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"Modern Analytical Chemistry" David Harvey, DePauw University Copyright (c) 2000 by The McGraw-Hill Companies, Inc. All rights reserved. Printed in the United States of America. Except as permitted under the United States Copyright Act of 1976, no part of this publication may be reproduced or distributed in any form or by any means, or stored in a data base or retrieval system, without the prior written permission of the publisher. This book is printed on acid-free paper. ISBN 0-07-237547-7 Vice president and editorial director: Kevin T. Kane Publisher: James M. Smith Sponsoring editor: Kent A. Peterson Editorial assistant: Jennifer L. Bensink Developmental editor: Shirley R. Oberbroeckling Senior marketing manager: Martin J. Lange Senior project manager: Jayne Klein Production supervisor: Laura Fuller Coordinator of freelance design: Michelle D. Whitaker Senior photo research coordinator: Lori Hancock Senior supplement coordinator: Audrey A. Reiter Compositor: Shepherd, Inc. Typeface: 10/12 Minion Printer: Quebecor Printing Book Group Kingsport Freelance cover interior designer: Elise Lansdon Cover image: © George Diebold The Stock Market Photo research: Roberta Spieckerman Associates Colorplates: 1-6, 8, 10: © David Harvey Marilyn E. Culler, photographer; 7: Richard Megna Fundamental Photographs; 9: © Alfred Pasieka Science Photo Library Photo Researchers, Inc.; 11: From H. Black, Environ. Sci. Technol., 1996, 30, 124A. Photos courtesy D. Pesiri and W. Tumas, Los Alamos National Laboratory; 12: Courtesy of Hewlett-Packard Company; 13: © David Harvey. Library of Congress Cataloging-in-Publication Data Harvey, David, 1956- Modern analytical chemistry / David Harvey. - 1st ed. p. cm. Includes bibliographical references and index. ISBN 0-07-237547-7 1. Chemistry, Analytic. I. Title. QD75.2.H374 543-dc21 -15120 CIP International Edition ISBN 0-07-116953-9 Copyright (c) 2000. Exclusive rights by The McGraw-Hill Companies, Inc. for manufacture and export. This book cannot be re-exported from the country to which it is consigned by McGraw-Hill. The International Edition is not available in North America. www.mhhe.com Contents: Preface xii Chapter 1 Introduction 1 A What is Analytical Chemistry? 1 B The Analytical Perspective 1 C Common Analytical Problems 1 D Key Terms 1 E Summary 1 F Problems 1 G Suggested Readings 1 H References Chapter 2 Basic Tools of Analytical Chemistry 11 A Numbers in Analytical Chemistry 11 A.1 Fundamental Units of Measure 11 A.2 Significant Figures 13 B Units for Expressing Concentration 15 B.1 Molarity and Formality 15 B.2 Normality 16 B.3 Molality 17 B.4 Weight, Volume, and Weight-to-Volume Ratios 18 B.5 Converting Between Concentration Units 20 B.6 p-functions 21 C Stoichiometric Calculations 23 C.1 Conservation of Mass 23 C.2 Conservation of Charge 24 C.3 Conservation of Protons 24 C.4 Conservation of Electron Pairs 25 C.5 Conservation of Electrons 26 C.6 Using Conservation Principles in Stoichiometry Problems 27 D Basic Equipment and Instrumentation 30 D.1 Instrumentation for Measuring Mass 30 D.2 Equipment for Measuring Volume 31 D.3 Equipment for Drying Samples 32 E Preparing Solutions 34 E.1 Preparing Stock Solutions 34 E.2 Preparing Solutions by Dilution 35 F The Laboratory Notebook 37 G Key Terms 38 H Summary 39 I Problems 40 J Suggested Readings 41 K References Chapter 3 The Language of Analytical Chemistry 45 A Analysis, Determination, and Measurement 45 B Techniques, Methods, Procedures, and Protocols 46 C Classifying Analytical Techniques 48 D Selecting an Analytical Method 50 D.1 Accuracy 50 D.2 Precision 51 D.3 Sensitivity 52 D.4 Selectivity 53 D.5 Robustness and Ruggedness 54 D.6 Scale of Operation 55 D.7 Equipment, Time, and Cost 56 D.8 Making the Final Choice 57 E Developing the Procedure 60 E.1 Compensating for Interferences 60 E.2 Calibration and Standardization 61 E.3 Sampling 64 E.4 Validation 65 F Protocols 67 G The Importance of Analytical Methodology 68 H Key Terms 69 I Summary 70 J Problems 71 K Suggested Readings 72 L References Chapter 4 Evaluating Analytical Data 75 A Characterizing Measurements and Results 75 A.1 Measures of Central Tendency 75 A.2 Measures of Spread 76 B Characterizing Experimental Errors 78 B.1 Accuracy 78 B.2 Precision 79 B.3 Error and Uncertainty 80 C Propagation of Uncertainty 82 C.1 A Few Symbols 82 C.2 Uncertainty When Adding or Subtracting 84 C.3 Uncertainty When Multiplying or Dividing 85 C.4 Uncertainty for Mixed Operations 86 C.5 Uncertainty for Other Mathematical Functions 87 C.6 Is Calculating Uncertainty Actually Useful? 92 D The Distribution of Measurements and Results 93 D.1 Populations and Samples 93 D.2 Probability Distributions for Populations 94 D.3 Confidence Intervals for Populations 95 D.4 Probability Distributions for Samples 96 D.5 Confidence Intervals for Samples 97 D.6 A Cautionary Statement 98 E Statistical Analysis of Data 100 E.1 Significance Testing 100 E.2 Constructing a Significance Test 103 E.3 One-Tailed and Two-Tailed Significance Tests 104 E.4 Errors in Significance Testing 105 F Statistical Methods for Normal Distributions - 107 F.1 Comparing X to μ 107 F.2 Comparing s² to σ² 108 F.3 Comparing Two Sample Variances 109 F.4 Comparing Two Sample Means 110 F.5 Outliers 111 G Detection Limits 113 H Key Terms 114 I Summary 115 J Suggested Experiments 116 K Problems 117 L Suggested Readings 118 M References Chapter 5 Calibrations, Standardizations, and Blank Corrections 121 A Calibrating Signals 121 B Standardizing Methods 123 B.1 Reagents Used as Standards 123 B.2 Single-Point versus Multiple-Point Standardizations 124 B.3 External Standards 125 B.4 Standard Additions 126 B.5 Internal Standards 127 C Linear Regression and Calibration Curves 129 C.1 Linear Regression of Straight-Line Calibration Curves 129 C.2 Unweighted Linear Regression with Errors in y 130 C.3 Weighted Linear Regression with Errors in y 131 C.4 Weighted Linear Regression with Errors in Both x and y 132 C.5 Curvilinear and Multivariate Regression 133 D Blank Corrections 136 E Key Terms 137 F Summary 138 G Suggested Experiments 140 H Problems 141 I Suggested Readings 142 J References Ключевые слова: rt ln, surface, ion, hg pt, chromatography, beerlambert law, ha aq, potato chip, equilibrium, electrode, deviation, analytical chemistry, faradays law, spray chamber, sample, rubber septum, north carolina, aq cu, acta, source, determination, ew, royal society, nm, chapter, educ, chemical, anal, separation, point, complex, weight, methods, acid, mole, aq, np, determined, measurement, case, standard, data, flow, rt, volume, absorbance, total, es, precipitate, response, chim, number, horseradish peroxidase, analyte, reaction, ph, water, titrant, emission, determine, wavelength, walden reductor, solute, curve, table, ppm, human eye, tr, procedure, internationally agreed, national institute, ha, c kw, hl aq, difference, acree, equation, technique, se iv, springer-verlag berlin, external generation, kw ka, level, weak, lattice defect, solid-phase microextraction, b mx, ag cn, absorption, liquid, fe cn, nb, mo vi, dietary supplement, granular, problem, capillary, mathematical functions, sampling, moll, specie, approach, result, aw, gas, chelating agent, aq e, ms, change, column, beers law, soxhlet extractor, ci, sa dl, solvent, ln, detector, ferguson, ohms law, analytical, collaborative tests, nobel prize, double-beam optic, ha a, wa, fw fw, natron lakes, hf f, aq aq, deerfield, analysis, time, indicator, automatic titrator, sa si, eriochrome black, current, hf aq, metal, modern analytical, sa, soft drink, reagent, international union, solid, signal, factor, chem, radiation, temperature, york, single, extraction, terpene hydrate, error, scn, phase, quantum mechanic, quantitative, material, bryan hanson, concentration, potential, dmg, wa wx, releasing agent, titration, alltech associates, min, cl br, laboratory, polydimethyl siloxane, cs, chemistry, american society, e ag, van atta, spectroscopy, mobile, mobile phase, protecting agent, ni fe, experiment, cell, form, xi, fiber-optic probe, mass, solution, chem educ, ni cn, particle, matrix, constant, measured, acetic anhydride, k mb, k t, calibration, modern, log, fisher scientific, buffers, base, rate, vo, method