Analytical Chemistry of Complex Matrices Analytical Chemistry of Complex Matrices w. Franklin Smyth University of Ulster @W1LEymTEUBNER A Partnership between John Wiley & Sons and B. G. Teubner Publishers Chichester· New York . Brisbane . Toronto . Singapore . Stuttgart· Leipzig Copyright 1996 by John Wiley & Sons Ltd and B. G. Teubner Softcover reprint of the hardcover 1s t edition 1996 John Wiley & Sons Ltd B.G. Teubner Baffins Lane IndustriestraBe 15 Chichester 70565 Stuttgart (Vaihingen) West Sussex PO 19 1u n Postfach 80 10 69 England 70510 Stuttgart Gennany National Chichester (01243) 779777 National Stuttgart (0711) 789 010 International +44 1243 779777 International +49711 789010 All rights reserved No part of this book may be reproduced by any means, or transmitted, or translated into a machine language without the written permission of the publisher. Designations used by companies to distinguish their products are often claimed as trademarks. In all instances where John Wiley & Sons Ltd and B.G. Teubner are aware of a claim, the product names appear in initial capital or all capital letters. Readers, however, should contact the appropriate companies for more complete information regarding trademarks and registration. Other Wiley Editorial Offices John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, USA Brisbane· Toronto· Singapore Other Teubner Editorial Offices B.G. Teubner, Verlagsgesellschaft mbH, Johannisgasse 16, D-04103 Leipzig, Germany Library of Congress Catllioging-in-Publication Data Smyth, W Franklin. Analytical chemistry of complex matrices / W Franklin Smyth. p. cm. Includes bibliographical references and index. ISBN-13: 978-3-322-87183-1 1. Chemistry, Analytic. I. Title. QD75.2.S69 1996 95-44666 543---dc20 CIP Die Deutsche Bibliothek -CIP-Einheitsaufuahme Smyth, W. Franklin: Analytical chemistry of complex matrices / W Franklin Smyth. -Stuttgart ; Leipzig ; Teubner : Chichester : New York Brisbane : Toronto : Singapore : Wiley, 199<? ISBN-13: 978-3-322-87183-1 British Library Catll/oguing in Publication Datil A catalogue record for this book is available from the Bnbsh Library ISBN-13: 978-3-322-87183-1 e-ISBN-13: 978-3-322-87182-4 DOl: 10.1007/978-3-322-87182-4 Typeset in 10112pt Times by Techset Composition Ltd, Salisbury, Wiltshire This book is printed on acid-free paper responsibly manufactured from sustainable forestation, for which at least two trees are planted for each one used for paper production. Dedication Analytical Chemistry of Complex Matrices is dedicated to my mentors in analytical chemistry over the years who, through my reading of their contributions to the literature and, in some cases, meeting them in person, have enhanced my under standing of analytical chemistry and its application to the complex matrices of today's world. Contents INTRODUCTION CHAPTER 1: HISTORICAL BACKGROUND 12 CHAPTER 2: UNIT PROCESSES OF ANALYTICAL PROCEDURES 18 2.1 Unit Process No.1. Definition of the Problem . . . . . . . . . . 19 2.2 Unit Process No.2. Choice of Method. . . . . . . . . . . . . . . 19 2.3 Unit Process No.3. Obtaining a Representative Sample and its Measurement. . . . . . . 37 2.3.1 Solid Materials. . 37 2.3.2 Liquid Materials . 39 2.3.3 Gaseous Materials 40 2.4 Unit Process No.4. Preliminary Treatment of Sample. 42 2.5 Unit Process No.5. Separation of Analyte(s) from Interferences and Each Other . . . . . . . . . . . 45 2.5.1 Separation by Masking. . . . . . . 45 2.5.2 Separation by Precipitation . . . . 45 2.5.3 Separation by Solvent Extraction. 46 2.5.4 Separation by Solid-Phase Extraction 48 2.5.5 Separation by Chromatography. 49 2.5.6 Separation by Electrophoresis. . . . . 49 2.6 Unit Process No.6. Measurement. . . . . . . 50 2.7 Unit Process No.7. Statistical Assessment of Measurements 51 2.8 Unit Process No.8. Calculation of Analytical Result and Solution to Problem. . . . . . . . . . . . . . . . 55 2.8.1 Quantitative Analysis. . . . . . . . . . 55 2.8.1.1 Calibration Curves. . . . . . 55 2.8.1.2 Standard Addition Method. 58 2.8.1.3 Internal Standard Method .. 59 viii Contents 2.8.1.4 Internal Nonnalization Method. . . . . . . . . 60 2.8.2 Qualitative Analysis. . . . . . . . . . . . . . . . . . . . . 61 2.9 Rule of Computers and Microprocessors in Modem Analytical Methods. . . . . . . . . . . . . . . . . 61 2.9.1 Instrument Operation. . . . . . 61 2.9.2 Data Recording and Storage. . 64 2.9.3 Data Processing and Analysis. 64 2.9.4 Validation Testing. . . . . . . . 65 2.9.5 Software for Method Development. 67 2.10 Automation of Unit Processes . . . . . . . . 70 2.1 0.1 Automation of Repetitive Analysis . 70 2.10.2 Continuous On-Line Monitoring. . 75 2.10.3 Laboratory Robotics . . . . . . . . . 76 2.10.4 Application of Robotics to Dissolution Tests 77 2.10.5 Application of Robotics to Drug Detennination in Biological Fluids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 CHAPTER 3: SELECTED ANALYTICAL PROBLEMS INVOLVING INORGANIC ANALYTES WHICH CONTAIN ELEMENTS FROM GROUPS lA-VIllA AND THE LANTHANIDES 79 3.1 Detennination of Sodium and Potassium in Mineral Water by Flame Emission Spectrometry . 79 3.1.1 Summary.. 79 3.1.2 Introduction... 79 3.1.3 Procedure . . . . 80 3.2 Detennination of Water Hardness, i.e. Total Calcium and Magnesium, by EDTA Titration . 80 3.2.1 Summary .. 80 3.2.2 Introduction 81 3.2.3 Procedure . 82 3.2.4 Calculation. 82 3.3 Gravimetric Detennination of Cerium in Ore. 83 3.3.1 Summary .. 83 3.3.2 Introduction .............. . 83 3.3.3 Procedure ............... . 83 3.4 Spectrophotometric Detennination of Titanium in Rock 84 3.4.1 Summary .. 84 3.4.2 Introduction 84 3.4.3 Procedure . 85 3.4.4 Calculation. 86 3.5 Detennination of Vanadium(V) in Sea Water by Adsorptive Stripping Voltammetry 87 3.5.1 Summary ......................... . 87 Contents IX 3.5.2 Introduction........................... 87 3.5.3 Procedure............................ 88 3.6 Detennination of Trace Concentrations of Molybdenum in Water Samples by Solvent Extraction of a Neutrally Charged Chelate Followed by Atomic Absorption Spectrometry 89 3.6.1 Summary.. 89 3.6.2 Introduction................ 90 3.6.3 Procedure ................ . 90 3.7 Differential Thennal Analysis (DTA) of a Complex Manganese Compound Mn(PH 0 )H 0 . 90 2 2 2 3.7.1 Summary .. 90 3.7.2 Introduction ..... . 90 3.7.3 Procedure ...... . 91 3.8 Detennination of Iron in an Ore by Redox Titration with Potassium Pennanganate . 92 3.8.1 Summary .. 92 3.8.2 Introduction. 92 3.8.3 Procedure .. 93 3.8.4 Calculation . 94 3.9 Detennination of Cobalt in Soil Samples by Visible Spectrophotometry . 94 3.9.1 Summary ......... . 94 3.9.2 Introduction ........ . 94 3.9.3 Procedure and Calculation. 94 3.10 Gravimetric Detennination of Nickel in Steel . 96 3.10.1 Summary .. 96 3.10.2 Introduction. 96 3.10.3 Procedure .. 97 CHAPTER 4: SELECTED ANALYTICAL PROBLEMS INVOLVING INORGANIC AND ORGANOMETALLIC ANALYTES WHICH CONTAIN ELEMENTS FROM GROUPS IB-VIIB 98 4.1 Detennination of Trace Concentrations of Copper in the Aqueous Environment by Stripping Voltarnmetry 98 4.1.1 Summary.. 98 4.1.2 Introduction. 98 4.1.3 Procedure .. 99 4.1.4 Calculation. 101 4.2 Detennination of Organomercury Compounds in Fish Samples by HPLC-Cold Vapour Atomic Absorption Spectrometry. 102 4.2.1 Summary.. 102 4.2.2 Introduction. 102 4.2.3 Procedure.. 104 x Contents 4.3 Determination of Zinc in a Pharmaceutical Formulation by Ion-Exchange Separation and Complexometric Titration . 104 4.3.1 Summary.. 104 4.3.2 Introduction...................... 105 4.3.3 Procedure . . . . . . . . . . . . . . . . . . . . . . . 108 4.4 Visible Spectrophotometric Determination of Boron in Plants . 108 4.4.1 Summary.. 108 4.4.2 Introduction 109 4.4.3 Procedure. 110 4.4.4 Calculation. 110 4.5 Determination of Organolead Compounds in Air Samples by Gas Chromatography-Atomic Absorption Spectrometry. 112 4.5.1 Summary... 112 4.5.2 Introduction................... 112 4.5.3 Procedure ................... . 113 4.6 Determination of Nitrogen Dioxide in Air Samples by Sorbent Tube Collection-Colorimetry. 113 4.6.1 Summary.. 113 4.6.2 Introduction 115 4.6.3 Procedure . 123 4.6.4 Calculation. 123 4.7 Determination of Arsenic in Hair Samples by Neutron Activation Analysis and in Wallpaper by X-ray Fluorescence Spectrometry. 125 4.7.1 Summary... 125 4.7.2 Introduction........................ 125 4.7.3 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . 127 4.8 Determination of Antimony in Liver Samples using Hydride Generation-Atomic Absorption Spectrometry 130 4.8.1 Summary.. 130 4.8.2 Introduction............... 130 4.8.3 Procedure . . . . . . . . . . . . . . . . 131 4.9 Determination of Selenium in Natural Waters by Spectrofiuorimetry. 132 4.9.1 Summary........... 132 4.9.2 Introduction........................ 132 4.9.3 Procedure and Calculation. . . . . . . . . . . . . . . . 133 4.10 Determination of Fluoride in Potable Water by Ion-Selective Electrode Measurements 135 4.10.1 Summary. . 135 4.10.2 Introduction 135 4.10.3 Procedure . 137 4.10.4 Calculation. 137 4.11 Multielement Analysis of a Biological Fluid by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). 139 4.11.1 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 139 Contents Xl 4.11.2 Introduction. 140 4.11.3 Procedure . . 141 CHAPTER 5: SELECTED ANALYTICAL PROBLEMS INVOLVING ORGANIC ANALYTES WHICH ARE THE MAJOR OR MINOR CONSTITUENTS OF A SAMPLE 143 5.l Comparison of Analytical Methods Based on Visible Spectrophotometry, Solvent Extraction-UV Spectrophotometry, Voltammetry, NMR and HPLC for the Detennination of the Active Constituents of Analgesic Fonnulations . 143 5.l.l Summary............... 143 5.1.2 Visible Spectrophotometric Method 144 5.1.2.l Introduction. 144 5.1.2.2 Procedure.......... 144 5.1.2.3 Calculation......... 145 5.1.3 Solvent Extraction-UV Spectrophotometric Method. 146 5.1.3.1 Introduction and Procedure 146 5.l.4 Vo1tammetric Method 147 5.1.4.l Introduction. 147 5.1.4.2 Procedure .. 147 5.1.5 NMR Method ..... 147 5.1.5.l Introduction. 147 5.1.5.2 Calculation. 149 5.1.6 HPLC Method .... 149 5.1.6.1 Introduction. 149 5.1.6.2 Procedure .. 150 5.2 Stability-Indicating High-Perfonnance Liquid Chromatographic Assay for Oxazepam Tablets and Capsules 150 5.2.1 Summary.. 150 5.2.2 Introduction.......... 150 5.2.3 Procedure........... 152 5.3 Separation of Water-Soluble Vitamins by Capillary Zone Electrophoresis and Micellar Electrophoretic Capillary Chromatography (MECC) . 154 5.3.1 Summary.. 154 5.3.2 Introduction..... 154 5.3.3 Procedure ..... . 155 5.4 Air-Segmented Continuous-Flow Visible Spectrophotometric Detennination of Cephalosporins in Drug Fonnu1ations by Alkaline Degradation to Hydrogen Sulphide and Fonnation of Methylene Blue 157 5.4.1 Summary.. 157 5.4.2 Introduction. 157 5.4.3 Procedure .. 157 Xll Contents 5.5 Use of IR Spectrometry to Identify an Active Raw Material, Procaine Penicillin G , Used in the Pharmaceutical Industry. 157 5.5.1 Summary... 157 5.5.2 Introduction.................. 158 5.5.3 Procedure . . . . . . . . . . . . . . . . . . . 160 5.6 Qualitative and Quantitative Analysis of a Polymeric Material using Thermogravimetric Analysis (TGA) 161 5.6.1 Summary .. 161 5.6.2 Introduction 164 5.6.3 Procedure . 164 CHAPTER 6: ORGANIC TRACE ANALYSIS OF LOW MOLECULAR WEIGHT ANALYTES IN ENVIRONMENTAL SAMPLES AND BIOLOGICAL MATERIALS 165 6.1 Determination of Aromatic and Aliphatic Isocyanates in Workplace Atmospheres by HPLC . 165 6.1.1 Summary.. 165 6.1.2 Introduction 165 6.1.3 Procedure . 165 6.1.4 Calculation. 167 6.2 Determination of Triazine Pesticide Residues in Environmental Samples by Enzyme-Linked Immunosorbent Assay (ELISA) 170 6.2.1 Summary.. 170 6.2.2 Introduction........ 170 6.2.3 Procedure . . . . . . . . . 171 6.3 Analysis of Alcoholic Beverages. 173 6.3.1 Summary .. 173 6.3.2 Introduction ....... . 173 6.3.3 Procedure ........ . 174 6.4 Determination of Contaminating Antibiotic Trace Concentrations in Dairy Feedstuffs by GC-MS 176 6.4.1 Summary.. 176 6.4.2 Introduction....... 176 6.4.3 Procedure . . . . . . .. 176 6.5 Extraction of Cocaine and its Metabolites from a Urine Sample by Solid-Phase Extraction 179 6.5.1 Summary.. 179 6.5.2 Introduction.. 179 6.5.3 Procedure . . . 183 6.6 Determination of Nitroglycerin, 2,4-Dinitrotoluene and Diphenylamine in Gunshot Residue by High-Performance Liquid Chromatography with Electrochemical Detection (HPLC-ED). 184 6.6.1 Summary............................. 184