Page iii Principles and Practice of Analytical Chemistry Fifth Edition F.W. Fifield Kingston University and D. Kealey University of Surrey Page iv © 2000 by Blackwell Science Ltd Editorial Offices: Osney Mead, Oxford OX2 0EL 25 John Street, London WC1N 2BL 23 Ainslie Place, Edinburgh EH3 6AJ 350 Main Street, Malden MA 02148 5018, USA 54 University Street, Carlton Victoria 3053, Australia 10, rue Casimir Delavigne 75006 Paris, France Other Editorial Offices: Blackwell Wissenschafts-Verlag GmbH Kurfürstendamm 57 10707 Berlin, Germany Blackwell Science KK MG Kodenmacho Building 7–10 Kodenmacho Nihombashi Chuo-ku, Tokyo 104, Japan The right of the Authors to be identified as the Authors of this Work has been asserted in accordance with the Copyright, Designs and Patents Act 1988. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher. First Edition published 1975 by Chapman & Hall Second Edition 1983 Third Edition 1990 Fourth Edition 1995 This Edition published 2000 Set in 10/12pt Times by DP Photosetting, Aylesbury, Bucks Printed and bound in the United Kingdom at the University Press, Cambridge The Blackwell Science logo is a trade mark of Blackwell Science Ltd, registered at the United Kingdom Trade Marks Registry DISTRIBUTORS Marston Book Services Ltd PO Box 269 Abingdon Oxon OX14 4YN (Orders: Tel: 01235 465500 Fax: 01235 465555) USA Blackwell Science, Inc. Commerce Place 350 Main Street Malden, MA 02148 5018 (Orders: Tel: 800 759 6102 781 388 8250 Fax: 781 388 8255) Canada Login Brothers Book Company 324 Saulteaux Crescent Winnipeg, Manitoba R3J 3T2 (Orders: Tel: 204 837-2987 Fax: 204 837-3116) Australia Blackwell Science Pty Ltd 54 University Street Carlton, Victoria 3053 (Orders: Tel: 03 9347 0300 Fax: 03 9347 5001) A catalogue record for this title is available from the British Library ISBN 0-632-05384-4 Library of Congress Cataloging-in-Publication Data Fifield, F.W. (Frederick William) Principles and practice of analytical chemistry/F.W. Fifield and D. Kealey. p. cm. Includes bibliographical references and index. ISBN 0-632-05384-4 (pbk). 1. Chemistry, Analytic. I. Kealey, D. (David) II. Title. QD75.2 .F53 2000 543 – dc21 99-059799 For further information on Blackwell Science, visit our website: www.blackwell-science.com Page v Contents Preface xi Acknowledgements xiii 1 Introduction 1 The Scope of Analytical Chemistry. The Function of Analytical Chemistry. Analytical Problems and Their Solution. The Nature of Analytical Methods. Trends in Analytical Methods and Procedures. Glossary of Terms. 2 The Assessment of Analytical Data 13 2.1 Definitions and Basic Concepts 13 2.2 The Nature and Origin of Errors 16 2.3 The Evaluation of Results and Methods 17 The Reliability of Measurements. The Analysis of Data. The Application of Statistical Tests. Limits of Detection. Quality Control Charts. Standardization of Analytical Methods. Chemometrics. Problems 34 3 pH, Complexation and Solubility Equilibria 37 3.1 Chemical Reactions in Solution 38 Equilibrium Constants. Kinetic Factors in Equilibria. 3.2 Solvents in Analytical Chemistry 41 Ionizing Solvents. Non-ionizing Solvents. 3.3 Acid–base Equilibria 43 Weak Acid and Weak Base Equilibria. Buffers and pH Control. The pH of Salt Solutions. 3.4 Complexation Equilibria 49 The Formation of Complexes in Solution. The Chelate Effect. 3.5 Solubility Equilibria 52 Solubility Products. Problems 53 4 Separation Techniques 54 4.1 Solvent Extraction 55 Efficiency of Extraction. Selectivity of Extraction. Extraction Systems. Extraction of Uncharged Metal Chelates. Methods of Extraction. Applications of Solvent Extraction. 4.2 Solid Phase Extraction 73 Solid Phase Sorbents. Solid Phase Extraction Formats. Automated Solid Phase Extraction. Solid Phase Microextraction. Applications of SPE and SPME. Page vi 4.3 Chromatography 80 4.3.1 Gas Chromatography. 4.3.2 High Performance Liquid Chromatography. 4.3.3 Supercritical Fluid Chromatography. 4.3.4 Thin-layer Chromatography. 4.3.5 Ion-exchange Chromatography. 4.3.6 Size Exclusion Chromatography. 4.4 Electrophoresis 170 Factors Affecting Ionic Migration. Effect of Temperature. pH and Ionic Strength. Electro-osmosis. Supporting Medium. Detection of Separated Components. Applications of Traditional Zone Electrophoresis. High-performance Capillary Electrophoresis. Capillary Electrochromatography. Applications of Capillary Electrochromatography. Problems 188 5 Titrimetry and Gravimetry 191 5.1 Titrimetry 191 Definitions. Titrimetric Reactions. Acid-base Titrations. Applications of Acid–base Titrations. Redox Titrations. Applications of Redox Titrations. Complexometric Titrations. Ethylenediaminetetraacetic Acid (EDTA). Applications of EDTA Titrations. Titrations with Complexing Agents Other Than EDTA. Precipitation Titrations. 5.2 Gravimetry 216 Precipitation Reactions. Practical Gravimetric Procedures. Applications of Gravimetry. Problems 226 6 Electrochemical Techniques 228 6.1 Potentiometry 232 Electrode Systems. Direct Potentiometric Measurements. Potentiometric Titrations. Null-point Potentiometry. Applications of Potentiometry. 6.2 Polarography, Stripping Voltammetry and Amperometric 247 Techniques Diffusion Currents. Half-wave Potentials. Characteristics of the DME. Quantitative Analysis. Modes of Operation Used in Polarography. The Dissolved Oxygen Electrode and Biochemical Enzyme Sensors. Amperometric Titrations. Applications of Polarography and Amperometric Titrations. 6.3 Electrogravimetry and Coulometry 260 Coulometry. Coulometry at Constant Potential. Coulometric Titrations. Applications of Coulometric Titrations. 6.4 Conductometric Titrations 264 Ionic Conductances. Problems 267 7 An Introduction to Analytical Spectrometry 270 Electromagenetic Radiation. Atomic and Molecular Energy. The Absorption and Emission of Electromagnetic Radiation. The Complexity of Spectra and the Intensity of Spectral Lines. Analytical Spectrometry. Instrumentation. Page vii 8 Atomic Spectrometry 284 8.1 Arc/Spark Atomic (Optical) Emission Spectrometry 289 Instrumentation. Sample Preparation. Qualitative and Quantitative Analysis. Interferences and Errors Associated with the Excitation Process. Applications of Arc/Spark Emission Spectrometry. 8.2 Glow Discharge Atomic Emission Spectrometry 295 Instrumentation. Applications. 8.3 Plasma Emission Spectrometry 298 Instrumentation. Sample Introduction for Plasma Sources. Analytical Measurements. Applications of Plasma Emission Spectrometry. 8.4 Inductively Coupled Plasma–mass Spectrometry (ICP–MS) 305 Principles. Instrumentation. Applications. 8.5 Flame Emission Spectrometry 312 Instrumentation. Flame Characteristics. Flame Processes. Emission Spectra. Quantitative Measurements and Interferenccs. Applications of Flame Photometry and Flame Atomic Emission Spectrometry. 8.6 Atomic Absorption Spectrometry 320 Absorption of Characteristic Radiation. Instrumentation. Sample Vaporization. Quantitative Measurements and Interferences. Applications of Atomic Absorption Spectrometry. 8.7 Atomic Fluorescence Spectrometry 333 8.8 X-ray Emission Spectrometry 335 X-ray Processes. Instrumentation. Applications of X-ray Emission Spectrometry. Problems 352 9 Molecular Spectrometry 354 9.1 Visible and Ultraviolet Spectrometry 363 Polyatomic Organic Molecules. Metal Complexes. Qualitative Analysis – The Identification of Structural Features. Quantitative Analysis – Absorptiometry. Choice of Colorimetric and Spectrophotometric Procedures. Fluorimetry. Applications of UV/Visible Spectrometry and Fluorimetry. 9.2 Infrared Spectrometry 378 Diatomic Molecules. Polyatomic Molecules. Characteristic Vibration Frequencies. Factors Affecting Group Frequencies. Qualitative Anlaysis – The Identification of Structural Features. Quantitative Analysis. Sampling Procedures. Near Infrared Spectrometry. Applications of Infrared Spectrometry. 9.3 Nuclear Magnetic Resonance (NMR) Spectrometry 396 Instrumentation. The NMR Process. Chemical Shift. Spin–spin Coupling. Carbon-13 NMR. Pulsed Fourier transform NMR (FT- NMR). Qualitative Analysis – The Identification of Structural Features. Quantitative Analysis. Applications of NMR Spectrometry. 9.4 Mass Spectrometry 426 Instrumentation. Principle of Mass Spectrometry. Characteristics and Interpretation of Molecular Mass Spectra. Applications of Mass Spectrometry. 9.5 Spectrometric Identification of Organic Compounds 440 [...]... metals are there in a tin of tuna fish? What is the purity and chemical structure of a newly prepared compound? These and a host of other questions concerning the composition and structure of matter fall within the realms of analytical chemistry The answers may be given by simple chemical tests or by the use of costly and complex instrumentation The techniques and methods employed and the problems encountered... choice of method and the interpretation of analytical data thereby minimizing the expenditure of time, effort and money The purpose of this book is to provide a basic understanding of the principles, instrumentation and applications of chemical analysis as it is currently practised The amount of space devoted to each technique is based upon its application in industry as determined in a national survey of. .. Netherlands Figure 8.25 from Brown and Dymott, The use of platform atomisation and matrix modification as methods of interference control in graphite furnace analysis, by permission of Philips Scientific and Analytical Equipment Figures 11.21 and 11.24 from Frearson and Haskins, Chromatography and Analysis, Issue 7, (1989) by permission of RGC Publications Figures 4.18, 4.32, 9.2(a), 11.11, 11.20, 12.1 and. .. 4.43 and 4.45 from Smith, Gas and Liquid Chromatography in Analytical Chemistry (1988); figures 4.42 and 13.2 from Berridge, Techniques for the Automated Optimisation of Hplc Separations (1985) reproduced by permission of John Wiley and Sons Limited; 11.1, 11.5, 11.6, 11.12, 11.13, 11.14, 11.18 and 11.19 from Wendlandt, Thermal Analysis, 3rd edn., (1986); reprinted by permission of John Wiley and Sons... permission of Rose Ward Publishing, Guildford, U.K Figure 4.23 from McNair and Bonelli, Basic Gas Chromatography; with permission from Varian Associates, Inc Figures 4.38(c) and (d), 4.40, 9.52(a) and (b) from de Hoffmann, Charette and Stroobant, Mass Spectrometry, Principles and Application (1996) by permission of John Wiley & Sons Figure 4.39 from Huang, Wachs, Conboy and Henion, Analytical Chemistry, ... International, U.K Figures 8.14 and 8.15 from Date and Gray, Applications of Inductively Coupled Plasma Mass Spectrometry (1989); figures 2.7 and 2.8 from Kealey, Experiments in Modern Analytical Chemistry (1986); by permission of Blackie, U.K Figure 8.24 from Manahan, Quantitative Chemical Analysis (1986) by permission of Brookes Cole, U.K Figures 8.27 and 8.28(a) and (b) from Allmand and Jagger, Electron Beam... right across the traditional divisions of inorganic, organic and physical chemistry as well as embracing aspects of such areas as bio -chemistry, physics, engineering and economics Analytical chemistry is therefore a subject which is broad in its scope whilst requiring a specialist and disciplined approach An enquiring and critical mind, a keen sense of observation and the ability to pay scrupulous attention... 501 12 Overall Analytical Procedures and Their Automation 12.1 Sampling and Sample Pretreatment 503 503 Representative Samples and Sample Storage Sample Concentration and Clean-up: Solid Phase Extraction 12.2 Examples of Analytical Problems and Procedures 506 1: Evaluation of Methods for the Determination of Fluoride in Water Samples 2: Analysis of a Competitive Product 3: The Assessment of the Heavy... generation and diagnostic testing of the system Microcomputers with sophisticated data handling and graphics software packages have likewise made a considerable impact on the collection, storage, processing, enhancement and interpretation of analytical data Laboratory Information and Management Systems (LIMS), for the automatic logging of large numbers of samples, Chemometrics, which involve computerized and. .. identification and determination of the element in a specific chemical form presents the analyst with some of the more difficult problems Glossary of Terms The following list of definitions, though by no means exhaustive, will help both in the study and practice of analytical chemistry Accuracy The closeness of an experimental measurement or result to the true or accepted value (p 13) Analyte Constituent of the . Scope of Analytical Chemistry. The Function of Analytical Chemistry. Analytical Problems and Their Solution. The Nature of Analytical Methods. Trends in Analytical. 0-632-05384-4 Library of Congress Cataloging-in-Publication Data Fifield, F.W. (Frederick William) Principles and practice of analytical chemistry/ F.W. Fifield and D.