| |
| |
| Preface | |
| |
| |
| |
| The Analytical Process: The Central Role of Analytical Chemistry | |
| |
| |
| |
| The Analytical Chemist's Job | |
| |
| |
| |
| General Steps in a Chemical Analysis | |
| |
| |
| |
| Constructing a Representative Sample | |
| |
| |
| |
| Measurements: Chemical Analysis in Environmental Science | |
| |
| |
| |
| SI Units | |
| |
| |
| |
| Chemical Concentrations | |
| |
| |
| |
| Preparing Solutions | |
| |
| |
| |
| Solutions and Stoichiometry | |
| |
| |
| |
| Tools of the Trade: Weighing Femtomoles of DNA | |
| |
| |
| |
| Safe, Ethical Handling of Chemicals and Waste | |
| |
| |
| |
| Disposal of Chemical Waste | |
| |
| |
| |
| The Lab Notebook | |
| |
| |
| |
| Analytical Balance | |
| |
| |
| |
| Burets | |
| |
| |
| |
| Volumetric Flasks | |
| |
| |
| |
| Pipets and Syringes | |
| |
| |
| |
| Filtration | |
| |
| |
| |
| Drying | |
| |
| |
| |
| Calibration of Volumetric Glassware | |
| |
| |
| |
| Introduction to Microsoft Excel | |
| |
| |
| |
| Graphing with Microsoft Excel | |
| |
| |
| |
| Experimental Error: Experimental Error | |
| |
| |
| |
| Significant Figures | |
| |
| |
| |
| Significant Figures in Arithmetic | |
| |
| |
| |
| Significant Figures and Graphs | |
| |
| |
| |
| Types of Error | |
| |
| |
| |
| Standard Reference Materials | |
| |
| |
| |
| Propagation of Uncertainty | |
| |
| |
| |
| Propagation of Uncertainty in the Product x [middle dot] x | |
| |
| |
| |
| Statistics: Is My Red Blood Cell Count High Today? | |
| |
| |
| |
| Gaussian Distribution | |
| |
| |
| |
| Confidence Intervals | |
| |
| |
| |
| Comparison of Means with Student's t | |
| |
| |
| |
| Analytical Chemistry and the Law | |
| |
| |
| |
| Comparison of Standard Deviations with the F Test | |
| |
| |
| |
| t Tests with a Spreadsheet | |
| |
| |
| |
| Q Test for Bad Data | |
| |
| |
| |
| Calibration Methods: A Historic Calibration Curve | |
| |
| |
| |
| Finding the "Best" Straight Line | |
| |
| |
| |
| Calibration Curves | |
| |
| |
| |
| Using a Nonlinear Calibration Curve | |
| |
| |
| |
| Standard Addition | |
| |
| |
| |
| Internal Standards | |
| |
| |
| |
| A Spreadsheet for Least Squares | |
| |
| |
| |
| Chemical Equilibrium: Chemical Equilibrium in the Environment | |
| |
| |
| |
| The Equilibrium Constant | |
| |
| |
| |
| Equilibrium and Thermodynamics | |
| |
| |
| |
| Solubility Product | |
| |
| |
| |
| The Common Ion Effect | |
| |
| |
| |
| Common Ion Effect | |
| |
| |
| |
| The Logic of Approximations | |
| |
| |
| |
| Separation by Precipitation | |
| |
| |
| |
| Complex Formation | |
| |
| |
| |
| Notation for Formation Constants | |
| |
| |
| |
| Protic Acids and Bases | |
| |
| |
| |
| pH | |
| |
| |
| |
| Strengths of Acids and Bases | |
| |
| |
| |
| The HCl Fountain | |
| |
| |
| |
| The Strange Behavior of Hydrofluoric Acid | |
| |
| |
| |
| Carbonic Acid | |
| |
| |
| |
| Let the Titrations Begin: Evolution of the Buret | |
| |
| |
| |
| Titrations | |
| |
| |
| |
| Titration Calculations | |
| |
| |
| |
| Reagent Chemicals and Primary Standards | |
| |
| |
| |
| Spectrophotometric Titrations | |
| |
| |
| |
| The Precipitation Titration Curve | |
| |
| |
| |
| Titration of a Mixture | |
| |
| |
| |
| Calculating Titration Curves with a Spreadsheet | |
| |
| |
| |
| End-Point Detection | |
| |
| |
| |
| Fajans Titration | |
| |
| |
| |
| Activity: Hydrated Radii | |
| |
| |
| |
| The Effect of Ionic Strength on Solubility of Salts | |
| |
| |
| |
| Effect of Ionic Strength on Ion Dissociation | |
| |
| |
| |
| Activity Coefficients | |
| |
| |
| |
| Salts with Ions of Charge [greater than or equal vertical bar]2[vertical bar] Do Not Fully Dissociate into Ions in Water | |
| |
| |
| |
| Using Activity Coefficients | |
| |
| |
| |
| pH Revisited | |
| |
| |
| |
| Systematic Treatment of Equilibrium: Acid Rain | |
| |
| |
| |
| Charge Balance | |
| |
| |
| |
| Mass Balance | |
| |
| |
| |
| Calcium Carbonate Mass Balance in Rivers | |
| |
| |
| |
| Systematic Treatment of Equilibrium | |
| |
| |
| |
| The Dependence of Solubility on pH | |
| |
| |
| |
| All Right, Dan, How Would You Really Solve the CaF[subscript 2] Problem? | |
| |
| |
| |
| pH and Tooth Decay | |
| |
| |
| |
| Monoprotic Acid-Base Equilibria: Measuring pH Inside Single Cells | |
| |
| |
| |
| Strong Acids and Bases | |
| |
| |
| |
| Concentrated HNO[subscript 3] Is Only Slightly Dissociated | |
| |
| |
| |
| Weak Acids and Bases | |
| |
| |
| |
| Weak-Acid Equilibria | |
| |
| |
| |
| Conductivity of Weak Electrolytes | |
| |
| |
| |
| Dyeing Fabrics and the Fraction of Dissociation | |
| |
| |
| |
| Weak-Base Equilibria | |
| |
| |
| |
| Buffers | |
| |
| |
| |
| Strong Plus Weak Reacts Completely | |
| |
| |
| |
| How Buffers Work | |
| |
| |
| |
| Polyprotic Acid-Base Equilibria: Proteins Are Polyprotic Acids and Bases | |
| |
| |
| |
| Diprotic Acids and Bases | |
| |
| |
| |
| Successive Approximations | |
| |
| |
| |
| Diprotic Buffers | |
| |
| |
| |
| Polyprotic Acids and Bases | |
| |
| |
| |
| Which Is the Principal Species? | |
| |
| |
| |
| Fractional Composition Equations | |
| |
| |
| |
| Isoelectric and Isoionic pH | |
| |
| |
| |
| Isoelectric Focusing | |
| |
| |
| |
| Acid-Base Titrations: Acid-Base Titration of a Protein | |
| |
| |
| |
| Titration of Strong Acid with Strong Base | |
| |
| |
| |
| 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 | |
| |
| |
| |
| Alkalinity and Acidity | |
| |
| |
| |
| Finding the End Point with Indicators | |
| |
| |
| |
| Indicators and the Acidity of CO[subscript 2] | |
| |
| |
| |
| What Does a Negative pH Mean? | |
| |
| |
| |
| World Record Small Titration | |
| |
| |
| |
| Practical Notes | |
| |
| |
| |
| The Leveling Effect | |
| |
| |
| |
| Calculating Titration Curves with Spreadsheets | |
| |
| |
| |
| EDTA Titrations: A Chelating Ligand Captures Its Prey | |
| |
| |
| |
| Metal-Chelate Complexes | |
| |
| |
| |
| EDTA | |
| |
| |
| |
| Chelation Therapy and Thalassemia | |
| |
| |
| |
| EDTA Titration Curves | |
| |
| |
| |
| Do It with a Spreadsheet | |
| |
| |
| |
| Auxiliary Complexing Agents | |
| |
| |
| |
| Metal Ion Hydrolysis Decreases the Effective Formation Constant for EDTA Complexes | |
| |
| |
| |
| Metal Ion Indicators | |
| |
| |
| |
| Metal Ion Indicator Color Changes | |
| |
| |
| |
| EDTA Titration Techniques | |
| |
| |
| |
| Water Hardness | |
| |
| |
| |
| Fundamentals of Electrochemistry: Harvesting Electricity from the Ocean Floor | |
| |
| |
| |
| Basic Concepts | |
| |
| |
| |
| Galvanic Cells | |
| |
| |
| |
| The Human Salt Bridge | |
| |
| |
| |
| Standard Potentials | |
| |
| |
| |
| Nernst Equation | |
| |
| |
| |
| E[degree] and the Cell Voltage Do Not Depend on How You Write the Cell Reaction | |
| |
| |
| |
| Silver and Gold Pennies | |
| |
| |
| |
| Latimer Diagrams: How to Find E[degree] for a New Half-Reaction | |
| |
| |
| |
| E[degree] and the Equilibrium Constant | |
| |
| |
| |
| Concentrations in the Operating Cell | |
| |
| |
| |
| Cells as Chemical Probes | |
| |
| |
| |
| Biochemists Use E[degree]' | |
| |
| |
| |
| Electrodes and Potentiometry: A Heparin Sensor | |
| |
| |
| |
| Reference Electrodes | |
| |
| |
| |
| Indicator Electrodes | |
| |
| |
| |
| Potentiometry with an Oscillating Reaction | |
| |
| |
| |
| What Is a Junction Potential? | |
| |
| |
| |
| How Ion-Selective Electrodes Work | |
| |
| |
| |
| pH Measurement with a Glass Electrode | |
| |
| |
| |
| Systematic Error in Rainwater pH Measurement: The Effect of Junction Potential | |
| |
| |
| |
| Ion-Selective Electrodes | |
| |
| |
| |
| Using Ion-Selective Electrodes | |
| |
| |
| |
| Solid-State Chemical Sensors | |
| |
| |
| |
| Redox Titrations: Chemical Analysis of High-Temperature Superconductors | |
| |
| |
| |
| The Shape of a Redox Titration Curve | |
| |
| |
| |
| Potentiometric Titration of Fe[superscript 2+] with MnO[superscript - subscript 1] | |
| |
| |
| |
| Finding the End Point | |
| |
| |
| |
| Adjustment of Analyte Oxidation State | |
| |
| |
| |
| Oxidation with Potassium Permanganate | |
| |
| |
| |
| Oxidation with Ce[superscript 4+] | |
| |
| |
| |
| Oxidation with Potassium Dichromate | |
| |
| |
| |
| Methods Involving Iodine | |
| |
| |
| |
| Environmental Carbon Analysis and Oxygen Demand | |
| |
| |
| |
| Iodometric Analysis of High-Temperature Superconductors | |
| |
| |
| |
| Electroanalytical Techniques: How Sweet It Is! | |
| |
| |
| |
| Fundamentals of Electrolysis | |
| |
| |
| |
| Electrochemical Writing | |
| |
| |
| |
| Electrogravimetric Analysis | |
| |
| |
| |
| Coulometry | |
| |
| |
| |
| Amperometry | |
| |
| |
| |
| Oxygen Electrodes | |
| |
| |
| |
| What Is an "Electronic Nose"? | |
| |
| |
| |
| Voltammetry | |
| |
| |
| |
| The Electric Double Layer | |
| |
| |
| |
| Karl Fischer Titration of H[subscript 2]O | |
| |
| |
| |
| The Karl Fischer Jacks of a pH Meter | |
| |
| |
| |
| Fundamentals of Spectrophotometry: The Ozone Hole | |
| |
| |
| |
| Properties of Light | |
| |
| |
| |
| Absorption of Light | |
| |
| |
| |
| Why Is There a Logarithmic Relation Between Transmittance and Concentration? | |
| |
| |
| |
| Absorption Spectra | |
| |
| |
| |
| Measuring Absorbance | |
| |
| |
| |
| Beer's Law in Chemical Analysis | |
| |
| |
| |
| What Happens When a Molecule Absorbs Light? | |
| |
| |
| |
| Luminescence | |
| |
| |
| |
| Fluorescence All Around Us | |
| |
| |
| |
| Instability of the Earth's Climate | |
| |
| |
| |
| Applications of Spectrophotometry: Observing Single DNA Molecules with Molecular Beacons | |
| |
| |
| |
| Analysis of a Mixture | |
| |
| |
| |
| Measuring an Equilibrium Constant: The Scatchard Plot | |
| |
| |
| |
| The Method of Continuous Variation | |
| |
| |
| |
| Flow Injection Analysis | |
| |
| |
| |
| Immunoassays and Aptamers | |
| |
| |
| |
| Sensors Based on Luminescence Quenching | |
| |
| |
| |
| Converting Light into Electricity | |
| |
| |
| |
| Spectrophotometers: Automobile Exhaust Analysis and Public Policy | |
| |
| |
| |
| Lamps and Lasers: Sources of Light | |
| |
| |
| |
| Monochromators | |
| |
| |
| |
| Blackbody Radiation and the Greenhouse Effect | |
| |
| |
| |
| Detectors | |
| |
| |
| |
| The Most Important Photoreceptor | |
| |
| |
| |
| Optodes | |
| |
| |
| |
| Fourier Transform Infrared Spectroscopy | |
| |
| |
| |
| Dealing with Noise | |
| |
| |
| |
| Atomic Spectroscopy: An Anthropology Puzzle | |
| |
| |
| |
| An Overview | |
| |
| |
| |
| Atomization: Flames, Furnaces, and Plasmas | |
| |
| |
| |
| How Temperature Affects Atomic Spectroscopy | |
| |
| |
| |
| Instrumentation | |
| |
| |
| |
| Interference | |
| |
| |
| |
| Inductively Coupled Plasma-Mass Spectrometry | |
| |
| |
| |
| Mass Spectrometry: Droplet Electrospray | |
| |
| |
| |
| What Is Mass Spectrometry? | |
| |
| |
| |
| Molecular Mass and Nominal Mass | |
| |
| |
| |
| How Ions of Different Masses Are Separated by a Magnetic Field | |
| |
| |
| |
| Oh, Mass Spectrum, Speak to Me! | |
| |
| |
| |
| Isotope Ratio Mass Spectrometry | |
| |
| |
| |
| Types of Mass Spectrometers | |
| |
| |
| |
| Chromatography/Mass Spectrometry | |
| |
| |
| |
| Matrix-Assisted Laser Desorption/Ionization | |
| |
| |
| |
| Introduction to Analytical Separations: Measuring Silicones Leaking from Breast Implants | |
| |
| |
| |
| Solvent Extraction | |
| |
| |
| |
| Crown Ethers | |
| |
| |
| |
| What Is Chromatography? | |
| |
| |
| |
| Extraction with Dithizone | |
| |
| |
| |
| A Plumber's View of Chromatography | |
| |
| |
| |
| Efficiency of Separation | |
| |
| |
| |
| Why Bands Spread | |
| |
| |
| |
| Gas Chromatography: What Did They Eat in the Year 1000? | |
| |
| |
| |
| The Separation Process in Gas Chromatography | |
| |
| |
| |
| Chiral Phases for Separating Optical Isomers | |
| |
| |
| |
| Sample Injection | |
| |
| |
| |
| Detectors | |
| |
| |
| |
| Sample Preparation | |
| |
| |
| |
| Method Development in Gas Chromatography | |
| |
| |
| |
| High-Performance Liquid Chromatography: In Vivo Microdialysis for Measuring Drug Metabolism | |
| |
| |
| |
| The Chromatographic Process | |
| |
| |
| |
| Monolithic Silica Columns | |
| |
| |
| |
| Supercritical Fluid Chromatography | |
| |
| |
| |
| Injection and Detection in HPLC | |
| |
| |
| |
| Method Development for Reversed-Phase Separations | |
| |
| |
| |
| Gradient Separations | |
| |
| |
| |
| Chromatographic Methods and Capillary Electrophoresis: Capillary Electrochromatography | |
| |
| |
| |
| Ion-Exchange Chromatography | |
| |
| |
| |
| Ion Chromatography | |
| |
| |
| |
| Surfactants and Micelles | |
| |
| |
| |
| Molecular Exclusion Chromatography | |
| |
| |
| |
| Affinity Chromatography | |
| |
| |
| |
| Principles of Capillary Electrophoresis | |
| |
| |
| |
| Molecular Imprinting | |
| |
| |
| |
| Conducting Capillary Electrophoresis | |
| |
| |
| |
| Gravimetric and Combustion Analysis: Tree Rings and Our Changing Environment | |
| |
| |
| |
| An Example of Gravimetric Analysis | |
| |
| |
| |
| Precipitation | |
| |
| |
| |
| Colloids and Dialysis | |
| |
| |
| |
| Examples of Gravimetric Calculations | |
| |
| |
| |
| Combustion Analysis | |
| |
| |
| |
| Sample Preparation: Extraction Membranes | |
| |
| |
| |
| Statistics of Sampling | |
| |
| |
| |
| Dissolving Samples for Analysis | |
| |
| |
| |
| Sample Preparation Techniques | |
| |
| |
| |
| Quality Assurance: The Need for Quality Assurance | |
| |
| |
| |
| Method Development and Optimization | |
| |
| |
| |
| Method Validation | |
| |
| |
| |
| The Horwitz Trumpet: Variation in Interlaboratory Tests | |
| |
| |
| |
| Quality Assessment | |
| |
| |
| |
| Identifying Sources of Error: Analysis of Variance | |
| |
| |
| Spreadsheet Topics | |
| |
| |
| |
| Introduction to Microsoft Excel | |
| |
| |
| |
| Graphing with Microsoft Excel | |
| |
| |
| |
| Average, standard deviation, normal distribution | |
| |
| |
| |
| t-Test | |
| |
| |
| |
| Slope and intercept | |
| |
| |
| |
| Linear least squares curve fitting | |
| |
| |
| |
| Precipitation titrations (found in Web site supplement) | |
| |
| |
| |
| Precipitation titration of mixture (found in Web site supplement) | |
| |
| |
| |
| Circular reference | |
| |
| |
| |
| Excel Goal Seek and naming cells | |
| |
| |
| |
| Acid-base titration curves | |
| |
| |
| |
| EDTA titrations | |
| |
| |
| |
| Redox titrations (found in Web site supplement) | |
| |
| |
| |
| Using Excel Solver | |
| |
| |
| |
| Solving simultaneous equations by matrix inversion | |
| |
| |
| |
| Correlation coefficient | |
| |
| |
| |
| Analysis of variance | |
| |
| |
| Notes and References | |
| |
| |
| Glossary | |
| |
| |
| Appendixes | |
| |
| |
| |
| 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) [characters not reproducible] ML(aq) | |
| |
| |
| Solutions to Exercises | |
| |
| |
| Answers to Problems | |
| |
| |
| Index | |