Harris Quantitative Chemical Analysis 8th edition PDF

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“The Experiment” by Sempé © C. Charillon, Paris QUANTITATIVE CHEMICAL ANALYSIS Publisher: Clancy Marshall Senior Acquisitions Editor: Jessica Fiorillo Marketing Manager: John Britch Media Editor: Dave Quinn Editorial Assistant: Kristina Treadway Photo Editor: Ted Szczepanski Cover and Text Designer...

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“The Experiment” by Sempé © C. Charillon, Paris

QUANTITATIVE CHEMICAL ANALYSIS

Publisher: Clancy Marshall Senior Acquisitions Editor: Jessica Fiorillo Marketing Manager: John Britch Media Editor: Dave Quinn Editorial Assistant: Kristina Treadway Photo Editor: Ted Szczepanski Cover and Text Designer: Vicki Tomaselli Senior Project Editor: Mary Louise Byrd Illustrations: Network Graphics, Precision Graphics Illustration Coordinators: Bill Page, Eleanor Jaekel Production Coordinator: Julia DeRosa Composition and Text Layout: Aptara, Inc. Printing and Binding: RR Donnelley

Library of Congress Control Number: 2009943186 ISBN-13: 978-1-4292-1815-3 ISBN-10: 1-4292-1815-0 © 2010, 2007, 2003, 1999 by W. H. Freeman and Company All rights reserved Printed in the United States of America First Printing W. H. Freeman and Company 41 Madison Avenue New York, NY 10010 Houndmills, Basingstoke RG21 6XS, England www.whfreeman.com

QUANTITATIVE CHEMICAL ANALYSIS Eighth Edition

Daniel C. Harris Michelson Laboratory China Lake, California

W. H. Freeman and Company New York

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BRIEF CONTENTS 0 The Analytical Process

1

1 Chemical Measurements

13

2 Tools of the Trade

29

3 Experimental Error

51

4 Statistics

68

5 Quality Assurance and Calibration Methods 6

Chemical Equilibrium

96 117

7 Activity and the Systematic Treatment of Equilibrium

142

8 Monoprotic Acid-Base Equilibria

162

9 Polyprotic Acid-Base Equilibria

185

10 Acid-Base Titrations

205

11 EDTA Titrations

236

12 Advanced Topics in Equilibrium

258

13 Fundamentals of Electrochemistry 279

18 Applications of Spectrophotometry

419

19 Spectrophotometers

445

20 Atomic Spectroscopy

479

21 Mass Spectrometry

502

22 Introduction to Analytical Separations

537

23 Gas Chromatography

565

24 High-Performance Liquid Chromatography

595

25 Chromatographic Methods and Capillary Electrophoresis

634

26 Gravimetric Analysis, Precipitation Titrations, and Combustion Analysis

673

27 Sample Preparation

699

Notes and References NR1

14 Electrodes and Potentiometry

308

Glossary GL1

15 Redox Titrations

340

Appendixes AP1

16 Electroanalytical Techniques

361

Solutions to Exercises S1

17 Fundamentals of Spectrophotometry

Answers to Problems AN1 393

Index I1

v

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CONTENTS Preface 0

The Analytical Process

1

3-5 Propagation of Uncertainty from Systematic Error

The “Most Important” Environmental Data Set of the Twentieth Century

1

4

0-1 Charles David Keeling and the Measurement of Atmospheric CO2 0-2 The Analytical Chemist’s Job 0-3 General Steps in a Chemical Analysis

1 6 11

Box 0-1 Constructing a Representative Sample 12

1

Box 3-2 Keeling’s Exquisitely Precise Measurement of CO2

xiii

Chemical Measurements Biochemical Measurements with a Nanoelectrode

1-1 1-2 1-3 1-4

SI Units Chemical Concentrations Preparing Solutions Stoichiometry Calculations for Gravimetric Analysis 1-5 Introduction to Titrations

Statistics Is My Red Blood Cell Count High Today?

4-1 Gaussian Distribution 4-2 Confidence Intervals 4-3 Comparison of Means with Student’s t

60

62

68 68

68 73 76

Box 4-1 Choosing the Null Hypothesis in Epidemiology

79

13 16 19

4-4 Comparison of Standard Deviations with the F Test 4-5 t Tests with a Spreadsheet 4-6 Grubbs Test for an Outlier 4-7 The Method of Least Squares 4-8 Calibration Curves

80 82 83 83 87

21 22

4-9 A Spreadsheet for Least Squares

13 13

Box 4-2 Using a Nonlinear Calibration Curve

88

89

Box 1-1 Reagent Chemicals and Primary Standards 23

1-6 Titration Calculations

2

Tools of the Trade Quartz Crystal Microbalance in Medical Diagnosis

2-1 Safe, Ethical Handling of Chemicals and Waste 2-2 The Lab Notebook 2-3 Analytical Balance 2-4 Burets 2-5 Volumetric Flasks 2-6 Pipets and Syringes 2-7 Filtration 2-8 Drying 2-9 Calibration of Volumetric Glassware 2-10 Introduction to Microsoft Excel® 2-11 Graphing with Microsoft Excel Reference Procedure Calibrating a 50-mL Buret

3

Experimental Error Experimental Error

3-1 Significant Figures 3-2 Significant Figures in Arithmetic 3-3 Types of Error Box 3-1 Case Study in Ethics: Systematic Error in Ozone Measurement

3-4 Propagation of Uncertainty from Random Error

24

5

29

Quality Assurance and Calibration Methods The Need for Quality Assurance

97

Box 5-1 Control Charts

99

5-2 Method Validation

49

51 51

51 52 55 55

57

96

5-1 Basics of Quality Assurance 29

30 31 31 35 37 38 40 41 42 43 46

96

Box 5-2 The Horwitz Trumpet: Variation in Interlaboratory Precision

5-3 Standard Addition 5-4 Internal Standards 5-5 Efficiency in Experimental Design

6

Chemical Equilibrium Chemical Equilibrium in the Environment

6-1 The Equilibrium Constant 6-2 Equilibrium and Thermodynamics 6-3 Solubility Product Box 6-1 Solubility Is Governed by More Than the Solubility Product Demonstration 6-1 Common Ion Effect

6-4 Complex Formation Box 6-2 Notation for Formation Constants

6-5 Protic Acids and Bases 6-6 pH 6-7 Strengths of Acids and Bases Demonstration 6-2 The HCl Fountain Box 6-3 The Strange Behavior of Hydrofluoric Acid Box 6-4 Carbonic Acid

100 103

106 109 110

117 117

118 119 121 122 122

124 124

126 128 130 131 132 134 vii

7

Activity and the Systematic Treatment of Equilibrium Hydrated Ions

7-1 The Effect of Ionic Strength on Solubility of Salts Demonstration 7-1 Effect of Ionic Strength on Ion Dissociation Box 7-1 Salts with Ions of Charge ⱖ| 2| Do Not Fully Dissociate

7-2 Activity Coefficients 7-3 pH Revisited 7-4 Systematic Treatment of Equilibrium Box 7-2 Calcium Carbonate Mass Balance in Rivers

7-5 Applying the Systematic Treatment of Equilibrium

219

10-6 Finding the End Point with Indicators

220 Box 10-2 What Does a Negative pH Mean? Demonstration 10-1 Indicators and the Acidity 221 of CO2

142 142

143

Box 10-3 Kjeldahl Nitrogen Analysis Behind the Headlines

143 145

145 149 150 153

223 223

10-7 Practical Notes 10-8 Kjeldahl Nitrogen Analysis

224

225

10-9 The Leveling Effect 10-10 Calculating Titration Curves with Spreadsheets Reference Procedure Preparing Standard Acid and Base

226 235

11 EDTA Titrations

236 236

Ion Channels in Cell Membranes

153

237

11-1 Metal-Chelate Complexes

8

Monoprotic Acid-Base Equilibria Measuring pH Inside Cellular Compartments

8-1 Strong Acids and Bases Box 8-1 Concentrated HNO3 Is Only Slightly Dissociated

8-2 Weak Acids and Bases 8-3 Weak-Acid Equilibria Demonstration 8-1 Conductivity of Weak Electrolytes Box 8-2 Dyeing Fabrics and the Fraction of Dissociation

8-4 Weak-Base Equilibria 8-5 Buffers Box 8-3 Strong Plus Weak Reacts Completely Demonstration 8-2 How Buffers Work

9

viii

163

11-2 11-3 11-4 11-5

238

EDTA EDTA Titration Curves Do It with a Spreadsheet Auxiliary Complexing Agents

240 243 245 246

Box 11-2 Metal Ion Hydrolysis Decreases the Effective Formation Constant for EDTA Complexes

163

165 166

11-6 Metal Ion Indicators Demonstration 11-1 Metal Ion Indicator Color Changes

167 169

11-7 EDTA Titration Techniques Box 11-3 Water Hardness

170 171 174 176

185

Proteins Are Polyprotic Acids and Bases

185

186

Box 9-1 Carbon Dioxide in the Air and Ocean Box 9-2 Successive Approximations

189 191

Diprotic Buffers Polyprotic Acids and Bases Which Is the Principal Species? Fractional Composition Equations Isoelectric and Isoionic pH

193 194 195 197 199

Box 9-3 Isoelectric Focusing

200

10 Acid-Base Titrations 10-1 10-2 10-3 10-4 10-5

162

Polyprotic Acid-Base Equilibria

9-1 Diprotic Acids and Bases 9-2 9-3 9-4 9-5 9-6

162

Box 11-1 Chelation Therapy and Thalassemia

12 Advanced Topics in Equilibrium 12-1 12-2 12-3 12-4

Acid-Base Titration of a Protein

205

Titration of Strong Base with Strong Acid Titration of Weak Acid with Strong Base Titration of Weak Base with Strong Acid Titrations in Diprotic Systems Finding the End Point with a pH Electrode

206 208 210 212 215

Box 10-1 Alkalinity and Acidity

216

249

251 253

258

Acid Rain

258

General Approach to Acid-Base Systems Activity Coefficients Dependence of Solubility on pH Analyzing Acid-Base Titrations with Difference Plots

259 262 265 270

13 Fundamentals of Electrochemistry 279 Lithium-Ion Battery

13-1 Basic Concepts Box 13-1 Ohm’s Law, Conductance, and Molecular Wire

13-2 Galvanic Cells

205

247

249

Demonstration 13-1 The Human Salt Bridge

13-3 Standard Potentials 13-4 Nernst Equation Box 13-2 E° and the Cell Voltage Do Not Depend on How You Write the Cell Reaction Box 13-3 Latimer Diagrams: How to Find E° for a New Half-Reaction

279

280 283

284 286

287 288 290 292

Contents

13-5 E° and the Equilibrium Constant Box 13-4 Concentrations in the Operating Cell

13-6 Cells as Chemical Probes 13-7 Biochemists Use E°⬘

14 Electrodes and Potentiometry Chem Lab on Mars

14-1 Reference Electrodes 14-2 Indicator Electrodes Demonstration 14-1 Potentiometry with an Oscillating Reaction

14-3 What Is a Junction Potential? 14-4 How Ion-Selective Electrodes Work 14-5 pH Measurement with a Glass Electrode

293

14-6 Ion-Selective Electrodes Box 14-2 Measuring Selectivity Coefficients for an Ion-Selective Electrode Box 14-3 How Was Perchlorate Discovered on Mars?

14-7 Using Ion-Selective Electrodes 14-8 Solid-State Chemical Sensors

15 Redox Titrations Chemical Analysis of High-Temperature Superconductors

15-1 The Shape of a Redox Titration Curve Box 15-1 Many Redox Reactions Are Atom-Transfer Reactions

15-2 Finding the End Point 15-3 15-4 15-5 15-6 15-7

295 297

308 309 311 313 314 317 322

323 324 328

330 331

340 340

341 342

344 345

348 349 350 351 351

How Sweet It Is!

16-1 Fundamentals of Electrolysis Demonstration 16-1 Electrochemical Writing

16-2 Electrogravimetric Analysis 16-3 Coulometry 16-4 Amperometry Box 16-1 Clark Oxygen Electrode

Contents

17 Fundamentals of Spectrophotometry The Ozone Hole

17-1 Properties of Light 17-2 Absorption of Light Box 17-1 Why Is There a Logarithmic Relation Between Transmittance and Concentration? Demonstration 17-1 Absorption Spectra

313

Adjustment of Analyte Oxidation State Oxidation with Potassium Permanganate Oxidation with Ce4⫹ Oxidation with Potassium Dichromate Methods Involving Iodine

16 Electroanalytical Techniques

16-6 Karl Fischer Titration of H2O

308

Demonstration 15-1 Potentiometric Titration of Fe2⫹ with MnO4⫺

Box 15-2 Environmental Carbon Analysis and Oxygen Demand Box 15-3 Iodometric Analysis of High-Temperature Superconductors

Box 16-3 The Electric Double Layer

293

Box 14-1 Systematic Error in Rainwater pH

Measurement: The Effect of Junction Potential

Box 16-2 What Is an “Electronic Nose”?

16-5 Voltammetry

352 355

361 361

362 363

367 369 371 371

17-3 17-4 17-5 17-6

Measuring Absorbance Beer’s Law in Chemical Analysis Spectrophotometric Titrations What Happens When a Molecule Absorbs Light? Box 17-2 Fluorescence All Around Us

17-7 Luminescence Box 17-3 Rayleigh and Raman Scattering

372

376 379

385

393 393

394 395 397 398

399 400 403 404 407

408 411

18 Applications of Spectrophotometry 419 Fluorescence Resonance Energy Transfer Biosensor

18-1 Analysis of a Mixture 18-2 Measuring an Equilibrium Constant: The Scatchard Plot 18-3 The Method of Continuous Variation 18-4 Flow Injection Analysis and Sequential Injection 18-5 Immunoassays and Aptamers 18-6 Sensors Based on Luminescence Quenching Box 18-1 Converting Light into Electricity Box 18-2 Upconversion

19 Spectrophotometers Cavity Ring-Down Spectroscopy: Do You Have an Ulcer?

19-1 Lamps and Lasers: Sources of Light Box 19-1 Blackbody Radiation and the Greenhouse Effect

19-2 Monochromators 19-3 Detectors Box 19-2 The Most Important Photoreceptor Box 19-3 Nondispersive Infrared Measurement of CO2 on Mauna Loa

19-4 Optical Sensors 19-5 Fourier Transform Infrared Spectroscopy 19-6 Dealing with Noise

419

419 424 425 427 431 433 434 437

445 445

447 448

450 454 456 460

461 467 472

ix

20 Atomic Spectroscopy

479

An Anthropology Puzzle

479

20-1 An Overview

480

Box 20-1 Mercury Analysis by Cold Vapor Atomic Fluorescence

482

20-2 Atomization: Flames, Furnaces, and Plasmas 20-3 How Temperature Affects Atomic Spectroscopy 20-4 Instrumentation 20-5 Interference 20-6 Inductively Coupled Plasma–Mass Spectrometry

495 497

502

Separated by a Magnetic Field

504

21-2 Oh, Mass Spectrum, Speak to Me!

Box 24-4 Choosing Gradient Conditions and Scaling Gradients

509

21-3 Types of Mass Spectrometers 21-4 Chromatography–Mass Spectrometry

512 519

Box 21-4 Matrix-Assisted Laser Desorption/Ionization

527

21-5 Open-Air Sampling for Mass Spectrometry

529

22 Introduction to Analytical Separations

537

Measuring Silicones Leaking from Breast Implants

537

22-1 Solvent Extraction

538

Demonstration 22-1 Extraction with Dithizone 540 Box 22-1 Crown Ethers and Phase Transfer Agents 542

What Is Chromatography? A Plumber’s View of Chromatography Efficiency of Separation Why Bands Spread

542 544 548 554

Box 22-2 Microscopic Description of Chromatography

558

565

What Did They Eat in the Year 1000?

23-1 The Separation Process in Gas Chromatography

565

565

Box 23-1 Chiral Phases for Separating

Optical Isomers

570

595 595

596 601 604 606

611 617 623 625 625

25 Chromatographic Methods and Capillary Electrophoresis

634

Capillary Electrochromatography

634

507

Box 21-3 Isotope Ratio Mass Spectrometry

x

24-2 Injection and Detection in HPLC 24-3 Method Development for Reversed-Phase Separations 24-4 Gradient Separations 24-5 Do It with a Computer

502

Box 21-1 Molecular Mass and Nominal Mass 504 Box 21-2 How Ions of Different Masses Are

23-2 23-3 23-4 23-5

Box 24-1 Monolithic Silica Columns Box 24-2 Structure of the Solvent–Bonded Phase Interface Box 24-3 “Green” Technology: Supercritical Fluid Chromatography

502

21-1 What Is Mass Spectrometry?

23 Gas Chromatography

24-1 The Chromatographic Process

487 488 493

Droplet Electrospray

22-2 22-3 22-4 22-5

Paleothermometry: How to Measure Historical Ocean Temperatures

482

Box 20-2 GEOTRACES

21 Mass Spectrometry

24 High-Performance Liquid Chromatography

25-1 Ion-Exchange Chromatography 25-2 Ion Chromatography Box 25-1 Surfactants and Micelles

635 642 645

25-3 Molecular Exclusion Chromatography 25-4 Affinity Chromatography

647 649

Box 25-2 Molecular Imprinting

650

Hydrophobic Interaction Chromatography Principles of Capillary Electrophoresis Conducting Capillary Electrophoresis Lab-on-a-Chip: Probing Brain Chemistry

650 650 657 665

25-5 25-6 25-7 25-8

26 Gravimetric Analysis, Precipitation Titrations, and Combustion Analysis 673 The Geologic Time Scale and Gravimetric Analysis

26-1 Examples of Gravimetric Analysis 26-2 Precipitation Demonstration 26-1 Colloids and Dialysis

26-3 26-4 26-5 26-6 26-7

Examples of Gravimetric Calculations Combustion Analysis Precipitation Titration Curves Titration of a Mixture Calculating Titration Curves with a Spreadsheet 26-8 End-Point Detection Demonstration 26-2 Fajans Titration

673

674 676 677

680 682 685 689 690 691 692

Box 23-2 Chromatography Column on a Chip

576

27 Sample Preparation

Sample Injection Detectors Sample Preparation Method Development in Gas Chromatography

577 579 584 587

Cocaine Use? Ask the River

699

27-1 Statistics of Sampling 27-2 Dissolving Samples for Analysis 27-3 Sample Preparation Techniques

701 705 710

699

Contents

Notes and References Glossary Appendixes A. B. C. D. E. F. G. H. I. J. K.

Logarithms and Exponents Graphs of Straight Lines Propagation of Uncertainty Oxidation Numbers and Balancing Redox Equations Normality Solubility Products Acid Dissociation Constants Standard Reduction Potentials Formation Constants Logarithm of the Formation Constant for the Reaction M(aq) ⫹ L(aq) Δ ML(aq) Analytical Standards

Solutions to Exercises Ans...