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This completely revised second edition of the standard work has been expanded by some twenty percent to include more information on the latest developments and new apparatus. In particular, sections have been added on microplasmas and new types of spectrometers, while that on the rapidly expanding field of speciations with practical examples from life and environmental sciences have been included.Still in one handy volume, the book covers all the important modern aspects of atomic fluorescence, emission and absorption spectroscopy as well as plasma mass spectroscopy in a readily comprehensible and practice-oriented manner. A thorough explanation of the physical, theoretical and technical basics, example applications including the concrete execution of analysis and comprehensive cross-references to the latest literature allow even newcomers easy access to the methodologies described.
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Jose´ A. C. Broekaert
Analytical Atomic Spectrometry with Flames and Plasmas Second, Completely Revised and Extended Edition
J. A. C. Broekaert Analytical Atomic Spectrometry with Flames and Plasmas
Jose´ A. C. Broekaert
Analytical Atomic Spectrometry with Flames and Plasmas Second, Completely Revised and Extended Edition
Prof. Dr. Jose´ A. C. Broekaert Universita¨t Hamburg Fachbereich Chemie Institut fu¨r Anorganische und Angewandte Chemie Martin-Luther-King-Platz 6 20146 Hamburg Germany
9 This book was carefully produced. Nevertheless, author and publisher do not warrant the information contained therein to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. First Edition 2002 Second, Completely Revised and Extended Edition 2005 Library of Congress Card No.: Applied for British Library Cataloguing-in-Publication Data: A catalogue record for this book is available from the British Library. Deutsche Bibliothek Cataloguing-inPublication Data: ( 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim (Federal Republic of Germany) All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Printed in the Federal Republic of Germany. Printed on acid-free paper. Composition: Asco Typesetters, Hong Kong Printing: betz-druck gmbh, Darmstadt Bookbinding: Litges & Dopf Buchbinderei GmbH, Heppenheim Cover Design: Schulz, Grafik-Design, Fußgo¨nheim ISBN-10: ISBN-13:
3-527-31282-X 978-3-527-31282-5
To my wife Paula and our daughters Ilse, Sigrid and Carmen
VII
Contents Preface
XI
Introduction
1
1
Basic Principles
1.1 1.2 1.3 1.4 1.5 1.6 1.7
Atomic structure 4 Plasmas 8 Emission and absorption of radiation Ionization 18 Dissociation 23 Sources for atomic spectrometry 26 Analytical atomic spectrometry 31
2
Spectrometric Instrumentation
2.1 2.2 2.2.1 2.2.2 2.2.3 2.2.4 2.3 2.3.1 2.3.2 2.3.3 2.3.4 2.4 2.5
Figures of merit of an analytical method Optical spectrometers 51 Optical systems 52 Radiation detectors 61 Miniaturized spectrometers 70 Non-dispersive spectrometers 73 Mass spectrometers 75 Types of mass spectrometers 76 Ion detection 84 Ion extraction 87 Ion optics and transmission 88 Data acquisition and treatment 89 Traceability 92
3
Sample Introduction Devices
3.1 3.2 3.3 3.4
Sample introduction by pneumatic nebulization 96 Ultrasonic nebulization 113 Hydride and other volatile sp