Analytical Chemistry
Fundamentals of Analytical Chemistry
Known for its readability and systematic, rigorous approach, this fully updated Ninth Edition of FUNDAMENTALS OF ANALYTICAL CHEMISTRY offers extensive coverage of the principles and practices of analytic chemistry and consistently shows students its applied nature. The book's award-winning authors begin each chapter with a story and photo of how analytic chemistry is applied in industry, medicine, and all the sciences. To further reinforce student learning, a wealth of dynamic photographs by renowned chemistry photographer Charlie Winters appear as chapter-openers and throughout the text. Incorporating Excel spreadsheets as a problem-solving tool, the Ninth Edition is enhanced by a chapter on Using Spreadsheets in Analytical Chemistry, updated spreadsheet summaries and problems, an "Excel Shortcut Keystrokes for the PC" insert card, and a supplement by the text authors, EXCEL APPLICATIONS FOR ANALYTICAL CHEMISTRY, which integrates this important aspect of the study of analytical chemistry into the book's already rich pedagogy. New to this edition is OWL, an online homework and assessment tool that includes the Cengage YouBook, a fully customizable and interactive eBook, which enhances conceptual understanding through hands-on integrated multimedia interactivity. Available with InfoTrac Student Collections http://gocengage.com/infotrac.
Table of contents :
Cover......Page 1
IFC2......Page 3
IFC3......Page 4
IFC6......Page 7
IFC7......Page 8
IFC9......Page 10
IFC10......Page 11
IFC11......Page 12
IFC12......Page 13
IFC13......Page 14
IFC14......Page 15
IFC15......Page 16
IFC16......Page 17
IFC17......Page 18
IFC18......Page 19
IFC19......Page 20
IFC20......Page 21
IFC21......Page 22
IFC22......Page 23
Statement......Page 24
Title......Page 25
Copyright......Page 26
Contents in Brief......Page 27
Contents......Page 29
Preface......Page 35
Introduction......Page 43
1A The Role of Analytical Chemistry......Page 44
1C A Typical Quantitative Analysis......Page 46
1D An Integral Role for Chemical Analysis: Feedback Control Systems......Page 51
Part I: Tools of Analytical Chemistry......Page 56
Introduction......Page 57
2A Selecting and Handling Reagents and Other Chemicals......Page 58
2B Cleaning and Marking of Laboratory Ware......Page 59
2D Measuring Mass......Page 60
2E Equipment and Manipulations Asociated with Weighing......Page 67
2F Filtration and Ignition of Solids......Page 70
2G Measuring Volume......Page 76
2H Calibrating Volumetric Glassware......Page 85
2I The Laboratory Notebook......Page 87
2J Safety in the Laboratory......Page 88
Introduction......Page 90
3A Keeping Records and Making Calculations......Page 91
3B More Complex Examples......Page 94
Questions and Problems......Page 103
4A Some Important Units of Measurement......Page 104
4B Solutions and Their Concentrations......Page 109
4C Chemical Stoichiometry......Page 117
Questions and Problems......Page 120
Introduction......Page 124
5A Some Important Terms......Page 126
5B Systematic Errors......Page 129
Questions and Problems......Page 134
6A The Nature of Random Errors......Page 135
6B Statistical Treatment of Random Errors......Page 140
6C Standard Deviation of Calculated Results......Page 152
6D Reporting Computed Data......Page 157
Questions and Problems......Page 161
Introduction......Page 165
7A Confidence Intervals......Page 166
7B Statistical Aids to Hypothesis Testing......Page 171
7C Analysis of Variance......Page 182
7D Detection of Gross Errors......Page 188
Questions and Problems......Page 191
8A Analytical Samples and Methods......Page 195
8B Sampling......Page 198
8C Automated Sample Handling......Page 206
8D Standardization and Calibration......Page 209
8E Figures of Merit for Analytical Methods......Page 228
Questions and Problems......Page 233
Part II: Chemical Equilibria......Page 238
9A The Chemical Composition of Aqueous Solutions......Page 239
9B Chemical Equilibrium......Page 244
9C Buffer Solutions......Page 261
Questions and Problems......Page 274
10A The Effect of Electrolytes on Chemical Equilibria......Page 277
10B Activity Coefficients......Page 281
Questions and Problems......Page 289
Introduction......Page 291
11A Solving Multiple-Equilibrium Problems Using a Systematic Method......Page 292
11B Calculating Solubilities by the Systematic Method......Page 298
11C Separation of Ions by Control of the Concentration of the Precipitating Agent......Page 310
Questions and Problems......Page 318
Part III: Classical Methods of Analysis......Page 321
12A Precipitation Gravimetry......Page 322
12B Calculation of Results from Gravimetric Data......Page 333
12C Applications of Gravimetric Methods......Page 336
Questions and Problems......Page 341
Introduction......Page 344
13A Some Terms Used in Volumetric Titrations......Page 345
13B Standard Solutions......Page 347
13C Volumetric Calculations......Page 348
13D Gravimetric Titrations......Page 356
13E Titration Curves......Page 357
Questions and Problems......Page 360
14A Solutions and Indicators for Acid/Base Titrations......Page 364
14B Titration of Strong Acids and Bases......Page 368
14C Titration Curves for Weak Acids......Page 374
14D Titration Curves for Weak Bases......Page 379
14E The Composition of Solutions During acid/Base Titrations......Page 383
Questions and Problems......Page 387
15A Mixtures of Strong and Weak Acids or Strong and Weak Bases......Page 390
15B Polyfunctional Acids and Bases......Page 394
15C Buffer Solutions Involving Polyprotic Acids......Page 396
15D Calculation of the pH of Solutions of NaHA......Page 398
15E Titration Curves for Polyfunctional Acids......Page 402
15F Titration Curves for Polyfunctional Bases......Page 411
15G Titration Curves for Amphiprotic Species......Page 413
15H Composition of Polyprotic Acid Solutions as a Function of pH......Page 415
Questions and Problems......Page 420
Introduction......Page 423
16A Reagents for Neutralization Titrations......Page 424
16B Typical Applications of Neutralization Titrations......Page 429
Questions and Problems......Page 438
17A The Formation of Complexes......Page 442
17B Titrations with Inorganic Complexing Agents......Page 448
17C Organic Complexing Agents......Page 455
17D Aminocarboxylic Acid Titrations......Page 456
Questions and Problems......Page 479
Part IV: Electrochemical Methods......Page 483
18A Characterizing Oxidation/Reduction Reactions......Page 484
18B Electrochemical Cells......Page 488
18C Electrode Potentials......Page 493
Questions and Problems......Page 512
19A Calculating Potentials of Electrochemical Cells......Page 515
19B Determining Standard Potentials Experimentally......Page 522
19C Calculating Redox Equilibrium Constants......Page 524
19D Constructing Redox Titration Curves......Page 530
19E Oxidation/Reduction Indicators......Page 544
Questions and Problems......Page 547
20A Auxiliary Oxidizing and Reducing Reagents......Page 551
20B Applying Standard Reducing Agents......Page 553
20C Applying Standard Oxidizing Agents......Page 557
Questions and Problems......Page 574
Introduction......Page 577
21A General Principles......Page 578
21B Reference Electrodes......Page 579
21C Liquid-Junction Potentials......Page 581
21D Indicator Electrodes......Page 582
21E Instruments for Measuring Cell Potential......Page 602
21F Direct Potentiometry......Page 605
21G Potentiometric Titrations......Page 611
21H Potentiometric Determination of Equilibrium Constants......Page 615
Questions and Problems......Page 617
Introduction......Page 620
22A The Effect of Current on Cell Potential......Page 621
22B The Selectivity of Electrolytic Methods......Page 628
22C Electrogravimetric Methods......Page 630
22D Coulometric Methods......Page 636
Questions and Problems......Page 647
Introduction......Page 652
23A Excitation Signals In Voltammetry......Page 653
23B Voltammetric Instrumentation......Page 654
23C Hydrodynamic Voltammetry......Page 660
23D Polarography......Page 675
23E Cyclic Voltammetry......Page 677
23F Pulse Voltammetry......Page 681
23G Applications of Voltammetry......Page 684
23H Stripping Methods......Page 685
23I Voltammetry with Microelectrodes......Page 687
Questions and Problems......Page 689
Part V: Spectrochemical Analysis......Page 691
Introduction......Page 692
24A Properties of Electromagnetic Radiation......Page 693
24B Interaction of Radiation and Matter......Page 696
24C Absorption of Radiation......Page 700
24D Emission of Electromagnetic Radiation......Page 716
Questions and Problems......Page 722
25A Instrument Components......Page 725
25B Ultraviolet/Visible Photometers and Spectrophotometers......Page 752
25C Infrared Spectrophotometers......Page 755
Questions and Problems......Page 761
26A Ultraviolet and Visible Molecular Absorption Spectroscopy......Page 764
26B Automated Photometric and Spectrophotometric Methods......Page 786
26C Infrared Absorption Spectroscopy......Page 788
Questions and Problems......Page 796
27A Theory of Molecular Fluorescence......Page 802
27B Effect of Concentration on Fluorescence Intensity......Page 806
27C Fluorescence Instrumentation......Page 807
27D Applications of Fluorescence Methods......Page 808
27E Molecular Phosphorescence Spectroscopy......Page 811
27F Chemiluminescence Methods......Page 812
Questions and Problems......Page 813
Introduction......Page 815
28A Origins of Atomic Spectra......Page 816
28B Production of Atoms and Ions......Page 818
28C Atomic Emission Spectrometry......Page 828
28D Atomic Absorption Spectrometry......Page 832
Questions and Problems......Page 841
29A Principles of Mass Spectrometry......Page 844
29B Mass Spectrometers......Page 846
29C Atomic Mass Spectrometry......Page 850
29D Molecular Mass Spectrometry......Page 853
Questions and Problems......Page 859
Part VI: Kinetics and Separations......Page 860
Introduction......Page 861
30A Rates of Chemical Reactions......Page 862
30B Determining Reaction Rates......Page 875
30C Applications of Kinetic Methods......Page 882
Questions and Problems......Page 886
Introduction......Page 889
31A Separation by Precipitation......Page 890
31C Separation by Extraction......Page 894
31D Separating Ions by Ion Exchange......Page 899
31E Chromatographic Separations......Page 903
Questions and Problems......Page 925
Introduction......Page 929
32A Instruments for Gas-Liquid Chromatography......Page 930
32B Gas Chromatographic Columns and Stationary Phases......Page 939
32C Applications of Gas-Liquid Chromatography......Page 943
Questions and Problems......Page 951
Introduction......Page 954
33A Instrumentation......Page 955
33B Partition Chromatography......Page 963
33C Adsorption Chromatography......Page 966
33D Ion Chromatography......Page 967
33E Size-Exclusion Chromatography......Page 969
33G Chiral Chromatography......Page 973
33H Comparison of High-Performance Liquid Chromatography and Gas Chromatography......Page 974
Questions and Problems......Page 975
34A Supercritical Fluid Separations......Page 977
34B Planar Chromatography......Page 982
34C Capillary Electrophoresis......Page 984
34D Capillary Electrochromatography......Page 991
34E Field-Flow Fractionation......Page 994
Questions and Problems......Page 999
Glossary......Page 1001
Appendix 1: The Literature of Analytical Chemistry......Page 1019
Appendix 2: Solubility Product Constants at 25°C......Page 1024
Appendix 3: Acid Dissociation Constants at 25°C......Page 1026
Appendix 4: Formation Constants at 25°C......Page 1028
Appendix 5: Standard and Formal Electrode Potentials......Page 1030
Appendix 6: Use of Exponential Numbers and Logarithms......Page 1033
Appendix 7: Volumetric Calculations Using Normality and Equivalent Weight......Page 1037
Appendix 8: Compounds Recommended for the Preparation of Standard Solutions of Some Common Elements......Page 1045
Appendix 9: Derivation of Error Propagation Equations......Page 1047
Answers to Selected Questions and Problems......Page 1052
Index......Page 1067
