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
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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

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

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

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

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
Page viii
10
Radiochemical Methods in Analysis
450
10.1 Nuclear Structure and Nuclear Reactions
451
Decay Reactions. The Kinetics of Decay Reactions. Bombardment
Reactions and the Growth of Radioactivity.

Analysis (DMA)
493
Instrumentation. Applications of TMA. Dynamic Mechanical
Analysis.

11.5 Pyrolysis-gas Chromatography
495
Instrumentation.

Problems
50112
Overall Analytical Procedures and Their Automation
503
12.1 Sampling and Sample Pretreatment
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 Metal Pollution in a River Estuary. 4: The
Analysis of Hydrocarbon Products in a Catalytic Reforming Study.

12.3 The Automation of Analytical Procedures
514


Answers to Problems
545
Index
549Page xi
Preface to the Fifth Edition
It is twenty-five years since the first edition was published, and at the beginning of the twenty-first
century it seems appropriate to reflect on the directions in which analytical chemistry is developing.
The opening statements from the preface to the first edition are as relevant now as they were in 1975,
viz
'Analytical chemistry is a branch of chemistry which is both broad in scope and requires a specialised and
disciplined approach. Its applications extend to all parts of an industrialised society.'
During this period, the main themes have remained constant, but differences in emphasis are readily
discerned. An increasing concern with the well-being of individuals and life in general has led to
initiatives for improvements in medicine and the world environment, and in these areas analytical
chemistry has particularly vital roles to play. The elucidation of the causes and effects of ill health or of
environmental problems often depends heavily upon analytical measurements. The demand for
analytical data in relation to manufactured goods is increasing. For example, in the pharmaceutical
industry much effort is being concentrated on combinatorial chemistry where thousands of potential
drugs are being designed, synthesised and screened. This activity generates considerable analytical
requirements, particularly for automated chromatographic and spectrometric procedures, to deal with
very large numbers of samples. The determination of ultra-trace levels and the speciation of analytes
continues to provide challenges in the manufacture of highly pure materials and environmental
monitoring.
A recurring theme throughout the discipline is the sustained impact of computers on both
instrumentation and data handling where real-time processing within a Windows environment is
becoming the norm. Data reliability in the context of policy development and legal proceedings is also

D. KEALEY
Page xiii
Acknowledgements
The following figures are reproduced with permission of the publishers:
Figure 7.8 from Christian and O'Reilly, Instrumental Analysis, 2nd edn., (1986) by permission of Allyn
and Bacon, U.K.
Figure 10.17 from Cyclic GMP RJA Kit, Product Information 1976, by permission of Amersham
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 X-ray Microanalysis
Systems, by permission of Cambridge Instruments Ltd., U.K.
Figures 4.25, 4.29(a) and (c) and 4.30 from Braithwaite and Smith, Chromatographic Methods (1985);
figures 11.2, 11.3, 11.4, 11.10 and 11.17 from Brown, Introduction to Thermal Analysis (1988) by
permission of Chapman and Hall.
Figures 11.23, 11.25 and 11.26 reprinted from Irwin, Analytical Pyrolysis (1982) by courtesy of marcel
Dekker Inc. NY.
Figure 4.31(b) from Euston and Glatz, A new Hplc Solvent Delivery System, Techn. Note 88–2 (1988)
by permission of Hewlett-Packard, Waldbronn, Germany.
Figures 4.15, 4.20, 6.4, 6.11(a) and (b), 6.12(a) and (b), 9.1, 9.4 and 9.51(a) and (b) from Principles of
Instrumental Analysis, 2nd edn, by Douglas Skoog and Donald West, Copyright © 1980 by Saunders
College/Holt, Rinehart and Winston, Copyright © 1971 by Holt, Rinehart and Winston. Reprinted by
permission of Holt, Rinehart and Winston, CBS College Publishing; figures 9.37, 9.38, 9.39, 9.40 and
problems 9.6, 9.7 and 9.8 from Introduction to Spectroscopy by Donald L. Pavia et al., Copyright ©
1979 by W.B. Saunders Company. Reprinted by permission of W.B. Saunders Company, CBS College
Publishing.
Figure 8.39 from X-ray Microanalysis of Elements in Biological Tissue, by permission of Link

ORION
' is a
registered trademark of Orion Research Incorporated.
Figure 4.8 from Solid Phase Extractions Guide and Bibliography, 6th ed. (1995) by permission of the
Walters Corporation, U.S.A.
Figure 4.10 from Solid Phase Microextraction (SPME), (Feb/Mar 1999) by 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, 62, 713A (1990) with the
permission of the authors.
Figures 4.53, 4.56, 4.57 and 4.58 from High Performance Capillary Electrophoresis, 2nd ed. (1992) by
courtesy of Hewlett-Packard GmbH, Waldbronn, Germany.
Figures 9.26(a) and (b) from FT-NIR Application Note (1998) by courtesy of the Perkin Elmer
Corporation.
Figure 4.13 from Snyder, Kirkland and Glajch, Practical Hplc Method Development, 2nd ed. (1997) by permission of John Wiley & Sons.Page 1
1—
Introduction
Is there any iron in moon dust? How much aspirin is there in a headache tablet? What trace 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

present constitutes a quantitative analysis. Sometimes information concerning the spatial arrangement
of atoms in a molecule or crystalline compound is required or confirmation of the presence or position
of certain organic functional groups is sought. Such examinations are described as structural analysis
and they may be considered as more detailed forms of analysis. Any species that are the subjects of
either qualitative or quantitative analysis are known as analytes.
There is much in common between the techniques and methods used in qualitative and quantitative
analysis. In both cases, a sample is prepared for analysis by physical and chemical 'conditioning', and
then a measurement of some property related to the analyte is made. It is in the degree of control over
the relation between a measurement and the amount of analyte present that the major difference lies.
For a qualitative analysis it is sufficient to be able to apply a test which has a known sensitivity limit so
that negative and positive results may be seen in the right perspective. Where a quantitative analysis is
made, however, the relation between measurement and analyte must obey a strict and measurable
proportionality; only then can the amount of analyte in the sample be derived from the measurement. To
maintain this proportionality it is generally essential that all reactions used in the preparation of a
sample for measurement are controlled and reproducible and that the conditions of measurement remain
constant for all similar measurements. A premium is also placed upon careful calibration of the methods
used in a quantitative analysis. These aspects of chemical analysis are a major pre-occupation of the
analyst.
The Function of Analytical Chemistry
Chemical analysis is an indispensable servant of modern technology whilst it partly depends on that
modern technology for its operation. The two have in fact developed hand in hand. From the earliest
days of quantitative chemistry in the latter part of the eighteenth century, chemical analysis has
provided an important basis for chemical development. For example, the combustion studies of La
Voisier and the atomic theory proposed by Dalton had their bases in quantitative analytical evidence.
The transistor

Page 3
provides a more recent example of an invention which would have been almost impossible to develop
without sensitive and accurate chemical analysis. This example is particularly interesting as it illustrates
the synergic development that is so frequently observed in differing fields. Having underpinned the

Large amounts of material are often involved, so that taken overall small differences in concentration
can be of considerable commercial significance. Accurate and reliable chemical analysis is thus
essential.

Page 4
(f)—
Medical and Clinical Studies
The levels of various elements and compounds in body fluids are important indicators of physiological
disorders. A high sugar content in urine indicating a diabetic condition and lead in blood are probably
the most well-known examples.
Analytical Problems and Their Solution
The solutions of all analytical problems, both qualitative and quantitative, follow the same basic
pattern. This may be described under seven general headings.
(1)—
Choice of Method
The selection of the method of analysis is a vital step in the solution of an analytical problem. A choice
cannot be made until the overall problem is defined, and where possible a decision should be taken by
the client and the analyst in consultation. Inevitably, in the method selected, a compromise has to be
reached between the sensitivity, precision and accuracy desired of the results and the costs involved.
For example, X-ray fluorescence spectrometry may provide rapid but rather imprecise quantitative
results in a trace element problem. Atomic absorption spectrophotometry, on the other hand, will supply
more precise data, but at the expense of more time-consuming chemical manipulations.
(2)—
Sampling
Correct sampling is the cornerstone of reliable analysis. The analyst must decide in conjunction with
technological colleagues how, where, and when a sample should be taken so as to be truly
representative of the parameter that is to be measured.
(3)—
Preliminary Sample Treatment
For quantitative analysis, the amount of sample taken is usually measured by mass or volume. Where a

mass spectrometric abundance of molecular fragments derived from the analyte
chromatographic physico-chemical properties of individual analytes after separation
thermal physico-chemical properties of the sample as it is heated and cooled
(6)—
Method Validation
It is pointless carrying out the analysis unless the results obtained are known to be meaningful. This can
only be ensured by proper validation of the method before use and subsequent monitoring of its
performance. The analysis of validated standards is the most satisfactory approach. Validated standards
have been extensively analysed by a variety of methods, and an accepted value for the appropriate
analyte obtained. A standard should be selected with a matrix similar to that of the sample. In order to
ensure continued accurate analysis, standards must be re-analysed at regular intervals.
(7)—
The Assessment of Results
Results obtained from an analysis must be assessed by the appropriate statistical methods and their
meaning considered in the light of the original problem.
The Nature of Analytical Methods
It is common to find analytical methods classified as classical or instrumental, the former comprising
'wet chemical' methods such as gravimetry and titrimetry. Such a classification is historically derived
andPage 6
largely artificial as there is no fundamental difference between the methods in the two groups. All
involve the correlation of a physical measurement with the analyte concentration. Indeed, very few
analytical methods are entirely instrumental, and most involve chemical manipulations prior to the
instrumental measurement.
A more satisfactory general classification is achieved in terms of the physical parameter that is
measured (Table 1.1).
Trends in Analytical Methods and Procedures
There is constant development and change in the techniques and methods of analytical chemistry. Better