QUANTITATIVE CHEMICAL ANALYSIS

Eighth Edition

Daniel C. Harris
Michelson Laboratory
China Lake, California

W. H. Freeman and Company

New York
This page intentionally left blank
 BRIEF CONTENTS

0 The Analytical Process 1 18 Applications

of Spectrophotometry 419
1 Chemical Measurements 13
19 Spectrophotometers 445
2 Tools of the Trade 29
20 Atomic Spectroscopy 479
3 Experimental Error 51
21 Mass Spectrometry 502
4 Statistics 68
22 Introduction to Analytical
5 Quality Assurance and
Separations 537
Calibration Methods 96
23 Gas Chromatography 565
6 Chemical Equilibrium 117
24 High-Performance Liquid
7 Activity and the Systematic
Chromatography 595
Treatment of Equilibrium 142
25 Chromatographic Methods
8 Monoprotic Acid-Base Equilibria 162
and Capillary Electrophoresis 634
9 Polyprotic Acid-Base Equilibria 185
26 Gravimetric Analysis,
10 Acid-Base Titrations 205 Precipitation Titrations, and
Combustion Analysis 673
11 EDTA Titrations 236
27 Sample Preparation 699
12 Advanced Topics in Equilibrium 258

13 Fundamentals of Electrochemistry 279

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

Answers to Problems AN1
17 Fundamentals of
Spectrophotometry 393 Index I1

v
This page intentionally left blank
 CONTENTS

Preface xiii Box 3-2 Keeling’s Exquisitely Precise

Measurement of CO2 60
3-5 Propagation of Uncertainty from
0 The Analytical Process 1 Systematic Error 62
The “Most Important” Environmental
Data Set of the Twentieth Century 1 4 Statistics 68
0-1 Charles David Keeling and the Measurement
of Atmospheric CO2 1 Is My Red Blood Cell Count High Today? 68
0-2 The Analytical Chemist’s Job 6 4-1 Gaussian Distribution 68
0-3 General Steps in a Chemical Analysis 11 4-2 Confidence Intervals 73
Box 0-1 Constructing a Representative Sample 12 4-3 Comparison of Means with Student’s t 76
Box 4-1 Choosing the Null Hypothesis in
Epidemiology 79
1 Chemical Measurements 13 4-4 Comparison of Standard Deviations with
Biochemical Measurements with a the F Test 80
Nanoelectrode 13 4-5 t Tests with a Spreadsheet 82
1-1 SI Units 13 4-6 Grubbs Test for an Outlier 83
1-2 Chemical Concentrations 16 4-7 The Method of Least Squares 83
1-3 Preparing Solutions 19 4-8 Calibration Curves 87
1-4 Stoichiometry Calculations for Box 4-2 Using a Nonlinear Calibration
Gravimetric Analysis 21 Curve 88
1-5 Introduction to Titrations 22 4-9 A Spreadsheet for Least Squares 89
Box 1-1 Reagent Chemicals and Primary Standards 23
1-6 Titration Calculations 24 5 Quality Assurance and
Calibration Methods 96
2 Tools of the Trade 29 The Need for Quality Assurance 96
Quartz Crystal Microbalance in 5-1 Basics of Quality Assurance 97
Medical Diagnosis 29 Box 5-1 Control Charts 99
2-1 Safe, Ethical Handling of Chemicals 5-2 Method Validation 100
and Waste 30 Box 5-2 The Horwitz Trumpet: Variation in
2-2 The Lab Notebook 31 Interlaboratory Precision 103
2-3 Analytical Balance 31 5-3 Standard Addition 106
2-4 Burets 35 5-4 Internal Standards 109
2-5 Volumetric Flasks 37 5-5 Efficiency in Experimental Design 110
2-6 Pipets and Syringes 38
2-7 Filtration 40 6 Chemical Equilibrium 117
2-8 Drying 41
2-9 Calibration of Volumetric Glassware 42 Chemical Equilibrium in the Environment 117
2-10 Introduction to Microsoft Excel® 43 6-1 The Equilibrium Constant 118
2-11 Graphing with Microsoft Excel 46 6-2 Equilibrium and Thermodynamics 119
Reference Procedure Calibrating a 6-3 Solubility Product 121
50-mL Buret 49 Box 6-1 Solubility Is Governed by More Than
the Solubility Product 122
3 Demonstration 6-1 Common Ion Effect 122
Experimental Error 51
6-4 Complex Formation 124
Experimental Error 51 Box 6-2 Notation for Formation Constants 124
3-1 Significant Figures 51 6-5 Protic Acids and Bases 126
3-2 Significant Figures in Arithmetic 52 6-6 pH 128
3-3 Types of Error 55 6-7 Strengths of Acids and Bases 130
Box 3-1 Case Study in Ethics: Systematic Error Demonstration 6-2 The HCl Fountain 131
in Ozone Measurement 55 Box 6-3 The Strange Behavior of
3-4 Propagation of Uncertainty from Hydrofluoric Acid 132
Random Error 57 Box 6-4 Carbonic Acid 134

vii
 7 Activity and the Systematic 10-6 Finding the End Point with Indicators 219
Box 10-2 What Does a Negative pH Mean? 220
Treatment of Equilibrium 142
Demonstration 10-1 Indicators and the Acidity
Hydrated Ions 142 of CO2 221
7-1 The Effect of Ionic Strength on Solubility 10-7 Practical Notes 223
of Salts 143 10-8 Kjeldahl Nitrogen Analysis 223
Demonstration 7-1 Effect of Ionic Strength Box 10-3 Kjeldahl Nitrogen Analysis Behind
on Ion Dissociation 143 the Headlines 224
Box 7-1 Salts with Ions of Charge ⱖ| 2| 10-9 The Leveling Effect 225
Do Not Fully Dissociate 145 10-10 Calculating Titration Curves with
7-2 Activity Coefficients 145 Spreadsheets 226
7-3 pH Revisited 149 Reference Procedure Preparing Standard
7-4 Systematic Treatment of Equilibrium 150 Acid and Base 235
Box 7-2 Calcium Carbonate Mass Balance
in Rivers 153 11 EDTA Titrations 236
7-5 Applying the Systematic Treatment
of Equilibrium 153 Ion Channels in Cell Membranes 236
11-1 Metal-Chelate Complexes 237
8 Box 11-1 Chelation Therapy and Thalassemia 238
Monoprotic Acid-Base Equilibria 162 11-2 EDTA 240
Measuring pH Inside Cellular Compartments 162 11-3 EDTA Titration Curves 243
8-1 Strong Acids and Bases 163 11-4 Do It with a Spreadsheet 245
Box 8-1 Concentrated HNO3 Is Only Slightly 11-5 Auxiliary Complexing Agents 246
Dissociated 163 Box 11-2 Metal Ion Hydrolysis Decreases
8-2 Weak Acids and Bases 165 the Effective Formation Constant for
8-3 Weak-Acid Equilibria 166 EDTA Complexes 247
Demonstration 8-1 Conductivity of Weak 11-6 Metal Ion Indicators 249
Electrolytes 167 Demonstration 11-1 Metal Ion Indicator
Box 8-2 Dyeing Fabrics and the Fraction of Color Changes 249
Dissociation 169 11-7 EDTA Titration Techniques 251
8-4 Weak-Base Equilibria 170 Box 11-3 Water Hardness 253
8-5 Buffers 171
Box 8-3 Strong Plus Weak Reacts Completely 174 12 Advanced Topics in Equilibrium 258
Demonstration 8-2 How Buffers Work 176
Acid Rain 258
12-1 General Approach to Acid-Base Systems 259
9 Polyprotic Acid-Base Equilibria 185 12-2 Activity Coefficients 262
Proteins Are Polyprotic Acids and Bases 185 12-3 Dependence of Solubility on pH 265
9-1 Diprotic Acids and Bases 186 12-4 Analyzing Acid-Base Titrations
Box 9-1 Carbon Dioxide in the Air and Ocean 189 with Difference Plots 270
Box 9-2 Successive Approximations 191
9-2 Diprotic Buffers 193 13 Fundamentals of Electrochemistry 279
9-3 Polyprotic Acids and Bases 194
9-4 Which Is the Principal Species? 195 Lithium-Ion Battery 279
9-5 Fractional Composition Equations 197 13-1 Basic Concepts 280
9-6 Isoelectric and Isoionic pH 199 Box 13-1 Ohm’s Law, Conductance,
Box 9-3 Isoelectric Focusing 200 and Molecular Wire 283
13-2 Galvanic Cells 284
Demonstration 13-1 The Human Salt
10 Acid-Base Titrations 205 Bridge 286
Acid-Base Titration of a Protein 205 13-3 Standard Potentials 287
10-1 Titration of Strong Base with Strong Acid 206 13-4 Nernst Equation 288
10-2 Titration of Weak Acid with Strong Base 208 Box 13-2 E° and the Cell Voltage Do
10-3 Titration of Weak Base with Strong Acid 210 Not Depend on How You Write the
10-4 Titrations in Diprotic Systems 212 Cell Reaction 290
10-5 Finding the End Point with a pH Electrode 215 Box 13-3 Latimer Diagrams: How to Find E°
Box 10-1 Alkalinity and Acidity 216 for a New Half-Reaction 292

viii Contents
13-5 E° and the Equilibrium Constant 293 Box 16-2 What Is an “Electronic Nose”? 372
Box 13-4 Concentrations in the 16-5 Voltammetry 376
Operating Cell 293 Box 16-3 The Electric Double Layer 379
13-6 Cells as Chemical Probes 295 16-6 Karl Fischer Titration of H2O 385
13-7 Biochemists Use E°⬘ 297
17 Fundamentals of
14 Electrodes and Potentiometry 308 Spectrophotometry 393
Chem Lab on Mars 308
The Ozone Hole 393
14-1 Reference Electrodes 309
17-1 Properties of Light 394
14-2 Indicator Electrodes 311
17-2 Absorption of Light 395
Demonstration 14-1 Potentiometry with an
Box 17-1 Why Is There a Logarithmic
Oscillating Reaction 313
Relation Between Transmittance and
14-3 What Is a Junction Potential? 313
Concentration? 397
14-4 How Ion-Selective Electrodes Work 314
Demonstration 17-1 Absorption Spectra 398
14-5 pH Measurement with a Glass Electrode 317
Box 14-1 Systematic Error in Rainwater pH
17-3 Measuring Absorbance 399
17-4 Beer’s Law in Chemical Analysis 400
Measurement: The Effect of Junction
17-5 Spectrophotometric Titrations 403
Potential 322
17-6 What Happens When a Molecule
14-6 Ion-Selective Electrodes 323
Absorbs Light? 404
Box 14-2 Measuring Selectivity Coefficients
Box 17-2 Fluorescence All Around Us 407
for an Ion-Selective Electrode 324
17-7 Luminescence 408
Box 14-3 How Was Perchlorate Discovered
Box 17-3 Rayleigh and Raman Scattering 411
on Mars? 328
14-7 Using Ion-Selective Electrodes 330
14-8 Solid-State Chemical Sensors 331 18 Applications of Spectrophotometry 419
Fluorescence Resonance Energy Transfer
15 Redox Titrations 340 Biosensor 419
Chemical Analysis of High-Temperature 18-1 Analysis of a Mixture 419
Superconductors 340 18-2 Measuring an Equilibrium Constant:
15-1 The Shape of a Redox Titration Curve 341 The Scatchard Plot 424
Box 15-1 Many Redox Reactions Are 18-3 The Method of Continuous Variation 425
Atom-Transfer Reactions 342 18-4 Flow Injection Analysis and Sequential
15-2 Finding the End Point 344 Injection 427
Demonstration 15-1 Potentiometric Titration
18-5 Immunoassays and Aptamers 431
of Fe2⫹ with MnO4⫺ 345
18-6 Sensors Based on Luminescence
15-3 Adjustment of Analyte Oxidation State 348 Quenching 433
Box 18-1 Converting Light into Electricity 434
15-4 Oxidation with Potassium Permanganate 349
15-5 Oxidation with Ce4⫹ 350 Box 18-2 Upconversion 437
15-6 Oxidation with Potassium Dichromate 351
15-7 Methods Involving Iodine 351 19 Spectrophotometers 445
Box 15-2 Environmental Carbon Analysis
and Oxygen Demand 352 Cavity Ring-Down Spectroscopy: Do You
Box 15-3 Iodometric Analysis of Have an Ulcer? 445
High-Temperature Superconductors 355 19-1 Lamps and Lasers: Sources of Light 447
Box 19-1 Blackbody Radiation and
the Greenhouse Effect 448
16 Electroanalytical Techniques 361 19-2 Monochromators 450
How Sweet It Is! 361 19-3 Detectors 454
16-1 Fundamentals of Electrolysis 362 Box 19-2 The Most Important Photoreceptor 456
Demonstration 16-1 Electrochemical Box 19-3 Nondispersive Infrared
Writing 363 Measurement of CO2 on Mauna Loa 460
16-2 Electrogravimetric Analysis 367 19-4 Optical Sensors 461
16-3 Coulometry 369 19-5 Fourier Transform Infrared
16-4 Amperometry 371 Spectroscopy 467
Box 16-1 Clark Oxygen Electrode 371 19-6 Dealing with Noise 472

Contents ix
20 Atomic Spectroscopy 479 24 High-Performance Liquid
An Anthropology Puzzle 479 Chromatography 595
20-1 An Overview 480 Paleothermometry: How to Measure
Box 20-1 Mercury Analysis by Cold Vapor Historical Ocean Temperatures 595
Atomic Fluorescence 482 24-1 The Chromatographic Process 596
20-2 Atomization: Flames, Furnaces, and Plasmas 482 Box 24-1 Monolithic Silica Columns 601
20-3 How Temperature Affects Atomic Box 24-2 Structure of the Solvent–Bonded
Spectroscopy 487 Phase Interface 604
20-4 Instrumentation 488 Box 24-3 “Green” Technology: Supercritical
20-5 Interference 493 Fluid Chromatography 606
20-6 Inductively Coupled Plasma–Mass 24-2 Injection and Detection in HPLC 611
Spectrometry 495 24-3 Method Development for Reversed-Phase
Box 20-2 GEOTRACES 497 Separations 617
24-4 Gradient Separations 623
21 Mass Spectrometry 502 24-5 Do It with a Computer 625
Box 24-4 Choosing Gradient Conditions
Droplet Electrospray 502 and Scaling Gradients 625
21-1 What Is Mass Spectrometry? 502
Box 21-1 Molecular Mass and Nominal Mass 504
Box 21-2 How Ions of Different Masses Are 25 Chromatographic Methods
Separated by a Magnetic Field 504 and Capillary Electrophoresis 634
21-2 Oh, Mass Spectrum, Speak to Me! 507 Capillary Electrochromatography 634
Box 21-3 Isotope Ratio Mass Spectrometry 509 25-1 Ion-Exchange Chromatography 635
21-3 Types of Mass Spectrometers 512 25-2 Ion Chromatography 642
21-4 Chromatography–Mass Spectrometry 519 Box 25-1 Surfactants and Micelles 645
Box 21-4 Matrix-Assisted Laser 25-3 Molecular Exclusion Chromatography 647
Desorption/Ionization 527 25-4 Affinity Chromatography 649
21-5 Open-Air Sampling for Mass Spectrometry 529 Box 25-2 Molecular Imprinting 650
25-5 Hydrophobic Interaction Chromatography 650
22 Introduction to Analytical 25-6 Principles of Capillary Electrophoresis 650
Separations 537 25-7 Conducting Capillary Electrophoresis 657
25-8 Lab-on-a-Chip: Probing Brain Chemistry 665
Measuring Silicones Leaking from Breast
Implants 537
22-1 Solvent Extraction 538
26 Gravimetric Analysis, Precipitation
Demonstration 22-1 Extraction with Dithizone 540 Titrations, and Combustion
Box 22-1 Crown Ethers and Phase Analysis 673
Transfer Agents 542 The Geologic Time Scale and Gravimetric
22-2 What Is Chromatography? 542 Analysis 673
22-3 A Plumber’s View of Chromatography 544 26-1 Examples of Gravimetric Analysis 674
22-4 Efficiency of Separation 548 26-2 Precipitation 676
22-5 Why Bands Spread 554 Demonstration 26-1 Colloids and Dialysis 677
Box 22-2 Microscopic Description of 26-3 Examples of Gravimetric Calculations 680
Chromatography 558 26-4 Combustion Analysis 682
26-5 Precipitation Titration Curves 685
23 Gas Chromatography 565 26-6 Titration of a Mixture 689
26-7 Calculating Titration Curves with a
What Did They Eat in the Year 1000? 565 Spreadsheet 690
23-1 The Separation Process in Gas 26-8 End-Point Detection 691
Chromatography 565 Demonstration 26-2 Fajans Titration 692
Box 23-1 Chiral Phases for Separating
Optical Isomers 570
27 Sample Preparation 699
Box 23-2 Chromatography Column on a Chip 576
23-2 Sample Injection 577 Cocaine Use? Ask the River 699
23-3 Detectors 579 27-1 Statistics of Sampling 701
23-4 Sample Preparation 584 27-2 Dissolving Samples for Analysis 705
23-5 Method Development in Gas Chromatography 587 27-3 Sample Preparation Techniques 710

x Contents
Notes and References NR1 25. Measuring Manganese in Steel by Spectrophotometry
with Standard Addition
Glossary GL1 26. Measuring Manganese in Steel by Atomic
Appendixes AP1 Absorption Using a Calibration Curve
27. Properties of an Ion-Exchange Resin
A. Logarithms and Exponents AP1 28. Analysis of Sulfur in Coal by Ion Chromatography
B. Graphs of Straight Lines AP2 29. Measuring Carbon Monoxide in Automobile Exhaust
C. Propagation of Uncertainty AP3 by Gas
D. Oxidation Numbers and Balancing Redox 30. Amino Acid Analysis by Capillary Electrophoresis
Equations AP5 31. DNA Composition by High-Performance Liquid
E. Normality AP8 Chromatography
F. Solubility Products AP9 32. Analysis of Analgesic Tablets by High-Performance
G. Acid Dissociation Constants AP11 Liquid Chromatography
H. Standard Reduction Potentials AP20 33. Anion Content of Drinking Water by Capillary
I. Formation Constants AP28 Electrophoresis
J. Logarithm of the Formation Constant for the 34. Green Chemistry: Liquid Carbon Dioxide Extraction
Reaction M(aq) ⫹ L(aq) Δ ML(aq) AP31 of Lemon Peel Oil
K. Analytical Standards AP32
Solutions to Exercises S1 Spreadsheet Topics
Answers to Problems AN1 2-100 Introduction to Microsoft Excel 43
2-11 Graphing with Microsoft Excel 46
Index I1 Problem 3-8 Controlling the appearance of a graph 66
4-1 Average, standard deviation 70
Experiments 4-1 Area under a Gaussian curve (NORMDIST) 71
4-3 t Distribution (TDIST) 80
Experiments are found at the Web site
Table 4-4 F Distribution (FINV) 81
www.whfreeman.com/qca8e
4-5 t Test 82
0. Green Chemistry 4-7 Equation of a straight line (SLOPE
1. Calibration of Volumetric Glassware and INTERCEPT) 85
2. Gravimetric Determination of Calcium as 4-7 Equation of a straight line (LINEST) 86
CaC2O4 ⴢ H2O 4-9 Spreadsheet for least squares 89
3. Gravimetric Determination of Iron as Fe2O3 4-9 Error bars on graphs 90
4. Penny Statistics 5-2 Square of the correlation coefficient,
5. Statistical Evaluation of Acid-Base Indicators R2 (LINEST) 101
6. Preparing Standard Acid and Base 5-5 Multiple linear regression and experimental
7. Using a pH Electrode for an Acid-Base Titration design (LINEST) 110
8. Analysis of a Mixture of Carbonate and Bicarbonate Problem 5-15 Using TRENDLINE 113
9. Analysis of an Acid-Base Titration Curve: The Gran Plot 7-5 Solving equations with Excel GOAL SEEK 158
10. Fitting a Titration Curve with Excel Solver Problem 7-29 Circular reference 161
11. Kjeldahl Nitrogen Analysis 8-5 Excel GOAL SEEK and naming cells 181
12. EDTA Titration of Ca2⫹ and Mg2⫹ in Natural Waters 10-10 Acid-base titration 226
13. Synthesis and Analysis of Ammonium Decavanadate 11-4 EDTA titrations 245
14. Iodimetric Titration of Vitamin C Problem 11-19 Auxiliary complexing agents
15. Preparation and Iodometric Analysis of High- in EDTA titrations 256
Temperature Superconductor Problem 11-21 Complex formation 256
16. Potentiometric Halide Titration with Ag⫹ 12-1 Using Excel SOLVER 261
17. Electrogravimetric Analysis of Copper 12-2 Activity coefficients with the Davies equation 262
18. Polarographic Measurement of an Equilibrium Constant 12-4 Fitting nonlinear curves by least squares 272
19. Coulometric Titration of Cyclohexene with Bromine 12-4 Using Excel SOLVER for more than one
20. Spectrophotometric Determination of Iron in Vitamin unknown 273
Tablets 18-1 Solving simultaneous equations with Excel
21. Microscale Spectrophotometric Measurement of Iron SOLVER 419
in Foods by Standard Addition 18-1 Solving simultaneous equations by
22. Spectrophotometric Measurement of an Equilibrium matrix inversion 422
Constant Problem 23-30 Binomial distribution for isotope
23. Spectrophotometric Analysis of a Mixture: Caffeine patterns (BINOMDIST) 593
and Benzoic Acid in a Soft Drink 24-5 Computer simulation of a chromatogram 625
24. Mn2⫹ Standardization by EDTA Titration 26-7 Precipitation titration curves 690

Contents xi
Dan’s grandson Samuel discovers that the periodic table
can take you to great places.
 PREFACE

Goals of This Book

M y goals are to provide a sound physical understanding of the principles of analytical chem-
istry and to show how these principles are applied in chemistry and related disciplines—
especially in life sciences and environmental science. I have attempted to present the subject
in a rigorous, readable, and interesting manner that will appeal to students whether or not their
primary interest is chemistry. I intend the material to be lucid enough for nonchemistry
majors, yet to contain the depth required by advanced undergraduates. This book grew out of
an introductory analytical chemistry course that I taught mainly for nonmajors at the
University of California at Davis and from a course for third-year chemistry students at
Franklin and Marshall College in Lancaster, Pennsylvania.

What’s New?
A significant change in this edition that instructors will discover is that the old Chapter 7 on
titrations from earlier editions is missing, but its content is dispersed throughout this edition.
My motive was to remove precipitation titrations from the critical learning path. Precipitation
titrations have decreased in importance and they have not appeared in the last two versions of
the American Chemical Society examination in quantitative analysis.* The introduction to
titrations comes in Chapter 1. Kjeldahl analysis is grouped with acid-base titrations in Chapter 10.
Spectrophotometric titrations appear in Chapter 17 with spectrophotometry. Efficiency in
titrimetric experimental design is now with quality assurance in Chapter 5. Precipitation titra-
tions appear with gravimetric analysis in Chapter 26. Gravimetric analysis and precipitation
titrations remain self-contained topics that can be covered at any point in the course.
A new feature of this edition is a short “Test Yourself” question at the end of each worked
example. If you understand the worked example, you should be able to answer the Test
Yourself question. Compare your answer with mine to see if we agree.
Chapter 0 begins with a biographical account of Charles David Keeling’s measure-
ment of atmospheric carbon dioxide. His results have been described as “the single most
important environmental data set taken in the 20th century.” Boxes in Chapters 3 and 19 pro-
vide detail on Keeling’s precise manometric and spectrometric techniques. Box 9-1 discusses
ocean acidification by atmospheric carbon dioxide.

Preindustrial Present
CO2 CO2
150
2 × Preindustrial CO2

120
[CO32− ] (μmol/kg)

90

Aragonite solubility limit

60

Calcite solubility limit

30 [CO32− ]

0
0 500 1 000 1 500 2 000 Effect of increasing atmospheric CO2 on the
Atmospheric CO2 (ppm by volume) ability of marine organisms to make calcium
carbonate shells and skeletons (Box 9-1).

*P. R. Griffiths, “Whither ‘Quant’? An Examination of the Curriculum and Testing Methods for Quantitative
Analysis Courses Taught in Universities and Colleges in the Western USA,” Anal. Bioanal. Chem. 2008, 391, 875.

Preface xiii
 New boxed applications include biochemical measurements with a nano-
electrode (Chapter 1), the quartz crystal microbalance in medical diagnosis
(Chapter 2), a case study of systematic error (Chapter 3), choosing the null
hypothesis in epidemiology (Chapter 4), a lab-on-a-chip example of iso-
electric focusing (Chapter 9), Kjeldahl nitrogen analysis in the headlines
(Chapter 10), lithium-ion batteries (Chapter 13), measuring selectivity
coefficients of ion-selective electrodes (Chapter 14), how perchlorate was
discovered on Mars (Chapter 14), an updated description of the Clark oxy-
gen electrode (Chapter 16), Rayleigh and Raman scattering (Chapter 17),
spectroscopic upconversion (Chapter 18), trace elements in the ocean
(Chapter 20), phase transfer agents (Chapter 22), gas chromatography on a
chip (Chapter 23), paleothermometry (Chapter 24), structure of the solvent-
bonded phase interface (Chapter 24), and measuring illicit drug use by
analyzing river water (Chapter 27).
Spreadsheet instructions are updated to Excel 2007, but instructions for
Phoenix Mars Lander discovered perchlorate earlier versions of Excel are retained. A new section in Chapter 2 describes how electronic
in Martian soil with ion-selective electrodes
balances work. Rectangular and triangular uncertainty distributions for systematic error are
(Chapter 14).
introduced in Chapter 3. Chapter 4 includes discussion of standard deviation of the mean and
“tails” in probability distributions. The Grubbs test replaces the Dixon Q test for outliers in
Chapter 4. Reporting limits are illustrated with trans fat analysis in food in Chapter 5.
Elementary discussion of the systematic treatment of equilib-
Polymer backbone
rium in Chapter 7 is enhanced with a discussion of ammonia
acid-base chemistry. Chapter 8 and the appendix now include
N N N N N N N N pKa for acids at an ionic strength of 0.1 M in addition to an
N N
+
N N N N N N
ionic strength of 0. Discussion of selectivity coefficients was
e− Os Os
improved in Chapter 14 and the iridium oxide pH electrode is
Glucose
dehydrogenase e− introduced. “Wired” enzymes and mediators for coulometric
e−
Poly(ethylene
e−
blood glucose monitoring are described in Chapter 16.
glycol) link
Voltammetry in Chapter 16 now includes a microelectrode
PQQ PQQH2 array for biological measurements. There is a completely new
section on flow injection analysis and sequential injection in
Chapter 18, and these techniques appear again in later exam-
Carbon ples. Chapter 19 on spectrophotometers is heavily updated.
Glucose Gluconolactone
electrode
Laser-induced breakdown and dynamic reaction cells for
atomic spectrometry are introduced in Chapter 20. Mass spec-
“Wired” enzymes described in Section 16-4 are trometry in Chapter 21 now includes the linear ion trap and the orbitrap, electron-transfer
at the heart of sensitive personal blood glucose dissociation for protein sequencing, and open-air sampling methods.
monitors. Numerous chromatography updates are found throughout Chapters 22–25. Stir-bar
sorption was added to sample preparation in Chapter 23. Polar embedded group stationary
phases, hydrophilic interaction chromatography, and the charged aerosol detector were
added to Chapter 24. There is a discussion of the linear solvent strength model in liquid chro-
matography and a new section that teaches how to use a spreadsheet to predict the effect of
solvent composition in isocratic elution. The supplement at www.whfreeman.com/qca
gives a spreadsheet for simulating gradient elution. Chapter 25 describes hydrophilic inter-
action chromatography for ion exchange, hydrophobic interaction chromatography for
protein purification,
Interaction of (R)- and (S)-naproxen with (S,S) stationary phase analyzing heparin
contamination by
electrophoresis, wall
charge control in elec-
Naphthalene
trophoresis, an update
group
on DNA sequencing
by electrophoresis,
Dinitrophenyl and microdialysis/
(S )-Naproxen group
Chiral stationary phase separates enantiomers
electrophoresis of
(R)-Naproxen
of the drug naproxen by high-performance
(S,S) (S,S) neurotransmitters
More stable adsorbate Less stable adsorbate
liquid chromatography (Figure 24-10). with a lab-on-a-chip.
Data from a round-
robin study of precision and accuracy of combustion analysis are included in Chapter 26.
The 96-well plate for solid-phase extraction sample preparation was added to
Chapter 27.

xiv Preface
 Servo amplifier

Null
Balance pan position
sensor
Force-transmitting lever Coil frame
Internal Load receptor
calibration Wire coil
mass

Parallel Permanent S NN S
guides magnet Precision
resistor
Firm anchor
Analog-
Coil frame to-digital
Firm anchor Mechanical converter
force

Wire coil Electromagnetic Balance display

force
Micro-
122.57 g processor
S N
There is a new discussion of the operation
of an electronic balance in Chapter 2,
Tools of the Trade.

Applications
A basic tenet of this book is to introduce and illustrate topics with concrete, interesting exam-
ples. In addition to their pedagogic value, Chapter Openers, Boxes, Demonstrations, and Color
Plates are intended to help lighten the load of a very dense subject. I hope you will find these
features interesting and informative. Chapter Openers show the relevance of analytical chem-
istry to the real world and to other disciplines of science. I can’t come to your classroom to
present Chemical Demonstrations, but I can tell you about some of my favorites and show
you color photos of how they look. Color Plates are located near the center of the book. Boxes
discuss interesting topics related to what you are studying or amplify points in the text.

Problem Solving
Nobody can do your learning for you. The two most impor-
tant ways to master this course are to work problems and to EXAM PLE How Many Tablets Should We Analyze?
gain experience in the laboratory. Worked Examples are a In a gravimetric analysis, we need enough product to weigh accurately. Each tablet
principal pedagogic tool designed to teach problem solving provides ⬃15 mg of iron. How many tablets should we analyze to provide 0.25 g of
and to illustrate how to apply what you have just read. Each Fe2O3?
worked example ends with a Test Yourself question that ⴢ
asks you to apply what you learned in the example. ⴢ
Exercises are the minimum set of problems that apply most ⴢ
major concepts of each chapter. Please struggle mightily Test Yourself If each tablet provides ⬃20 mg of iron, how many tablets should we
analyze to provide ⬃0.50 g of Fe2O3? (Answer: 18)
with an Exercise before consulting the solution at the back
of the book. Problems at the end of the chapter cover the
entire content of the book. Short answers to numerical problems are at the back of the book
and complete solutions appear in the Solutions Manual that can be made available for purchase
if your instructor so chooses.
Spreadsheets are indispensable tools for sci- A B C D
ence and engineering. You can cover this book 1 Mg(OH) 2 Solubility
2 Spreadsheets are introduced as an
without using spreadsheets, but you will never _ _ 3 _ important problem-solving tool.
regret taking the time to learn to use them. The 3 Ksp = [OH ]guess = [OH ] /(2 + K1[OH ]) =

text explains how to use spreadsheets and some 4 7.1E-12 0.0002459 7.1000E-12

problems ask you to apply them. If you are com- 5 K1 =

6 3.8E+02 [Mg2+] = [MgOH+] = Set cell: D4
fortable with spreadsheets, you will use them
even when the problem does not ask you to. A 7 0.0001174 0.0000110
To value: 7.1E-12
few of the powerful built-in features of Microsoft 8
By changing cell: C4
Excel are described as they are needed. These 9 D4 = C4^3/(2+A6*C4)
10 C7 = A4/C4^2
features include graphing in Chapters 2 and 4, OK Cancel
11 D8 = A6*C7*C4
statistical functions and regression in Chapter 4,

Preface xv
 multiple regression for experimental design in Chapter 5, solving equations with Goal Seek in
Chapters 7, 8, and 12, Solver in Chapters 12 and 18, and matrix operations in Chapter 18.

Other Features of This Book

Terms to Understand Essential vocabulary, highlighted in bold in the text, is col-
lected at the end of the chapter. Other unfamiliar or new terms are italic in the text, but not
listed at the end of the chapter.

Glossary All bold vocabulary terms and many of the italic terms are defined in the glossary.

Appendixes Tables of solubility products, acid dissociation constants, redox potentials,

and formation constants appear at the back of the book. You will also find discussions of log-
arithms and exponents, equations of a straight line, propagation of error, balancing redox
equations, normality, and analytical standards.

Notes and References Citations in the chapters appear at the end of the book.

Supplements
The Solutions Manual for Quantitative Chemical Analysis (ISBN 1-4292-3123-8) contains
complete solutions to all problems.
The student Web site, www.whfreeman.com/qca8e, has directions for experiments,
which may be reproduced for your use. “Green chemistry” is introduced in Chapter 2 of the
textbook and “green profiles” of student experiments are included in the instructions for
experiments at the Web site. There are instructions for two new experiments on fitting an acid-
base titration curve with a spreadsheet and liquid carbon dioxide extraction of lemon peel oil.
At the Web site, you will also find lists of experiments from the Journal of Chemical
Education. Supplementary topics at the Web site include spreadsheets for precipitation titra-
tions, microequilibrium constants, spreadsheets for redox titrations curves, analysis of vari-
ance, and spreadsheet simulation of gradient liquid chromatography. Online quizzing helps
students reinforce their understanding of the chapter content.
The instructors’ Web site, www.whfreeman.com/qca8e, has all artwork and tables
from the book in preformatted PowerPoint slides and as JPG files, an online quizzing grade-
book, and more.
For instructors interested in online homework management, W. H. Freeman and
WebAssign have partnered to deliver WebAssign Premium. WebAssign Premium combines
over 600 questions with a fully interactive DynamicBook at an affordable price. To learn more
WebAssign Premium logo. or sign up for a faculty demo account, visit www.webassign.net.
DynamicBook for Quantitative Chemical Analysis, Eighth Edition, is an electronic
version of the text that gives you the flexibility to fully tailor content to your presentation of
course material. It can be used in conjunction with the printed text, or it can be adopted on its
own. Please go to www.dynamicbooks.com for more information, or speak with your W. H.
Freeman sales representative.

The People
A book of this size and complexity is the work of many people. Jodi Simpson—the most
thoughtful and meticulous copy editor—read every word with a critical eye and improved the
exposition in innumerable ways. At W. H. Freeman and Company, Jessica Fiorillo provided
overall guidance and was especially helpful in ferreting out opinions from instructors. Mary
Louise Byrd shepherded the manuscript through production with her magic wand. Kristina
Treadway managed the process of moving the book into production, and Anthony Petrites
coordinated the reviewing of every chapter. Ted Sczcepanski located several hard-to-find pho-
tographs for the book. Dave Quinn made sure that the supplements were out on time and that
the Web site was up and running with all its supporting resources active. Katalin Newman, at
Aptara, did an outstanding job of proofreading.
At the Scripps Institution of Oceanography, Ralph Keeling, Peter Guenther, David Moss,
Lynne Merchant, and Alane Bollenbacher shared their knowledge of atmospheric CO2 mea-
surements and graciously provided access to Keeling family photographs. I am especially
delighted to have had feedback from Louise Keeling on my story of her husband, Charles
David Keeling. This material opens the book in Chapter 0. Sam Kounaves of Tufts University

xvi Preface
devoted a day to telling me about the Phoenix Mars Lander Wet Chemistry Laboratory, which
is featured in Chapter 14. Jarda Ruzika of the University of Washington brought the importance
of flow injection and sequential injection to my attention, provided an excellent tutorial, and
reviewed my description of these topics in Chapters 18 and 19. David Sparkman of the
University of the Pacific had detailed comments and suggestions for Chapter 21 on mass spec-
trometry. Joerg Barankewitz of Sartorius AG provided information and graphics on balances
that you will find in Chapter 2.
Solutions to problems and exercises were checked by two wonderfully careful students,
Cassandra Churchill and Linda Lait of the University of Lethbridge in Canada. Eric Erickson
and Greg Ostrom provided helpful information and discussions at Michelson Lab.
My wife, Sally, works on every aspect of every edition of this book and the Solutions
Manual. She contributes mightily to whatever clarity and accuracy we have achieved.

In Closing
This book is dedicated to the students who use it, who occasionally smile when they read it,
who gain new insight, and who feel satisfaction after struggling to solve a problem. I have
been successful if this book helps you develop critical, independent reasoning that you can
apply to new problems. I truly relish your comments, criticisms, suggestions, and corrections.
Please address correspondence to me at the Chemistry Division (Mail Stop 6303), Research
Department, Michelson Laboratory, China Lake CA 93555.

Acknowledgments
I am indebted to many people who asked questions and provided suggestions and new infor-
mation for this edition. They include Robert Weinberger (CE Technologies), Tom Betts
(Kutztown University), Paul Rosenberg (Rochester Institute of Technology), Barbara Belmont
(California State University, Dominguez Hills), David Chen (University of British Columbia),
John Birks (2B Technologies), Bob Kennedy (University of Michigan), D. Brynn Hibbert
(University of New South Wales), Kris Varazo (Francis Marion University), Chongmok Lee
(Ewha Womans University, Korea), Michael Blades (University of British Columbia), D. J.
Asa (ESA, Inc.), F. N. Castellano and T. N. Singh-Rachford (Bowling Green State University),
J. M. Kelly and D. Ledwith (Trinity College, University of Dublin), Justin Ries (University of
North Carolina), Gregory A. Cutter (Old Dominion University), Masoud Agah (Virginia
Tech), Michael E. Rybak (U.S. Centers for Disease Control and Prevention), James Harnly
(U.S. Department of Agriculture), Andrew Shalliker (University of Western Sydney),
R. Graham Cooks (Purdue University), Alexander Makarov (Thermo Fisher Scientific, Bremen),
Richard Mathies (University of California, Berkeley), A. J. Pezhathinal and R. Chan-Yu-King
(University of Science and Arts of Oklahoma), Peter Licence (University of Nottingham), and
Geert Van Biesen (Memorial University of Newfoundland).
People who reviewed parts of the eighth edition manuscript or who reviewed the seventh
edition to make suggestions for the eighth edition include Rosemari Chinni (Alvernia
College), Shelly Minteer (St. Louis University), Charles Cornett (University of
Wisconsin–Platteville), Anthony Borgerding (St. Thomas College), Jeremy Mitchell-Koch
(Emporia State University), Kenneth Metz (Boston College), John K. Young (Mississippi
State University), Abdul Malik (University of Southern Florida), Colin F. Poole (Wayne State
University), Marcin Majda (University of California, Berkeley), Carlos Garcia (University of
Texas, San Antonio), Elizabeth Binamira-Soriaga (Texas A&M University), Erin Gross
(Creighton University), Dale Wood (Bishop’s University), Xin Wen (California State
University, Los Angeles), Benny Chan (The College of New Jersey), Pierre Herckes (Arizona
State University), Daniel Bombick (Wright State University), Sidney Katz (Rutgers
University), Nelly Matteva (Florida A&M University), Michael Johnson (University of
Kansas), Dmitri Pappas (Texas Tech University), Jeremy Lessmann (Washington State
University), Alexa Serfis (Saint Louis University), Stephen Wolf (Indiana State University),
Stuart Chalk (University of North Florida), Barry Lavine (Oklahoma State University),
Katherine Pettigrew (George Mason University), Blair Miller (Grand Valley State University),
Nathalie Wall (Washington State University), Kris Varazo (Francis Marion University), Carrie
Brennan (Austin Peay State University), Lisa Ponton (Elon University), Feng Chen (Rider
University), Eric Ball (Metropolitan State College of Denver), Russ Barrows (Metropolitan
State College of Denver), and Mary Sohn (Florida Institute of Technology).

Preface xvii