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Analytical Chemistry, 6th Edition
by
Christian, Gary D., Univ. of Washington
Publisher: John Wiley & Sons
Publishing Date: 2003/03/14
eText ISBN-10
0-470-26555-8
eText ISBN-13
978-0-470-26555-0
Print ISBN-10
0-471-21472-8
Print ISBN-13
978-0-471-21472-4
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Analytical Chemistry, 6th Edition
by
Christian, Gary D., Univ. of Washington
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Copyright, ii
Dedication, iii
About the Author, iv
Preface, v
Contents, xi
List of Spreadsheets Used...
Chapter 1. Analytical Obj...
Chapter 2. Basic Tools an...
Chapter 3. Data Handling ...
Chapter 4. Good Laborator...
Chapter 5. Stoichiometric...
Chapter 6. General Concep...
Chapter 7. Acid–Base Equi...
Chapter 8. Acid–Base Titr...
Chapter 9. Complexometric...
Chapter 10. Gravimetric A...
Chapter 11. Precipitation...
Chapter 12. Electrochemic...
Chapter 13. Potentiometri...
Chapter 14. Redox and Pot...
Chapter 15. Voltammetry a...
Chapter 16. Spectrochemic...
Chapter 17. Atomic Spectr...
Chapter 18. Sample Prepar...
Chapter 19. Chromatograph...
Chapter 20. Gas Chromatog...
Chapter 21. Liquid Chroma...
Chapter 22. Kinetic Metho...
Chapter 23. Automation in...
Chapter 24. Clinical Chem...
Chapter 25. Century of th...
Chapter 26. Environmental...
EXPERIMENTS, 727
Appendix A. LITERATURE OF...
Appendix B. REVIEW OF MAT...
Appendix C. TABLES OF CON...
Appendix D. SAFETY IN THE...
Appendix E. PERIODIC TABL...
Appendix F. ANSWERS TO EV...
INDEX, 818
Table of Contents
Copyright, ii
Dedication, iii
About the Author, iv
Preface, v
Contents, xi
List of Spreadsheets Used throughout the Text, xviii
Chapter 1. Analytical Objectives, or: What Analytical Chemists Do, 1
1.1. What Is Analytical Science?, 1
1.2. Qualitative and Quantitative Analysis: What Does Each Tell Us?, 2
1.3. Getting Started: The Analytical Process, 5
1.4. Validation of a Method—You Have to Prove It Works!, 14
1.5. Range—What Size Sample?, 14
1.6. Some Useful Websites, 15
Chapter 2. Basic Tools and Operations of Analytical Chemistry, 20
2.1. The Laboratory Notebook—Your Critical Record, 20
2.2. Laboratory Materials and Reagents, 23
2.3. The Analytical Balance—The Indispensible Tool, 24
2.4. Volumetric Glassware—Also Indispensible, 32
2.5. Preparation of Standard Base Solutions, 43
2.6. Preparation of Standard Acid Solutions, 44
2.7. Other Apparatus—Handling and Treating Samples, 44
2.8. Igniting Precipitates—Gravimetric Analysis, 51
2.9. Obtaining the Sample—Is It Solid, Liquid, or Gas?, 52
2.10. Operations of Drying and Preparing a Solution of the Analyte, 53
2.11. Laboratory Safety, 60
Chapter 3. Data Handling and Spreahsheets in Analytical Chemistry, 65
3.1. Accuracy and Precision: There Is a Difference, 65
3.2. Determinate Errors—They Are Systematic, 66
3.3. Indeterminate Errors—They Are Random, 67
3.4. Significant Figures: How Many Numbers Do You Need?, 68
3.5. Rounding Off, 73
3.6. Ways of Expressing Accuracy, 73
3.7. Standard Deviation—The Most Important Statistic, 74
3.8. Use of Spreadsheets in Analytical Chemistry, 78
3.9. Propagation of Errors—Not Just Additive, 82
3.10. Significant Figures and Propagation of Error, 88
3.11. Control Charts, 89
3.12. The Confidence Limit—How Sure Are You?, 90
3.13. Tests of Significance—Is There a Difference?, 92
3.14. Rejection of a Result: The
Q
Test, 98
3.15. Statistics for Small Data Sets, 100
3.16. Linear Least Squares—How to Plot the Right Straight Line, 102
3.17. Correlation Coefficient and Coefficient of Determination, 106
3.18. Using Spreadsheets for Plotting Calibration Curves, 107
3.19. Slope, Intercept, and Coefficient of Determination, 109
3.20. LINEST for Additional Statistics, 110
3.21. Statistics Software Packages, 111
3.22. Detection Limits—There Is No Such Thing as Zero, 111
3.23. Statistics of Sampling—How Many, How Large?, 113
Chapter 4. Good Laboratory Practice: Quality Assurance of Analytical Measurements, 124
4.1. What Is Good Laboratory Practice?, 125
4.2. Validation of Analytical Methods, 126
4.3. Quality Assurance—Does the Method Still Work?, 133
4.4. Laboratory Accreditation, 134
4.5. Electronic Records and Electronic Signatures: 21 CFR, Part 11, 135
4.6. Some Official Organizations, 136
Chapter 5. Stoichiometric Calculations: The Workhorse of the Analyst, 141
5.1. Review of the Fundamentals, 141
5.2. How Do We Express Concentrations of Solutions?, 144
5.3. Expressions of Analytical Results—So Many Ways, 152
5.4. Volumetric Analysis: How Do We Make Stoichiometric Calculations?, 158
5.5. Volumetric Calculations—Let’s Use Molarity, 160
5.6. Normality—A Different Way to do Volumetric Calculations, 172
5.7. Titer—How to Make Rapid Routine Calculations, 179
5.8. Weight Relationships—You Need These for Gravimetric Calculations, 180
Chapter 6. General Concepts of Chemical Equilibrium, 189
6.1. Chemical Reactions: The Rate Concept, 189
6.2. Types of Equilibria, 191
6.3. Gibbs Free Energy and the Equilibrium Constant, 191
6.4. Le Châtelier’s Principle, 192
6.5. Temperature Effects on Equilibrium Constants, 193
6.6. Pressure Effects on Equilibria, 193
6.7. Effect of Concentrations on Equilibria, 193
6.8. Catalysts, 193
6.9. Completeness of Reactions, 194
6.10. Equilibrium Constants for Dissociating or Combining Species—Weak Electrolytes and Precipitates, 194
6.11. Calculations Using Equilibrium Constants—How Much Is in Equilibrium?, 195
6.12. The Common Ion Effect—Shifting the Equilibrium, 202
6.13. Systematic Approach to Equilibrium Calculations—How to Solve Any Equilibrium Problem, 203
6.14. Heterogeneous Equilibria—Solids Don’t Count, 209
6.15. Activity and Activity Coefficients—Concentration Is Not the Whole Story, 210
6.16. The Diverse Ion Effect: The Thermodynamic Equilibrium Constant and Activity Coefficients, 214
Chapter 7. Acid–Base Equilibria, 219
7.1. Acid–Base Theories—Not All Are Created Equal, 219
7.2. Acid–Base Equilibria in Water, 221
7.3. The pH Scale, 224
7.4. pH at Elevated Temperatures: Blood pH, 227
7.5. Weak Acids and Bases—What Is the pH?, 228
7.6. Salts of Weak Acids and Bases—They Aren’t Neutral, 230
7.7. Buffers—Keeping the pH Constant (or Nearly So), 234
7.8. Polyprotic Acids and Their Salts, 241
7.9. Physiological Buffers—They Keep You Alive, 251
7.10. Buffers for Biological and Clinical Measurements, 253
7.11. Diverse Ion Effect on Acids and Bases: K°
a
and K°
b
—Salts Change the pH, 254
7.12. Logarithmic Concentration Diagrams—How to View Large Concentration Changes, 255
Chapter 8. Acid–Base Titrations, 266
8.1. Strong Acid versus Strong Base—The Easy Titrations, 266
8.2. Detection of the End Point: Indicators, 270
8.3. Standard Acid and Base Solutions, 272
8.4. Weak Acid versus Strong Base—A Bit Less Straightforward, 272
8.5. Weak Base versus Strong Acid, 278
8.6. Titration of Sodium Carbonate—A Diprotic Base, 279
8.7. Titration of Polyprotic Acids, 281
8.8. Mixtures of Acids or Bases, 284
8.9. Titration of Amino Acids—They Are Acids and Bases, 286
8.10. Kjeldahl Analysis: Protein Determination, 287
Chapter 9. Complexometric Reactions and Titrations, 294
9.1. Complexes and Formation Constants—How Stable Are Complexes?, 294
9.2. Chelates: EDTA—The Ultimate Titrating Agent for Metals, 297
9.3. Metal–EDTA Titration Curves, 303
9.4. Detection of the End Point: Indicators—They Are Chelating Agents, 305
9.5. Other Uses of Complexes, 307
9.6. Fraction of Dissociating Species in Polyligand Complexes: β Values—How Much of Each Species?, 308
Chapter 10. Gravimetric Analysis and Precipitation Equilibria, 313
10.1. How to Perform a Successful Gravimetric Analysis, 313
10.2. Gravimetric Calculations—How Much Analyte Is There?, 320
10.3. Examples of Gravimetric Analysis, 324
10.4. Organic Precipitates, 325
10.5. Precipitation Equilibria: The Solubility Product, 326
10.6. The Diverse Ion Effect on Solubility: Activity Coefficients, 332
Chapter 11. Precipitation Reactions and Titrations, 339
11.1. Effect of Acidity on Solubility of Precipitates: The Conditional Solubility Product, 339
11.2. Mass Balance Approach for Multiple Equilibria, 341
11.3. Effect of Complexation on Solubility: Conditional Solubility Product, 345
11.4. Precipitation Titrations, 346
Chapter 12. Electrochemical Cells and Electrode Potentials, 354
12.1. What Are Redox Reactions?, 354
12.2. Electrochemical Cells—What Electroanalytical Chemists Use, 355
12.3. Nernst Equation—Effects of Concentrations on Potentials, 361
12.4. Formal Potential—Use It for Defined Nonstandard Solution Conditions, 365
12.5. Limitations of Electrode Potentials, 366
Chapter 13. Potentiometric Electrodes and Potentiometry, 369
13.1. Metal Electrodes for Measuring the Metal’s Cation, 369
13.2. Metal–Metal Salt Electrodes for Measuring the Salt’s Anion, 371
13.3. Redox Electrodes—Inert Metals, 373
13.4. Voltaic Cells without Liquid Junction—For Maximum Accuracy, 374
13.5. Voltaic Cells with Liquid Junction—The Practical Kind, 375
13.6. Reference Electrodes: The Saturated Calomel Electrode, 378
13.7. Measurement of Potential, 380
13.8. Determination of Concentrations from Potential Measurements, 382
13.9. Residual Liquid-Junction Potential—It Should Be Minimum, 382
13.10. Accuracy of Direct Potentiometric Measurements—Voltage Error versus Activity Error, 383
13.11. Glass pH Electrode—Workhorse of Chemists, 384
13.12. Standard Buffers—Reference for pH Measurements, 389
13.13. Accuracy of pH Measurements, 391
13.14. Using the pH Meter—How Does It Work?, 391
13.15. pH Measurement of Blood—Temperature Is Important, 393
13.16. pH Measurements in Nonaqueous Solvents, 394
13.17. Ion-Selective Electrodes, 395
13.18. Solid-State ISFET Electrodes, 408
Chapter 14. Redox and Potentiometric Titrations, 414
14.1. First: Balance the Reduction–Oxidation Reaction, 414
14.2. Calculation of the Equilibrium Constant of a Reaction—Needed to Calculate Equivalence Point Potentials, 415
14.3. Calculating Redox Titration Curves, 418
14.4. Visual Detection of the End Point, 422
14.5. Titrations Involving Iodine: Iodimetry and Iodometry, 423
14.6. Titrations with Other Oxidizing Agents, 429
14.7. Titrations with Other Reducing Agents, 430
14.8. Preparing the Solution—Getting the Analyte in the Right Oxidation State before Titration, 431
14.9. Potentiometric Titrations (Indirect Potentiometry), 433
Chapter 15. Voltammetry and Electrochemical Sensors, 446
15.1. Voltammetry, 446
15.2. Amperometric Electrodes—Measurement of Oxygen, 451
15.3. Electrochemical Sensors: Chemically Modified Electrodes, 452
5.4. Ultramicroelectrodes, 454
Chapter 16. Spectrochemical Methods, 457
16.1. Interaction of Electromagnetic Radiation with Matter, 458
16.2. Electronic Spectra and Molecular Structure, 464
16.3. Infrared Absorption and Molecular Structure, 469
16.4. Near-Infrared Spectrometry for Nondestructive Testing, 470
16.5. Spectral Databases—Identifying Unknowns, 472
16.6. Solvents for Spectrometry, 473
16.7. Quantitative Calculations, 474
16.8. Spectrometric Instrumentation, 483
16.9. Types of Instruments, 495
16.10. Diode Array Spectrometers—Getting the Entire Spectrum at Once, 498
16.11. Fourier Transform Infrared Spectrometers, 499
16.12. Near-IR Instruments, 501
16.13. Spectrometric Error in Measurements, 501
16.14. Deviation from Beer’s Law, 503
16.15. Fluorometry, 505
16.16. Optical Sensors: Fiber Optics, 511
Chapter 17. Atomic Spectrometric Methods, 522
17.1. Flame Emission Spectrometry, 522
17.2. Distribution between Ground and Excited States—Most Atoms Are in the Ground State, 524
17.3. Atomic Absorption Spectrophotometry, 525
17.4. Internal Standard and Standard Addition Calibration, 533
Chapter 18. Sample Preparation: Solvent and Solid-Phase Extraction, 541
18.1. Distribution Coefficient, 541
18.2. Distribution Ratio, 542
18.3. Percent Extracted, 543
18.4. Solvent Extraction of Metals, 544
18.5. Accelerated and Microwave-Assisted Extraction, 546
18.6. Solid-Phase Extraction, 547
Chapter 19. Chromatography: Principles and Theory, 555
19.1. Principles of Chromatographic Separations, 556
19.2. Classifications of Chromatographic Techniques, 558
19.3. Theory of Column Efficiency in Chromatography, 560
19.4. Chromatography Simulation Software, 570
19.5. Freebies: Company Searchable Chromatogram Databases, 571
Chapter 20. Gas Chromatography, 574
20.1. Performing GC Separations, 574
20.2. Gas Chromatography Columns, 577
20.3. Gas Chromatography Detectors, 584
20.4. Temperature Selection, 587
20.5. Quantitative Measurements, 589
20.6. Headspace Analysis, 590
20.7. Thermal Desorption, 591
20.8. Purging and Trapping, 591
20.9. Small and Fast, 592
20.10. Gas Chromatography–Mass Spectrometry, 593
Chapter 21. Liquid Chromatography, 604
21.1. High Performance Liquid Chromatography, 604
21.2. Size Exclusion Chromatography, 620
21.3. Ion Exchange Chromatography, 622
21.4. Ion Chromatography, 625
21.5. Thin-Layer Chromatography, 627
21.6. Electrophoresis, 631
21.7. Capillary Electrophoresis, 632
Chapter 22. Kinetic Methods of Analysis, 643
22.1. Kinetics—The Basics, 643
22.2. Enzyme Catalysis, 646
Chapter 23. Automation in Measurements, 660
23.1. Principles of Automation, 660
23.2. Automated Instruments: Process Control, 661
23.3. Automatic Instruments, 664
23.4. Flow Injection Analysis, 665
23.5. Microprocessors and Computers, 674
Chapter 24. Clinical Chemistry, 678
24.1. Composition of Blood, 678
24.2. Collection and Preservation of Samples, 680
24.3. Clinical Analyses—Common Determinations, 681
24.4. Immunoassay, 683
Chapter 25. Century of the Gene—Genomics and Proteomics: DNA Sequencing and Protein Profiling, 693
25.1. Of What Are We Made?, 693
25.2. What Is DNA?, 695
25.3. Human Genome Project, 695
25.4. How Are Genes Sequenced?, 697
25.5. Replicating DNA: The Polymerase Chain Reaction, 697
25.6. Plasmids and Bacterial Artificial Chromosomes, 699
25.7. DNA Sequencing, 700
25.8. Whole Genome Shotgun Sequencing, 703
25.9. Single-Nucleotide Polymorphisms, 703
25.10. DNA Chips, 704
25.11. Draft Genome, 705
25.12. Genomes and Proteomics: The Rest of the Story, 705
Chapter 26. Environmental Sampling and Analysis, 712
26.1. Getting a Meaningful Sample, 712
26.2. Air Sample Collection and Analysis, 713
26.3. Water Sample Collection and Analysis, 720
26.4. Soil and Sediment Sampling, 722
26.5. Sample Preparation for Trace Organics, 722
26.6. Contaminated Land Sites—What Needs to Be Analyzed?, 723
26.7. EPA Methods and Performance-based Analyses, 723
EXPERIMENTS, 727
USE OF APPARATUS, 727
Experiment 1. Use of the Analytical Balance, 727
Experiment 2. Use of the Pipet and Buret and Statistical Analysis, 729
GRAVIMETRY, 730
Experiment 3. Gravimetric Determination of Chloride, 730
Experiment 4. Gravimetric Determination of SO3 in a Soluble Sulfate, 733
Experiment 5. Gravimetric Determination of Nickel in a Nichrome Alloy, 735
ACID–BASE TITRATIONS, 736
Experiment 6. Determination of Replaceable Hydrogen in Acid by Titration with Sodium Hydroxide, 736
Experiment 7. Determination of Total Alkalinity of Soda Ash, 738
Experiment 8. Determination of Bicarbonate in Blood Using Back-Titration, 740
COMPLEXOMETRIC TITRATION, 742
Experiment 9. Determination of Water Hardness with EDTA, 742
PRECIPITATION TITRATIONS, 744
Experiment 10. Determination of Silver in an Alloy: Volhard’s Method, 744
Experiment 11. Determination of Chloride in a Soluble Chloride: Fajans’ Method, 745
POTENTIOMETRIC MEASUREMENTS, 746
Experiment 12. Determination of the pH of Hair Shampoos, 746
Experiment 13. Potentiometric Determination of Fluoride in Drinking Water Using a Fluoride Ion-Selective Electrode, 748
REDUCTION–OXIDATION TITRATIONS, 750
Experiment 14. Analysis of an Iron Alloy or Ore by Titration with Potassium Dichromate, 750
Experiment 15. Analysis of Commercial Hypochlorite or Peroxide Solution by Iodometric Titration, 753
Experiment 16. Iodometric Determination of Copper, 755
Experiment 17. Determination of Antimony by Titration with Iodine, 757
Experiment 18. Microscale Quantitative Analysis of Hard Water Samples Using an Indirect Potassium Permanganate Redox Titration, 759
POTENTIOMETRIC TITRATIONS, 762
Experiment 19. pH Titration of Unknown Soda Ash, 762
Experiment 20. Potentiometric Titration of a Mixture of Chloride and Iodide, 763
SPECTROCHEMICAL MEASUREMENTS, 765
Experiment 21. Spectrophotometric Determination of Iron, 765
Experiment 22. Determination of Nitrate Nitrogen in Water, 766
Experiment 23. Spectrophotometric Determination of Lead on Leaves Using Solvent Extraction, 767
Experiment 24. Spectrophotometric Determination of Inorganic Phosphorus in Serum, 769
Experiment 25. Spectrophotometric Determination of Manganese and Chromium in Mixture, 770
Experiment 26. Ultraviolet Spectrophotometric Determination of Aspirin, Phenacetin, and Caffeine in APC Tablets Using Solvent Extraction, 773
Experiment 27. Infrared Determination of a Mixture of Xylene Isomers, 774
Experiment 28. Fluorometric Determination of Ribofiavin (Vitamin B2), 775
ATOMIC SPECTROMETRY MEASUREMENTS, 776
Experiment 29. Determination of Calcium by Atomic Absorption Spectrophotometry, 776
Experiment 30. Flame Emission Spectrometric Determination of Sodium, 778
CHROMATOGRAPHY, 780
Experiment 31. Thin-Layer Chromatography Separation of Amino Acids, 780
Experiment 32. Gas Chromatographic Analysis of a Tertiary Mixture, 781
Experiment 33. Qualitative and Quantitative Analysis of Fruit Juices for Vitamin C Using High-Performance Liquid Chromatography, 783
Experiment 34. Analysis of Analgesics Using High-Performance Liquid Chromatography, 784
KINETIC ANALYSIS, 785
Experiment 35. Enzymatic Determination of Glucose in Blood, 785
FLOW INJECTION ANALYSIS, 786
Experiment 36. Characterization of Physical Parameters of a Flow Injection Analysis System, 786
Experiment 37. Single-Line FIA: Spectrophotometric Determination of Chloride, 789
Experiment 38. Three-Line FIA: Spectrophotometric Determination of Phosphate, 790
TEAM EXPERIMENTS, 793
Experiment 39. Method Validation and Quality Control Study, 793
Experiment 40. Proficiency Testing: Determination of
z
Values of Class Experiments, 795
Appendix A. LITERATURE OF ANALYTICAL CHEMISTRY, 796
Appendix B. REVIEW OF MATHEMATICAL OPERATIONS: EXPONENTS, LOGARITHMS, AND THE QUADRATIC FORMULA, 800
Appendix C. TABLES OF CONSTANTS, 804
Table C.1. Dissociation Constants for Acids, 804
Table C.2. Dissociation Constants for Bases, 805
Table C.3. Solubility Product Constants, 806
Table C.4. Formation Constants for Some EDTA Metal Chelates, 807
Table C.5. Some Standard and Formal Reduction Electrode Potentials, 808
Appendix D. SAFETY IN THE LABORATORY, 810
Appendix E. PERIODIC TABLES ON THE WEB, 811
Appendix F. ANSWERS TO EVEN-NUMBERED PROBLEMS, 812
INDEX, 818
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