4. SOMEREN, E. H. S. VAN, F. LACHMAN, F. T. BIRKS. Spectrochemical Abstracts. Vol. X: 1963-
1964. 116 pp. Hilger and Watts, London, 1965. C.A. 64, 18757 (1966).
5. SOMEREN, E. H. S. VAN, F. LACHMAN, F. T. BIRKS. Spectrochemical Abstracts. Vol. XI: 1964-
1965.94 pp. Hilger and Watts, London, 1966.
13.1.6 CHAPTERS IN BOOKS AND RELATED MATERIAL
1. American Society for Testing Materials. Methods for Emission Spectrochemical Analysis,
4th ed. 862 pp. Philadelphia. Pa., 1964.
2. BENNETT, H., W. G. HAWLEY. Methods of Silicate Analysis. 350 pp. Academic Press, Inc.,
New York, 1965.
3. Compressed Gas Association, Inc. Handbook of Compressed Gases. 398 pp. Reinhold Publ.
Corp., New York, 1966.
4. Gmelins Handbook of Inorganic Chemistry. E. H. E. Pietsch (ed.) (in German) 8th ed., System-
Number 21(2), Natrium, Spectral-analytical methods, pp. 685-782. Verlag Chemie, Weinheim/
Bergstr., W. Germany, 1965.
5. HALO, P. M., W. B. MASON. Sodium and potassium by flame photometry, pp. 165-185 in D.
Seligson (ed.) Standard Methods of Clinical Chemistry, vol. 2. Academic Press, Inc., New
York, 1958. C.A. 53, 2342 (1959).
6. HERRMANN, R. Spectroscopic atomic emission and absorption methods for the detection and
determination of elements in toxicology, pp. 540-560 in E. Graf and R. Preuss (eds.) Gada-
mer's Textbook of Chemical Toxicology and Introduction to the Detection of Poisons. (in
German) Vandenhoeck and Ruprecht, G5ttingen, 1966.
13.1] EMISSION 657
7. HUME, D. N. The analysis of water for trace metals: present capabilities and limitations.
Massachusetts Institute of Technology Report MIT-90S-6S, 24 pp. (1966). (to be published
in Advances in Chemistry Series.)
8. KAISER, H. Systems of data and literature retrieval in spectroscopy. Hilger J. 9, 64-73 (1965).
9. MILNER, O. I. International Series of Monographs on Analytical Chemistry. Analysis of Pe-
troleum for Trace Elements. vol. 14, 128 pp. Pergamon Press, New York, 1963. C.A. 60,
10449 (1964).
10. MITCHELL, R. L. The Spectrochemical Analysis of Soils, Plants and Related Materials. 225 pp.
Techn. Comm. No. 44 A, Commonwealth Agricultural Bureau, Farnham Royal, Bucks,
England, 1964.
11. MORRISON, G. H., R. K. SKOGERBOE. Generolaspects of trace analysis, pp.I-23 inG. H. Morri-
son (ed.) Trace Analysis, Physical Methods. Interscience-Wiley, New York, 1965.
12. Proceeding; XII Colloquium Spectroscopicum Internationale, Exeter, 1965.702 pp. Hilgerand
Watts, London, 1966.
13. RITSCHL, R., G. HOLDT (eds.). Emission Spectroscopy. 411 pp. Proceedings Symposium in
Gorlitz, 1962. Akademie-Verlag, Berlin, 1964.
14. VALLEE, B. L., R. E. THIERS. Flame photometry, pp. 3463-3533, vol. 6, pt. I in I. M. Kolthoff
and P. J. Elving (eds.) Treatise on Analytical Chemistry. Interscience-Wiley, N ew York, 1965.
15. WEBERLlNG, R. P., J. F. COSGROVE. Flame emission and absorption methods, pp. 245-269 in
G. H. Morrison (ed.) Trace Analysis, Physical Methods. Interscience-Wiley, New York, 1965.
13.1.7 FUNDAMENTAL WORKS
Subject Index
Atlas of flame spectra 340

Books 337, 464
Bibliographies 63, 199, 393
Theses 51, 60, 203, 204, 213, 414, 451, 477
Reviews 9, 78, 139, 164,242,250,282, 301, 302, 351, 432, 439, 462, 463, 476
Flame, analytical 10, 64, 73,133,143,145,171,235,294,295,299,328,366,452,468,469
Flame temperature 16, 32, 34, 39, 40, 41, 42, 44, 46, 62, 69, 81, 82, 85, 88, 90, 100, 108,
109, 110, 111, 112, 113, 114, 115, 120, 121, 125, 128, 131, 134, 146, 147, 156, 159, 168,
169, 172, 199,205,215,219,221,223,238,239,240,245,251,253, 262, 263, 264, 274,
276, 280, 291, 303, 312, 356, 357, 358, 362, 363, 368, 372, 373, 380, 387, 390, 395, 408,
410,412,415,420,437,438,442,445,446,457,465,466,474
Flame geometry 6, 18, 25, 26, 50, 66, 90, 92, 94, 124, 142, 157, 158, 162, 163, 165, 167,
168, 174, 175, 176, 189, 196, 226, 241, 243, 244, 247, 267, 268, 301, 355, 376, 389, 396,
416,443,447,448,449,457,467
Flame radiation 4, 10, 35, 36, 43, 45, 46, 47, 48, 69, 71, 73, 75, 79, 81, 88, 89, 99, 107, 122,
123,130, 140, 141, 142, 143, 145, 149, 151, 153, 154, 178, 184, 185, 187, 190, 191, 197,
208,214,215,216,217,218,221,227,228,231,232,235, 236, 237, 241, 242, 244, 246,
248, 249, 271, 272, 285, 293, 296, 297, 298, 300, 306, 313, 314, 317, 322, 323, 326, 327,
328, 330, 331, 332, 333, 334, 335, 339, 340, 341, 342, 343, 344, 345, 349, 350, 352, 354,
355,361,362,366,367,369,370,371,374,375,377,378,382,383,387,388,390,392,399,
407,417,427,436,444,446,450,452,456,458,467,468,471,472,478,479,480
Flame reaction 1, 2, 3, 5, 7, 8, 11, 12, 13, 14, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30,
31,32,33,37,38,47,49,52,53,54,55,56,57,58,61,62, 64, 65, 67, 70, 72, 77, 80, 83, 86,
87,91,92,93,95,96, 101, 103, 104, 105, 116, 119, 120, 121, 122, 125, 126, 127, 129, 132,
658 BmLlOORAPHY ON FLAME SPECTROSCOPY [13
135,144,150,151,152,153,154,155,160,161,165,166, 170, 173, 177, 179, 180, 186, 187,

188, 189, 192, 193, 194, 195, 198, 201, 202, 206, 207, 209, 210, 211, 212, 214, 215, 216,
220, 222, 224, 225, 229, 233, 235, 236, 246, 254, 255, 259, 261, 265, 266, 269, 270, 275,
277, 279, 280, 281, 283, 284, 286, 287, 288, 289, 290, 297, 298, 304, 315, 316, 318, 319,
320, 321, 324, 325, 329, 336, 338, 346, 347, 348, 359, 360, 364, 365, 368, 379, 382, 383,
384, 385, 386, 389, 394, 398, 399, 400, 402, 403, 407, 409, 411, 415, 418, 419, 421, 422,
423, 424, 425, 426, 427, 430, 431, 432, 433, 434, 439, 440, 441, 443, 445, 446, 454, 457,
458,459,460,461,467,470,475,476,477,478,479,480
Ions inflames 7,10,15,52,59,61,68,74,76,83,84,102,106,117,118,135, 136, 137, 138,
148,154, 181,182, 183,200,230,234,252,256,257,258,260,273,278,292,305,307,308,
309,310,311,349,353,370,378,388,391,397,401,404,405,406,410,413,427,428,429,
435,453,455,473
Flame fluorescence 17, 294, 469
Isotope separation by flames 97,98
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13.1.8 INSTRUMENTATION
Subject Index
General instrumentation 3, 4, 5, 9, 11, 21, 24, 39, 50, 52, 54, 55, 64, 66, 73, 82, 88, 89, 92,
98, 100, 102, 104, 105, 106, 110, 122, 124, 126, 127, 130, 133
Atomization 2, 14, 18, 26, 27, 33, 45, 48, 49, 50, 51, 53, 58, 65, 67, 70, 72, 77, 78, 79, 85,
87,90,93,96,97,107,108,109,110,111,112,116,120,129,132
Burners 1, 6, 8, 10, 12, 13, 14, 16, 17, 19,20,22,28,29,30,31,32,34,36,37, 40, 42, 43, 44,
47,50,55,60,61,62,65,68,69,71,74,75,76,81,86,90, 91, 94, 95, 96, 99, 103, 107, 108,
110,114,115,117,118,119,120,123,125,128,129,131,132
Optical filters 7, 23, 41, 84, 121
Photoelectric photometry 15, 25, 56, 83, 92, 101, 11 0, 113
Multichannel instruments 38,46,56,57,63
Interference spectroscopy 35, 59, 80
Cross Index
See also the following references in:
13.1.7 Fundamental Works 79, 157, 226, 303, 359
13.1.9 Analytical Procedures 117, 126,216,240,247,270,284,346,396
13.2.1 Atomic Absorption 309
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13.1.9 ANALYTICAL PROCEDURES
Subject Index
General consideration on analytical procedures 11, 24, 55, 79, 80, 88, 102, 126, 127, 142,
177,178,179, 180, 190,203,212,272,297,325,326,346,361,370,414,445,446,447,449,
450,469,486,487,488,500,528,551,585,586,595
Atomic flame fluorescence 26, 120, 121, 122, 162,225, 226, 300, 414, 565, 584, 587
Materials Analyzed
Air 81,408
Alcoholic beverages and vinegar 40, 132, 134, 175,273, 274, 326, 337, 353
Biological materials 20, 25, 28, 29, 30, 38,43,49, 56, 59, 66, 69, 73, 91, 92, 94, 99, 108,
131,133, 139, 141, 148, 150, 161, 163, 164, 172, 173, 174, 186, 187, 194, 196,219,222,235,
237,238,244,246,249,250,255,256,257,259,260,261,263,265,267,270,271,282,283,
292,293,298,301,305,310,313,316,320,323,326,330,340,345,351,354,355,359,374,
375,383,384,385,386,392,394,399,401,402,427,436,437,443,444,448,457,461,468,
476,481,483,484,489,490,491,496,498,501,516,519,523,529,531,533,537,546,549,
553,559,561,564,569,570,575,583,589
Catalysts 454
Chemical compounds 5,6, 7, 36,48,50,58,63,78,85,89,90,93, 100, 103, 143, 147, 166,
181, 192, 193,221,232,264,268,289,306,309,315,350,368,369,372, 393,396,397,438,
13.1] EMISSION 685
455,459,465,467,473,480,482,485,512,522,527,542,550,557,566,578,594,596,598,
601
Coals 15, 195,211,333,335,591
Dairy products 60,70,75,154,161,238,331,434,498,576,580
Electronic materials 390
Engine deposits and furnace gas 420, 588
Fertilizers 23, 98, 183, 290, 309, 329, 344, 356, 371,398,403,479,510,555,556,560,572
Filtration 140, 155, 185,466
Foods 65, 95,106,107,111,137,153,216,217,238,298,311,331,358, 362, 377, 378,417,
435,478,495,506,515,517,521,530,544,567,597
Isotope analysis 151
Metals, alloys, and metallurgic products 71, 143, 149, 165, 207, 223, 224, 229, 258, 266,
277,280,281,326,349,400,406,473,474,475,493,526,532,541,554,573
Minerals, ores, rocks 1, 2, 41, 44, 46, 67, 68, 110, 115, 156, 157, 182,201,204,206,208,
218,228,241,248,302,314,318,326,327,328,332,342,347,360,363,366,369,376,402,
407,419,421,428,430,431,439,453,460,463,464,471,472,494,499,524,552,558,592,
600
Organic solvents and compounds inflame spectrophotometry 3,5,7,12,17,40,109, 112,
128,132,152,166, 184,213,216,217,238,240,242,247,256,285,292,299,348,368,373,
408,409,413,427,458,470,480,492,505,512,513,520,535,546,561,566,568,593,596
Paper products 287, 308, 352, 462, 509
Petroleum products 33, 158,432,433,535
Pharmaceuticals 84, 85, 86, 87, 326,418
Plants 34,52,53,57, 70, 72, 74, 77, 83, 97, 104, 118, 138, 161, 168, 183,202,214,239,242,
262,279,291,296,303,304,312,319,326,329,344,364,373,398,404,462,477,534,545,
563,576,579,590,602
Plastics 497
Silicates, glass, cement, refractory materials 4, 5, 13, 21, 22, 37, 53, 61, 62, 64, 100, 105,
119,125,129,130,144,145,146,147,188,189, 191, 197,209,253,254,288,294,317,326,
339,357,379,380,410,412,451,452,525,543,547
Soils 3, 10, 14,27, 35, 39, 42, 51, 70, 101, 104, 109, 113, 119, 123, 124, 135, 136, 152, 159,
160, 161, 183,200,204,215,220,227,230,243,245,252,288,295,307,321,334,338,343,
389,391,398,402,473,475,499,508,518,536, 540,545, 579,582
Steam and boiler deposits 31, 322
Test solutions 17, 85, 176, 199, 205, 206, 210, 299, 324, 336, 340, 367, 381, 388, 415, 470,
504,513,520,538,539,550,562,571
Uranium and nuclear compounds 32, 184,233,234,387,424,425,460,511,574
Waters 8, 9,16,18,47,82,96,151,167,169,170,171,231,236,251, 275, 382,416,419,
422,423,441,456,471,502,503,507,514,527,548,577,581,599
Elements Determined
Aluminium 128, 189,243,395,396,423,568

Antimony 127
Arsenic 513
Barium 16,17,18,24,54,127,206,424,425,430,442,467,497, 538, 565, 595
Beryllium 349
Bismuth 513, 565, 584
Boron 5,127,322,369,505
Cadmium 120, 225, 226, 372, 565, 584, 587, 595
Carbon 526
Calcium 1, 2, 21, 24,34,39,40,52,54,66,68,69,74, 76, 78, 81, 89, 93, 103, 107, 118, 126,
128,133,136,137,141,149,152,153,160,162,166,172, 173, 175, 184,204,210,220,233,
238,243,244,250,251,252,256,257,260,265,271,287,296,303,304,308,309,311,321,
331,339,347,350,352,354,358,362,364,368,369,379,387,388,394,398,402,416,417,
422,426,427,430,435,441,448,454,461,464,467,468,470,471,473,474,475,476,480,
488,489,490,491,497,498,501,503,512,517,519,524,529,530,531,534,535,538,539,
544,558,562,565,576,578,580,589,595,597
Cesium 24, 79, 80, 116, 161, 169, 170, 176,241,268,310,370,419,429,439,440,441,463,
593
Chromium 423, 573, 595
Cobalt 120, 127, 162,423,595
Copper 120, 172,225,299,420,423,424,425,446,493,565,575,584,587,595
Gallium 224, 225, 565, 584, 595
Gold 565
Halogens 49, 212, 213, 216, 269, 276, 284, 285, 286, 323, 324
Indium 281, 584, 595
Iron 120, 127,243, 367, 369, 396, 420, 423, 493
Lanthanum 369, 513
Lead 120, 467, 565, 584
Lithium 6, 7, 8, 24, 32, 71, 79, 80, 116, 129, 169, 199, 218, 223, 231, 289, 322, 341, 350,
369, 381, 387, 392, 393, 409, 422, 424, 425, 429, 439, 440, 441, 459, 463, 464, 466, 507,
511, 527, 537, 538, 566, 574, 592, 593
Magnesium 39, 46, 50, 52, 54, 68, 76, 108, 120, 124, 126, 152, 153, 159, 162,200,208,229,
238, 243, 245, 251, 252, 296, 331, 339, 350, 372, 374, 388,422, 424, 425, 427, 441, 446,
448,455,470,493,517,534,559,561,565,575,580,584,595
Manganese 52, 120,280,372,423,446,493,507,573,595
Mercury 584
Molybdenum 396
lVickeI26,420,423, 565, 573, 584,595
lViobium 127
Organo-halogens 240
Oxygen 58, 221
Palladium 397, 413
Phosphorus (phosphate) 109,216,217,240,247,269,284,285,286,394,492
Potassium 1, 2, 4, 6, 10, 13, 14, 15,21,23,24,25,27,28,29,30,32,35,36,37,38, 39, 40,
41,42,43,44,45,47,50,51,53,56,57, 59, 60, 61, 62, 63, 64, 70, 76, 79, 80, 81, 84, 90, 91,
93,94,95,96,97,98,99,100,104,105,106,108,110,111,112, 113, 114, 115, 116, 118,
123, 124, 125, 126, 129, 132, 133, 134, 137, 138, 139, 143, 144, 147, 148, 150, 152, 153, 154,
156,157,158,163,164,167,168,169,173,174,181,186, 192, 193, 194, 196, 197, 198, 199,
201,202,204,209,211,214,215,219,227,228,230,231,236,237,238,241,242,244,246,
249,250,251,253,254,255,257,259,261,263,266,267,268,270,274,277,279,282,283,
288,290,291,292,293,294,295,298,301,302,305,307,308,309,311,312,313,314,316,
317,319,320,321,322,327,328,329,330,331,332,334,335,337,338,340,342,343,344,
345,347,350,351,353,355,356,357,358,359,360,362,363,369,370,371,376,377,378,
379,380,381,383,384,385,386,388,389,391,392,393,398,400,404,405,409,410,418,
13.1] EMISSION 687
421,422,424,425,427,428,435,436,438,439,441,443,444,448,452,453,454,456,457,
459,461,463,464,468,472,474,475,476,478,479,481,482,483,484,488,490,491,494,
495,496,498,499,501,503,504,506,507,508,510,511,515,516,517,519,520,521,522,
529,531,534,535,538,544,545,547,549,550,553,554,555,556,560,563,564,566,567,
569,570,571,579,580,583,593,594,599,600,602
Rare earths 55, 368, 396, 397,411, 513
Rhodium 278
Rubidium 24,80, 169, 170, 176,218,241,317,369,370,409,419,429,439,440,441,463,
507,514,538, 593
Scandium 411, 513
Selenium 121, 122
Silver 120, 162, 323, 324, 369, 396, 493, 565, 584, 595
Sodium 1,2,3,4,13,15,19,20,21,24,25,28,29,30,31,32,36,37,38, 40,42,43,44,48,
50, 53, 56, 57, 58, 59, 61, 62, 63, 64, 65, 66, 72, 76, 79, 80, 81, 83, 85, 87, 89, 90, 91, 93, 95,
96,97, 100, 101, 105, 106, 108, 110, 111, 114, 124, 125, 126, 129, 130, 132, 133, 134,135,
1~1~1~1~1~1~1~1~1~1~1~1~1~1~1~1~1~1~1~
173,174,181,184,185,186,187,191,192,193,194,195, 196, 197, 198,204,209,211,215,
216,217,219,228,229,231,232,234,235,236,237,238,244,248,249,250,251,253,254,
255,257,258,259,261,263,266,267,270,273,277,282,283,288,291,292,293,294,298,
301,302,305,308,309,311,313,314,315,316,317,318,322, 327, 331, 333, 335, 337, 340,
345,347,350,351,355,358,359,362,363,366,369,375,379,380,381,383,384,385,387,
388,392,393,398,399,400,404,410,412,415,420,422,424,425,427,428,432,433,435,
436,437,438,439,441,443,444,448,451,452,453,454,457,459,460,461,463,464,465,
468,472,474,475,476,478,481,482,483,484,485,488,490,491,494,495,496,498,501,
503,504,506,509,511,516,517,518,519,520,523,529,531,532,533,534,535,536,538,
541,542,544,545,547,548,549,550,553,554,557,564,566,569,571,572,578,580,581,
583,587,588,590,591,593,594,599,600,601
Strontium 9, 16, 17, 18,24,54,67,68,75,76, 103, 131,205,218,222,251,336,341,382,
401,402,417,422,430,431,434,441,467,470,489,502,503,507,524,538,546,558,576,
595,598
Sulfur (sulfate) 117
Tellurium 121, 122, 372
Thallium 120, 225, 565, 584, 595
Tin 127, 365
Titanium 513
Vanadium 127, 513
Yttrium 411
Zinc 120, 162,225,300,372,507,565,584
Cross Index

13.1.7 Fundamental works 10, 133, 143, 145, 171,328,366,452,468,469
13.1.8 Instrumentation 5, 9, 11, 15, 16, 22, 24, 25, 46, 55, 56, 57, 63, 66, 83, 94, 95, 98,
99, 101, 110, 119, 129
13.2.1 Atomic absorption 5, 9, 33, 51, 88,97, 103, 107, 142, 185, 209, 281, 293, 309, 355,
356,358,362,367,368,370,389,390,400,439,457,466
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581. WHITE, J. M., J. G. WINGO, L. M. ALLIGOOD, G. R. COOPER, J. GUTRIDGE, W. HYDAKER,
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592. YOFE, J., M. STILLER. Direct flame-photometric determination of lithium in Dead Sea brine.
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13.1] EMISSION 713
Z
594. ZABIYAKO, V. I., I. B. BULYCHEVA. Flame-photometric determination of sodium and potassium
in ammonium chromate and dichromate (reagent grade). Tr. Ural'sk. Nauchn.-Issled. Khirn.
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595. ZACHA, K., J. D. WINEFORDNER. Use of an Ar-H-entrained air flame with a total-consumption
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mination. Anal. Chern. 38, 1537-1539 (1966). C.A. 66, 16267 (1967).
596. ZADO, F. M., R. S. JUVET, JR. New selective-nonselective flame photometric detector for gas
chromatography. Anal. Chern. 38, 569-573 (1966). C.A. 65, 4 (1966).
597. ZAORSKA, H. Automatic calcium determination and control of II saturation. Zeszyty Probl.
Postepow Nauk Rolniczych No. 62b, 323-328 (1966). C.A. 65, 20341-20342 (1966).
598. ZAREMBA, J. Spectrographic determination of strontium in barytes and other barium salts.
Chern. Anal. (Warsaw) 7, 245-249 (1962).
599. ZATSEPA, V. S. Determination of sodium and potassium in natural waters by using the portable
PPF-UNIIZ flame photometer. Gidrokhirn. Materialy 40, 198-201 (1965). C.A. 64, 13914
(1966).
600. ZINCHENKO, O. V. Alkali metals and thallium in some rocks of the northwestern parts of the
Ukrainian crystalline massif. Morfol., Svoistva i Genezis Mineralov, Akad. Nauk Ukr. SSR
1965, 163-171. C.A. 63, 17733 (1965).
601. ZOLOTAVIN, V. L., Yu. F. BUKREEV, L. K. TOLSTOV, I. YA. BEZRUKOV. Flame-photometric
determination of sodium in pure vanadium pentoxide. Zh. Prikl. Spektroskopii, Akad. Nauk
Belorussk. SSR 2, 461-462 (1965). C.A. 64, 1348 (1966).
602. ZVARA, J., L. JURGA. Determination of potassium in plant material without mineralization by
means offlame photometer. Biologia (Bratislava) 21,54-56 (1966). C.A. 64,20182 (1966).
13.1.10 LESS FAMILIAR FLAMES
Subject Index
Ammonia 16
Bromine and hydrobromic acid 3
Chlorine and hydrochloric acid 4,5, 17,26
Cyanogen 2, 11, 30
Fluorine 2, 4, 15,23,24,25,29
Metal powder flames 7
Oxygen fluoride 27
Ozone 28
Perchloric acid 8, 9, 10, 19, 20, 21, 22
Perchloryl fluoride 29
Nitrogen chloride 18
Nitrogen fluoride 6, 12, 13, 29
Nitrogen oxide 1, 11, 14,30
Cross Index

Fundamental works 86,116,126,130,140,142,188,190,227,228,331,332,369,470
References
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(1965).
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Combust., 10th, Univ. Cambridge, Cambridge, Engl.1964, 65-75 (pub. 1965). C.A. 63,17199
(1965).
6. CROOMES, E. F. The combustion of hydrocarbons and fluoro-substituted hydrocarbons with ni-
trogen trifluoride and nitrogen trifluoride-oxygen mixtures. Combust. Flame 10,71-77 (1966).
7. CUEILLERON, J., H. SCARTAZZINI. Combustion of aluminum in oxygen. Compt. Rend. 228,
489-490 (1949). Sci. Abstr. AS2, 6885 (1949); C.A. 43, 4593-4594 (1949).
8. CUMMINGS, G. A. McD., A. R. HALL. Perchloric acidflames. I. Premixedflames with methane
and other fuels. Symp. Combust., 10th, Univ. Cambridge, Cambridge, Engl. 1964, 1365-1372
(pub. 1965). C.A. 63, 17788 (1965).
9. CUMMINGS, G. A. McD., A. R. HALL. Perchloric acid flames: Part III. Some flame temperatures
and burning velocities. Rocket Propulsion Establishment Westcott (England) Rept. No. RPE-
TR-65/6, 20 pp. (1965). AD-476588.
10. CUMMINGS, G. A. McD., G. S. PEARSON. Flame supported by perchloric acid. Part II. The
decomposition flame. NASA Accession No. N65-20675, RPE-TN-226, 11 pp. (1963). Sci.
Tech. Aerospace Rept. 3,1743 (1965).
11. FISHBURNE, E. S., K. T. RAO, J. M. WEINBERG. Rotational temperature of cyanogen-nitrous
oxide flames as determined by irifrared spectroscopy. Combust. Flame 9, 425-426 (l965).
C.A. 64, 15190 (1966).
12. GOODFRIEND, P. L., H. P. WOODS. Emission spectra of flames of NF-containing oxidizers.
Combust. Flame 9,421-422 (1965). C.A. 64,13567 (1966).
13. GOODFRIEND, P. L., H. P. WOODS. Decomposition chemistry of NF2 compounds. AD-642190,
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14. GRAY, P., R. MACKINVEN, D. B. SMITH. Combustion of hydrogen and oxygen with ammonia
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mixtures. Combust. Flame 11, 109-119 (1967). C.A. 67, 26183 (1967).
15. JANIN, J., A. BOUVIER, J. CHEVALEYRE. Temperature of the fluorine-hydrogen flame. Compt.
Rend. 263B, 291-294 (1966). C.A. 65,16070 (1966).
16. JANIN, J., H. MATHIAS. Methane-ammonia-oxygen flame. Rev. Inst. Franc. Petrole Ann.
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18. PAILLARD, c., R. MOREAU, J. COMBOURIEU, P. LAFFITTE. General characteristics of the decom-
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(1967).
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1895 (1966).
20. PEARSON, G. S. Perch/oric acid flames. IV. Methane-rich flames. Combust. Flame 11, 89-96
(1967). [See also: Rocket Propulsion Establishment, Westcott, England Rept. RPE-TR-6516
(1965); AD-477254, 37 pp. (1965).]
21. PEARSON, G. S. Perchloric acid flames. V. Ethylene-rich flames. Combust. Flame 11, 97-102
(1967). [See also: Rocket Propulsion Establishment, Westcott, England Rept. RPE-TR-66/1
Pt. 5, 33 pp. (1966); AD-645817, also AD-477254.]
22. PEARSON, G. S. Perch/oric acid flames. VI. Ethane-rich flames. Combust. Flame 11, 103-108
(1967). C.A. 67, 101564 (1967).
23. PRIEST, H. F., A. V. GROSSE. Welding of copper with the hydrogen-fluorine flame. U.S. Patent
No. 2,421,649 (1947). C.A. 41, 5088 (1947).
24. RUSIN, L. Yu. Spectra of flames arising in the interaction of fluorine with certain halogen-con-
taining compounds. Zh. Prikl. Spektroskopii, Akad. Nauk Belorussk. SSR 4, 117-121 (1966).
13.2] ATOMIC ABSORPTION SPECTROSCOPY 715
C.A.64, 18715 (1966).

25. SIMMONS, F. S., C. B. ARNOLD, E. F. LIRETTE. Infrared spectroscopic study of hydrogen-fluor-
ine flames. I. Experimental data. AD-481616, 50 pp. (1966).
26. SIMMONS, R. F., H. G. WOLFHARD. The structure of chlorine flames. Jet Propulsion 27, 44-48
(1957). C.A. 51, 6121 (1957).
27. STRENG, A. G. Oxygen difluoride-stream flame. Combust. Flame 10, 203-204 (1966). C.A. 65,
15142 (1966).
28. STRENG, A. G., A. V. GROSSE. Pure ozone flame and the combustion of various fuel gases in
pure ozone. Advances Chem. Ser. 21, 38-43 (1959). C.A. 54, 4122 (1960).
29. TOENISKOETTER, R. H. Fluorine oxidizers. Rept. No. UCRI-349, AD-475950, 81 pp. (1965).
30. WEINBERG, J. M. The infrared emission spectrafrom CzNz + NzO flame. 211 pp. Thesis, Ohio
State Univ., Columbus. Dissertation Abstr. 26, 6788 (1966); C.A. 65, 8194 (1966).
13.2 Atomic absorption spectroscopy
13.2.1 ATOMIC ABSORPTION
Subject Index
Earlier papers 98, 237

Bibliographies 28,467,470
Books 114, 238, 413, 424
Theses 83, 129, 136, 139, 180,268, 378, 433
Reviews and articles in books 8, 9, 18, 32, 68, 78, 88, 101, 103, 107, 116, 149, 150, 153, 174,
179, 182, 198,201,212,223,228,229,248,249,251,252,254,256,260,263,288,292,301,
302,315,316,319,320,328,343,355,356, 358,376,392, 393,394, 396,400,411,414,419,
432,444,450,462,463,464,466,468,473,475,484,494,496,499,503,506,517,519,520,
521,526,527,528,532,533,534,535,537,543,550
Periodical publications 27, 37, 518
Theoretical and general papers 11, 29, 141, 142, 146, 147, 153, 177, 188,200,219,223,269,
270,283,284,287,294,295,300,306,307,314,330,333,349,350,352,353,367,368,373,
378,391,402,411,412,455,458,472,484,490,526,527,530,545
Instrumental 9, 11, 15, 52, 54, 55, 67, 72, 80, 85, 91, 99, 100, 108, 113, 121, 122, 123, 129,
142,143,144,148,169,175, 190, 191,199,202,208,220,223,224,225,226,227,231,239,
251,252,255,256,285, 304, 309, 311, 312, 320, 321, 329, 348, 350, 357, 386, 387, 400, 401,
404,405,410,414,419,421,426,434,435,437,439,443,447,457,465,466,469,472,481,
486,490,504,511,523,527,539
Various discharges as emitting sources 21, 35, 67, 233, 234, 318, 349, 350
Continuous source 121, 122, 136, 137, 141, 152, 300, 455
RF-discharge used as an absorption source 123, 529
Use ofgraphite oven as an absorption source 294, 295, 296, 322, 323, 512
Organic solvents 22, 23, 24, 26, 65, 73, 81, 82, 96, 102, 126, 128, 132, 140, 173, 183, 208,
209,219,221,223,231,233,240,243,246,255,264,276,335,336,339,370,380,383,417,
440,441,448,481,482,488,495,501,502,504,505,516,522,552
Plasma jet as an absorption source 139, 140
Hollow cathode as an absorption source 226
Resonance detectors 10, 50, 53, 344, 490
Material Analyzed
Air 82, 286, 399, 442, 507

Beer, wine, cider 8, 56, 483, 547
Biological materials 4, 5, 6, 34, 39, 43, 53, 59, 61, 62, 63, 83, 84, 86, 87, 89, 92, 101, 112,
116,128,134,135,148,154,155,157,158,160,161,162,167, 170, 179, 180, 184, 185, 186,
192, 193, 194,200,203,204,205,206,207,216,217,221,242,245,257,258,260,262,263,
267,268,282,289,293,303,354,362,365,366,379,382,389,395,403,422,425,426,427,
432,433,435,445,449,451,452,464,478,479,491,492,493,514,537,550,551,552
Dairy products 3,159,173,346,377,383
Cellulose, paper 19, 45, 127
Cement, refractory and related materials 2, 210, 222, 250, 334
Chemical reagents 34,66,93, 102, 150, 151, 153,230,232,235,259, 274, 318, 332, 347,
360,375,420,429,430,431,453,456,474,476,486,487,488,495,497,502,516,531,536,
537,544
Coal 50, 505
Fertilizers 149, 297, 298, 299
Food 364,449,473, 531, 543, 546
Fungicides, insecticides 171
Gasoline (petroleum products) 33, 47, 48, 58, 77, 247, 335, 340, 540
Glass and silicates 1, 2, 218, 241, 351, 369, 370, 385
Isotope analysis 163, 164, 310
Lubricating oils and greases 58, 247, 327, 337, 340
Metals and alloys 13, 14, 15,24,25,26,31,34,40,41,46,67,75, 76, 77, 78, 79, 93, 96, 107,
110,115,117,166,168,172,176,183, 189, 196,214,215,232,246,250,253,259,264,265,
266,272,301,302,313,338,339,345,446,456,461,474,477,486,500,502,509,537,542
Ores, minerals and rocks 7,35,38,42,49,70, 74, 79, 120, 133, 145, 156, 178, 182,210,211,
261,332,361,372,385,423,428,436,438,459,463,476,482,510,513,524,548,549
Photographic materials 277,278,290
Plants 12, 30, 44,57,69,73,90,108,109,111,187,213,242,268,280,324, 325, 363, 371,
384,397,449,454,480,485,489,508,515,525
Rubber 326
Soils 106, 111, 197,280,281,359,486,538
Teflon and organic polymers 271,347,498
Test solutions 20,34,36,44, 54, 60, 80, 81, 94, 95, 104, 105, 144,236, 398,415,418,440,
471, 522, 541
AVater34, 51, 68, 73,82,118, 130,131, 132,138,256,273,293,371,381,388,399,442,449,
481,486, 537
AVaters: marine 16,17,64,65,71,94,95,119,243,244,293,332
AVaters: industrial 380, 381, 463
Elements Determined
Aluminium 102, 115, 140, 309, 423

Antimony 51, 302, 339,429,430,431,446
Arsenic 51, 323
Barium 241, 294, 427
Bismuth 51, 233, 262, 263, 317,446

Boron 164
Cadmium 40, 97, 120, 133, 176,233,278,286,295, 302,326, 380, 395,399,443,446,449,
487,488,501,542
Calcium 1, 7,19,30,34,39,42,44,50,51,52,61,62,63,69,79,80,92, 104, 112, 118,130,
131,135,145,147,148,155,161,166,167,173,178,180, 186, 187, 193,204,213,219,225,
241,245,247,250,267,271,273,282,289,297,298,309,313,318,324,347,360,362,365,
374,381,398,415,418,432,445,446,476,493,498,504,513, 514,515,525
Cesium 34, 190, 236, 294, 390
Chlorine 536
Chromium 7,31,40,46, 51, 110, 118, 128, 144, 151, 162,215,244,272,286,294,327, 340,
360,379,418,510
Cobah54, 118, 132, 176, 181,241,244,302,334,418,442,477,486,515
Copper 3, 19,24,30,33,34,38,40,45,46,51,56,57,65, 71, 72, 87, 89, 94, 95, 108, 118,
130,131,148,150,153,157,158,159, 180, 187,206,226,227,231,232,241,244,264,273,
274,276,298,302,313,326,327,335,359,360,365,366,370,372,380,381,385,399,415,
418,421,428,432,443,446,453,476,477,478,483,486,489, 501,504,515
Gallium 233,341
Gold20, 72, 74, 361, 375, 385, 459, 461, 482
Indium 232,233,341,446
Iridium 308, 342
Iron 7, 19, 22, 33, 40, 42, 49, 51, 54, 56, 71, 79, 89, 93, 118, 148, 171, 178, 180, 187, 203,
241,243,244,246,250,286,298,313,318,326,327,365,369,380,381,385,409,417,418,
425,432,442,446,453,456,476,478,486, 501,504,515, 524,544,551,552
Lead 51, 56,81,82,96, 132,218,241,286,302,326,327,335,340,346,347,379,380,418,
422,428,446,453,476,479,486,501,507,540,547
Lithium 16, 34,40,53, 71, 118, 119, 130, 131,241,247, 310, 371, 385, 549
Magnesium 1,4,5,6, 7, 12, 15, 19,22,30,34,40,42,44,45,46, 51,57, 79, 83, 84, 86, 89,
90,106,109,110,111,112,118,119,120,130,131,134,135,138, 145, 148, 154, 155, 160,
161,166,170,173,177,178,180,184,185,186,187, 194, 197,204,205,207,213,216,217,
231,241,242,245,250,271,273,280,281,286,289,298,302,303,318,324,326,327,348,
351,360,365,374,377,381,389,396,398,415,418,421,432,436,445,446,451,452,474,
477, 493, 495, 504, 505, 509, 513, 515, 538, 541
Manganese 25, 30, 40, 42, 46, 51, 56, 67, 71, 72, 75, 87, 108, 110, 118, 126, 127, 130, 131,
171,180, 187,215,222,231,241,243,244,294,298,313, 365,381,415,418,442,443,446,
454,476,477,489,501,504,515
Mercury 60, 279, 291, 363, 364,447, 531, 548, 553
Molybdenum 73, 244,265, 266, 337, 338, 340, 379, 546
Nickel 7, 33,40,46,51,54,71, 118, 132,215,231,235,241,244,246,259,272,318,327,
335,360,372,381,406,409,442,443,446,456,476,477,491,492,500,501
Nitrogen dioxide (N0 2 ) 237
Nitrate 276
Noble gases 165
Palladium 501, 502
Phosphorus 275, 546
Potassium 7, 19, 30, 34, 36,42,47, 51, 72, 112, 118, 119, 130, 131, 135, 148, 180, 190,225,
241,250,281,294,296,298,299,311,326,365,383,390,408,415,418,429,430,431,445,
446,497,508,515
Rare earths 240,261, 305

Rhenium 448
Rhodium 195
Ruthenium 125
Rubidium 35, 49, 71, 72, 118, 119, 190, 236, 331, 332, 346, 390, 471, 485
Selenium 51, 124,407,460
Silicon 423
Silver 72, 133, 189, 196,211, 277, 290, 327, 385, 420, 428, 438, 446, 486, 501, 536
Sodium 7, 19, 34,42, 45, 51, 66, 72, 112, 118, 130, 131, 135, 180, 190, 208, 209, 230, 241,
247,250,297,298,311,326,365,383,390,415,416,445,515
Strontium 7, 17,48, 71, 118, 119, 130, 131, 176,210,213,221,294, 309, 397, 513
Sulfur 427
Tellurium 232, 262, 263, 446
Thallium 408, 522
Tin 51, 76, 327, 443, 446
Titanium 183, 423
Uranium 163
Vanadium 77, 140, 423, 440, 441
Zinc 14, 19,26, 30, 38, 40, 41, 43, 51, 56, 57, 70, 71, 72, 75, 83, 84, 87, 89, 105, 108, 112,
117,130,131,133,148,150,157,171,176,180, 187, 192,205,233,241,244,257,273,284,
295,298,313,325,326,335,340, 347,354,365, 366,369,372,380,381,382,384,385, 399,
415,418,421,428,432,443,446,449,453,478,504,515
Zirconium 516
Cross Index

Fundamental works 296, 299, 322, 323, 387
Instrumentation 50, 57, 67, 105, 126
Analytical procedures 72, 118, 121, 122, 126, 128, 156, 180, 203, 226, 275, 407, 414, 445,
446,447,449,450,470,498,501,551
References
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elements in glass by atomic absorption spectrometry. Anal. Chern. 38, 630-633 (1966). C.A. 64,
17218 (1966).
2. ADAMs, P. B., W. O. PASSMORE, D. E. CAMPBELL. The determination of trace elements in
glasses and refractory materials by flame emission and atomic absorption spectroscopy. Proc.
Symp. Trace Characterization - Chemical and Physical 1966, 104-113. Natl. Bur. Stds.,
Gaithersburg, Maryland.
3. ADDA, J., F. ROUSSELET, G. MOCQUET. A solution to the problem of copper in the butter in-
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13.2.2 HOLLOW CATHODE DISCHARGE TUBES
Subject Index
Discharge parameters and mechanism 2,3,4,6,7,9, 10, 11, 13, 15, 19, 30, 32,43,44,45,
46,47,49,51,52,59,65,69,74,75,76
Instrumental 5, 16, 18,24, 50, 66, 67, 72, 73, 75
High intensity tubes 1, 14, 17, 33
Discharge tubes for atomic absorption 17, 20, 22, 23, 27, 28, 35, 53, 60, 70, 71, 77, 78, 79
Analytical applications 8, 12, 16,21,25,26,29,31,34,36,37,38,39,40,41,42,43,48,54,
55,56,57,58,61,62,63,64,68,80,81,82
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13.3 Electrical discharges having the aspect of combustion flames
13.3.1 THE RADIO-FREQUENCY DISCHARGE
Subject Index
Discharges in closed vessels at various pressures 1, 2, 3,4,6,7,8,9,10,11,12,17,18,21,23,

24,25,26,27,31,33,34,36,37,38,39,40,41,42,43,44,45, 46, 47, 48, 49,54,55,56,59,
62,66
Discharges at atmospheric pressure 5, 13, 14, 15, 16, 19, 20, 22, 28, 29, 30, 32, 35, 50, 51,
52,53,57,60,63,64,65
Theses 58, 61
Temperature o/the discharge 5,12,18,21,35,37,44,49
Analytical applications 1, 2, 3, 6, 9,13,19,20,22,29,30,32,33,34,38,45,55,60,61,63,
64,65
Cross Index
See also the following reference in:

13.1.9 Analytical procedures 151
References
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748 amLiOGRAPHY ON FLAME SPECTROSCOPY [13
60. WENDT, R. H. Spectroscopic properties and analytical applications of induction-coupled plasmas.

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66. ZAJDEL, A. N., N. M. ORLOVA, A. A. PETROV, T. YA. CHELIDZE. Relative intensity of hydro-
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13.3.2 PLASMA ARCS
Subject Index
Books 22,35
Bibliographies
Reviewing articles 48, 50, 61, 62, 79, 96
Characteristics of the discharge 2,7,13,17,24,25,26,29,36,42,43,46,49,50,52,53,
56, 57, 68, 70, 71, 72, 87, 88, 98, 101, 102, 103
Temperature of the plasma 3, 6, 7, 8, 9, 10, 14, 15, 16, 18, 22, 28, 32, 39, 41, 44, 51, 55,
57, 58, 67, 71, 75, 81, 85, 86, 87, 88, 90, 91, 93, 94, 95, 97, 102
Instrumental 4, 18, 30, 33, 40, 45, 46, 53, 74, 76, 80, 86, 92, 100
Analytical applications 5, 11, 12, 19, 20, 21, 31, 33, 34, 37, 38, 40, 47, 48, 53, 54, 59, 60,
63, 64, 69, 75, 76, 80, 82, 83, 84, 89, 92, 99
Laser 23, 27, 65, 66, 73, 77, 78
Cross Index
Fundamental works 63,221,239, 240
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spectroscopic use. Emissionsspektroskopie (1962 Symp. in G6rlitz) 1964, 160-172.

54. KRANZ, E. The properties and applications of a new plasma burner for spectroscopic use.
Proc. XII Colloq. Spectry, Intern., Exeter, 1965, 574-577.
55. KUSTANOVICH, I. M., A. A. OVSYANNIKOV, L. S. POLAK, N. M. RYTOVA. Optical pyrometry
of plasma jets. Kinetika i Termodinam. Khim. Reaktsii v Nizkoternperaturnoi Plazme,
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56. LOCHTE-HoLTGREVEN, W. Spectroscopic diagnostics in the physics of hot plasmas. Colloq.
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57. McGREGOR, W. K., M. T. DOOLEY. Spectroscopic diagnostics ofa Gerdien-type plasma stream
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58. MCGREGOR, W. K., JR., M. T. DOOLEY, L. E. BREWER. Diagnostics of a plasma flame ex-
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59. MALENFANT, A. L., D. N. HUME. Plasma emission spectroscopy. Mass. Inst. of Techno!.,
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60. MALENFANT, A. L., D. N. HUME. Plasma emission spectroscopy. Mass. Inst. of Techno!.,
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61. MANCEAUX, M. Plasma generators - the principles and applications. Ind. Chim. (paris) 53
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62. MARCHANDISE, H. The plasma gun and its applications. EUR-2439.F: TID-22136, 242 pp.
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63. MARGOSHES, M. Recent advances in excitation of atomic spectra. Proc. XII Colloq. Spectry.
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64. MARINKOVIC, M. D. Some properties of a d.c. gas-stabilized arc in an argon atmosphere as a
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65. MENTALL, J. E., R. W. NICHOLLS. Spectroscopic temperature measurements on laser-produced
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77. RASBERRY, S. D., B. F. SCRIBNER, M. MARGOSHES. Laser probe excitation in spectrochemical
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81. ROBINSON, D., P. D. LENN. Plasma diagnostics by spectroscopic methods. Appl. Optics 6,
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82. ROETGER, K. Simple, specific, and rapid determination of silicon in urine with the three-chamber
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86. SHIMANOVICH, V. D., L. I. KISELEVSKII. Production and investigation of a stationary thermal
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88. SHIPLEY, K. L. Some spectroscopic measurements of a supersonic plasmajet. Appl. Spectry. 20,
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89. STAMM, D., K. ROETGER. Determination ofphosphatide phosphorus by high-temperature flame
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90. SUCKEWER, Sz. Device rod gun "DP." I. Theory of spectroscopic measurements in plasma guns.
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91. SUCKEWER, Sz. Device rod gun "DP." II. Measurements of plasma temperature. Inst. NucI.
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92. TAKEI, S., M. YAMAMOTO. Plasma jet generator. U. S. Patent No. 3,225,245. Dec. 21, 1965.
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95. TOURIN, R. H. Spectroscopy of plasma jets and electric arcs. Appl. Spectry. 20, 1-5 (1966).
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96. TSUTSUMJ, S. Plasma-jet and organic synthesis. Yuki Gosei Kagaku Kyokai Shi 24, 28-38
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97. VANHAUWERMEIREN, R. A spectrographic method for determining electron density. J. Nucl.
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98. VURZEL, F. B., L. S. POLAK. Conversion to acetylene and olefins of straight-run gasoline and
some hydrocarbons in a plasma jet. Kinetika i Termodinarn. Khirn. Reaktsii v Nizkoternpera-
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99. WEBB, M. S. W., P. C. WILDY, M. L. WORDINGHAM. The performance of a direct-current
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103. YAMAMOTO, M. Profile of ionized-calcium lines in an arc-plasma jet. Phys. Rev. 146, 137-139
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13.3.3 ARC-AND-SPARK-IN-FLAMB
1. CHEN, D. C. C., J. LAWTON, F. J. WEINBERG. Augmenting flames with electric discharges.

Symp. Combust., 10th, Univ. Cambridge, Cambridge, Engl. 1964, 743-754 (pub. 1965). C.A.
64, 519 (1966).
2. GAWEN, J. C., J. H. HARKER, I. FELLS. Nonseeded electrically augmented flame systems. Nature
210, 1149-1150 (1966). C.A. 65, 6458 (1966).
3. KLEIN, S. Electrical potential distribution in a flame, in the presence of layers of negative ions,
between two electrodes. Compt. Rend. Ser. A, B 263, 1208-1210 (1966). C.A. 66, 50147 (1967).
4. MARYNOWSKI, C. W., T. J. HIRT. Electrical augmentation of natural gas flames. Amer. Chern.
Soc., Div. Fuel Chern., Preprints 9, 43-54 (1965). C.A. 66, 67547 (1967).
5. MARYNOWSKI, C. W., B. KARLOVITZ, T. J. HIRT. Electrical augmentation of natural-gas flames.
Ind. Eng. Chern., Process Des. Develop. 6, 375-379 (1967). C.A. 67, 34171 (1967).
6. PONCELET, J., P. ZETIWOOG. Increase of the temperature offlames by addition of electrical energy.
Journees Intern. Combust. Conversion Energie, Paris 1964, 685-698. C.A. 65, 14566 (1966).
SUBJECT INDEX
This brief Subject Index should be considered as a complement to the detailed Table of Con-
tents located at the beginning of this book. The entries recorded in this Index were selected
with emphasis on particular topics, and the reader should use both the Table of Contents and
the Subject Index to find the information in which he is interested.
A
ammonium fluoborate . • . . . . . . 200f
Absorption. . . . · 419 ammonium pyrrolidine dithiocarbamate.64, 67
from a continuum · 428 amount of sample required . . . . . . 483
absorption flame spectroscopy, see atomic amplifiers, chopper
absorption spectroscopy, molecular ab- 146-150, 541, 596, 608
sorption flame spectroscopy chopper-stabilized . . . 150
absorption method, elements determined in differential .147, 174
biological material. . . . . . 487 drift-free . . .148-150
absorption spectra of the rare earth ele- lock-in. . . .150, 156
ments . . . . . . . . . . 392 operational. .147, lSI, 153, 154
absorption spectroscopy. 160, 525 if non-linear. . . . . . 154
absorption tube . 56 tuned. . . . . . . . 156
AC Amplifier . . . . . 608 analog circuits. .145,146-161
AC galvanometer . . . 608 analog-to-digital conversion. .146, 161, 173
AC phase-sensitive amplifier. 608 analysis, offertilizers . 473
acetone, flame determination of 218 of plants 452
acetylacetone . . . . . . . .64, 67 of rocks. 437
acetylene flame, see nitrous oxide-acetylene of soils. 437
flame, oxyacetylene flame of water 464
accuracy . . . . . . . 47,52,69 analyte. . 62
addition . . . . . . 151 analytical curves. 616
afterglow, of nitrogen. · 231 analytical methods. 432
of sulfur dioxide. . · 288 AND gate .165-166,172,177
agricultural applications of flame photo- aphanoscope . . . . . . . . . 203f
metry . . . . . . . . . . . . . . 431 arc-and-spark-in-flame . . . . . . 752
air-acetylene flame. . . . . . .380,383,387 argon, atomic absorption spectroscopy for 357
air-hydrogen flame, see hydrogen flame cross section of . . . 185
alcohols . . . . . . . 63 electric discharges for. . . 357
flame determination of . . . . . . . 218 enhancement by. . . . . 272
alkali flame detector . . . . . . . . . 267 flame emission detector for 357
aluminium . . . . . . . 438,470,472, 568 argon-hydrogen flame. 54, 185
amidogen (NH 2 ), spectrum of for arsenic . . . 275
23lf, 234, 238, 298 for boron. . . . 211
amines, determination of . . . . . . 233 for phosphorus .250, 262
ammonia alpha bands for selenium. . . 308
231f, 234, 238, 298 for sulfur. . . .282,292
ammonia flame . . . . . .231-233 for tellurium. . 320
ammonium, flame determination of. . . 235 arsenate, indirect determination of . . 275
756 SUBJECT INDEX
arsenic. . . . . . . . . . . . . . . 54 atomic fluorescence spectrometer. . . . 607

atomic absorption spectroscopy for atomic fluorescence spectrophotometry. 451
185, 275f 568 atomic fluorescence spectroscopy, for arse-
atomic fluorescence spectroscopy for. 275 nic 275,621
atomic spectrum of. . 269ff, 273ff for selenium . . . . . . . . . 308, 622
combustion of. . . . . . . 273 for tellurium . . . . . . . . . 320, 622
continuum of. . . . . .271,273 atomization . .535-539,546,550-551,595-596
detection limit of. .270ff, 274-276 atomize, definition of. . . 185
excitation of. . . . . 272 atomizer-burner, name of. 185
gas chromatography for. .271,275 automatic sequences . .161,162,176
indirect determination of 275 automation. . . .485, 507
induction torch for. . . 276 averaging circuit. . • • .153, 158
interferences on . . 274f
linearity of . . . . .271,272 B
radiance of. . . . .270, 273
sensitized detectors for . . 276 Background effects in flame .557,580,585
solvents for. . . . . .271,274 background noise 48
dissociation energy of. . . 273 band emission. . . . 546
reduction of. . . 272 bandwidth . . . .149,154
spectrum of . . . . . . . 269-271,272f equivalent noise .155-156
arsine, flame of. . . . . . . 273 barium . . . . . . .448,461,469,470,568
aspiration chamber burner. 5, 614 in indirect determination of boron 212
aspirator-burner, term . . 185 in indirect determination of sulfur. 295
astatine, spectrum of. . . . 323 overexcitation of. . . . . . . . 185
astigmatic correction of gratings .101,104 barium bisulfate. . . . . . . . . 201
atmosphere, monitoring of, see monitoring barium bromide (BaBr), for bromine detec-
atomic absorption . . . . 47,48,58, 525, 715 tion . . . . . . . . . . . . . .344, 352
atomic absorption spectra . . . .387,392 spectrum of. . . . . . . . . . 352
atomic absorption spectrometry . . 60, 525ff barium chloride (BaCl), for chlorine detec-
sensitivity . . . . . . • . . . 62, 525ff tion . . . . . . . . . . . 328, 338f, 344
atomic absorption spectroscopy 182,213,715 spectrum of. . . . . . . . . . .328, 329
for arsenic . 275f, 568 barium fluoride (BaF), for determination of
for boron. . 213, 569 fluorine. . . . 321
for chlorine . 349, 570 spectrum of . . . . . . 320f
for fluorine . 322, 572 barium iodide (BaI), for iodine detec-
indirect. . .182,227,235, 266, 322, 349, 356 tion . . . . . . . .344, 355
foriodine. . . . . . . . . . . . . 356 spectrum of . . . . . . 355
long-path 235, 275; see also Fuwa tube basic instrumentation in atomic fluores-
for nitrogen. . 235f cence. . . . . . . . . . 606
for noble gases. . 357 BCD code. . . . . . . .173, 176
for phosphorus . . . 266f,578 Beilstein detector for gas chromatogra-
sampling boat for 275f, 308, 319 phy . . . . . . 234
for selenium .185,308,580 Beilstein test, for bromine. . 332f, 334ff, 352
for silicon .225,227,581 for chlorine
for sulfur . . 296,582 324,328,329~ 331,332f~ 340f~ 344
for tellurium 319,582 for fluorine . . .322, 343
atomic fluorescence, direct line. 600 foriodine. . . . . 354
energy transfer 600 mechanism of . .333,340
intensity . . 600 for nitrogen. 233f ,343
mechanism . . 599 benzene. . 66
stepwise line. . 600 beryllium. . . 501,568
theoretical considerations . 599 bias . . . . . .480, 484
atomic fluorescence flame spectrometry 599 BH, see boron hydride
SUBJECT INDEX 757
bibliography . · . 651 Broida cavity . . . . . . . . . . . 612

binary counter. · . 172 bromine, Beilstein test for. 332f, 334ff, 352
binary number. .146,173 continuum of. . . . . • . 351
biology. . . . · . 479 detection of. . . 334ff, 342, 352f
bismuth overexcitation of . · . 184 detection limit of 342,344, 352f
bismuth halides, spectra of. .328, 352, 355 determination of. 353
blank solution, preparation. • 504 electric discharges for. . . 353
BO, B0 2, B20 3 , see boron oxides flamespectraof . . . . . 35lf
Boltzmann distribution law 38 indirect detection of . .352, 353
Boon's flame photometer .204,205 metallic band spectra of. . . 35lf
borane monitor . . . . . 212 monitor for. . . . . . . • 352
boric acid detection of 197, 20lf, 210 sensitized detectors for . 350, 352f
flame bands of. . 194 bromine (Br2), spectrum of . 351
boron . . . . . . . . . . . 464 bromine oxide (BrO), spectrum of. . . 351
in acetylene flame . . . . . 204f burner, aspiration chamber . . . • 5, 614
alcohol test for. . . . . . 196ff, 201, 210f laminar-flow . . . .537-539, 543, 548, 597
atomic absorption spectroscopy for 213, 569 long-path slot. . . . 6, 392
atomic spectrum of. 195f, 205, 208, 210, 213 oxyacetylene premixed . 384
chemiluminescence of. 196 total consumption . . 6,614
combustion of. 195 turbulent-flow
continuum of. . . 192 536-537,539,548,569,579,583
detection of. . . . . 196ff burner-atomizer, see sprayer-burner
detection of, in food . 197ff, 201 butyl borate . . . . . . . . . . . . 211
detection limit of. . 196ff, 207, 209, 211-213
determination of flame photometric, . 204ff
determination of visual, . . 201ff C
flame spectrum of . . . . 188ff
fluctuation bands of . . 194 C 2, see carbon (C 2)
indirect determination of 212 C 3 , see carbon (C 3 )
induction plasma torch for. 213 C 2 or CH bands. . .414,419
interferences on cadmium. . . . . 451,569
197ff, 201-205,207, 209, 211f overexcitation of. .184,185
interference of sodium on . .205, 210 caesium. . 75,447,460,469,503,570
laser excitation of . . . . . 213 calcination . . . . . . . . . . . . . 495
monitoring of. . . . . . . . . 212 calcium. . . . . .443,454,455,466,499, 569
plasma jet determination of . . 213 in indirect determination of fluoride. . 322
radiance of. . . 189, 192f calcium bromide (CaBr), spectrum of. . 352
spark-in-flame for . . 213 calcium chloride (CaC!), for chlorine detec-
turmeric test for . . . 196 tion . . . . . . . . . . . . . . . 328
Turner's testfor . .196, 200 spectrum of. . . . . . . . • . . . 328f
boron fluoride, in flame. .196, 200 calcium fluoride (CaF), for determination
boron hydride (BH) . . 195 of fluorine. . . . . . . . . . . . 321f
boron oxide (BO), dissociation of 196 spectrum of. . . . . . . . . . .320, 321
dissociation energy of. . . . . 195 calcium iodide (CaI), spectrum of. . . 355
spectrum of . . . . . . . . . .195,213 calibration and measuring techniques. . 564
boronoxide(B0 2),absorption spectrum of 195 calibration graphs, curvature of
flame spectrum of 188ff, 194f, 205, 212 534,539,559-561,565,578,581
isotope shift of. . 195 calibration methods . 433
laser excitation of 213 camera, spectroscopic. . . . . . . . 102
boron oxide (B 20 3 ) 194 carbohydrogen . . . . •• . . . . 214
BrO, spectrum of. . 351 carbon, atomic spectrum of. .214,219,230
Brody-Chaney burner band spectrum of see carbon (C2)
244,257,260,262,264,282,286,287,290,292 detection limit of. . • • • • • • .217-219
758 SUBJECT INDEX
determination of flame photometric. . 216ff chemical composition of the sample in bio-

electric discharges for. 219 logy and medicine . . . . . 486
excitation of. . . . . . . 214 chemiionization. . . . . . . . 185f
flame spectra of . . . . . 214 chemiluminescence. . . 66, 184ff, 272
gas chromatography for. . 216ff of arsenic . . . . .269,271,272,274
indirect determination of 218 of boron . . . . 196
laser excitation of . . . 219 of indium chloride . 345
microwave discharge for. 218 of phosphorus, see HPO
monitoring of. . . 217f of phosphorus oxide 251f
plasma torch for. . 219 of selenium . .296, 306
Tesla discharge for. 218 of silicon. . . . 225
vapor of, in flame . 225 of sulfur . . 252, 284, 286f
carbon (C 2 ), in clorine detection 323f of tellurium . 315f
Mulliken bands of. . . . . 229 oftin. . . . 218
Swan bands of. . . 183, 214f, 216,219,229 suprathermal 41
carbon (C 3 ), spectrum of . . . . . . . 215 chloride indirect determination of. 349
carbon bromide (CBr), spectrum of. . . 351 chlorine . . . . . . . . . . . .459, 502
carbon chloride (CCl), spectrum of. .324,350 atomic absorption spectroscopy for 349,570
carbon dioxide, flame determination of . 218 Beilstein test for 324, 329f, 331, 332ff, 340ff
carbon disulfide, flames of, burners for . . . . . . . . . 333, 341f
279-281,283,284,286,288,326,354 carbon spectra enhancement by. .323,324
in Sell's lamp . . . . . . . . . . . 281 continuum of. . . 324
carbon fluoride (CF), spectrum of. . . . 321 in copper arc . . ..... . . 331
carbon mono sulfide (CS), application of copper spectra of. ..... . . 324ff
288-290, 294-296 detection of. . . .324, 326, 329ff, 344ff
dissociation of. . . . . . . . . 294 detection limit of
flame emission of. . . . .278, 283, 295 335, 337, 339, 341-345, 349, 350
in microwave discharge . . . 296 determination of. . . 336ff, 342ff
radiance of. . . . . . . . . 284f electric discharges for. . . . . 350
spectrum of. . . . . . . 283, 284f flame colors of. . . . . 323f
carbon monoxide, CuCI in. 326f,328 flames of. . . . . . . .323, 325, 328
excitation of. . . . . . 185f flame spectra of . . . . . . . 324ff
flame of. . . . . . . . 187 gas chromatography of 323, 336ff, 340, 344
reaction of in overexcitation indirect detection of. . . . . . . 325, 344
196,225,252,272,316 indirect determination of . . . . . . 349
spectrum of. . . . . . . . . . 215 indium burner for . . .329, 331, 340f, 344ff
carbon selenide (CSe), spectrum of . 296f interferences on . . .335,337,339,341,349
carbon telluride (CTe), spectrum of. 309 linearity of . . 340f, 342, 343, 345, 348, 350
carbon tetrachloride 66 metallic band spectra of. . . . . . . 324ff
cathodic sputtering. .535, 545, 584 monitors for. . . . . 336f, 338f, 340, 344ff
CBr, spectrum of. . . 351 sensitized detectors for . . 329ff,344ff, 350
CCl, spectrum of. .324,350 chlorine (CI 2 ), spectrum of. . . . . . 324
cells, long path. . . . 112 chlorine oxide (ClO), spectrum of. . . 324
sampling. . 111,156 chlorine trifluoride flames. .321,324
ceramic, absorption tube. 56 chloroform. . . . . . . 66
CF, spectrum of. . . . . 321 CHO, spectrum of. . . . . . 215f
CH, in chlorine detection .323, 324 choice of the instrument in biological and
in overexcitation. . . . 185f medical applications. . . . . . . 483
spectrum of. . . . . 186f, 215, 216, 219 choice of the spectral line for biological
Chaffee-Keyes burner. . . . . . . 56 and medical analyses. . . . . . . . 490
chamber-type nebulizer, separate burner. 5 chopper amplifier . . . . . . . . . . 150
check solution. 505 chopper-stabilized amplifiers. . . . . . 150
chelate. . . . . . . . . . . . . . . 64 chromium. . . . . . .470,472,451,503,449
SUBJECT INDEX 759
gas chromatography of. . . . . . 275 flame spectrum of . . . . . 324ff

for indirect determination of iodine . 356 as impurity spectrum. . . . 326ff
chromyl chloride, flame color of 201 suppression of sodium by . 327
CIO, spectrum of. 324 copper chloride (CuCI2 ), flame colors of. 325f
clock pulses. . . .161,163,174 copper deuteride. . • . • . . . • • . 187
clogging . . . . . . . . 485 copper fluoride (CuF), for detection of
CN, see cyanogen fluorine. . . . . . . . 322
CO, see carbon monoxide spectrum of. . . . .320, 321
coal flame, boron in 189 copper hydride (CuH), for determining
copper in . . . . .326,327,332 atomic hydrogen.. • . • • • • 187
cobalt . . . . . . 470,571 flame spectrum of . • . .187,325,327,343
overexcitation of. .184,185 in halogen detectors . . • . • • • . 342
code,BCD .173,176 copper hydroxide (CuOH), for determining
binary . . . 173 chlorine .332f, 334ff, 340ff
decimal. . . 173 for determining hydroxyl . • • • . • 187
hexadecimal. 173 flame spectrum of . • . . • 325f, 327, 332
cold calcination at reduced pressure and copper iodide (CuI), flame spectrum of . 354
temperature with atomic oxygen . . . 495 for iodine detection. . . . . • . .342, 353
cold flame of phosphorus .240,247,248,253 copper oxide (CuO), flame emission of
collimator. . . . . . . 86 187,325,327
comet-head bands . . . . 215 counters . .161,170,176
comparison of different flame spectrometric binary . .171-172
methods . • . . . . . 615 decimal. . . . . 172
with other methods. . . 436 CS, see carbon monosulfide
compensation principle . 79,104 CSe, see carbon selenide
components. . . . 53 Cfe, see carbon telluride
computer program . 178 CuBr, CuCI, CuF, CuI, see copper bro-
computer on-line. . .177-179 mideetc.
concentration limit. 182 CuH, see copper hydride
concentration range covered in emission cyanides, detection of. . . . . 233f, 335, 337
flame photometry . . . 481 flame spectra of . . . • . . . . • • 232
continuous light sources 527. 534-535,557,613 cyanogen (CN), band spectra of215, 219, 228ff
continuum primary source.. . . . . 392 in indirect detection offluotine . . . 323
controifunction. . . . . . .162,164,177 cyanogen flame .187,214
conversion, analog-to-digital. .146,161,173 arsenic in . 269
digital-to-analog. . . . . . . . 146,175 boron in • . 196
copper . . .60,61,449,450,462,470,500,571 carbon in. . 214f
in Beilstein test with fluorine. 276f
233, 322, 324, 332ff, 340ff, 344, 352,354 iodine in . . 355
in coal fire. . . . . . . . . .326,327,332 spectrum of . .228ff, 232
flame spectrum of .187,325ff, 327,332,343 cyclohexane. • 66
in indirect amine determination. . . . 233 Czerny-Turner spectrometer 60
in indirect chlorine determination. .343, 349
in indirect nitrate determination . . . 236 D
reactions of, in flame. . .326,327,333,340
copper bromide (CuBr), for bromine detec- Dark current . . . . . .149,158
tion . . . . . . . . . . . .342, 352, 353 data reduction. . . .146,177,178
flame spectrum of . . . . . . . . . 351f DC electrometer amplifier. 608
copper chloride (CuCl), absorption spectrum decimal counter . . . 172
of. . . . . . . . • . . . . . . . 326 decimal number. . . 173
for chlorine determination degree of dissociation. 25
330, 334ff, 340f, 342f of ionization. . 34
in coal fire . . . . . . . . .326, 327, 332 deproteinization. . . 494
760 SUBJECT INDEX
desolvated aerosol particles, composition 15 double-beam systems. . . • . . . .542, 563

particle composition . . . . . 15 Driigerwerk burner
rate of volatilization . . . . . .17,15 241,247,258,282,331,341t345
desolvation, of spray in the flame. 13 drift-free amplifiers. . . . . .148-150
testing incomplete . . . . . . 12 droplet size . . . . . . . 63
detection limits, see also limits of detection dysprosium. . . . .383, 384, 392, 572
47,48,182,480,483,621
definition of. . . . . . .192,223,274,317 E
and linearity. . . . . . . 288f
for the rare earth elements. . 392 Ebert monochromator . . . . . . 59,61, l2lf
terminology of. . . . . 192 electric circuit. . . . . . . . . . . . 61
detection system. . . . . .53,61 electric discharges, see discharges
detector/amplifier systems 608 having the aspects of combustion flames 745
detectors . . . . . . . . .541-542, 596 electrodeless discharges, see induction plasma
determination, of major elements. . .437,466 torch, microwave discharge, radiofrequency
of other elements. . • . . . . . . . 474 plasma torch, Tesla discharge
of trace elements. • . . . . .460,469,470 electrodeless discharge lamp. 54,534, 610
deuterium, flame determination of . 187 electrodeless discharge tube . . 610
diatomic band emission spectra. . . . . 380 electronicinstrumentation. . .145-180
diatomic monoxide (MO) molecules. . . 379 electronic noise . . . . . . .146, 165
diborane, combustion of . . . . . .195,205 elements, determined in biological material
monitor for. . . . . . . . . . . . 212 by emission method and absorption method
diethylammonium diethyldithiocarbamate 57 487
differential amplifier .147, 174 which can be determined by flame photo-
differentiation. . . . . . . .150,152 metry . . . . . . . . . . . 431
diffraction, slit. . . . . . . 90 with high dissociation energies. 481
digital-to-analog conversion. .146, 175 emission, flame . . . . 414
digital circuits . .145,146,161-177 analytical procedures. 684
digital readout. . . . 542 bibliographies. . . . 656
dilution. . . . . . . 493 books . . . . . . . 654
diphenylthiocarbazone 67 chapters in books and related material. 656
direct-current discharge, for bromine 353 early works. . . . 653
for carbon . 219 fundamental works. 657
for chlorine. 350 instrumentation. . 678
for fluorine . 323 less familiar flames. 713
foriodine. . 356 reviews. . . . . . 655
for nitrogen. 238 theses . . . . . . 654
direct line atomic fluorescence 600 emission flame photometry, signal 1
discharges, electric, see direct-current dis- basis. . . . . . . . . . 2
charge, induction plasma torch, micro- general principle. . . . . 2
wave discharge,plasma torch, radiofrequency emission method, elements determined in
plasma torch, Tesla discharge biological material. . . . . . . . . 487
disk-stabilized arc . .228,268 emission spectra of the rare earth elements 393
dispersing element. . . . . . 91 emission spectrometric detection limits for
dispersion, angular. . . . . . 92 the rare earth elements . . . . . . . . 388
dissociation, in hydrogen flame. 185 encrustation. . . . . . . . . . . . . 485
of molecular metal species. . 24 energy transfer (sensitized) atomic fluores-
in nitrous oxide-acetylene flame. 186 cence. . . . . . . . . . . . . . . 600
testing incomplete . 30 equilibrium dissociation, mass-action law 25
dissociation energy. . . . .185,187 equilibrium excitation. . . . . . 38
elements with high. . . . . 481 equilibrium ionization, Saha's law 34
of rare earth monoxides. 383 equipment . . . . . . . 434
Doppler broadening.. . . 53, 527, 530, 545 equivalent noise bandwidth . . . .155-156
SUBJECT INDEX 761
erbium. . . . . . . . . . . . . 392, 572 flame enussIOn detectors for gas chromato-

ethyl borate. . . . . . . . 196ff, 202f,210 graphy
ethyl bromide flame bands, see bromine oxide 217~244,257f~ 277,289,294,336f~ 357
BrO flame emission spectra of rare earth elements
excess flame radicals, H, OH, 0, N 2 , CO 2 , 387
H 2 0. . . . . . . 8 flame emission spectrometry. . . . . .48, 58
role of. . . . . . 28 flame ionization detector, see sensitized flame
excitation, see also overexcitation detector
of atoms . . . 526 flame monitors, see monitors
of metal vapor. 38 flame photometer, see Boon, Brody-Chaney,
exclusive OR . . .167-169 Driigerwerk
execution of the method of flame photo- flame photometry, agricultural applications
metry in biology and medicine . . . . 489 431
extraction. . . . . . . . . 63-66, 496 in biology and medicine. . . . . 479
see also solvent extraction elements which can be determined. 431
extraterrestrial soil analysis . . 264,289 ionic species. . . . . . . . . 33
europium . . . . . 382,392,572 molecular metal species. . . . 24
evaporation effects . 514 flame spectroscopy, bibliography. 651
Evenson cavity . . . . . 54,612 early work in, . . 182ff
flame speeds. . . . . . . 546
flame temperature . . . . 58, 545-546, 597
F flame thermionic detector . . . . . 267
flicker, see noise
flip-flop. . . . . . . . . .162,164,174
Fe absorption, with a continuum source. 422 fluctuation, see noise
with a line source. . . . . 424, 574 fluctuational detection limit 182
Fe emission spectrum of a low-pressure fluctuation bands. . . . . 194
oxyacetylen flame . . . . . . . 417 fluorescence power efficiency. 604
feedback . . . . . , .147,149,151,179 fluorine, atomic absorption spectroscopy
fertilizers, analysis of . . . . . 473 b. . . . . . . ll~~2
filters. . . . . . . . . . .539-540 Beilstein test for . .322, 343
flame, air-acetylene. . .380,383,387 detection of. . . .320, 323
desolvation of the spray in the 13 detection limit of. .322, 323
experimental information. . . . . . 412 determination of. . . 321ff
fuel-rich oxyacetylene.382, 384, 387, 389, 392 electric discharges for. . . 323
laminar. . . . . . . . . . . 614 flames of. .276,279,282,283,321,328,354
laminar premixed . . . . . . . . . 6 flame spectra of . . . . 320f
as light source. . . . . .534, 572, 583, 595 gas chromatography for. 322
low-pressure oxyacetylene. . . . . . 411 indirect determination of 322
as means of atomization interferences on . . . . 322
536-539,545-548,597-598 microwave discharge for. .228,323
metal vapour as a component of the. . 12 monitor for. . . .322,331
oxyacetylene. . . . . . . . . . .380, 383 free-atom formation . . 382
oxyhydrogen . . . . . . . . 379,381,392 Freon, detection of. 324, 336f, 350
premixed fuel-rich oxyacetylene 389 frequency divider . .162, 172
premixed oxyacetylene . . 387 frequency response. 148
seeded. . . . . . . .416,422 furnace. . . . 59
turbulent. . . . . . 614 fuel gases. . . . . .537-538
turbulent un-premixed 7 fuel-rich flame. . . 66
flame cells. . . . 613 fuel-rich oxyacetylene flame .
flame colorimetry . 202ff 382,384,387,389,392
flame emission. 47 fuel-rich reducing flames . . . . . . 383
sensitivity. . . 62 Fuwa tube . . . . . . . .275,296,308,319
762 SUBJECT INDEX
G H
Gain stability. . . .146,149 Hafnium, in indirect determination of fluor-
gain-bandwidth product. . . 149 ine. . . . . . . . . . . . 322
gallium . . . . . . . 451,572 halide meter. . . . . . . .331,350
gas chromatographic detectors, see Bei!- halogens, Beilstein test for. . . 332ff
stein detector, Brody-Chaney burner, direct- flame spectroscopy of. . . . 320ff
current discharge, flame emission detector, leak detector for . . 332, 333, 336ff, 340ff
microwave discharge, sensitized detectors helium, atomic absorption spectroscopy
gas chromatographic determination of, arse- for. . . . . . . . . . . 357
nic. . . . . . . . .271,275 flame emission detector for. 357
carbon. . . . . . . . . 216ff microwave discharge for. . 357
chlorine . .323, 336ff, 340, 344 helium-glow discharge 58
chromium. 275 Hell burner . . . . . . 213,227,275,308,319
fluorine. 322 hexadecimal number . 173
iodine . 356 high-brightness lamp. 53
nitrogen .234f, 237f high-dispersion instrument . . 59
oxygen. . . . 277 high-frequency excited lamps. . 54, 534, 595
phosphorus . . . . .244, 257, 260ff, 267f high-intensity hollow-cathode lamps
rhodium . . . . . . . . . . . 275 533, 595. 646
sulfur . . .257,264,289, 290ff, 294,296 high-precision measurement. . . . .• 70
titanium. ........ 275 high-resolving monochromator. . . . . 60
zirconium. . . . . . . . . . . . 275 history of flame spectroscopy 182ff; see also
gas-stabilized arc, see plasma jet generation gap
gates, AND. .165-166,172,177 HNO, dissociation energy of . . . . . 251
logic. . .162, 165 spectrum of. . . . . . . . . . . . 231
NAND. 169 hollow-cathode, a-c and pulsed operation
NOR 169 638-640, 645
OR .165-167,177 basic types . . 646
pulse. . .162,163-165,174,177 cathodes . .628-632
generation gap in spectroscopy. 182f, 239,279 cleanup. . . . 640
Geoffroy's test, see boron, alcohol test for current limits . . 635
Giuffrida detector 267, 331; see also sensitized effect of bandpass .642-643
flame detectors effect of current . .636, 640
glyceryl borate. . . . . . . . . . 200 effect of line width on absorption. . . 641
graphite crucible. . . . . . . .535,595 electrical characteristics. .633, 634, 639
graphite-tube resistance furnace 59 envelope . . . . . . . . . . . 627
grating, aspherical. . 110 exhaust. . . . . . . . . . . . 640
blaze and efficiency. 96 gas fill, type and pressure .628,632-633
diffraction . . . . 95 intensity, a-c and pulsed. .639, 645
free spectral range . 95 intensity during warmup. . . .636-638
ghosts and satellites. 97 interferences . . . . . .632,641
holographic, see photographic life. . . . . . . . . .631,635-640
mountings . 102 line width of copper. . . . 641
Merton. . . 97 manufacturers, list of . .648-649
multipartite. 95 multi-element types. . . . 648
photographic 97 power supply requirements .634-635
plane. . . 99, 100 signal-to-noise ratio . . .642-644
reflection. . 99 single elementtypes. . . .647-648
replica. . . 98 windows, transmission of .627-628, 630
resolving power 97 various elements. . . . . . .642-643
spherical. . . 97,100 hollow-cathode discharge lamps
transmission. . 98 53,531-534,559,595,609,741
with curved grooves .95,97 HPO, application of . . . . • • . . . 257ff
SUBJECT INDEX 763
dissociation energy of. . . . . . . . 251 8-hydroxyquinoline. • 67

excitation of. . . . . • .240f, 248, 250ff
identity of. . . .239, 247f I
isotope effect in . . 248 IF, spectrum of . . . . . 354
quenching of . . . 250f ilIumination,ofspectrometer. . • 105
radiance of . . .248, 250 for astigm. instruments. . .108,110
spectrum of . .239ff, 245ff, 255 for stigmaticinstr. . • . . 106
structure of . 248 imidogen (NH), dissociation energy of. . 251
HS, see hydrogen sulfide (HS) in indirect detection of fluorine . . . . 323
HSe . . . . . . . . . . . . 296 spectrum of. . . . . . .186f. 228ff
HTe, spectrum of. . . . . . . 309 inclusive OR. . . . . . . 167
hydrocarbons, detection of, by flame photo- indirect flame spectroscopy . . . 181
metry. . . . . . . . . . . . . 218 for arsenic. . . . . . . 275
hydrocarbon flames, overemission in . . 185f atomic absorption .182,227,235,266,322
hydrocarbon flame bands, Vaidya's . . 215f 570,572,579,582
hydrogen, atomic 187, 250ff, 281,284, 286f, for boron . . . . 212
determination of. . . 187 for bromine. . . . 352,353
electric discharges for. . 188 for carbon .. . . . . 218
flame spectroscopy for . . 186ff for chlorine . 325, 344f, 349
indirect determination of 188 for fluorine . 322
hydrogen bromide, spectrum of. 351 for hydrogen 188
hydrogen chloride, formation of in flame, 328 for iodine . . 356
spectrum of. . . . . . . . . 324 for nitrogen . 233,235f
hydrogen flame, argon-diluted, see argon- for oxygen . 277
hydrogen flame for phosphorus 266
oxygen-, see oxyhydrogen flame for selenium. 307
radiance of, 193,248,250, 254f, 298, 305, 316 for silicon. . 227
hydrogen flame (cool), arsenic in . . . . 275 for sulfur . . .295,296
phosphorus in 239-252; see also HPO for tellurium. . . 319
selenium in . . . . .281,297,301,303,308 indirect methods of determination of ele-
silicon in . . . . . . . . . . . . . 219f ments . . . . .570,572,578,579,581,582
sulfur in .252, 279-284, 286f, 290ff, 294ff indium. . . . . . . . . . . . . 451,573
tellurium in.. . . . . . 309, 312ff as sensitizer, see indium burner
temperature of. . . 247f, 250,282,283,286 indium bromide (InBr), spectrum of. . . 352
tin in. . . . . . . .185,218 indium burner, for bromine . . . . .352,353
hydrogen-free flames. 187 for chlorine . . . . . 329, 331, 340f, 344ff
hydrogen lamp, radiance of 186 for iodine. . . . . . . . . . . .355,356
hydrogen selenide (HSe). 296 indium chloride (InCI), for detecting chlorine
hydrogen sulfide (SH), dissociation energy 340f,344f
of. . . . . . 286 spectrum of . . . . . . . 329, 345, 346ff
formation of. . . . . . . .279, 286 indium iodide (InI), spectrum of. .355,356
spectrum of. . . . . . . 278f, 286 induction plasma torch, for arsenic 276
hydrogen sulfide (H 2 S), combustion of for boron. . 213
279-281, 286f, 288 for nitrogen. . 238
dissociation energy of. 286 for oxygen . . 278
flame spectrum of . . . . . . . . 279 for phosphorus 268
hydrogen telluride (HTe) . . . . . . 309 for silicon. . . 228
hydroxyl (OH), for carbon determination 218 inert gases, see noble gases
determination of. . . . 187 inhomogeneity of the starting material. 491
for oxygen determination 277 inner cone, see reaction zone
in phosphorus excitation 251f insecticides, see pesticides
spectrum of. . . . 186f, 230, 277 instrumentation, electronic . .145-180
in sulfur excitation. . . . . . 252,287 integrated system for measuring absorp-
764 SUBJECT INDEX
tion . . . . . . . . . . . . . .542, 563 iron . . • . • • • • .441,462,470,501, 574

integration . . . . 70,150,152,161,173,179 for detecting halogens. . . . . . 340f
intensity, of atomic fluorescence . . 600 in indirect determination of iodine 356
spectrophotometric. . . . . . . .192, 223 overexcitation of. . . . . . . . 184
interconal zone . . . . . . . . . . . 384 isopropanol, flame determination of. 218
interference, chemical. 539,555-557,573,574, isotopes, determination of. .530,535,575,584
575,577,579,580,582,583 isotope shift, of boron. 195
due to chemical reaction with other sub- of phosphorus. 248
stances. . . • . . . . . . . . . . 489 of selenium . . 301
excitation. . . . . . . . . . . . . 552 isotopic analysis . 187
ionization 33ff, 552-555, 568, 570, 572, 579,
580, 582, 598 K
non-specific. . . . . . . . . 617 Karmen detector.. . 267,331, 338f, 350
due to physical reaction with other sub- Karmen-Giuffrida detector 267, 329; see also
stances. 489 sensitized flame detectors
reducing . . • . . .509 kerosene . . . 66
specific. . . . • . 617 ketones . . . . . . . . . 63
spectral or radiation .551,598,616 Kniseley burner
with zero level. . . 510 185,208,226,271,272,274,317,318
intermediate standards 506 krypton, atomic absorption spectroscopy
intermediate zone . . 7 for. . . . . . . . • . . . . . 357
internal standardization. 74
10, spectrum of . . . • 353f L
iodine atomic absorption spectroscopy for 356 Laminar flames . . . . 614
Beilstein test for. . . . . . . .332f, 334ff laminar premixed flame. . 6, 539
continuum of . . . . . . • . . . . 354 LaO. . . • . . • . . .380, 382
detection of. . . .334ff, 342, 350, 353, 355f laser, for vaporization of samples. 596
detection limit of. .342, 344, 355, 356 laser spectroscopy, for boron. . . 213
determination of. .355,356 for carbon. . . . . . 219
electric discharges for. 356 lead . . . . . . . . . . . 501,574
flame spectra of . . • 353f overexcitation of. . . . . . . 184
gas chromatography for. 356 leak detection. .324,331,332, 336f, 338f, 350
indirect determination of 356 lens collimator. . . . . .. 87
linearity of . . . . . . 356 light choppers . .156,157,159,160
metallic band spectra of. 354f light guide. . . 59,274
sensitized detectors for . 350, 355f light sources. . . . . . .531, 595
iodine (1 2), spectrum of. . 354 light trap. . . . . . . .• 60
iodine fluoride (IF), spectrum of 354 limits of detection, see also detection limits
iodine oxide (10), excitation of. 354 545,605,616
for iodine determination. 355 linearity . . . . . . . . . 148
spectrum of. . . . . . . . 353f line-to-background ratio 59
ion exchange . . . . . . . . 497 line-width. . . . . . . . . .527,530
ionic species in flame photometry. 33 lithium. . . . .73,75,447,460,469,501,575
ionization. . . . . . . . 392 lock-in amplifiers. .150,156
see also chemiionization logic circuits. . . . . .161-170
degree of . . . . . 34 logic gates. . . • . .162, 165
in flames, extent of . .552-555, 582, 584 logicinversion. .162,167,172
of metal species 33 logic "ONE" . .162,165,167
testing partial. . . . . . . .. 36 logic "ZERO" .162,165,167
ionization buffers . . . . . . .. 73 long-path slot burner. . . . . 392
ionization detector, see sensitized flame ioni- long-tube technique 536-537,557,569,576,583
zation detector low-dispersion instrument. . . 59
ionization effects. . . . . . . . . . . 513 low-pressure oxyacetylene flame . . . . 411
SUBJECT INDEX 765
L'vov . . . • • . . . • . . . . 59 mixing chamber. . . • . . . . . . . 57

L'vov furnace, see graphite crucible molecular absorption, see background effects
in flame . . . . . .
M molecular absorption flame spectroscopy,
for nitrogen. . · . 235
Magnesium . . 61,443,454,457,466,500,575 for sulfur . . . · . 296
in indirect determination of fluorine. . 322 molecular bands . .414,419
magnesium bromide (MgBr), spectrum of 352 molybdenum . . 383,577
magnesium chloride (MgCI), spectrum of 328f flame color of . · . 201
magnesium fluoride (MgF), spectrum in indirect determination of silicon · • 227
of . . . . . . . . . . . . . . . 320,321 monitors, see also sensitized flame detectors
magnesium iodide (MgI), spectrum of. . 355 for boron . . 212
major elements, determination. . . .437,466 for bromine. 352
manganese, overexcitation of calibration of 294
184,449,450,462,470,472 for carbon . 217f
mass-action-Iaw. . . . 25 for chlorine . .336f, 338f, 344ff, 349, 350
mathematical operations . . . . . . . 150 for fluorine . .322,331
matrix effect. . . • . . . . . . . . . 64 for nitrogen. • . • . . . . . 234f,238
measuring techniques, see calibration and for phosphorus
measuring techniques 244,246,247,257,260,262,264
mechanism of atomic fluorescence . . . 599 sample feed for. . . . . . • . . . 293f
medicine. . . . . . . . . . . . . . 479 for sulfur. .• .257,264,289,290, 292ff
Melpar flame photometer, see Brody-Chaney monochromators. 59,102,114,539-540
burner requirements . 482
memory circuit. . . . . . .162,164 monoxide bands. 380
mercury . . . . . . . . 451,576 monoxide band systems. 382
metal species, ionization of. 33 monoxide molecules . .382, 386
metal vapour arc lamps. . 609 MoO. . . . . . . . 383
metal vapor as a component of the flame. 12 multielement analysis. .532,541,543,596
methanol, flame detection of. . . . . . 218 multiple reflection cell. . . . . . . 414
methine, see CH multiple pass systems . 112-114,561-562
methyl borate. . . . . . .196,198, 201ff multiple standard addition. 73
methyl iodide flame bands. 353 multiplier phototubes.. . . . . . . 62
methyl isobutyl ketone 64
MgO . . . . . . . . . . 383 N
micro methods. . . . . . 508
microwave discharge, as arsenic lamp 275 NAND gate. . . 169
for bromine. 353 NC, see cyanogen
for carbon . 218 NdO . . . . . . 382
for chlorine. 350 nebulization and nebulizers
for fluorine . 323 536-537,543,548-549,596
for helium .. 357 nebulizer, terminology of 185
for hydrogen 188 nebulizer-burner. . . . 53
for iodine . . 356 total-consumption. . 6
for nitrogen. 238 nebulizer-burner system. • 4, 55
for oxygen . 278 negative flame emission detector
for phosphorus 268 218,277,332,357
as selenium lamp. 308 neodyntium . . . . . . . . . . . 392,577
for silicon. . . . 228 neon, atomic absorption spectroscopy for 357
for sulfur . . . . 296 radiofrequency plasma torch for . • . 357
microwave-excited lamps, see high-frequency NH, see imidogen
excited lamps NH 2 , see amidogen
mirror collimator • • • . • • . • •. 88 NHO. . . . . . . . . . . . • . .231,251
766 SUBJECT INDEX
nickel . . . . . • . • • • • . . 470,577 number representation • • • • • • .172-173

for detection of halogens • . 332,340f, 344
nitrate, flame determination of. . . • . 236 o
nitric oxide (NO), absorption spectrum of 235
dissociation energy of. 251 OH, see hydroxyl
spectrum of. .229ff, 285 OHbands. . . . • . 414
nitrogen . . . . . . . 503 on-line computers • . . . . . . .177-179
afterglow of. . . . . 231 operating personnel, requirements · • 482
atmospheric in flames. 233 operation costs. . • . · . 485
atomic absorption spectroscopy for. 235f operational amplifier. . .147, lSI, 153, 154
Beilstein test for . . . . . . 233f, 343 optics . . . • . . • . 53,59,79-140
detection of. . . . . . . . . . 232 and monochromator . 606
detection limit of. .232, 233, 235ff, 238 optimization. . • . . . 53
determination of. . 232ff of experimental conditions. 606
electric discharges for. . . . 238 ORgate . . . . • . • . . .165-167, 177
flame spectrum of . . . . . 228ff organic acids . . . • . • . 63
indirect determination of .233, 235f organic compounds, see carbon, determina-
interferences on • . . . .235, 238 tion of
organic, detection of . .233f, 237f organic ligands . 67
radiance of . . • . . .232f, 236f organic samples . 64
sensitized detectors for 237f organic solvents . 63
nitrogen dioxide (N02)' continuum of. 231 oscillator strengths, ultraviolet. 186
determination of. • . . . . . .• 238 osmium, overexcitation of. 184
nitrogen hydride (NH), see imidogen osramlamp . . . 53
nitrogen hydride (NH 2), see amidogen outer cone . . • 7
nitrogen trifluoride-hydrogen flame.. 276 overatomization . .185,186
nitrous oxide, flame determination of . 233 overemission . . · . 185
nitrous oxide-acetylene flame overexcitation 66, 184ft', 272; see also chemi-
186,213,227,235,266,322,387,392,538 luminescence
N-nitrophenylhydroxylamine 67 overionization. • . . . • • . . . 35,185f
NO, see nitric oxide oxide reduction in flames . • • . . 186
noble gases . . • . . • • . 181, 356f oxyacetylene burner, premixed. . . 384
atomic absorption spectroscopy for. 357 oxyacetylene flame. .380, 383
electric discharges for. • • . . . . . 357 carbon in. . . . . 214
negative flame emission detector for. . 357 fuel-rich • .• .382,384,387,389,392
noise, electronic. . . . .146,165 premixed 185; see also Kniseley burner
equivalent bandwidth. . . . 155-156 radiance of . . . . . . .193,284,305
random. . . . • 155 rich . . . 222-227, 256, 283f, 294, 305, 306
of sprayer-burner. . .192,223,289 spectrum of. . . • . . . • . . • . 215
thermal. . . . . . 155 oxycyanogen flame, see cyanogen flame
non-aqueous solvents. 63 oxygen, atomic, determination of. 354
non-equilibrium dissociation. 28 detection limit of. . • 277
non-equilibrium ionization . 35 flame determination of • 276f
non-flame cells. . . . . . . . 59, 535, 615 flame spectra of . . . • 277
non-linear function. . . . . . . .154, 178 indirect determination of 277f
non-metals, atomic absorption by. . .544-545 induction torch for. . . 278
flame spectroscopy of. . . . • . . . 181ff microwave discharge for. 278
indirect determination of .570, 572, 579, 582 oxygen-free flames . 276f
non-specific effects. . • . 511 oxygen-sheath. . . 56,244
non-specific interferences • 617 oxyhydrogen flame. .379, 382, 392
non-thermal excitation, testing. 42 radiance of . 189, 192f
NOR gate. . . . . . 169 reversed .• .271,274
null-point instrument. . . . . 542 spectrum of . 187
SUBJECT INDEX 767
P dissociation energy of. .251,256

excitation energy of. 251f
Palladium, in tellurium spectrum. . . • 315 in HPO excitation . 250f
Pb emission spectrum of a low-pressure in phosphorus glow. 253
oxyacetylene flame. . . . . 419 radiance of . . . . .252f, 254f
pentaborane, combustion of. 195 spectrum of. • . . .251, 252ff
monitor for. . . . . . . 212 phosphorus oxyhydride, see HPO
percentual detection limit. . 182 phosphorus sulfide (PS), band spectrum
perchlorate, indirect determination of . 349 of. . . . . . . . .268,296
perchloryl fluoride flames. . . . . .321,329 photosensitive surface. . . . . . 62
permanganate, in aphanoscope. . . . . 203 phototube. . . . . . . . . . . 62
pesticides, analysis of, for chlorine physical reaction with other substances,
340f, 343, 348f interference . 489
for phosphorous. .257,258ff, 264,267,268 plants . . . . . 431
for sulfur. . . . .282, 289, 290ff analysis of. . • . 452
pharoid, collimator. . ••• 89,106 plasmas. . . . .536, 596
PH, see phosphorus hydride plasma arcs, bibliography 748
PHO, see HPO plasma jet, plasma torch. 182
phosphate, indirect determination of 266 for boron. . . . . . . 213
phosphine, continuum of 255 for carbon. . . . . . . 219
determination of. 268 platinum chloride, flame spectrum of 184
flame of. . . . . . . .239,253, 255 polychromator. . . . • . . . . . 104
phosphorus. • . . . . . . .460, 503 potassium . 73, 75, 443, 454, 466, 473, 498, 579
atomic absorption spectroscopy for 266f, 578 power requirements for electrodeless dischar-
atomic spectrum of. . . • . . . .256,260 ge tubes. . . . . . 611
burners for . 241,244, 246f, 257ff, 264,282 praseodymium filter. . . . . . . . . 204
chemiluminescence of, see HPO precipitation reactions . . . . . . . 497
cold flame of. . .240,247, 278, 253 preCISIon. . . . . . . 47,52,69,480,484
combustion of. . . . . . . . . . . 255 pre-concentration techniques. 64
continuum of . "premix" burner. . . . • . . . . . 57
238f, 255f, 257, 258, 260, 262, 266 premixed oxyacetylene burner . . . . 384
detection of. . • . . • . . . . . . 256f premixed fuel-rich oxyacetylene flame. 389
detection limit of premixed oxyacetylene flame. . . . . 387
254f, 256, 257, 259, 261, 263, 264,268 preparation, and handling of samples .453, 564
determination of. . . . . 257ff of reference and blank solutions . 504
electric discharges fOT. . . 268 pressure broadening . . 527
excitation energy of. • .256, 266 primary reaction zonc. .6, 384
flame spectrum of . . . . 238ff prism, dispersion. . . 92
gas chromatography for. .257, 260ff, 267f liquid. . . . . . . 95
Geissler spectrum of . • 240 with curved surfaces .82,93, 117, 118
green flame of see HPO with plane surfaces . • . . . 89,106
indirect determination of 266 properties of the starting material in medical
interferences on 257,259, 261, 263, 264ff, 267 and biological investigations. . . • . 486
linearity of PS, see phosphorus sulfide
250,251,256,257,259,261,263-266 pulse gate. . • . . . .162, 163-165, 174, 177
monitor for see monitors pulsed operation of hollow-cathode lamps 534
phosphorescence of. . . .240,241,253,255 1-(2-pyridylazo)-2-naphtol. . . . • . . 67
radiance of . . . . . .248, 250, 252f, 254f
sensitized detectors for 267f
Q
phosphorus hydride (PH) . . . . . . 247f
dissociation energy of. . . . . . . 251 Quartz, absorption tube . • . . . 56
phosphorus oxide (PO), applications of Quenching, in argon-acetylene flame 272
258,260,262,266 in argon-hydrogen flame. . • . . 185
768 SUBJECT INDEX
quinolines, detection of. . . . . . .233, 335 rubidium sulfate, for sensitized nitrogen de-
tector. . . . . . . . . . . . 238
R S
Radiance, measurement of. 189 S2, see sulfur (S2)
ultraviolet. . . . . . . 186 Saha equation 552
units of. . . . . . . . .189,223 Saha's law . . . 34
radiofrequency plasma torch. 182, 219, 238, 357 sample modulation. .158-160,179
random error . . . . 48 sample preparation. .432, 453, 489, 490
random noise . . . . 155 sample, taking and preserving . . 490
rare earth band spectra 382 sample pumping. . . . . . . . 317
rare earth elements. . 63 sample vaporization . . . . . . . .345,348
absorption spectra sampling boat,. . . . . . 275f, 308,319,596
392, 570-575, 579, 580, 582-584 SC, see carbon monosulfide
detection limits . . . . . . . . . • 392 scandium. . . . . . . . . . . . 385, 580
emission spectra. . . . . . . . . . 393 scale expansion . . . . . . 71,562-563,565
emission spectrometric detection limits 388 scattering, see background effects in flame
flame atomic spectra . 387 Se2, see selenium (Se2)
flame emission spectra . . . . . . . 387 SeC, see carbon selenide (CSe)
rare earth monoxides. . . . . . . . . 382 secondary combustion or reaction zone .7,384
rare earth monoxide band emission spectra seeded flames . . . . . . . . . . .416,422
380,381 SeH . . . . . . . . . . . . . . . . 296
rare earth monoxide band systems . . . 382 selective modulated hollow-cathode lamps
rare earth monoxide dissociation equilibrium 534,595
382 selectivity. . . . . . . . . . . . . . 616
rare gases, see noble gases selenium absorption spectrum of. . 297, 302f
reaction zone, overexcitation in atomic absorption spectroscopy for
41f, 185f, 196,269,317 185,308,580
readout systems . .541-542,596 atomic fluorescence spectroscopy for 308,622
recording system. 53 atomic spectrum of. . . . . 305, 306f 308
rectifier 154 chemiluminescence of. . . . . . . . 306
red feather . . . 186 combustion of. 297,298,303, 304f, 306
reducing flames, fuel-rich 383 continuum of . . .297,298,301,303,305
reference solution, preparation. .504, 506 detection of. . . . • . . . . 296
refrigerant leak detector. . . .324, 336f, 338f detection limit of. 298, 305, 306f, 308
requirements to be met by the monochromator determination of. . . . . . . 308
482 flame spectra of . . . . . . . 296ff
requirements to be met by the operating per- Geissler spectrum of . .299,300, 302f, 305
sonnel . . . . . . . . . . . . . . 482 indirect determination of . . . . . . 307
resolution. . . . . . . . . . . . . . 92 in indirect determination of iodine . . 356
resolving power . . . . . . . . . . . 92 linearity of . . . . . . . . .298, 306, 308
resonance broadening. . . . . . 527 radiance of. . . . . . . . .298, 305, 406
resonance detection (resonance monochro- radiofrequency discharge for. . . . . 300f
mators) spectrum of. . . . . . . .298, 299, 30lff
538,540-541,570,572,575,576,578,579,581 selenium (Se2), absorption spectrum of . 30lff
reversed oxyhydrogen flame. . . .271,274 excitation of. . . . . . . . . . . . 296
rhenium, flame color of. . . . . 201 spectrum of. . . . . . . .298, 299, 30lff
rhodium, gas chromatography for. 275 selenium carbide (SeC), spectrum of. . . 296f
rocks. . . . . . . . . . 431 selenium dioxide, flames of . . 304f, 306
analysis of. . . . . . . 437 spectrum of. . . . . . . . .299,301,306
role of excess flame radicals 28 selenium hydride (SeH). . . . . . . . 296
Rowland circle 101 selenium oxide (SeQ), excitation of. . . 296
rubidium. • . • . 75, 447, 460, 469, 502, 580 isotope shift in. . . . . . . . . .299, 301
SUBJECT INDEX 769
spectrum of . .298ff, 303 detection limit of. . . . . . . • .223-228

self-reversal. 53 determination of . . . . . . . . 225ff
Sell's lamp . . . . . 281 electric discharges for • . . 228
sensitivity. . . .47,52,60,61 excitation of . . . . . .223, 225
in determination of metals. . . .528-529 flame spectrum of . . . . . . 219ff
sensitized electrical detectors . . 331f, 350,353 indirect determination of . . . 227
sensitized flame detectors, mechanism of. 268 radianc&of . . . . . . . 22lf, 223, 224
sensitivity of. . . . . . • . . . . . 267 spark-in-flame for . . . 228
terminology for . . . . . . . .267, 329ff silicon oxide (SiO), dissociation of 225
sensitized flame emission detectors . 329ff, 332 dissodation energy of. . . . . 225
for boron. . 218 flame spectrum of . . . . . . 22lf
for bromine. . . . . . . . . . . . 352f silver, in indirect bromine determination. 353
for chlorine in indirect chlorine determination. 349
329f, 331ff, 334ff, 340ff, 344ff in indirect iodine determination. 356
for iodine. . 355f overexcitation of. . . .184,185
negative . . . . . . . . . . . . 332 single-beam systems . . . . . . 542
for phosphorus . . . . . . . . . . 266 single standard addition. . . . . 73
sensitized flame ionization detectors slit illumination, see illumination
267f, 329, 330, 33lf slit widening. 223
for arsenic. . . . . . 276 slit width. . . .59,90
for bromine. . . . 350,353 optimal. . . . 223
for chlorine. .331,344,350 slurry spraying. .187,295
for iodine . . · .350,356 SO, see sulfur monoxide
for nitrogen . · 237f,330 Sodium . . 61,75,443,454,455,466,499,581
for phosphorus · . . 267f analysis of, for oxygen . . . . 277f
sensitizer. . . . .329, 330ff emission of, in sensitized flame detectors
gaseous. . . . .330,331 218,266
temperature of. 342 flame monitor for . . . . 212
SeO, see selenium oxide in indirect chlorine determination. 349
separated flames 597 as sensitizer for halogens
sequences. . . . . . . .161-162,176 338f, 344, 345, 350, 352f, 355f
SR, see hydrogen sulfide (RS) suppression of, by CuCI. . . . . 327
SH 2 , see hydrogen sulfide (H 2 S) thermionic detector. . . . . .267,329
shape of analytical curves . . . 604 sodium diethy1dithiocarbamate. 67
sharp-line sources . . . . . . . .530,558 sodium tetraphenylborate . 67
sheath burner. . . . . . . . . 55,244 soils. . . . . . . . . . 431
sheated sprayer-burner, for boron. 205 analysis of. . . . . . . 436
for carbon monoxide flame 187 solar-blind photomultiplier 595
for cyanogen flame. 187 solid spraying. . . . . . .187,292
for nitrogen. . 234 solution concentration . . . . 607
for phosphorus 244f,255 solvent extraction 63-66, 563-564,569,571,573,
for silicon. . . · .221-227 574,576,577,581,588
for sulfur . . . .244,283-285,290,294 solvents, non-aqueous. .63,549-550,574
signal averaging . .153,158 source . . . . . . . 53
signal-to-noise ratio 148 of excitation. . . . · . 608
silane flame. . . . 221 SP, see phosphorus sulfide
silicon . . . . . . 503 spark-in-flame. . . . .213,228
atomic absorption spectroscopy for specific effects. . . · . 512
225,227,581 specific interferences · . 617
atomic spectrum of. . . 223ff specificity factor. . .238,257,289
chemiluminescence of. 225 spectra, beauty of. • I83e
continuum of 219 spectral interferences . 616
in detection of fluorine 323 spectral lines used for the analysis of
770 SUBJECT INDEX
particular elements. . . . 497 strontium. . . . .448,461,469,470,500,582

spectral vapour lamps. . • . 531 in indirect determination of sulfur. . . 295
spectrocolorimetry, flame . . 202ff sulfuric acid, detection of . . . .279,280,292
spectrometer, optical system astigmatic sulfur monoxide (SO), continuum of. . . 288
.
104,108 dissociation energy of. . . . . . . . 286
Bunsen . • • 81,83,93, 103 spectrum of. . . . . . . . .278, 279, 286
Callier. . ... .. 82 sulfur hydride (SH), see hydrogen sulfide (HS)
Czemy-turner .81,83,100, 104, 119 suspension spraying . . . . . . . .187,295
Desvignes . . . . . 82,118 sulfur (Sz), absorption spectrum of. . . 281
Ebert-Fastie . .84,100,103,121 applications of. . . . . . .288, 289ff, 294f
F6ry. . . . . . .92,94,116,117 burners for . . . . 282f, 286,289,292, 294
grazing incidence. . . . 85,100,101 chemiluminescence of. . . . 252, 284, 286f
Littrow. . . . .80, 81, 83, 95, 100, 116 dissociation energy of. . . . . . .286, 287
Monk-Gillieson 84,100,104 excitation of. . . . . 252,284, 286f, 295
multiple pass . 115 formation of. . . . . . 286f
Paschen-Runge 84 Geissler spectrum of . . . . . .280, 281
Rowland. . . . 84,100 identification of.. . . . . . .279,283
Seya-Namioka . 85,100 linearity of emission of .286f, 288f, 291, 293
stigmatic. . . . 104 separation of, from HPO emission
Wadsworth . 85, 100, 104 252,282,287,289
precision of . . . . . 183 spectrum of. . . . . . . . . .278ff, 283
spectrophotometry, atomic fluorescence sulfur carbide (SC), see carbon monosulflde
451, 599-623 sulfur dioxide, absorption spectrum of 278, 296
spectroscopy, visual . . . . . • . . . 184 afterglow of. . . . . . . . . . . . 288
spectroscopic equipment . . . 79-144,413 dissociation energy of. . . . . . . . 286
spectrometry, definition of. . . . . . . 205 linearity of . . . 286,287, 288f, 291,293
spray chamber. . . .537-538, 543, 549 monitoring of . . .289, 290, 292ff
heated . . . . . . . . . . .549, 570, 583 precision for. . .289,291,293,294
spraying efficiency. . . . . . . . . 9 radiance of. . . .284, 285
sprayer-burner, for carbon monoxide . 187 reactions ofin flames. .283f, 286f
for cyanogen . . . . . . . . . . 187 determination of. . . .286, 288ff
name of. . . . . . . . . . . . . 185 electric discharges for. . 296
premixing 185; see Kniseley burner. flame spectra of . . . . . . 278ff
sheated 187,205,221-226,234, 244f, 255, gas chromatography for.
283-285, 290, 294 257,264,289,290ff, 294,296
sprayer, definition of. . . • . . . . . 185 indirect determination of . . . . .295, 296
sputtering, see cathodic sputtering interferences on . . . . .289,291,293,295
synchronous detection .150, 156, 158-160, 178 sulfur, see also sulfur (Sz) 458
stabilization of electrodeless discharge tubes atomic absorption spectroscopy for 296, 582
613 atomic spectrum of. . • . . . . . . 296
stainless steel . . . . . . . . . . . . 57 blue flame of see sulfur (Sz)
starting material, inhomogeneity. . . . 492 combustion of . .279-281,288
variation of the composition with time. 492 continuum of. . . 288
stepwise line atomic fluorescence. . . . 600 detection of. . . . . . . . 280
standard addition method . . 73-74, 565-566 detection limit of.
strontium iodide (SrI), spectrum of. . . 355 279-281,284,289,291-293,295,296
strontium chloride (SrCl), for chlorine detec- sulfate, determination of. .295, 502
tion . . . . . . . . . • . . . . . 328 subtraction . . . . . . 151
spectrum of. . . . . . . . . . . . 328f surface tension. . . . . . 63,487
strontium fluoride (Srp), for determination surface-active agents . . 63
of fluorine. . . . . . . . . . . .321,322 suprathermal chemiluminescence 41
spectrum of. . . . . . . . . . .320, 321 Swan bands . . .183, 214f, 216,219,229, 323f
strontium bromide (SrBr), spectrum of.. 352
sUBmcr INDEX 771
T overexcitation of. • . . . . . 184-186,218

titanium, gas chromatography for. . . . 275
Taking and preserving the sample. 490 in indirect determination of ammonium 235
tapered cavity. . . . • 612 in indirect determination offluorine. • 322
Te2, see tellurium (fe2) total-consumption burner. • . . . 55,614
Tee. . . . . . . . . 309 name of. . . • . . . . . . . . 185
TeH. . . . . • . . • 309 total consumption nebulizer-burner. 6
tellurium, arc spectrum of • 31Of, 315, 319 trace elements. . 447
atomic absorption spectroscopy for 319, 582 determination. . . . . . . .460,469,470
atomic fluorescence spectroscopy for320, 622 transducer . . . . . . . . • . . • • 145
atomic spectrum of. . . 315ff transition probabilities, see oscillator strengths
chemiluminescence of. . . . . . . 315f triple condenser. 108
combustion of. . . . . • . 309 tuned amplifier. . . . . . . 156
continuum of . . .309,314,315,317 turbulent flames . . . . . . 614
detection of. . • . . 309 turbulent un-premixed flame. 7
detection limit of. .316-320 turmeric test for boron 196
determination of. . • 316ff Turner's test. . . . . . .196, 200
electrodeless discharge for. 31Of,315
flame spectra of • . . . . . 308ff
Geissler spectrum of.. . .310f,312ff u
indirect determination of • • 319 UItramicro methods 508
interference on. .317,319 ultrasonic nebulization 596
ionization of. . . 316 ultrasonic sprayer . . 276
linearity of . 317f, 320 ultraviolet sources, radiance of . 186
radianceof. .315-317
tellurium (fe2)' 309,311, 314f
tellurium carbide (feC) . . . . . 309 v
tellurium dioxide, absorption spectrum of 310f
tellurium hydride (feH). • . . . . 309 Van der Smissen burner, see Drligerwerk
tellurium oxide (feO) application of. • . 317f burner
identity of. . . . . . . . . . . . . 314f vapor pressure, measurement of . . .264, 265
spectrum of. . . . . . . . . . 309ff, 316 variation of atomic concentration. . . . 602
temperature, see flame temperature variation of the composition of the starting
temperature effects 512 material with time . . . . . . 492
temperature measurements 426 visual flame spectrocolorimetry. . 202ff
terbium. . . . . . . . . 392,582 visualspectroscopy. . . . . . 184
Tesla discharge . . . . . .188,218,238 volatility . . . . . . . . . . 63
testing, incomplete desolvation. 12 volatilization, testing incomplete. 19
incomplete dissociation . 30 viscosity . . . . . . . 63, 488
incomplete volatilization 19
non-thermal excitation . 42 W
partial ionization. • . . 36
tetraphenylarsonium chloride 67 Water . . . . . 431
thallium . . . . . . . . . .449,451,583 analysis of. . . 464
2-phenoyltrifluoroacetone .64,67 cross section of. 185
thermal noise . . • . . . 155 detection of, by discharge . .188,278
thermal radiation. . . • . 38 detection of, in flame . 187
thermal radiation intensity. 40 spectrum of. . . . .186,277
thermionic flame detector . 267 water-miscible solvents . 63
thiocyanates, detection of . 234 wavelength, selection. . . . 53,61
tin, for carbon determination. 218 wavelength selectors . . .531,539
oscillator strengths of. 186 width of spectral lines, see linewidth
overatomization of. . . . 185 Will-o' -the wisp, origin of . . 253
772 SUBmCT INDEX
x z
Xenon, atomic absorption spectroscopy Zeeman scanning. . . . . 425
for . . 357 zinc . • . . . . .451,504,585
xenon arc . . . . • . . . 534 overexcitation. . . . • 184
zirconium, gas chromatography for. . . 275
y in indirect determination of ammonium
235,322
YO . . . . • . • • • • . 382 in indirect determination offluorine. • 322
ytterbium. . • • • .382, 391, 584
ytterbium, overexcitation of . · . . . 185
yttrium. • • • • . • • • • .390, 392, 584

Analytical Flame Spectroscopy Selected Topics by C. Th. J. Alkemade, R. Bleekrode, J. C. Burger, C. C. Butler, P. G. Cath, V. A. Fassel, P. T. Gilbert, W. Gillies, R. Herrmann, R. N. Kni

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Analytical Flame Spectroscopy Selected Topics by C. Th. J. Alkemade, R. Bleekrode, J. C. Burger, C. C. Butler, P. G. Cath, V. A. Fassel, P. T. Gilbert, W. Gillies, R. Herrmann, R. N. Kni

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ANALYTICAL FLAME SPECTROSCOPY

PHILIPS TECHNICAL LIBRARY

ANALYTICAL FLAME SPECTROSCOPY

C. Th. J. Alkemade, R. Bleekrode, J. C. Burger, C. C. Butler, P. G. Cath, V. A. Fassel,

© N.V. Philips' Gloeilampenfabrieken 1970

May 1969 R. Mavrodineanu

11. R. Mavrodineanu Present address: Analytical Chemistry Division

1.6.2 The degree of ionization . . . . . . . . . 34

2.5 Criteria for improvement of precision and accuracy. 69

4.2 Analog circuits. . . . . . . . . . . 146

5.3.10 Flame-emission monitoring of boron 212

5.8.4 Flame spectrophotometry of arsenic. 273

5.14.7 The Beilstein test. . . . . . . . . . . . . . 340

R. N. KNISELEY, v. A. PASSEL, C. C. BUTLER

8.4.2 Determination of the major elements: sodium, potasSIum,

9.5 Sample preparation and execytion of the method. 489

10.5.4 Calibration and measuring techniques 564

10.6.46 Rhenium 579

11.3.2Hollow cathode discharge lamps. . . . . . . 609

J. C. BURGER, W. GILLIES, G. K. YAMASAKI

Subject Index . . . . . . . . . . . . . 755

FROM SAMPLE TO SIGNAL IN EMISSION FLAME

1.2 Brief outline of the basis of emission flame photometry

1.2.1 GENERAL PRINCIPLE AND ANALYTICAL ADVANTAGES

1.2.1.1 General principle

Emission flame photometry is a method of spectrochemical analysis that is based on the

decomposition atomization l ight omission

bulizer is a measure ofthe metal concentration (e.g., in mg/l or parts-per-million, p.p.m.).

1.2.1.2 Analytical advantages

The advantages of emission flame photometry compared to chemical methods of analysis

1.2.2 THE NEBULIZER AND BURNER SYSTEM

1.2.2.1 Chamber-type nebulizer with separate burner

1.2.2.2 Total-consumption nebulizer-burner

1.2.3 THE FLAME

1.2.3.1 Laminar premixed flame

1.2.3.2 Turbulent un-premixed flame

Property Premixed flame Un-premixed flame

structure distinct zones blurred zones

1.2.3.3 Excess flame radicals

1.2.4 THE SPRAYING EFFICffiNCY (8)

increasing height in the flame (corresponding to an increased residence time of the

1.2.4.2 Experimental methods of determination

1.2.4.3 Experimental results

1.2.4.4 The metal vapor as a trace component of the flame gas

It may be interesting to compare the range of metal concentrations to be expected in the

1.3 Desolvation of spray in the flame

1.3.1 THE RATE OF DESOLVATION

1.3.2 EXPERIMENTAL METHODS FOR TESTING INCOMPLETE DESOLVATION

1.4 Volatilization of desolvated aerosol

1.4.1 THE COMPOSmON AND RATE OF VOLATILIZATION OF DESOLVATED AEROSOL PARTICLES

1.4.1.1 Particle composition

Type of compound Melting

2 MX -+ MxO v '" MgCl 2 'H 2 0 -+ MgO ... 3070 [41]

4 (MX; organ.)-M·organ .. (MgCI 2 ; EDTA)-+ Mg·EDTA ... (d) [86]

1.4.1.2 Rate of volatilization

1.4.2 EXPERIMENTAL METHODS FOR TESTING INCOMPLETE VOLATILIZATION

1.5 Dissociation of molecular metal species

1.5.1 SOME IMPORTANT MOLECULAR METAL SPECIES IN FLAME PHOTOMETRY

1.5.2 THE DEGREE OF DISSOCIATION

1.5.2.1 Equilibrium dissociation; the mass-action-law

[M] [X]/[MX] = KiT). (12)

* According to calculations performed by Dr P. J. Th. Zeegers at the Physical Laboratory,

1.5.2.2 Non-equilibrium dissociation; the role of excess flame radicals

MO + C-'>- M + CO. (15)