House Principles of Chemical Kinetics

2. Auflage 2007
ISBN: 978-0-08-055050-3
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 336 Seiten, Web PDF

James House's revised Principles of Chemical Kinetics provides a clear and logical description of chemical kinetics in a manner unlike any other book of its kind. Clearly written with detailed derivations, the text allows students to move rapidly from theoretical concepts of rates of reaction to concrete applications.
Unlike other texts, House presents a balanced treatment of kinetic reactions in gas, solution, and solid states. The entire text has been revised and includes many new sections and an additional chapter on applications of kinetics. The topics covered include quantitative relationships between molecular structure and chemical activity, organic/inorganic chemistry, biochemical kinetics, surface kinetics and reaction mechanisms. Chapters also include new problems, with answers to selected questions, to test the reader's understanding of each area. A solutions manual with answers to all questions is available for instructors.
A useful text for both students and interested readers alike, Dr. House has once again written a comprehensive text simply explaining an otherwise complicated subject.
* Provides an introduction to all the major areas of kinetics and demonstrates the use of these concepts in real life applications
* Detailed derivations of formula are shown to help students with a limited background in mathematics
* Presents a balanced treatment of kinetics of reactions in gas phase, solutions and solids
* Solutions manual available for instructors

James E. House is Emeritus Professor of Chemistry at Illinois State University, and an Adjunct Professor of Chemistry at Illinois Wesleyan University. He received BS and MA degrees from Southern Illinois University and a PhD from the University of Illinois, Urbana. In his 32 years at Illinois State University, he taught a variety of courses in inorganic and physical chemistry. He has authored almost 150 publications in chemistry journals, many dealing with reactions in solid materials, as well as books on chemical kinetics, quantum mechanics, and inorganic chemistry. He was elected Professor of the Year in 2011 by the student body at Illinois Wesleyan University.

Autoren/Hrsg.

House, James E.

Inhaltsverzeichnis

1;Front Cover;1
2;Principles of Chemical Kinetics;4
3;Copyright Page;5
4;Preface;6
5;Contents;8
6;Chapter 1: Fundamental Concepts of Kinetics;12
6.1;1.1 Rates of Reactions;13
6.2;1.2 Dependence of Rates on Concentration;15
6.2.1;1.2.1 First-Order;16
6.2.2;1.2.2 Second-Order;19
6.2.3;1.2.3 Zero-Order;21
6.2.4;1.2.4 Nth-Order Reactions;24
6.3;1.3 Cautions on Treating Kinetic Data;24
6.4;1.4 Effect of Temperature;27
6.5;1.5 Some Common Reaction Mechanisms;31
6.5.1;1.5.1 Direct Combination;32
6.5.2;1.5.2 Chain Mechanisms;33
6.5.3;1.5.3 Substitution Reactions;34
6.6;1.6 Catalysis;38
6.7;References for Further Reading;41
6.8;Problems;42
7;Chapter 2: Kinetics of More Complex Systems;48
7.1;2.1 Second-Order Reaction, First-Order in Two Components;48
7.2;2.2 Third-Order Reactions;54
7.3;2.3 Parallel Reactions;56
7.4;2.4 Series First-Order Reactions;58
7.5;2.5 Series Reactions with Two Intermediates;64
7.6;2.6 Reversible Reactions;69
7.7;2.7 Autocatalysis;75
7.8;2.8 Effect of Temperature;80
7.9;References for Further Reading;86
7.10;Problems;86
8;Chapter 3: Techniques and Methods;90
8.1;3.1 Calculating Rate Constants;90
8.2;3.2 The Method of Half-Lives;92
8.3;3.3 Initial Rates;94
8.4;3.4 Using Large Excess of a Reactant (Flooding);97
8.5;3.5 The Logarithmic Method;98
8.6;3.6 Effects of Pressure;100
8.7;3.7 Flow Techniques;105
8.8;3.8 Relaxation Techniques;106
8.9;3.9 Tracer Methods;109
8.10;3.10 Kinetic Isotope Effects;113
8.11;References for Further Reading;118
8.12;Problems;119
9;Chapter 4: Reactions in the Gas Phase;122
9.1;4.1 Collision Theory;122
9.2;4.2 The Potential Energy Surface;127
9.3;4.3 Transition State Theory;130
9.4;4.4 Unimolecular Decomposition of Gases;135
9.5;4.5 Free Radical or Chain Mechanisms;142
9.6;4.6 Adsorption of Gases on Solids;147
9.6.1;4.6.1 Langmuir Adsorption Isotherm;149
9.6.2;4.6.2 B-E-T Isotherm;153
9.6.3;4.6.3 Poisons and Inhibitors;154
9.7;4.7 Catalysis;156
9.8;References for Further Reading;158
9.9;Problems;159
10;Chapter 5: Reactions in Solutions;164
10.1;5.1 The Nature of Liquids;164
10.1.1;5.1.1 Intermolecular Forces;165
10.1.2;5.1.2 The Solubility Parameter;170
10.1.3;5.1.3 Solvation of Ions and Molecules;174
10.1.4;5.1.4 The Hard-Soft Interaction Principle (HSIP);176
10.2;5.2 Effects of Solvent Polarity on Rates;178
10.3;5.3 Ideal Solutions;180
10.4;5.4 Cohesion Energies of Ideal Solutions;183
10.5;5.5 Effects of Solvent Cohesion Energy on Rates;186
10.6;5.6 Solvation and Its Effects on Rates;188
10.7;5.7 Effects of Ionic Strength;193
10.8;5.8 Linear Free Energy Relationships;196
10.9;5.9 The Compensation Effect;200
10.10;5.10 Some Correlations of Rates with Solubility Parameter;202
10.11;References for Further Reading;209
10.12;Problems;210
11;Chapter 6: Enzyme Catalysis;216
11.1;6.1 Enzyme Action;216
11.2;6.2 Kinetics of Reactions Catalyzed by Enzymes;219
11.2.1;6.2.1 Michaelis-Menten Analysis;219
11.2.2;6.2.2 Lineweaver-Burk and Eadie Analyses;224
11.3;6.3 Inhibition of Enzyme Action;226
11.3.1;6.3.1 Competitive Inhibition;227
11.3.2;6.3.2 Noncompetitive Inhibition;229
11.3.3;6.3.3 Uncompetitive Inhibition;230
11.4;6.4 The Effect of pH;231
11.5;6.5 Enzyme Activation by Metal Ions;234
11.6;6.6 Regulatory Enzymes;235
11.7;References for Further Reading;237
11.8;Problems;238
12;Chapter 7: Kinetics of Reactions in the Solid State;240
12.1;7.1 Some General Considerations;240
12.2;7.2 Factors Affecting Reactions in Solids;245
12.3;7.3 Rate Laws for Reactions in Solids;246
12.3.1;7.3.1 The Parabolic Rate Law;247
12.3.2;7.3.2 The First-Order Rate Law;248
12.3.3;7.3.3 The Contracting Sphere Rate Law;249
12.3.4;7.3.4 The Contracting Area Rate Law;251
12.4;7.4 The Prout–Tompkins Equation;254
12.5;7.5 Rate Laws Based on Nucleation;257
12.6;7.6 Applying Rate Laws;260
12.7;7.7 Results of Some Kinetic Studies;263
12.7.1;7.7.1 The Deaquation-Anation of [Co(NH3)5H2O]Cl3;263
12.7.2;7.7.2 The Deaquation-Anation of [Cr(NH3)5H2O]Br3;266
12.7.3;7.7.3 The Dehydration of Trans-[Co(NH3)4Cl2]IO3bull 2H2O;267
12.7.4;7.7.4 Two Reacting Solids;270
12.8;References for Further Reading;272
12.9;Problems;273
13;Chapter 8: Nonisothermal Methods in Kinetics;278
13.1;8.1 TGA and DSC Methods;279
13.2;8.2 Kinetic Analysis by the Coats and Redfern Method;282
13.3;8.3 The Reich and Stivala Method;286
13.4;8.4 A Method Based on Three (alpha,T) Data Pairs;287
13.5;8.5 A Method Based on Four (alpha,T) Data Pairs;290
13.6;8.6 A Differential Method;291
13.7;8.7 A Comprehensive Nonisothermal Kinetic Method;291
13.8;8.8 The General Rate Law and a Comprehensive Method;292
13.9;References for Further Reading;298
13.10;Problems;299
14;Chapter 9: Additional Applications of Kinetics;300
14.1;9.1 Radioactive Decay;300
14.1.1;9.1.1 Independent Isotopes;301
14.1.2;9.1.2 Parent-Daughter Cases;302
14.2;9.2 Mechanistic Implications of Orbital Symmetry;308
14.3;9.3 A Further Look at Solvent Properties and Rates;314
14.4;References for Further Reading;324
14.5;Problems;325
15;Index;328