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Instrumental Multi Element Chemical Analysis

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Instrumental Multi-Element Chemical Analysis

Instrumental Multi-Element
Chemical Analysis

Edited by
Z.B. ALF ASSI

Department of Nuclear Engineering
Ben-Gurion University of the Negev

Beer-Sheeva
Israel

SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.

Library of Congress Catalog Card number: 98-66852

ISBN 978-94-010-6078-3 ISBN 978-94-011-4952-5 (eBook)
DOI 10.1007/978-94-011-4952-5

Printed an acid-free paper

AII Rights Reserved
© 1998 Springer Science+Business Media Dordrecht
Originally pubIished by Kluwer Academic PubIishers in 1998

No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical,
incIuding photocopying, recording, or by any information storage and
retrieval system, without prior permis sion from the copyright owner.

Typeset in 10/12pt Times by AFS Image Setters Ltd, Glasgow

to Sabina
with love

Contents

List of contributors

Preface

1

2

3

4

Preparation of samples
Z.B. Alfassi and S. Felix
1.1 Introduction
1.2 Dissolution of geological and environmental inorganic samples
1.3 Dissolution of biological (organic) material
1.4 Contamination from reagents and equipment
References

Separation and preconcentration of trace inorganic elements
Z.B. Alfassi
2.1 Introduction
2.2 Precipitation
2.3 Separation and preconcentration of trace elements by columns

(ion exchange and sorption)
2.4 Preconcentration of trace elements by solvent extraction
2.5 Preconcentration by formation of volatile compounds
2.6 Electrochemical preconcentration
References

Quality assurance, control and assessment
Z.B. Alfassi
3.1 Introduction
3.2 Quality assessment
3.3 Statistical methods
3.4 Significance tests
3.5 Errors in instrumental analysis - calibration lines
References

Activation analysis
M.D. Glascock
4.1 Introduction
4.2 Nuclear structure
4.3 Nuclear reactions
4.4 Decay rates
4.5 Irradiation sources
4.6 Detection and measurement of radiation
4.7 Activation analysis techniques
4.8 Special activation analysis methods
4.9 Exercises and solutions
References

xi

xiii

1

I
2
5

15
17

19

19
20

30
43
49
51
53

55

55
56
56
62
81
92

93

93
94
98

105
112
115
127
141
146
149

Vlll CONTENTS

5 Inductively coupled plasma optical emission and mass spectrometry 151
N. De Silva and D.C. Gregoire

6

7

8

9

5.1 Inductively coupled plasma as an analytical source
5.2 Inductively coupled plasma optical emission spectrometry
5.3 Inductively coupled plasma mass spectrometry
5.4 Sample introduction
References

Electroanalytical methods
P.e. Hauser
6.1 Introduction
6.2 Fundamentals
6.3 Potentiometry
6.4 Conductometry
6.5 Electrogravimetry and coulometry
6.6 Voltammetry and amperometry
References

Atomic absorption spectrometry
I.Z. Pelly
7.1 Introduction
7.2 Theory
7.3 Major components and instrument types
7.4 Atomization
7.5 Hydride generation
7.6 Interferences
7.7 Instrumental background corrections
7.8 Modifiers, standards and chemicals
7.9 Sample preparation and automation
References

X-ray fluorescence analysis
P. Wobrauschek, P. Kregsamer and M. Mantler
8.1 Introduction
8.2 Wavelength- and energy-dispersive XRF
8.3 X-ray tubes and radioisotope sources
8.4 Methods of quantitative analysis
8.5 Scattered radiation
8.6 Electron probe micro-analysis
8.7 Other XRF techniques
8.8 Examples
8.9 Appendix
References

Analysis of ions using high-performance liquid chromatography
S. Levin
9.1 What is ion chromatography?
9.2 Fundamentals of the chromatographic process
9.3 Principles of the separation
9.4 Types of stationary phases
9.5 Properties of mobile phases
9.6 Ion suppression in ion chromatography
9.7 Detection in ion chromatography
9.8 Applications - summary
References

151
156
168
192
199

201

201
203
214
233
236
239
250

251

251
256
257
269
282
283
291
295
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302

302
306
315
319
326
329
330
336
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345

346

346
348
351
352
357
359
369
375
376

10 Scattering methods
E. Rauhala
10.1 Introduction

CONTENTS

10.2 Theoretical considerations
10.3 The experimental arrangement
10.4 Spectrum analysis
10.5 Numerical methods
10.6 Applications to elemental analysis
References

11 Elemental analysis of surfaces
M. Polak

IX

379

379
382
404
407
426
427
435

438

11.1 Introduction: overview of surface phenomena and major techniques 438
11.2 Auger electron spectroscopy and X-ray photoelectron spectroscopy 441
11.3 Secondary-ion mass spectrometry 471
11.4 Comparative evaluation of the performance of the three techniques 484
11.5 Summary 489
References 490

Index 493

Contributors

Prof. Z.B. Alfassi

Prof. N. De Silva

S.Felix

Dr M.D. Glascock

Dr D.e. Gregoire

Prof. P.e. Hauser

Dr P. Kregsamer

Dr S. Levin

Prof. M. Mantler

Prof. I,.Z. Pelly

Prof. M. Polak

Department of Nuclear Engineering, Ben-Gurion
University of the Negev, Beer-Sheeva 84102,
Israel

Department of Chemistry, Carleton University,
Ottawa, Ontario, Canada KIS 5B6

Unit for Characterization of Materials, Institute
for Applied Research, Ben-Gurion University of
the Negev, Beer-Sheeva 84105, Israel

Research Reactor Center, University of
Missouri, Columbia, MO 65211, USA

Geological Survey of Canada, 601 Booth Street,
Ottawa, Ontario, Canada KIA OE8

Department of Chemistry, University of Basel,
Spitalstrasse 51, 5046 Basel, Switzerland

Atominstitut der Osterreichischen Universitaten,
Schiittelstrasse 115, A-I020 Wien, Austria

Medtechnica, Efal St. 5 Kiriat Arie, Petach
Tikva 49511, Israel

Institut fUr Angewandte und Technische Physik,
Technische Universtitat Wien, Wiedner
Hauptstrasse 8-10, A-I040 Wien, Austria

Department of Geological and Environmental
Sciences, Ben-Gurion University of the Negev,
Beer-Sheeva 84105, Israel

Department of Materials Engineering, Ben-
Gurion University of the Negev, Beer-Sheeva
84105, Israel

xii CONTRIBUTORS

Prof. E. Rauhala Accelerator Laboratory, Department of Physics,
PO Box 9, University of Helsinki, 00014
Helsinki, Finland

Prof. P. Wobrauschek Atominstitut der Osterreichischen Universitaten,
Schiittelstrasse 115, A-l020 Vienna, Austria

Preface

Classical analytical methods such as gravimetry and absorption of special
titrimetry complexes remain in use in many laboratories and are still widely
taught in first-year analytical courses. These courses and particularly the
laboratory experiments attached to them are excellent for training students
in the work of an experimental chemist. These methods are also still the main
ones when very high analysis of the major elements of a matrix is required.
However, most analyses are now performed by instrumental analysis, and a
rough estimate is that at least 99% of current analytical measurements are
done by instrumental techniques such as emission and absorption spec-
trometry, electrochemical methods, mass spectrometry, various methods of
gas and liquid chromatography or radiochemical methods. Several proper-
ties common to many of these methods are the reason for the shift from
classical analytical chemistry to modem instrumental methods.
• Sensitivity Instrumental methods can reach detection limits undreamed

of in classical methods. These higher sensitivities completely change
the range of what is called trace elements. While not so long ago
trace elements were those at a concentration of parts per thousand
(permill, 10-3), nowadays instrumental measurements of parts per
million