Analytical Chemistry

Gary D. Christian, University of Washington, WAPurnendu K. Dasgupta, University of Texas Arlington, TX.Kevin A. Schug, University of Texas Arlington, TX.

• Chapter 1 Analytical Objectives, or: What Analytical Chemists Do 11.1 What Is Analytical Science?, 21.2 Qualitative and Quantitative Analysis: What Does Each Tell Us?, 31.3 Getting Started: The Analytical Process, 61.4 Validation of a Method—You Have to Prove It Works!, 151.5 Analyze Versus Determine—They Are Different, 161.6 Some Useful Websites, 16Chapter 2 Basic Tools and Operations of Analytical Chemistry 202.1 The Laboratory Notebook—Your Critical Record, 202.2 Laboratory Materials and Reagents, 232.3 The Analytical Balance—The Indispensible Tool, 232.4 Volumetric Glassware—Also Indispensible, 302.5 Preparation of Standard Base Solutions, 422.6 Preparation of Standard Acid Solutions, 422.7 Other Apparatus—Handling and Treating Samples, 432.8 Igniting Precipitates—Gravimetric Analysis, 482.9 Obtaining the Sample—Is It Solid, Liquid, or Gas?, 492.10 Operations of Drying and Preparing a Solution of the Analyte, 512.11 Laboratory Safety, 57Chapter 3 Statistics and Data Handling in Analytical Chemistry 623.1 Accuracy and Precision: There Is a Difference, 623.2 Determinate Errors—They Are Systematic, 633.3 Indeterminate Errors—They Are Random, 643.4 Significant Figures: How Many Numbers Do You Need?, 653.5 Rounding Off, 713.6 Ways of Expressing Accuracy, 713.7 Standard Deviation—The Most Important Statistic, 723.8 Propagation of Errors—Not Just Additive, 753.9 Significant Figures and Propagation of Error, 813.10 Control Charts, 833.11 The Confidence Limit—How Sure Are You?, 843.12 Tests of Significance—Is There a Difference?, 863.13 Rejection of a Result: The Q Test, 953.14 Statistics for Small Data Sets, 983.15 Linear Least Squares—How to Plot the Right Straight Line, 993.16 Correlation Coefficient and Coefficient of Determination, 1043.17 Detection Limits—There Is No Such Thing as Zero, 1053.18 Statistics of Sampling—How Many Samples, How Large?, 1073.19 Powering a Study: Power Analysis, 1103.20 Use of Spreadsheets in Analytical Chemistry, 1123.21 Using Spreadsheets for Plotting Calibration Curves, 1173.22 Slope, Intercept, and Coefficient of Determination, 1183.23 LINEST for Additional Statistics, 1193.24 Statistics Software Packages, 120Chapter 4 Good Laboratory Practice: Quality Assurance and Method Validation 1324.1 What Is Good Laboratory Practice?, 1334.2 Validation of Analytical Methods, 1344.3 Quality Assurance—Does the Method Still Work?, 1434.4 Laboratory Accreditation, 1444.5 Electronic Records and Electronic Signatures: 21 CFR, Part 11, 1454.6 Some Official Organizations, 146Chapter 5 Stoichiometric Calculations: The Workhorse of the Analyst 1495.1 Review of the Fundamentals, 1495.2 How Do We Express Concentrations of Solutions?, 1525.3 Expressions of Analytical Results—So Many Ways, 1595.4 Volumetric Analysis: How Do We Make Stoichiometric Calculations?, 1665.5 Volumetric Calculations—Let’s Use Molarity, 1695.6 Titer—How to Make Rapid Routine Calculations, 1795.7 Weight Relationships—You Need These for Gravimetric Calculations, 180Chapter 6 General Concepts of Chemical Equilibrium 1886.1 Chemical Reactions: The Rate Concept, 1886.2 Types of Equilibria, 1906.3 Gibbs Free Energy and the Equilibrium Constant, 1916.4 Le Châtelier’s Principle, 1926.5 Temperature Effects on Equilibrium Constants, 1926.6 Pressure Effects on Equilibria, 1926.7 Concentration Effects on Equilibria, 1936.8 Catalysts, 1936.9 Completeness of Reactions, 1936.10 Equilibrium Constants for Dissociating or Combining Species—Weak Electrolytes and Precipitates, 1946.11 Calculations Using Equilibrium Constants—Composition at Equilibrium?, 1956.12 The Common Ion Effect—Shifting the Equilibrium, 2036.13 Systematic Approach to Equilibrium Calculations—How to Solve Any Equilibrium Problem, 2046.14 Some Hints for Applying the Systematic Approach for Equilibrium Calculations, 2086.15 Heterogeneous Equilibria—Solids Don’t Count, 2116.16 Activity and Activity Coefficients—Concentration Is Not the Whole Story, 2116.17 The Diverse Ion Effect: The Thermodynamic Equilibrium Constant and Activity Coefficients, 217Chapter 7 Acid–Base Equilibria 2227.1 The Early History of Acid—Base Concepts, 2227.2 Acid–Base Theories—Not All Are Created Equal, 2237.3 Acid–Base Equilibria in Water, 2257.4 The pH Scale, 2277.5 pH at Elevated Temperatures: Blood pH, 2317.6 Weak Acids and Bases—What Is the pH?, 2327.7 Salts of Weak Acids and Bases—They Aren’t Neutral, 2347.8 Buffers—Keeping the pH Constant (or Nearly So), 2387.9 Polyprotic Acids and Their Salts, 2457.10 Ladder Diagrams, 2477.11 Fractions of Dissociating Species at a Given pH: α Values—How Much of Each Species?, 2487.12 Salts of Polyprotic Acids—Acid, Base, or Both?, 2557.13 Physiological Buffers—They Keep You Alive, 2617.14 Buffers for Biological and Clinical Measurements, 2637.15 Diverse Ion Effect on Acids and Bases: cKa and cKb—Salts Change the pH, 2667.16 log C—pH Diagrams, 2667.17 Exact pH Calculators, 269Chapter 8 Acid–Base Titrations 2818.1 Strong Acid versus Strong Base—The Easy Titrations, 2828.2 The Charge Balance Method—An Excel Exercise for the Titration of a Strong Acid and a Strong Base, 2858.3 Detection of the End Point: Indicators, 2888.4 Standard Acid and Base Solutions, 2908.5 Weak Acid versus Strong Base—A Bit Less Straightforward, 2908.6 Weak Base versus Strong Acid, 2958.7 Titration of Sodium Carbonate—A Diprotic Base, 2968.8 Using a Spreadsheet to Perform the Sodium Carbonate—HCl Titration, 2988.9 Titration of Polyprotic Acids, 3008.10 Mixtures of Acids or Bases, 3028.11 Equivalence Points from Derivatives of a Titration Curve, 3048.12 Titration of Amino Acids—They Are Acids and Bases, 3098.13 Kjeldahl Analysis: Protein Determination, 3108.14 Titrations Without Measuring Volumes, 312Chapter 9 Complexometric Reactions and Titrations 3229.1 Complexes and Formation Constants—How Stable Are Complexes?, 3229.2 Chelates: EDTA—The Ultimate Titrating Agent for Metals, 3259.3 Metal–EDTA Titration Curves, 3319.4 Detection of the End Point: Indicators—They Are Also Chelating Agents, 3349.5 Other Uses of Complexes, 3369.6 Cumulative Formation Constants β and Concentrations of Specific Species in Stepwise Formed Complexes, 336Chapter 10 Gravimetric Analysis and Precipitation Equilibria 34210.1 How to Perform a Successful Gravimetric Analysis, 34310.2 Gravimetric Calculations—How Much Analyte Is There?, 34910.3 Examples of Gravimetric Analysis, 35310.4 Organic Precipitates, 35310.5 Precipitation Equilibria: The Solubility Product, 35510.6 Diverse Ion Effect on Solubility: Ksp and Activity Coefficients, 361Chapter 11 Precipitation Reactions and Titrations 36611.1 Effect of Acidity on Solubility of Precipitates: Conditional Solubility Product, 36611.2 Mass Balance Approach for Multiple Equilibria, 36811.3 Effect of Complexation on Solubility: Conditional Solubility Product, 37211.4 Precipitation Titrations, 374Chapter 12 Electrochemical Cells and Electrode Potentials 38312.1 What Are Redox Reactions?, 38412.2 Electrochemical Cells—What Electroanalytical Chemists Use, 38412.3 Nernst Equation—Effects of Concentrations on Potentials, 39012.4 Formal Potential—Use It for Defined Nonstandard Solution Conditions, 39412.5 Limitations of Electrode Potentials, 395Chapter 13 Potentiometric Electrodes and Potentiometry 39913.1 Metal Electrodes for Measuring the Metal Cation, 40013.2 Metal–Metal Salt Electrodes for Measuring the Salt Anion, 40113.3 Redox Electrodes—Inert Metals, 40213.4 Voltaic Cells without Liquid Junction—For Maximum Accuracy, 40413.5 Voltaic Cells with Liquid Junction—The Practical Kind, 40513.6 Reference Electrodes: The Saturated Calomel Electrode, 40713.7 Measurement of Potential, 40913.8 Determination of Concentrations from Potential Measurements, 41113.9 Residual Liquid-Junction Potential—It Should Be Minimized, 41113.10 Accuracy of Direct Potentiometric Measurements—Voltage Error versus Activity Error, 41213.11 Glass pH Electrode—Workhorse of Chemists, 41313.12 Standard Buffers—Reference for pH Measurements, 41813.13 Accuracy of pH Measurements, 42013.14 Using the pH Meter—How Does It Work?, 42113.15 pH Measurement of Blood—Temperature Is Important, 42213.16 pH Measurements in Nonaqueous Solvents, 42313.17 Ion-Selective Electrodes, 42413.18 Chemical Analysis on Mars using Ion-Selective Electrodes, 432Chapter 14 Redox and Potentiometric Titrations 43714.1 First: Balance the Reduction–Oxidation Reaction, 43714.2 Calculation of the Equilibrium Constant of a Reaction—Needed to CalculateEquivalence Point Potentials, 43814.3 Calculating Redox Titration Curves, 44114.4 Visual Detection of the End Point, 44514.5 Titrations Involving Iodine: Iodimetry and Iodometry, 44714.6 Titrations with Other Oxidizing Agents, 45214.7 Titrations with Other Reducing Agents, 45414.8 Preparing the Solution—Getting the Analyte in the Right Oxidation State before Titration, 45414.9 Potentiometric Titrations (Indirect Potentiometry), 456Chapter 15 Voltammetry and Electrochemical Sensors 46615.1 Voltammetry, 46715.2 Amperometric Electrodes—Measurement of Oxygen, 47215.3 Electrochemical Sensors: Chemically Modified Electrodes, 47215.4 Ultramicroelectrodes, 47415.5 Microfabricated Electrochemical Sensors, 47415.6 Micro and Ultramicroelectrode Arrays, 475Chapter 16 Spectrochemical Methods 47716.1 Interaction of Electromagnetic Radiation with Matter, 47816.2 Electronic Spectra and Molecular Structure, 48416.3 Infrared Absorption and Molecular Structure, 48916.4 Near-Infrared Spectrometry for Nondestructive Testing, 49116.5 Spectral Databases—Identifying Unknowns, 49316.6 Solvents for Spectrometry, 49316.7 Quantitative Calculations, 49416.8 Spectrometric Instrumentation, 50416.9 Types of Instruments, 51916.10 Array Spectrometers—Getting the Entire Spectrum at Once, 52216.11 Fourier Transform Infrared Spectrometers, 52316.12 Near-IR Instruments, 52516.13 Spectrometric Error in Measurements, 52616.14 Deviation from Beer’s Law, 52716.15 Fluorometry, 53016.16 Chemiluminescence, 53816.17 Fiber-Optic Sensors, 540Chapter 17 Atomic Spectrometric Methods 54817.1 Principles: Distribution between Ground and Excited States—Most Atoms Are in the Ground State, 55017.2 Flame Emission Spectrometry, 55317.3 Atomic Absorption Spectrometry, 55617.4 Sample Preparation—Sometimes Minimal, 56717.5 Internal Standard and Standard Addition Calibration, 56717.6 Atomic Emission Spectrometry: The Induction Coupled Plasma (ICP), 56917.7 Atomic Fluorescence Spectrometry, 574Chapter 18 Sample Preparation: Solvent and Solid-Phase Extraction 57918.1 Distribution Coefficient, 57918.2 Distribution Ratio, 58018.3 Percent Extracted, 58118.4 Solvent Extraction of Metals, 58318.5 Accelerated and Microwave-Assisted Extraction, 58518.6 Solid-Phase Extraction, 58618.7 Microextraction, 59018.8 Solid-Phase Nanoextraction (SPNE), 593Chapter 19 Chromatography: Principles and Theory 59619.1 Countercurrent Extraction: The Predecessor to Modern Liquid Chromatography, 59819.2 Principles of Chromatographic Separations, 60319.3 Classification of Chromatographic Techniques, 60419.4 Theory of Column Efficiency in Chromatography, 60719.5 Chromatography Simulation Software, 616Chapter 20 Gas Chromatography 61920.1 Performing GC Separations, 62020.2 Gas Chromatography Columns, 62320.3 Gas Chromatography Detectors, 63020.4 Temperature Selection, 63820.5 Quantitative Measurements, 63920.6 Headspace Analysis, 64120.7 Thermal Desorption, 64120.8 Purging and Trapping, 64220.9 Small and Fast, 64320.10 Separation of Chiral Compounds, 64420.11 Two-Dimensional GC, 645Chapter 21 Liquid Chromatography and Electrophoresis 64921.1 High-Performance Liquid Chromatography, 65121.2 Stationary Phases in HPLC, 65421.3 Equipment for HPLC, 66521.4 Ion Chromatography, 69221.5 HPLC Method Development, 70021.6 UHPLC and Fast LC, 70121.7 Open Tubular Liquid Chromatography (OTLC), 70221.8 Thin-Layer Chromatography, 70221.9 Electrophoresis, 70821.10 Capillary Electrophoresis, 71121.11 Electrophoresis Related Techniques, 724Chapter 22 Mass Spectrometry 73522.1 Principles of Mass Spectrometry, 73522.2 Inlets and Ionization Sources, 74022.3 Gas Chromatography–Mass Spectrometry, 74122.4 Liquid Chromatography–Mass Spectrometry, 74622.5 Laser Desorption/Ionization, 75022.6 Secondary Ion Mass Spectrometry, 75222.7 Inductively Coupled Plasma–Mass Spectrometry, 75322.8 Mass Analyzers and Detectors, 75322.9 Hybrid Instruments and Tandem Mass Spectrometry, 764Chapter 23 Kinetic Methods of Analysis 76923.1 Kinetics—The Basics, 76923.2 Catalysis, 77123.3 Enzyme Catalysis, 772Chapter 24 Automation in Measurements 78424.1 Principles of Automation, 78424.2 Automated Instruments: Process Control, 78524.3 Automatic Instruments, 78724.4 Flow Injection Analysis, 78924.5 Sequential Injection Analysis, 79124.6 Laboratory Information Management Systems, 792Clinical Chemistry C125.1 Composition of Blood, C125.2 Collection and Preservation of Samples, C325.3 Clinical Analysis—Common Determinations, C425.4 Immunoassay, C6Chapter 26 Environmental Sampling and Analysis EN126.1 Getting a Meaningful Sample, EN126.2 Air Sample Collection and Analysis, EN226.3 Water Sample Collection and Analysis, EN926.4 Soil and Sediment Sampling, EN1126.5 Sample Preparation for Trace Organics, EN1226.6 Contaminated Land Sites—What Needs to Be Analyzed?, EN1226.7 EPA Methods and Performance-Based Analyses, EN13Century of the Gene—Genomics and Proteomics: DNA Sequencing and Protein Profiling G1G.1 Of What Are We Made?, G1G.2 What Is DNA?, G3G.3 Human Genome Project, G3G.4 How Are Genes Sequenced?, G5G.5 Replicating DNA: The Polymerase Chain Reaction, G6G.6 Plasmids and Bacterial Artificial Chromosomes (BACs), G7G.7 DNA Sequencing, G8G.8 Whole Genome Shotgun Sequencing, G11G.9 Single-Nucleotide Polymorphisms, G11G.10 DNA Chips, G12G.11 Draft Genome, G13G.12 Genomes and Proteomics: The Rest of the Story, G13APPENDIX A LITERATURE OF ANALYTICAL CHEMISTRY 794APPENDIX B REVIEW OF MATHEMATICAL OPERATIONS: EXPONENTS, LOGARITHMS, AND THE QUADRATIC FORMULA 797APPENDIX C TABLES OF CONSTANTS 801Table C.1 Dissociation Constants for Acids, 801Table C.2a Dissociation Constants for BasicSpecies, 802Table C.2b Acid Dissociation Constants forBasic Species, 803Table C.3 Solubility Product Constants, 803Table C.4 Formation Constants for SomeEDTA Metal Chelates, 805Table C.5 Some Standard and FormalReduction Electrode Potentials, 806APPENDIX D SAFETY IN THE LABORATORY S1APPENDIX E PERIODIC TABLES ON THE WEB P1APPENDIX F ANSWERS TO PROBLEMS 808Experiments E1Use of ApparatusExperiment 1 Use of the Analytical Balance, E1Experiment 2 Use of the Pipet and Buret and Statistical Analysis, E2Experiment 3 Analysis of Volumetric Measurements Using Spectrophotometric Microplate Readers and Spreadsheet Calculations, E4GravimetryExperiment 4 Gravimetric Determination of Chloride, E6Experiment 5 Gravimetric Determination of SO3 in a Soluble Sulfate, E9Experiment 6 Gravimetric Determination of Nickel in a Nichrome Alloy, E11Acid–Base TitrationsExperiment 7 Determination of Replaceable Hydrogen in Acid by Titration with Sodium Hydroxide, E12Experiment 8 Determination of Total Alkalinity of Soda Ash, E14Experiment 9 Determination of Aspirin Using Back Titration, E16Experiment 10 Determination of Hydrogen Carbonate in Blood Using Back-Titration, E18Complexometric TitrationExperiment 11 Determination of Water Hardness with EDTA, E19Precipitation TitrationsExperiment 12 Determination of Silver in an Alloy: Volhard’s Method, E21Experiment 13 Determination of Chloride in a Soluble Chloride: Fajans’ Method, E23Potentiometric MeasurementsExperiment 14 Determination of the pH of Hair Shampoos, E24Experiment 15 Potentiometric Determination of Fluoride in Drinking Water Using a Fluoride Ion-Selective Electrode, E25Reduction–Oxidation TitrationsExperiment 16 Analysis of an Iron Alloy or Ore by Titration with Potassium Dichromate, E27Experiment 17 Analysis of Commercial Hypochlorite or Peroxide Solution by Iodometric Titration, E30Experiment 18 Iodometric Determination of Copper, E32Experiment 19 Determination of Antimony by Titration with Iodine, E34Experiment 20 Microscale Quantitative Analysis of Hard-Water Samples Using an Indirect Potassium Permanganate Redox Titration, E36Potentiometric TitrationsExperiment 21 pH Titration of Unknown Soda Ash, E38Experiment 22 Potentiometric Titration of a Mixture of Chloride and Iodide, E40Spectrochemical MeasurementsExperiment 23 Spectrophotometric Determination of Iron, E41Experiment 24 Spectrophotometric Determination of Iron in Vitamin Tablets Using a 96 Well Plate Reader, E43Experiment 25 Determination of Nitrate Nitrogen in Water, E46Experiment 26 Spectrophotometric Determination of Lead on Leaves Using Solvent Extraction, E47Experiment 27 Spectrophotometric Determination of Inorganic Phosphorus in Serum, E48Experiment 28 Spectrophotometric Determination of Manganese and Chromium in Mixture, E50Experiment 29 Spectrophotometric Determination of Manganese in Steel Using a 96 Well Plate Reader, E52Experiment 30 Ultraviolet Spectrophotometric Determination of Aspirin, Phenacetin, and Caffeine in APC Tablets Using Solvent Extraction, E54Experiment 31 Infrared Determination of a Mixture of Xylene Isomers, E56Experiment 32 Fluorometric Determination of Riboflavin (Vitamin B2), E57Atomic Spectrometry MeasurementsExperiment 33 Determination of Calcium by Atomic Absorption Spectrophotometry, E57Experiment 34 Flame Emission Spectrometric Determination of Sodium, E60Solid-Phase Extraction and ChromatographyExperiment 35 Solid-Phase Extraction with Preconcentration, Elution, and Spectrophotometric Analysis, E61Experiment 36 Thin-Layer Chromatography Separation of Amino Acids, E67Experiment 37 Gas Chromatographic Analysis of a Tertiary Mixture, E69Experiment 38 Qualitative and Quantitative Analysis of Fruit Juices for Vitamin C Using High-Performance Liquid Chromatography, E70Experiment 39 Analysis of Analgesics Using High-Performance Liquid Chromatography, E71Mass SpectrometryExperiment 40 Capillary Gas Chromatography-Mass Spectrometry, E72Kinetic AnalysisExperiment 41 Enzymatic Determination of Glucose in Blood, E74Flow Injection AnalysisExperiment 42 Characterization of Physical Parameters of a Flow Injection Analysis System, E76Experiment 43 Single-Line FIA: Spectrophotometric Determination of Chloride, E79Experiment 44 Three-Line FIA: Spectrophotometric Determination of Phosphate, E80Team ExperimentsExperiment 45 Method Validation and Quality Control Study, E82Experiment 46 Proficiency Testing: Determination of z Values of Class Experiments, E84Index 815

“All up, this is a great student text. It is well presented, well illustrated, well backed-up and user-friendly.”  (Chemistry in Australia, 1 July 2015)“This is a very well written, enjoyable textbook of analytical chemistry. It may be used in different contexts: in a first course of analytical chemistry for chemists; for teaching equilibrium calculations in a general chemistry course; as an invaluable source of teaching ideas and resources for professors who use other textbooks; and, finally, as a reference work for practicing analytical chemists. Thus this book should certainly have a place on the bookshelf of any analyticalchemistry student, professor, or professional.”  (Anal Bioanal Chem, 21 June 2014)