An Introduction to Analytical Atomic Spectrometry

225 Pages·2005·2.35 MB·English

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An Introduction to Analytical Atomic Spectrometry
Contributing Authors:
L. Ebdon
E.H. Evans
A.S. Fisher
S.J. Hill
University of Plymouth, UK
Edited by:
E.H. Evans
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Library of Congress Cataloging-in-Publication Data
An introduction to analytical atomic spectroscopy / contributing
authors, L. Ebdon . . . [et al.]; edited by E.H. Evans.
p. cm.
Includes bibliographical references and index.
ISBN 0-471-97417-X (alk. paper). — ISBN 0-471-97418-8 (pbk.:
alk. paper)
1. Atomic spectroscopy. I. Ebdon, L. II. Evans, E. Hywel.
QD96.A8158 1998
543'.0873 — dc21 97-31697
CIP
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library
ISBN 0 471 97417 X (cloth)
ISBN 0 471 97418 8 (paper)
Typeset in 10/12 pt Palatino by Laser Words, Madras, India
Printed and bound in Great Britain by Biddles Ltd, Guildford, Surrey.
This book is printed on acid-free paper responsibly manufactured from sustainable
forestry, in which at least two trees are planted for each one used for paper production.
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Contents
Preface ix
Acknowledgements xi
1 1
Overview of Analytical Atomic Spectrometry
1.1 Historical 1
1.1.1 Optical spectroscopy 1
1.1.2 Mass spectrometry 3
1.2 Basic Instrumentation 4
1.2.1 Optical spectroscopy 4
1.2.2 Mass spectrometry 4
1.3 Basic Theory 6
1.3.1 Atomic absorption 6
1.3.2 Atomic emission 6
1.3.3 Atomic fluorescence 7
1.3.4 Atomic mass spectrometry 7
1.4 Practice 8
1.4.1 Calibration and analysis 8
1.4.2 Sensitivity and limit of detection 10
1.5 Interferences and Errors 11
1.5.1 Interferences 11
1.5.2 Operator errors 13
1.6 Applications 14
1.6.1 Clinical, food and organic samples 14
1.6.2 Petrochemicals 14
1.6.3 Agricultural samples 15
1.6.4 Waters and effluents 15
1.6.5 Geochemical and mineralogical samples 15
1.6.6 Metals 15
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2 17
Flame Atomic Absorption Spectrometry
2.1 Theory 17
2.2 Instrumentation 20
2.2.1 Sources 20
2.2.2 Flames 23
2.2.3 Sample introduction and sample atomization 29
2.2.4 Burner design 33
2.2.5 Spectrometers 34
2.3 Sensitivity and Limit of Detection 43
2.4 Interferences and Errors 43
2.4.1 Spectral interferences 46
2.4.2 Ionization interferences 46
2.4.3 Chemical interferences 47
2.4.4 Applications 50
3 51
Electrothermal Atomization
3.1 Historical Development 51
3.2 Heated Graphite Atomizers 54
3.3 Other Atomizers 57
3.4 Atomization Mechanisms 58
3.4.1 Thermodynamic considerations 58
3.4.2 Kinetic considerations 59
3.5 Interferences 60
3.5.1 Physical interferences 61
3.5.2 Background absorption 61
3.5.3 Memory effects 61
3.5.4 Chemical interferences 61
3.6 Methods of Overcoming Interferences 63
3.6.1 Control of furnace temperature 63
3.6.2 The effect of the orientation of tube heating 63
3.6.3 Isothermal operation 64
3.6.4 Matrix modification 65
3.6.5 The STPF concept 66
3.7 Other Electrothermal Techniques 66
3.7.1 Furnace atomic non-thermal excitation spectrometry 67
(FANES)
3.7.2 Furnace atomization plasma emission spectrometry 67
(FAPES)
3.8 Applications 68
3.9 The Relative Merits of Electrothermal Atomization 69
3.9.1 Advantages of electrothermal atomization 69
3.9.2 Disadvantages of electrothermal atomization 70
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4 73
Plasma Atomic Emission Spectrometry
4.1 Theory 73
4.1.1 Atomic transitions 73
4.1.2 Broadening 75
4.2 Excitation Sources 78
4.2.1 Flame sources 78
4.2.2 Plasma sources 78
4.2.3 Flames vs plasmas 79
4.3 Flame Atomic Emission Spectrometry 82
4.4 Inductively Coupled Plasma Atomic Emission Spectrometry 83
4.4.1 Plasma generation 83
4.4.2 Radiofrequency generators 86
4.4.3 Sample introduction 87
4.4.4 Excitation 92
4.4.5 Monochromators 93
4.4.6 Detectors 99
4.4.7 Data handling 103
4.4.8 Performance characteristics 103
4.4.9 Applications 107
4.5 Other Flame-like Plasma Sources 108
4.5.1 Microwave plasmas 108
4.5.2 Direct current plasmas 110
4.6 Solid Sampling Plasma Sources 111
4.6.1 Arcs and sparks 111
4.6.2 Glow discharges 112
5 115
Inductively Coupled Plasma Mass Spectrometry
5.1 Sample Introduction 115
5.2 Ionization 116
5.3 Ion Sampling 118
5.4 Mass Analysis 120
5.4.1 Quadrupole mass analysis 120
5.4.2 Magnetic sector mass analysis 123
5.4.3 Resolution 124
5.5 Ion Detection and Signal Handling 125
5.6 Performance 128
5.7 Applications 130
5.7.1 Isotope ratio analysis 131
5.7.2 Isotope dilution analysis 134