Handbook of Flame Spectroscopy

490 Pages·1975·12.66 MB·English

by  M. L. Parsons

B.W. Smith · M.L. Parsons
G.E. Bentley
Handbook of Flame
Spectroscopy
HANDBOOK OF
FLAME SPECTROSCOPY
HANDBOOK OF
FLAME SPECTROSCOPY
M. L. Parsons, B. W. Smith, and G. E. Bentley
Department of Chemistry
Arizona State University
Tempe, Arizona
SPRINGER SCIENCE+BUSINESS MEDIA, LLC
Library of Congress Cataloging in Publication Data
Parsons, Michael Loewen, 1940-
Handbook of flame spectroscopy.
1. Flame spectroscopy. 1. Smith, Benjamin William, 1951- joint author.
11. Bentley, Glenn Edward, joint author. III. Title.
OD96.F5P37 543' .085 75-17865
ISBN 978-1-4757-0862-2 ISBN 978-1-4757-0860-8 (eBook)
DOI 10.1007/978-1-4757-0860-8
© 1975 Springer Science+Business Media New York
Originally published by Plenum Press New York in 1975
Ali rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted,
in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
Acknowledgment
The authors would like to express their appreciation to the Ari
zona State University Computing Center for both computer time
and help in preparing the computer-generated portions of the
book.
PREFACE
Analytical flame spectroscopy is a rich and growing disci
pline, rooted in the broad fields of physics and chemistry. Its
applications abound not only in these large areas, but also thrive
in the geosciences, materials science, and clinical and biochemical
analysis. As an inevitable corollary of the field's growth, the
scientist seeking to develop a fluent expertise has been forced to
assimilate and master a rapidly increasing quantity of information.
Our guiding hope in creating the present work has therefore been to
provide the investigator with a single reference source for nearly
all the material ever likely to be required in the daily conduct
of basic or applied research.
Flame spectroscopy is not a new analytical field. It has seen
at least three major eras, in each of which much new information
was developed - the Bunsen-Kirchhoff years, the Beckman D.U. years,
and finally the atomic absorption years. In the Bunsen-Kirchhoff
era, several new elements were discovered. During the Beckman years
- nearly all the early flame emission data were taken on modified
Beckman D.U. spectrometers - trace metal analysis for the alkaline
metals and for many alkaline earth elements reached a new high (low?)
- the parts per million level. More recently, trace metal analysis
has in general achieved a new maturity with the advent of atomic
absorption analysis, which was co-discovered by C. Th. J. Alkemade
and Alan Walsh in 1955. Many elements are now analyzed in the
parts per million range, and at least several to the parts per
billion level. The next era is undoubtedly just around the corner.
Many researchers, we fear, do not appreciate the similarities
among the flame techniques, nor do they appreciate fully the dif
ferences between flames and the other, often much more energetic,
excitation sources such as the d.c. arc or the spark. The informa
tion in this volume - which has been rather painstakingly compiled,
calculated, tabulated, and critically evaluated - applies nearly
equally to all three flame spectrometric techniques.
viii PREFACE
But because one must stop somewhere within reason, the book
is in certain senses woefully incomplete. Further, the literature
itself suffers gaping holes. As an example, transition probability
data are only sporadically provided, and their improvement must be
come a higher priority among the research community active in the
field. Undoubtedly, too, we have accidentally overlooked some data
sources, and therefore hope for the forebearance of our audience,
and their aid in locating these data for future editions of the
work.
In sum then, the book, however incomplete, represents our
best efforts to bring together for the first time most of the im
portant and useful information in the field of flame spectroscopy.
I sincerely trust we have achieved a small measure of success.
CONTENTS
List of Tables ix
Chapter I BASIC INTRODUCTION 1
A. Theory and Practice 1
1. Nomenclature 1
2. Basic Atomic Theory 3
3. Basic Experimental Setup 5
4. Experimental Procedure 14
5. Standards... . . . . . 14
6. Experimental Parameter Settings 24
B. Scientific Literature of Flame Spectroscopy 27
C. Flames and Sample Cells 32
1. Flames 32
2. Non-Flame Cells 32
D. Excitation Sources 37
1. Hollow Cathode Discharge Lamps 37
2. Electrodeless Discharge Lamps 37
3. Lasers .... 38
4. Continuum Sources 38
E. Interferences 61
1. Chemical 61
2. Spectral 62
F. Figures of Merit 67
ix
x CONTENTS
Chapter II ATLAS OF SPECTRAL LINES 69
A. "Best" Analysis Lines • . • • • 69
1. Cornmon Analysis Lines Used in Atomic
Absorption Spectrometry • 70
2. Common Analysis Lines Used in Atomic
Emission Spectrometry • . 72
3. Common Analysis Lines Used in Atomic
Fluorescence Spectrometry 74
B. Experimentally Observed Transitions 76
1. Experimentally Observed Atomic Absorption
Lines in Analytical Flames 80
2. Experimentally Observed Atomic Absorption
Lines in Non-Flame Cells 131
3. Experimentally Observed Atomic
Emission Lines 153
4. Experimentally Observed Atomic
Fluorescence Lines 243
Chapter III FUNDAMENTAL INFORMATION 287
A. Fundamental Expressions . 287
B. Fundamental Constants and Data 295
1. Spectral Data • • • • 295
2. Electronic Partition Functions, Z 362
3. Percent of Atoms in the Lower Energy Levels 367
4. Ionization Potentials of the Elements 375
5. Molecular Dissociation Energies 379
6. Free Atom Fractions, the 8 Factor 396
7. Spectral Line Width Data • 405
8. Spectral Interference Data 433
9. Miscellaneous Data . • . 466
a. Selected Fundamental Constants 467
b. Selected Unit Abbreviations 469
c. Selected Energy Conversion Factors
and Equivalents • • • • • • 470
d. Selected Conversion Factors 471
e. Values of Absorbance for Percent
Absorption 475
f. Student's t-Distribution •... 478
LIST OF TABLES
I.A.l. International Union of Pure and Applied
Chemistry (IUPAC) Recommended
Classification of Methods and
Instruments • . • 2
I.A.2. General Information on Periodicity of
Resonance Transitions • • 6
I.A.3. Standard Solutions - Compounds and
Procedures 16
I.A.4. Critical Parameters for Optimization in
Flame Spectrometric Techniques 25
I.B.l. Selected Reference Works in Atomic
Spectroscopy 28
I.B.2. Common Basic Journals and Frequency of
Citation in Bibliography and
Review Articles . • • • . . 29
LB.3. Miscellaneous Supporting Library Material 31
LC.l. Flame Temperatures and References on
Temperature Measurements • • • • • • • . 33
LC.2. Mole Fraction of Major Species in
Analytical Flames • . • • 34
LD.l. Relative Intensities of Hollow Cathode
Lines (Relative to most intense
line for each element) ••••• 40
xi