Quantitative Chemical Analysis

by Harris, Daniel C.

• ISBN13: 9780716728818
• ISBN10: 0716728818
• Edition: 5th
• Format: Hardcover
• Copyright: 1998-08-01
• Publisher: W H Freeman & Co

Summary

For instructors who wish to focus on practical, industrial, or research chemistry. Includes case studies, applications boxes, and spreadsheet applications.

Table of Contents

Preface	xvii
Chapter 0 The Analytical Process Actions and Consequences	1	(12)
0-1 Analytical Chemists Are Sleuths--And Sometimes Life Is Messy!	1	(6)
0-2 Sampling and Sample Preparation	7	(1)
0-3 General Steps in a Chemical Analysis	8	(1)
Box 0-1 Constructing a Representative Sample	9	(4)
Chapter 1 Measurements	13	(16)
Measuring the Universe	12	(1)
1-1 SI Units	13	(3)
1-2 Chemical Concentrations	16	(4)
1-3 Preparing Solutions	20	(2)
1-4 Solutions and Stoichiometry	22	(7)
Chapter 2 Tools of the Trade	29	(22)
Weighing Femtomoles of DNA	28	(1)
2-1 Safe, Ethical Handling of Chemicals and Waste	29	(2)
Box 2-1 Disposal of Chemical Waste	29	(2)
2-2 The Lab Notebook	31	(1)
2-3 Analytical Balance	31	(5)
Box 2-2 Quartz Crystal Microbalance	34	(2)
2-4 Burets	36	(2)
2-5 Volumetric Flasks	38	(2)
2-6 Pipets and Syringes	40	(1)
2-7 Filtration	41	(2)
2-8 Drying	43	(2)
2-9 Calibration of Volumetric Glassware	45	(6)
Chapter 3 Experimental Error	51	(18)
Experimental Error	50	(1)
3-1 Significant Figures	51	(1)
3-2 Significant Figures in Arithmetic	52	(3)
3-3 Significant Figures and Graphs	55	(1)
3-4 Types of Error	56	(2)
Box 3-1 Standard Reference Materials	57	(1)
3-5 Propagation of Uncertainty	58	(11)
Chapter 4 Statistics and Spreadsheets	69	(24)
Is My Red Blood Cell Count High Today?	68	(1)
4-1 Gaussian Distribution	69	(5)
4-2 Confidence Intervals	74	(3)
4-3 Comparison of Means with Student's t	77	(4)
4-4 Control Charts	81	(1)
Box 4-1 Analytical Chemistry and the Law	81	(1)
4-5 Q Test for Bad Data	82	(1)
4-6 Spreadsheets	83	(10)
Chapter 5 Calibration Methods	93	(20)
A Historic Calibration Curve	92	(1)
5-1 Finding the "Best" Straight Line	93	(4)
5-2 Calibration Curves	97	(4)
Box 5-1 Using a Nonlinear Calibration Curve	99	(2)
5-3 Standard Addition	101	(3)
5-4 Internal Standards	104	(2)
5-5 A Spreadsheet for Least Squares	106	(7)
Chapter 6 Chemical Equilibrium	113	(36)
Chemical Equilibrium in the Environment	112	(1)
6-1 The Equilibrium Constant	113	(2)
6-2 Equilibrium and Thermodynamics	115	(3)
6-3 Solubility Product	118	(1)
6-4 The Common Ion Effect	119	(3)
Demonstration 6-1 Common Ion Effect	120	(1)
Box 6-1 The Logic of Approximations	121	(1)
6-5 Separation by Precipitation	122	(1)
6-6 Complex Formation	123	(3)
Box 6-2 Notation for Formation Constants	124	(2)
6-7 Protic Acids and Bases	126	(3)
6-8 pH	129	(2)
6-9 Strengths of Acids and Bases	131	(18)
Demonstration 6-2 The HCI Fountain	132	(1)
Box 6-3 The Strange Behavior of Hydrofluoric Acid	133	(3)
Box 6-4 Carbonic Acid	136	(13)
Chapter 7 Let the Titrations Begin	149	(26)
Evolution of the Buret	148	(1)
7-1 Titrations	149	(2)
7-2 Titration Calculations	151	(2)
7-3 Spectrophotometric Titrations	153	(2)
7-4 The Precipitation Titration Curve	155	(6)
7-5 Titration of a Mixture	161	(1)
7-6 Calculating Titration Curves with a Spreadsheet	162	(2)
7-7 End-Point Detection	164	(11)
Demonstration 7-1 Fajans Titration	166	(9)
Chapter 8 Activity	175	(16)
Hydrated Radii	174	(1)
8-1 The Effect of Ionic Strength on Solubility of Salts	175	(3)
Demonstration 8-1 Effect of Ionic Strength on Ion Dissociation	177	(1)
Box 8-1 Salts with Ions of Charge is grater than equal to (2) Do Not Fully Dissociate into Ions in Water	178	(1)
8-2 Activity Coefficients	178	(5)
8-3 Using Activity Coefficients	183	(2)
8-4 pH Revisited	185	(6)
Chapter 9 Systematic Treatment of Equilibrium	191	(20)
Acid Rain	190	(1)
9-1 Charge Balance	191	(1)
9-2 Mass Balance	192	(2)
9-3 Systematic Treatment of Equilibrium	194	(3)
Box 9-1 Calcium Carbonate Mass Balance in Rivers	195	(2)
9-4 The Dependence of Solubility on pH	197	(14)
Box 9-2 All Right, Dan, How Would You Really Solve The CaF(2) Problem?	200	(2)
Box 9-3 pH and Tooth Decay	202	(9)
Chapter 10 Monoprotic Acid-Base Equilibria	211	(28)
Measuring pH Inside Single Cells	210	(1)
10-1 Strong Acids and Bases	211	(3)
10-2 Weak Acids and Bases	214	(1)
10-3 Weak-Acid Equilibria	215	(4)
Demonstration 10-1 Conductivity of Weak Electrolytes	218	(1)
10-4 Weak-Base Equilibria	219	(3)
Box 10-1 Dyeing Fabrics and the Fraction of Dissociation	220	(2)
10-5 Buffers	222	(17)
Box 10-2 Strong Plus Weak Reacts Completely	227	(1)
Demonstration 10-2 How Buffers Work	228	(11)
Chapter 11 Polyprotic Acid-Base Equilibria	239	(26)
Proteins Are Polyprotic Acids and Bases	238	(1)
11-1 Diprotic Acids and Bases	239	(10)
Box 11-1 Successive Approximations	246	(3)
11-2 Diprotic Buffers	249	(1)
11-3 Polyprotic Acids and Bases	250	(2)
11-4 Which Is the Principal Species?	252	(2)
11-5 Fractional Composition Equations	254	(2)
11-6 Isoelectric and Isoionic pH	256	(9)
Box 11-2 Isoelectric Focusing	258	(7)
Chapter 12 Acid-Base Titrations	265	(42)
Acid-Base Titration of a Protein	264	(1)
12-1 Titration of Strong Acid with Strong Base	265	(3)
12-2 Titration of Weak Acid with Strong Base	268	(4)
12-3 Titration of Weak Base with Strong Acid	272	(2)
12-4 Titrations in Diprotic Systems	274	(3)
12-5 Finding the End Point with a pH Electrode	277	(1)
Box 12-1 Alkalinity and Acidity	277	(5)
12-6 Finding the End Point with Indicators	282	(5)
Box 12-2 What Does a Negative pH Mean?	284	(1)
Demonstration 12-1 Indicators and the Acidity of CO(2)	284	(3)
Box 12-3 World Record Small Titration	287	(1)
12-7 Practical Notes	287	(2)
12-8 Titrations in Nonaqueous Solvents	289	(3)
12-9 Calculating Titration Curves with Spreadsheets	292	(15)
Chapter 13 EDTA Titrations	307	(30)
A Chelating Ligand Captures Its Prey	306	(1)
13-1 Metal-Chelate Complexes	307	(3)
13-2 EDTA	310	(6)
Box 13-1 Chelation Therapy and Thalassemia	310	(6)
13-3 EDTA Titration Curves	316	(3)
13-4 Do It with a Spreadsheet	319	(1)
13-5 Auxiliary Complexing Agents	320	(3)
13-6 Metal Ion Indicators	323	(2)
Demonstration 13-1 Metal Ion Indicator Color Changes	325	(1)
13-7 EDTA Titration Techniques	325	(12)
Box 13-2 Water Hardness	328	(9)
Chapter 14 Fundamentals of Electrochemistry	337	(38)
An Atomic-Scale Galvanic Cell	336	(1)
14-1 Basic Concepts	337	(4)
14-2 Galvanic Cells	341	(4)
Demonstration 14-1 The Human Salt Bridge	344	(1)
14-3 Standard Potentials	345	(2)
14-4 Nernst Equation	347	(6)
Box 14-1 E(Digree) and the Cell Voltage Do Not Depend on How You Write the Cell Reaction	349	(2)
Box 14-2 Latimer Diagrams: How to Find E(Digree) for a New Half-Reaction	351	(2)
14-5 E(Digree) and the Equilibrium Constant	353	(3)
Box 14-3 Concentrations in the Operating Cell	353	(3)
14-6 Cells as Chemical Probes	356	(3)
14-7 Biochemists Use E(Digree)'	359	(16)
Chapter 15 Electrodes and Potentiometry	375	(40)
A Heparin Sensor	374	(1)
15-1 Reference Electrodes	375	(3)
15-2 Indicator Electrodes	378	(2)
15-3 What Is a Junction Potential?	380	(1)
15-4 pH Measurement with a Glass Electrode	381	(10)
Demonstration 15-1 Potentiometry with an Oscillating Reaction	382	(9)
15-5 Ion-Selective Electrodes	391	(7)
Box 15-1 Systematic Error in Rainwater pH Measurement: The Effect of Junction Potential	392	(6)
15-6 Using Ion-Selective Electrodes	398	(2)
15-7 Solid-State Chemical Sensors	400	(15)
Chapter 16 Redox Titrations	415	(28)
Chemical Analysis of High-Temperature Superconductors	414	(1)
16-1 The Shape of a Redox Titration Curve	415	(6)
16-2 Redox Indicators	421	(3)
Demonstration 16-1 Potentiometric Titration of Fe(2+) with MnO(4)	422	(2)
16-3 Adjustment of Analyte Oxidation State	424	(2)
16-4 Oxidation with Potassium Permanganate	426	(2)
16-5 Oxidation with Ce(4+)	428	(1)
16-6 Oxidation with Potassium Dichromate	429	(1)
16-7 Methods Involving Iodine	429	(14)
Box 16-1 Environmental Carbon Analysis and Oxygen Demand	430	(4)
Box 16-2 Iodometric Analysis of High-Temperature Superconductors	434	(9)
Chapter 17 Electrogravimetric and Coulometric Analyses	443	(28)
How Sweet It Is!	442	(1)
17-1 Electrolysis: Putting Electrons to Work	443	(2)
17-2 Why Voltage Changes When Current Flows	445	(6)
Demonstration 17-1 Electrochemical Writing	446	(5)
17-3 Electrogravimetric Analysis	451	(6)
Demonstration 17-2 Silver and Gold Pennies	455	(2)
17-4 Coulometric Analysis	457	(3)
17-5 Mediators	460	(11)
Box 17-1 Electrical Wiring of Redox Enzymes	462	(9)
Chapter 18 Voltammetry	471	(40)
Oxygen Sensors for Automobile Pollution Control	470	(1)
18-1 Why We Use a Mercury Electrode in Polarography	471	(1)
18-2 Shape of the Polarogram	472	(9)
Box 18-1 The Electric Double Layer	477	(4)
18-3 Polarography in Chemical Analysis	481	(2)
18-4 Pulse Polarography	483	(4)
18-5 Stripping Analysis	487	(2)
18-6 Cyclic Voltammetry	489	(4)
Box 18-2 An Optically Transparent Thin-Layer Electrode	492	(1)
18-7 Amperometry	493	(4)
Box 18-3 Oxygen Electrodes	494	(3)
18-8 Karl Fischer Titration of H(2)O	497	(14)
Demonstration 18-1 The Karl Fischer Jacks of a pH Meter	499	(12)
Chapter 19 Fundamentals of Spectrophotometry	511	(34)
The Ozone Hole	510	(1)
19-1 Properties of Light	511	(1)
19-2 Absorption of Light	512	(5)
Box 19-1 Why Is There a Logarithmic Relation Between Transmittance and Concentration?	515	(1)
Demonstration 19-1 Absorption Spectra	516	(1)
19-3 The Spectrophotometer	517	(4)
19-4 Beer's Law in Chemical Analysis	521	(4)
19-5 What Happens When a Molecule Absorbs Light?	525	(5)
Box 19-2 Fluorescence All Around Us	529	(1)
19-6 Luminescence	530	(15)
Chapter 20 Applications of Spectrophotometry	545	(32)
Fiber-Optic Glucose Sensor	544	(1)
20-1 Analysis of a Mixture	545	(5)
20-2 Measuring an Equilibrium Constant: The Scatchard Plot	550	(1)
20-3 The Method of Continuous Variation	551	(3)
20-4 Flow Injection Analysis	554	(2)
20-5 Immunoassays	556	(3)
20-6 Sensors Based on Luminescence Quenching	559	(18)
Box 20-1 Converting Light into Electricity	560	(17)
Chapter 21 Spectrophotometers	577	(38)
The Most Important Photoreceptor	576	(1)
21-1 Interaction of Light with Matter	577	(6)
Box 21-1 Blackbody Radiation and the Greenhouse Effect	582	(1)
21-2 The Spectrophotometer	583	(1)
21-3 Lamps and Lasers: Sources of Light	584	(2)
21-4 Monochromators	586	(3)
21-5 Detectors	589	(5)
21-6 Errors in Spectrophotometry	594	(2)
21-7 Optodes	596	(4)
Box 21-2 On the Road to an "Electronic Nose"	598	(2)
21-8 Fourier Transform Infrared Spectroscopy	600	(6)
21-9 Dealing with Noise	606	(9)
Chapter 22 Atomic Spectroscopy	615	(26)
An Anthropology Puzzle	614	(1)
22-1 An Overview	615	(4)
22-2 Atomization: Flames, Furnaces, and Plasmas	619	(6)
22-3 How Temperature Affects Atomic Spectroscopy	625	(2)
22-4 Instrumentation	627	(5)
22-5 Interference	632	(9)
Box 22-1 A Smokestack Metal Emission Monitor: Challenges in Sampling and Calibration	632	(9)
Chapter 23 Introduction to Analytical Separations	641	(34)
Analytical Separations and Chemical Problem Solving	640	(1)
23-1 Solvent Extraction	641	(5)
Demonstration 23-1 Extraction with Dithizone	646	(1)
23-2 What Is Chromatography?	646	(3)
Box 23-1 Crown Ethers	647	(2)
23-3 A Plumber's View of Chromatography	649	(5)
23-4 Efficiency of Separation	654	(6)
23-5 Why Bands Spread	660	(15)
Chapter 24 Gas Chromatography	675	(38)
What Did They Eat in the Year 1000?	674	(1)
24-1 The Separation Process in Gas Chromatography	675	(10)
Box 24-1 Chiral Phases For Separating Optical Isomers	680	(5)
24-2 Sample Injection	685	(4)
24-3 Detectors	689	(5)
24-4 Sample Preparation	694	(2)
24-5 Method Development in Gas Chromatography	696	(3)
24-6 What Is Mass Spectrometry?	699	(5)
Box 24-2 How the Magnetic Sector Mass Spectrometer Separates Ions of Different Mass	702	(2)
24-7 Mass Spectrometry in Analytical Chemistry	704	(9)
Box 24-3 Isotope Ratio Mass Spectrometry	704	(9)
Chapter 25 High-Performance Liquid Chromatography	713	(42)
In Vivo Microdialysis for Measuring Drug Metabolism	712	(2)
25-1 The Chromatographic Process	714	(13)
Box 25-1 Designer Stationary Phases	718	(6)
Box 25-2 Supercritical Fluid Chromatography	724	(3)
25-2 Injection and Detection in HPLC	727	(6)
25-3 Method Development for Reversed-Phase Separations	733	(6)
25-4 Gradient Separations	739	(3)
25-5 Liquid Chromatography/Mass Spectrometry	742	(13)
Chapter 26 Chromatographic Methods and Capillary Electrophoresis	755	(40)
The Shape of the Future: Analysis on a Chip	754	(1)
26-1 Ion-Exchange Chromatography	755	(7)
26-2 Ion Chromatography	762	(4)
26-3 Molecular Exclusion Chromatography	766	(3)
26-4 Affinity Chromatography	769	(1)
26-5 Capillary Electrophoresis	769	(26)
Box 26-1 Chemical Analysis of a Single Cell	771	(24)
Chapter 27 Gravimetric and Combustion Analysis	795	(22)
Tree Rings and Our Changing Environment	794	(1)
27-1 An Example of Gravimetric Analysis	795	(2)
27-2 Precipitation	797	(6)
Demonstration 27-1 Colloids and Dialysis	798	(5)
27-3 Examples of Gravimetric Calculations	803	(3)
27-4 Combustion Analysis	806	(11)
Chapter 28 Sample Preparation	817	(26)
Extraction Membranes	816	(2)
Box 28-1 The Horwitz Trumpet: Variation in Interlaboratory Tests	818	(1)
28-1 Statistics of Sampling	819	(5)
28-2 Dissolving Samples for Analysis	824	(7)
28-3 Sample Preparation Techniques	831	(4)
28-4 Analytical Standards	835	(8)
Chapter 29 Experiments	843	(32)
29-1 Calibration of Volumetric Glassware	843	(1)
29-2 Gravimetric Determination of Calcium as CaC(2)O(4)H(2)O	844	(1)
29-3 Gravimetric Determination of Iron as Fe(2)O(3)	845	(1)
29-4 Statistical Evaluation of Acid-Base Indicators	846	(2)
29-5 Preparing Standard Acid and Base	848	(1)
29-6 Using a pH Electrode for an Acid-Base Titration	849	(1)
29-7 Analysis of a Mixture of Carbonate and Bicarbonate	850	(2)
29-8 Analysis of an Acid-Base Titration Curve: The Gran Plot	852	(1)
29-9 EDTA Titration of Ca(2+) and Mg(2+) in Natural Waters	853	(1)
29-10 Synthesis and Analysis of Ammonium Decavanadate	853	(3)
29-11 Iodimetric Titration of Vitamin C	856	(1)
29-12 Preparation and Iodometric Analysis of High-Temperature Superconductor	856	(3)
29-13 Potentiometric Halide Titration with Ag(+)	859	(2)
29-14 Electrogravimetric Analysis of Copper	861	(1)
29-15 Polarographic Measurement of an Equilibrium Constant	861	(1)
29-16 Coulometric Titration of Cyclohexene with Bromine	862	(1)
29-17 Spectrophotometric Determination of Iron in Vitamin Tablets	863	(1)
29-18 Microscale Spectrophotometric Measurement of Iron in Foods by Standard Addition	864	(1)
29-19 Spectrophotometric Measurement of an Equilibrium Constant	865	(1)
29-20 Properties of an Ion-Exchange Resin	866	(2)
29-21 Analysis of Sulfur in Coal by Ion Chromatography	868	(1)
29-22 Measuring Carbon Monoxide in Automobile Exhaust by Gas Chromatography	868	(1)
29-23 Amino Acid Analysis by Capillary Electrophoresis	869	(2)
29-24 DNA Composition by High-Performance Liquid Chromatography	871	(4)
Glossary	875
Appendixes	AP1
A Logarithms and Exponents	AP1	(1)
B Graphs of Straight Lines	AP2	(2)
C Propagation of Uncertainty	AP4	(1)
D Oxidation Numbers and Balancing Redox Equations	AP5	(5)
E Normality	AP10	(2)
F Solubility Products	AP12	(3)
G Acid Dissociation Constants	AP15	(12)
H Standard Reduction Potentials	AP27	(12)
I Stepwise Formation Constants	AP39	(3)
J Logarithm of the Formation Constant for the Reaction M(aq) + L(aq) = ML(aq)	AP42
Solutions to Exercises	SE1
Answers to Problems	AN1
Index	I1