Principles and Practice of Analytical Chemistry

680 Pages·2003·6.3 MB·English

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
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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
Preface xi
Acknowledgements xiii
1 1
Introduction
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 13
The Assessment of Analytical Data
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 37
pH, Complexation and Solubility Equilibria
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 54
Separation Techniques
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
5 191
Titrimetry and Gravimetry
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
6 228
Electrochemical Techniques
6.1 Potentiometry 232
Electrode Systems. Direct Potentiometric Measurements.
Potentiometric Titrations. Null-point Potentiometry. Applications of
Potentiometry.
247
6.2 Polarography, Stripping Voltammetry and Amperometric
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
7 270
An Introduction to Analytical Spectrometry
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
8 284
Atomic Spectrometry
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
9 354
Molecular Spectrometry
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