Fundamentals of Analytical Chemistry (with CD-ROM and InfoTrac)

by Skoog, Douglas A.; West, Donald M.; Holler, F. James; Crouch, Stanley R.

• ISBN13: 9780030355233
• ISBN10: 0030355230
• Edition: 8th
• Format: Hardcover w/CD
• Copyright: 2003-08-07
• Publisher: Brooks Cole

Summary

FUNDAMENTALS OF ANALYTICAL CHEMISTRY, EIGHTH EDITION is known for its readability combined with a systematic, rigorous approach that characterizes this classic text. Extensive coverage of the principles and practices of quantitative chemistry ensures suitability for chemistry majors. These award-winning authors include applications throughout industry, medicine, and all the sciences. The text's new design and wealth of new photographs by renowned chemistry photographer Charlie Winters serve to reinforce student learning through dynamic visuals. Reflecting the increased emphasis of spreadsheets as a tool in analytical chemistry, this new edition adds an additional chapter, new problems and a new supplement, EXCEL? APPLICATIONS FOR ANALYTICAL CHEMISTRY, that integrate this important aspect of the study of analytical chemistry into its already rich pedagogy. In addition, the INTERACTIVE ANALYTICAL CHEMISTRY CD-ROM, packaged FREE with every new text, enhances conceptual understanding through hands-on integrated multimedia interactivity.

Table of Contents

Chapter 1 The Nature of Analytical Chemistry	2	(15)
1A The Role of Analytical Chemistry	3	(1)
1B Quantitative Analytical Methods	4	(1)
1C A Typical Quantitative Analysis	5	(5)
1D An Integral Role for Chemical Analysis: Feedback Control Systems	10	(2)
Feature 1-1 Deer Kill: A Case Study Illustrating the Use of Analytical Chemistry to Solve a Problem in Toxicology	12	(5)
PART I Tools of Analytical Chemistry	17	(208)
A Conversation with Richard N. Zare	18	(208)
Chapter 2 Chemicals, Apparatus, and Unit Operations of Analytical Chemistry	20	(34)
2A Selecting and Handling Reagents and Other Chemicals	21	(1)
2B Cleaning and Marking of Laboratory Ware	22	(1)
2C Evaporating Liquids	23	(1)
2D Measuring Mass	23	(7)
2E Equipment and Manipulations Associated with Weighing	30	(3)
2F Filtration and Ignition of Solids	33	(6)
2G Measuring Volume	39	(9)
2H Calibrating Volumetric Glassware	48	(3)
2I The Laboratory Notebook	51	(1)
2J Safety in the Laboratory	52	(2)
Chapter 3 Using Spreadsheets in Analytical Chemistry	54	(17)
3A Keeping Records and Making Calculations: Spreadsheet Exercise 1	55	(5)
3B Calculating Molar Masses Using Excel: Spreadsheet Exercise 2	60	(11)
Chapter 4 Calculations Used in Analytical Chemistry	71	(19)
4A Some Important Units of Measurement	71	(2)
Feature 4-1 Atomic Mass Units and the Mole	73	(3)
4B Solutions and Their Concentrations	76	(7)
4C Chemical Stoichiometry	83	(7)
Chapter 5 Errors in Chemical Analyses	90	(15)
5A Some Important Terms	92	(3)
5B Systematic Errors	95	(10)
Chapter 6 Random Errors in Chemical Analysis	105	(37)
6A The Nature of Random Errors	105	(4)
Feature 6-1 Flipping Coins: A Student Activity to Illustrate a Normal Distribution	109	(1)
6B Statistical Treatment of Random Error	110	(3)
Feature 6-2 Calculating the Areas under the Gaussian Curve	113	(3)
Feature 6-3 The Significance of the Number of Degrees of Freedom	116	(8)
Feature 6-4 Equation for Calculating the Pooled Standard Deviation	124	(3)
6C Standard Deviation of Calculated Results	127	(6)
6D Reporting Computed Data	133	(9)
Chapter 7 Statistical Data Treatment and Evaluation	142	(33)
7A Confidence Intervals	143	(5)
Feature 7-1 Breath Alcohol Analyzers	148	(1)
7B Statistical Aids to Hypothesis Testing	149	(11)
7C Analysis of Variance	160	(7)
7D Detection of Gross Errors	167	(8)
Chapter 8 Sampling, Standardization, and Calibration	175	(53)
8A Analytical Samples and Methods	175	(3)
8B Sampling and Sample Handling	178	(13)
Feature 8-1 Lab-on-a-Chip	191	(1)
8C Standardization and Calibration	192	(1)
Feature 8-2 A Comparison Method for Aflatoxins	192	(16)
Feature 8-3 Multivariate Calibration	208	(6)
8D Figures of Merit for Analytical Methods	214	(11)
PART II Chemical Equilibria	225	(86)
A Conversation with Sylvia Daunert	226	(86)
Chapter 9 Aqueous Solutions and Chemical Equilibria	228	(39)
9A The Chemical Compositions of Aqueous Solutions	228	(5)
9B Chemical Equilibrium	233	(3)
Feature 9-1 Stepwise and Overall Formation Constants for Complex Ions	236	(1)
Feature 9-2 Why [H20] Does Not Appear in Equilibrium Constant Expressions for Aqueous Solutions	237	(7)
Feature 9-3 Relative Strengths of Conjugate Acid/Base Pairs	244	(4)
Feature 9-4 The Method of Successive Approximations	248	(3)
9C Buffer Solutions	251	(1)
Feature 9-5 The Henderson-Hasselbalch Equation	252	(7)
Feature 9-6 Acid Rain and the Buffer Capacity of Lakes	259	(8)
Chapter 10 Effect of Electrolytes on Chemical Equilibria	267	(14)
10A The Effect of Electrolytes on Chemical Equilibria	267	(4)
10B Activity Coefficients	271	(3)
Feature 10-1 Mean Activity Coefficients	274	(7)
Chapter 11 Solving Equilibrium Calculations for Complex Systems	281	(33)
11A Solving Multiple-Equilibrium Problems by a Systematic Method	282	(5)
11B Calculating Solubilities by the Systematic Method	287	(7)
Feature 11-1 Algebraic Expressions Needed to Calculate the Solubility of CaC204 in Water	294	(6)
11C Separation of Ions by Control of the Concentration of the Precipitating Agent	300	(4)
Feature 11-2 Immunoassay: Equilibria in the Specific Determination of Drugs	304	(7)
PART III Classical Methods of Analysis	311	(176)
A Conversation with Larry R. Faulkner	312	(176)
Chapter 12 Gravimetric Methods of Analysis	314	(23)
12A Precipitation Gravimetry	315	(7)
Feature 12-1 Specific Surface Area of Colloids	322	(4)
12B Calculation of Results from Gravimetric Data	326	(3)
12C Applications of Gravimetric Methods	329	(8)
Chapter 13 Titrimetric Methods; Precipitation Titrimetry	337	(31)
13A Some Terms Used in Volumeric Titrimetry	338	(2)
13B Standard Solutions	340	(1)
13C Volumetric Calculations	341	(5)
Feature 13-1 Another Approach to Example 13-6(a)	346	(1)
Feature 13-2 Rounding the Answer to Example 13-7	347	(2)
13D Gravimetric Titrimetry	349	(1)
13E Titration Curves in Titrimetric Methods	350	(3)
13F Precipitation Titrimetry	353	(8)
Feature 13-3 Calculating the Concentration of Indicator Solutions	361	(7)
Chapter 14 Principles of Neutralization Titrations	368	(27)
14A Solutions and Indicators for Acid/Base Titrations	368	(4)
14B Titration of Strong Acids and Strong Bases	372	(3)
Feature 14-1 Using the Charge-Balance Equation to Construct Titration Curves	375	(3)
Feature 14-2 How Many Significant Figures Should We Retain in Titration Curve Calculations?	378	(1)
14C Titration Curves for Weak Acids	378	(3)
Feature 14-3 Determining Dissociation Constants for Weak Acids and Bases	381	(2)
14D Titration Curves for Weak Bases	383	(2)
Feature 14-4 Determining the pK Values for Amino Acids	385	(2)
14E The Composition of Solutions During Acid/Base Titrations	387	(1)
Feature 14-5 Locating Titration End Points from pH Measurements	388	(7)
Chapter 15 Titration Curves for Complex Acid/Base Systems	395	(33)
15A Mixtures of Strong and Weak Acids or Strong and Weak Bases	398	(1)
15B Polyfunctional Acids and Bases	399	(2)
15C Buffer Solutions Involving Polyprotic Acids	401	(2)
15D Calculation of the pH of Solutions of NaHA	403	(4)
15E Titration Curves for Polyfunctional Acids	407	(8)
Feature 15-1 The Dissociation of Sulfuric Acid	415	(1)
15F Titration Curves for Polyfunctional Bases	416	(1)
15G Titration Curves for Amphiprotic Species	417	(1)
Feature 15-2 Acid/Base Behavior of Amino Acids	418	(1)
15H The Composition of Solutions of a Polyprotic Acid as a Function of pH	419	(1)
Feature 15-3 A General Expression for Alpha Values	420	(2)
Feature 15-4 Logarithmic Concentration Diagrams	422	(6)
Chapter 16 Applications of Neutralization Titrations	428	(21)
16A Reagents for Neutralization Titrations	429	(6)
16B Typical Applications of Neutralization Titrations	435	(1)
Feature 16-1 Determining Total Serum Protein	435	(1)
Feature 16-2 Other Methods for Determining Organic Nitrogen	436	(6)
Feature 16-3 Equivalent Weights of Acids and Bases	442	(7)
Chapter 17 Complexation Reactions and Titrations	449	(41)
17A The Formation of Complexes	449	(3)
Feature 17-1 Calculation of Alpha Values for Metal Complexes	452	(3)
17B Titrations with Inorganic Complexing Agents	455	(1)
Feature 17-2 Determination of Hydrogen Cyanide in Acrylonitrile Plant Streams	456	(1)
17C Organic Complexing Agents	457	(1)
17D Aminocarboxylic Acid Titrations	458	(1)
Feature 17-3 Species Present in a Solution of EDTA	459	(3)
Feature 17-4 EDTA as a Preservative	462	(11)
Feature 17-5 EDTA Titration Curves When a Complexing Agent Is Present	473	(7)
Feature 17-6 How Masking and Demasking Agents Can Be Used to Enhance the Selectivity of EDTA Titrations	480	(2)
Feature 17-7 Test Kits for Water Hardness	482	(5)
PART IV Electrochemical Methods	487	(220)
A Conversation with Allen J. Bard	488	(220)
Chapter 18 Introduction to Electrochemistry	490	(33)
18A Characterizing Oxidation/Reduction Reactions	490	(2)
Feature 18-1 Balancing Redox Equations	492	(2)
18B Electrochemical Cells	494	(4)
Feature 18-2 The Daniell Gravity Cell	498	(1)
18C Electrode Potentials	499	(5)
Feature 18-3 Why We Cannot Measure Absolute Electrode Potentials	504	(9)
Feature 18-4 Sign Conventions in the Older Literature	513	(2)
Feature 18-5 Why Are There Two Electrode Potentials for Br2 in Table 18-1?	515	(8)
Chapter 19 Applications of Standard Electrode Potentials	523	(37)
19A Calculating Potentials of Electrochemical Cells	523	(7)
19B Determining Standard Potentials Experimentally	530	(2)
19C Calculating Redox Equilibrium Constants	532	(1)
Feature 19-1 Biological Redox Systems	532	(5)
Feature 19-2 A General Expression for Calculating Equilibrium Constants from Standard Potentials	537	(1)
19D Constructing Redox Titration Curves	538	(9)
Feature 19-3 The Inverse Master Equation Approach for Redox Titration Curves	547	(5)
Feature 19-4 Reaction Rates and Electrode Potentials	552	(1)
19E Oxidation/Reduction Indicators	552	(3)
19F Potentiometric End Points	555	(5)
Chapter 20 Applications of Oxidation/Reduction Titrations	560	(28)
20A Auxiliary Oxidizing and Reducing Reagents	560	(2)
20B Applying Standard Reducing Agents	562	(4)
20C Applying Standard Oxidizing Agents	566	(2)
Feature 20-1 Determination of Chromium Species in Water Samples	568	(5)
Feature 20-2 Antioxidants	573	(15)
Chapter 21 Potentiometry	588	(45)
21A General Principles	589	(1)
21B Reference Electrodes	590	(2)
21C Liquid-Junction Potentials	592	(1)
21D Indicator Electrodes	593	(13)
Feature 21-1 An Easily Constructed Liquid-Membrane Ion-Selective Electrode	606	(2)
Feature 21-2 The Structure and Performance of Ion Selective Field Effect Transistors	608	(4)
Feature 21-3 Point-of-Care Testing: Blood Gases and Blood Electrolytes with Portable Instrumentation	612	(2)
21E Instruments for Measuring Cell Potential	614	(1)
Feature 21-4 The Loading Error in Potential Measurements	614	(1)
Feature 21-5 Operational Amplifier Voltage Measurements	615	(1)
21F Direct Potentiometry	616	(7)
21G Potentiometric Titrations	623	(4)
21H Potentiometric Determination of Equilibrium Constants	627	(6)
Chapter 22 Bulk Electrolysis: Electrogravimetry and Coulometry	633	(32)
22A The Effect of Current on Cell Potential	634	(7)
Feature 22-1 Overvoltage and the Lead/Acid Battery	641	(1)
22B The Selectivity of Electrolytic Methods	641	(2)
22C Electrogravimetric Methods	643	(6)
22D Coulometric Methods	649	(9)
Feature 22-2 Coulometric Titration of Chloride in Biological Fluids	658	(7)
Chapter 23 Voltammetry	665	(45)
23A Excitation Signals	666	(1)
23B Linear Sweep Voltammetry	667	(22)
23C Pulse Polarographic and Voltammetric Methods	689
Feature 23-1 Voltammetric Instruments Based on Operational Amplifiers	668	(26)
23D Cyclic Voltammetry	694	(3)
Feature 23-2 Modified Electrodes	697	(2)
23E Stripping Methods	699	(4)
23F Voltammetry with Microelectrodes	703	(4)
PART V Spectrocherical Methods	707	(168)
A Conversation with Gary M. Hieftje	708	(168)
Chapter 24 Introduction to Spectrochemical Methods	710	(34)
24A Properties of Electromagnetic Radiation	711	(3)
24B Interaction of Radiation and Matter	714	(3)
Feature 24-1 Spectroscopy and the Discovery of Elements	717	(1)
24C Radiation Absorption	718	(2)
Feature 24-2 Deriving Beer's Law	720	(5)
Feature 24-3 Why Is a Red Solution Red?	725	(9)
24D Emission of Electromagnetic Radiation	734	(10)
Chapter 25 Instruments for Optical Spectrometry	744	(40)
25A Instrument Components	744	(4)
Feature 25-1 Laser Sources: The Light Fantastic	748	(6)
Feature 25-2 Derivation of Equation 25-1	754	(2)
Feature 25-3 Ruling Gratings	756	(3)
Feature 25-4 Deriving Equation 25-2	759	(2)
Feature 25-5 Signals, Noise, and the Signal-to-Noise Ratio	761	(8)
Feature 25-6 Measuring Photocurrents with Operational Amplifiers	769	(2)
25B Ultraviolet-Visible Photometers and Spectrophotometers	771	(5)
25C Infrared Spectrophotometers
Feature 25-7 How Does a Fourier Transform Infrared Spectrometer Work?	776	(8)
Chapter 26 Molecular Absorption Spectrometry	784	(41)
26A Ultraviolet and Visible Molecular Absorption Spectroscopy	784	(23)
26B Automated Photometric and Spectrophotometric Methods	807	(4)
26C Infrared Absorption Spectroscopy	811	(7)
Feature 26-1 Using The Fourier Transform To Produce Infrared Spectra	818	(7)
Chapter 27 Molecular Fluorescence Spectroscopy	825	(14)
27A Theory of Molecular Fluorescence	825	(4)
27B Effect of Concentration On Fluorescence Intensity	829	(1)
27C Fluorescence Instruments	830	(1)
27D Applications of Fluorescence Methods	831	(1)
Feature 27-1 Use of Fluorescence Probes in Neurobiology: Probing the Enlightened Mind	832	(2)
27E Molecular Phosphorescence Spectroscopy	834	(1)
27F Chemiluminescence Methods	835	(4)
Chapter 28 Atomic Spectroscopy	839	(39)
28A Origins of Atomic Spectra	840	(3)
28B Production of Atoms and Ions	843	(11)
28C Atomic Emission Spectrometry	854	(4)
28D Atomic Absorption Spectrometry	858	(7)
Feature 28-1 Determining Mercury by Cold-Vapor Atomic Absorption Spectroscopy	865	(3)
28E Atomic Fluorescence Spectrometry	868	(1)
28F Atomic Mass Spectrometry	868	(7)
PART VI Kinetics and Separations	875	(146)
A Conversation with Isiah M. Warner	876	(146)
Chapter 29 Kinetic Methods of Analysis	878	(28)
29A Rates of Chemical Reactions	879	(7)
Feature 29-1 Enzymes	886	(6)
29B Determining Reaction Rates	892	(1)
Feature 29-2 Fast Reactions and Stopped-Flow Mixing	892	(8)
29C Applications of Kinetic Methods	900	(1)
Feature 29-3 The Enzymatic Determination of Urea	901	(5)
Chapter 30 Introduction to Analytical Separations	906	(41)
30A Separation by Precipitation	907	(4)
30B Separation of Species by Distillation	911	(1)
30C Separation by Extraction	911	(2)
Feature 30-1 Derivation of Equation 30-3	913	(3)
30D Separating Ions by Ion Exchange	916	(3)
Feature 30-2 Home Water Softeners	919	(1)
30E Chromatographic Separations	920	(10)
Feature 30-3 What is the Source of the Terms Plate and Plate Height?	930	(17)
Chapter 31 Gas Chromatography	947	(26)
31A Instruments for Gas-Liquid Chromatography	948	(10)
31B Gas Chromatography Columns and Stationary Phases	958	(5)
31C Applications of Gas-Liquid Chromatography	963	(2)
Feature 31-1 Use of GCIMS to identify a Drug Metabolite in Blood	965	(4)
Feature 31-2 High-Speed Gas Chromatography	969	(1)
31D Gas-Solid Chromatography	970	(3)
Chapter 32 High-Performance Liquid Chromatography	973	(23)
32A Instrumentation	974	(6)
Feature 32-1 Liquid Chromatography (LC)/Mass Spectrometry (MS) and LC/MS/NS	980	(2)
32B High-Performance Partition Chromatography	982	(4)
32C High-Performance Adsorption Chromatography	986	(1)
32D Ion-Exchange Chromatography	986	(2)
32E Size-Exclusion Chromatography	988	(1)
Feature 32-2 Buckyballs: The Chromatographic Separation of Fullerenes	989	(2)
32F Affinity Chromatography	991	(1)
32G Chiral Chromatography	991	(1)
32H Comparison of High-Performance Liquid Chromatography and Gas Chromatography	992	(4)
Chapter 33 Miscellaneous Separation Methods	996	(28)
33A Supercritical-Fluid Chromatography	996	(4)
33B Planar Chromatography	1000	(3)
33C Capillary Electrophoresis	1003	(7)
Feature 33-1 Capillary Array Electrophoresis in DNA Sequencing	1010	(1)
33D Capillary Electrochromatography	1011	(2)
33E Field-Flow Fractionation	1013	(8)
PART VII Practical Aspects of Chemical Analysis	1021
A Conversation with Julie Leary	1022
Chapter 34 Analysis of Real Samples	1024	(10)
34A Real Samples	1024	(2)
34B Choice of Analytical Method	1026	(5)
34C Accuracy in the Analysis of Complex Materials	1031	(3)
Chapter 35 Preparing Samples for Analysis	1034	(7)
35A Preparing Laboratory Samples	1034	(2)
35B Moisture in Samples	1036	(3)
35C Determining Water in Samples	1039	(2)
Chapter 36 Decomposing and Dissolving the Sample	1041
36A Sources of Error in Decomposition and Dissolution	1042	(1)
36B Decomposing Samples With Inorganic Acids in Open Vessels	1042	(2)
36C Microwave Decompositions	1044	(3)
36D Combustion Methods for Decomposing Organic Samples	1047	(2)
36E Decomposition of Inorganic Materials by Fluxes	1049	(543648336)
Chapter 37 Selected Methods of Analysis
This chapter is only available as an Adobe Acrobat° PDF file on the Analytical Chemistry CD-ROM enclosed in this book or on our Web site at http://chemistry.brookscole.comlskoogfacl.
37A An Introductory Experiment
37B Gravimetric Methods of Analysis
37C Neutralization Titrations
37D Precipitation Titrations
37E Complex-Formation Titrations with EDTA
37F Titrations with Potassium Permanganate
37G Titrations with Iodine
37H Titrations with Sodium Thiosulfate
37I Titrations with Potassium Bromate
37J Potentiometric Methods
37K Electrogravimetric Methods
37L Coulometric Titrations
37M Voltammetry
37N Methods Based on the Absorption of Radiation
37O Molecular Fluorescence
37P Atomic Spectroscopy
37Q Application of Ion Exchange Resins
37R Gas-Liquid Chromatography
Glossary	G-1
APPENDIX 1 The Literature of Analytical Chemistry	A-1
APPENDIX 2 Solubility Product Constants at 25°C	A-6
APPENDIX 3 Acid Dissociation Constants at 25°C	A-8
APPENDIX 4 Formation Constants at 25°C	A-10
APPENDIX 5 Standard and Formal Electrode Potentials	A-12
APPENDIX 6 Use of Exponential Numbers and Logarithms	A-15
APPENDIX 7 Volumetric Calculations Using Normality and Equivalent Weight	A-19
APPENDIX 8 Compounds Recommended for the Preparation of Standard Solutions of Some Common Elements	A-27
APPENDIX 9 Derivation of Error Propagation Equations	A-29
Answers to Selected Questions and Problems	A-34
Index	I-1