**0 The Analytical Process**

Opener: The “Most Important” Environmental Data Set of the 20th Century

0-1 Charles David Keeling and the Measurement of Atmospheric CO2

0-2 The Analytical Chemist's Job

0-32 General Steps in a Chemical Analysis

Box 0-1 Constructing a Representative Sample

**1 Chemical Measurements**

Opener: Biochemical Measurements with a Nanoelectrode

1-1 SI Units

1-2 Chemical Concentrations

1-3 Preparing Solutions

1-4 Stoichiometry Calculations for Gravimetric Analysis

7-1 Introduction to Titrations

Box 1-1 Reagent Chemicals and Primary Standards

7-2 Titration Calculations

**2 Tools of the Trade**

Opener: 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**

Opener: 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

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

3-5 Propagation of Uncertainty from Systematic Error

**4 Statistics**

Opener: 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

Box 4-1 Choosing the Null Hypothesis in Epidemiology

4-4 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

Box 4-2 Using a Nonlinear Calibration Curve

4-9 A Spreadsheet for Least Squares

**5 Quality Assurance and Calibration Methods**

Opener: The Need for Quality Assurance

5-1 Basics of Quality Assurance

Box 5-1 Control Charts

5-2 Method Validation

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**

Opener: 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

**7 Activity and the Systematic Treatment of Equilibrium**

Opener: 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 = 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

**8 Monoprotic Acid-Base Equilibria**

Opener: 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 Polyprotic Acid-Base Equilibria**

Opener: Proteins are Polyprotic Acids and Bases

9-1 Diprotic Acids and Bases

Box 9-1 Carbon Dioxide in the Air and Ocean (new)

Box 9-2 Successive Approximations

9-2 Diprotic Buffers

9-3 Polyprotic Acids and Bases

9-4 Which Is the Principal Species?

9-5 Fractional Composition Equations

9-6 Isoelectric and Isoionic pH

Box 9-3 Isoelectric Focusing

**10 Acid-Base Titrations**

Opener: Acid-Base Titration of a Protein

10-1 Titration of Strong Base with Strong Acid

10-2 Titration of Weak Acid with Strong Base

10-3 Titration of Weak Base with Strong Acid

10-4 Titrations in Diprotic Systems

10-5 Finding the End Point with a pH Electrode

Box 10-1 Alkalinity and Acidity

10-6 Finding the End Point with Indicators

Demonstration 10-1 Indicators and the Acidity of CO2

Box 10-2 What Does a Negative pH Mean?

10-7 Practical Notes

10-8 Kjeldahl Nitrogen Analysis

Box 10-3 Kjeldahl Nitrogen Analysis Behind the Headline

10-9 Leveling Effect

10-10 Calculating Titration Curves with Spreadsheets

Reference Procedure: Preparing Standard Acid and Base

**11 EDTA Titrations**

Opener: Ion Channels in Cell Membranes

11-1 Metal-Chelate Complexes

Box 11-1 Chelation Therapy and Thalassemia

11-2 EDTA

11-3 EDTA Titration Curves

11-4 Do It with a Spreadsheet

11-5 Auxiliary Complexing Agents

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

EDTA Complexes

11-6 Metal Ion Indicators

Demonstration 13-1 Metal Ion Indicator Color Changes

11-7 EDTA Titration Techniques

Box 11-3 Water Hardness

**12 Advanced Topics in Equilibrium**

Opener: Acid Rain

12-1 General Approach to Acid-Base Systems

12-2 Activity Coefficients

12-3 Dependence of Solubility on pH

12-4 Analyzing Acid-Base Titrations with Difference Plots

**13 Fundamentals of Electrochemistry**

Opener: Lithium-Ion Battery

13-1 Basic Concepts

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

13-2 Galvanic Cells

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

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**

Opener: 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

Box 14-1 Systematic Error in Rainwater pH Measurement The Effect of Junction Potential

14-6 Ion-Selective Electrodes

Box 14-2 Measuring Selectivity Coefficients for an Ion-Selective Electrode (new)

Box 14-3 How Was Perchlorate Discovered on Mars? (new)

14-7 Using Ion-Selective Electrodes

14-8 Solid-State Chemical Sensors

**15 Redox Titrations**

Opener: 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

Demonstration 15-1 Potentiometric Titration of Fe2+ with MnO4-

15-2 Finding the End Point

15-3 Adjustment of Analyte Oxidation State

15-4 Oxidation with Potassium Permanganate

15-5 Oxidation with Ce4+

15-6 Oxidation with Potassium Dichromate

Box 15-2 Environmental Carbon Analysis and Oxygen Demand

15-7 Methods Involving Iodine

Box 15-3 Iodometric Analysis of High-Temperature Superconductors

**16 Electroanalytical Techniques**

Opener: How Sweet It Is!

Demonstration 16-1 Electrochemical Writing

16-1 Fundamentals of Electrolysis

16-2 Electrogravimetric Analysis

16-3 Coulometry

16-4 Amperometry

Box 16-1 Clark Oxygen Electrode

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

16-5 Voltammetry

Box 16-3 The Electric Double Layer

16-6 Karl Fischer Titration of H2O

**17 Fundamentals of Spectrophotometry**

Opener: 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

17-3 Measuring Absorbance

17-4 Beer's Law in Chemical Analysis

17-5 Spectrophotometric Titrations

17-6 What Happens When a Molecule Absorbs Light?

Box 17-2 Fluorescence All Around Us

17-7 Luminescence

Box 17-3 Rayleigh and Raman Scattering

**18 Applications of Spectrophotometry**

Opener: 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**

Opener: 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 Nondisperesive Infrared Measurement of CO2 on Mauna Loa

19-4 Optical Sensors

19-5 Fourier Transform Infrared Spectroscopy

19-6 Dealing with Noise

**20 Atomic Spectroscopy**

Opener: An Anthropology Puzzle

20-1 An Overview

Box 20-1 Mercury Analysis by Cold Vapor Atomic Fluorescence

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

Box 20-2 GEOTRACES

**21 Mass Spectrometry**

Opener: Droplet Electrospray

21-1 What Is Mass Spectrometry?

Box 21-1 Molecular Mass and Nominal Mass

Box 21-2 How Ions of Different Masses Are Separated by a Magnetic Field

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

Box 21-3 Isotope Ratio Mass Spectrometry

21-3 Types of Mass Spectrometers

21-4 Chromatography–Mass Spectrometry

Box 21-4 Matrix-Assisted Laser Desorption/Ionization

21-5 Open-Air Sampling for Mass Spectrometry

**22 Introduction to Analytical Separations**

Opener: Measuring Silicones Leaking from Breast Implants

22-1 Solvent Extraction

Demonstration 22-1 Extraction with Dithizone

Box 22-1 Crown Ethers and Phase Transfer Agents

22-2 What Is Chromatography?

22-3 A Plumber's View of Chromatography

22-4 Efficiency of Separation

22-5 Why Bands Spread

Box 22-2 Microscopic Description of Chromatography

**23 Gas Chromatography**

Opener: What Did They Eat in the Year 1000?

23-1 The Separation Process in Gas Chromatography

Box 23-1 Chiral Phases for Separating Optical Isomers

Box 23-2 Chromatography Column on a Chip (new)

23-2 Sample Injection

23-3 Detectors

23-4 Sample Preparation

23-5 Method Development in Gas Chromatography

**24 High-Performance Liquid Chromatography**

Opener: Paleothermometry: How to Measure Historical Ocean Temperatures

24-1 The Chromatographic Process

Box 24-1 Monolithic Silica Columns

Box 24-2 Structure of the Solvent–Bonded Phase Interface

Box 24-3 “Green” Technology: Supercritical Fluid Chromatography

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!

Box 24-4 Choosing Gradient Conditions and Scaling Gradients

**25 Chromatographic Methods and Capillary Electrophoresis**

Opener: Capillary Electrochromatography

25-1 Ion-Exchange Chromatography

25-2 Ion Chromatography

Box 25-1 Surfactants and Micelles

25-3 Molecular Exclusion Chromatography

25-4 Affinity Chromatography

Box 25-2 Molecular Imprinting

25-5 Hydrophobic Interaction Chromatography (new)

25-6 Principles of Capillary Electrophoresis

25-7 Conducting Capillary Electrophoresis

25-8 Lab-on-a-Chip: Probing Brain Chemistry

**26 Gravimetric Analysis, Precipitation Titrations, and Combustion Analysis**

Opener: The Geologic Time Scale and Gravimetric Analysis

26-1 Examples of Gravimetric Analysis

26-2 Precipitation

Demonstration 26-1 Colloids and Dialysis

26-3 Examples of Gravimetric Calculations

26-4 Combustion Analysis

26-5 Precipitation Titration Curves

26-6 Titration of a Mixture

26-7 Calculating Titration Curves with a Spreadsheet

26-8 End-Point Detection

Demonstration 26-2 Fajans Titration

**27 Sample Preparation**

Opener: Cocaine Use? Ask the River

27-1 Statistics of Sampling

27-2 Dissolving Samples for Analysis

27-3 Sample Preparation Techniques

**Notes and References**

**Glossary**

**Appendices**

A. Logarithms and Exponents

B. Graphs of Straight Lines

C. Propagation of Uncertainty

New material added

D. Oxidation Numbers and Balancing Redox Equations

E. Normality

F. Solubility Products

G. Acid Dissociation Constants

H. Standard Reduction Potentials

I. Formation Constants

J. Logarithm of the Formation Constant for the Reaction M(aq) + L(aq) ML(aq)

K. Analytical Standards

Solutions to Exercises

Answers to Problems

Index

**Experiments**

Experiments are found at the web site www.whfreeman.com/qca/

0. Green Chemistry

1. Calibration of Volumetric Glassware

2 Gravimetric Determination of Calcium as CaC2O4.H2O

3. Gravimetric Determination of Iron as Fe2O3

4. Penny Statistics

5. Statistical Evaluation of Acid-Base Indicators

6. Preparing Standard Acid and Base

7. Using a pH Electrode for an Acid-Base Titration

8. Analysis of a Mixture of Carbonate and Bicarbonate

9. Analysis of an Acid-Base Titration Curve: The Gran Plot

10. Fitting a Titration Curve with Excel Solver®

11. Kjeldahl Nitrogen Analysis

12. EDTA Titration of Ca2+ and Mg2+ in Natural Waters

13. Synthesis and Analysis of Ammonium Decavanadate

14. Iodimetric Titration of Vitamin C

15. Preparation and Iodometric Analysis of High-Temperature Superconductor

16. Potentiometric Halide Titration with Ag+

17. Electrogravimetric Analysis of Copper

18. Polarographic Measurement of an Equilibrium Constant

19. Coulometric Titration of Cyclohexene with Bromine

20. Spectrophotometric Determination of Iron in Vitamin Tablets

21. Microscale Spectrophotometric Measurement of Iron in Foods by Standard Addition

22. Spectrophotometric Measurement of an Equilibrium Constant

23. Spectrophotometric Analysis of a Mixture: Caffeine and Benzoic Acid in a Soft Drink

24. Mn2+ Standardization by EDTA Titration

25. Measuring Manganese in Steel by Spectrophotometry with Standard Addition

26. Measuring Manganese in Steel by Atomic Absorption Using a Calibration Curve

27. Properties of an Ion-Exchange Resin

28. Analysis of Sulfur in Coal by Ion Chromatography

29. Measuring Carbon Monoxide in Automobile Exhaust by Gas Chromatography

30. Amino Acid Analysis by Capillary Electrophoresis

31. DNA Composition by High-Performance Liquid Chromatography

32. Analysis of Analgesic Tablets by High Performance Liquid Chromatography

33. Anion Content of Drinking Water by Capillary Electrophoresis

34. Green Chemistry: Liquid Carbon Dioxide Extraction of Lemon Peel Oil

Spreadsheet Topics (Not yet Updated for 8e)

2-10 Introduction to Microsoft Excel

2-11 Graphing with Microsoft Excel

Problem 3-8 Controlling the appearance of a graph

4-1 Average, standard deviation, normal distribution

4-5 t-Test

4-7 Equation of a straight line

4-9 Spreadsheet for least squares

Problem 4-25 Adding error bars to a graph

5-2 Square of the correlation coefficient (R2)

Problem 5-14 Using TRENDLINE

6-8 Solving equations with Excel GOAL SEEK

7-6 Precipitation titration curves

7-8 Multiple linear regression and experimental design

8-5 Using GOAL SEEK in equilibrium problems

Problem 8-27 Circular reference

9-5 Excel GOAL SEEK and naming cells

11-9 Acid-base titration curves

12-4 EDTA titrations

Problem 12-18 Auxiliary complexing agents in EDTA titrations

Problem 12-20 Complex formation

13-1 Using Excel SOLVER

13-2 Activity coefficients with the Davies equation

13-4 Fitting nonlinear curves by least squares

13-4 Using Excel SOLVER for more than one unknown

19-1 Solving simultaneous equations with Excel SOLVER

19-1 Solving simultaneous equations by matrix inversion

Problem 24-29 Binomial distribution function for isotope patterns