Chemical Kinetics The Study of Reaction Rates

Chemical Kinetics The Study of Reaction Rates in Solution Kenneth A. Connors This chemical kinetics book blends physical theory, phenomenology and empiricism to provide a guide to the experimental practice and interpretation of reaction kinetics in solution. It is suitable for courses in chemical kinetics at the graduate and advanced undergraduate levels. This book will appeal to students in physical organic chemistry, physical inorganic chemistry, biophysical chemistry, biochemistry, pharmaceutical chemistry and water chemistry--all fields concerned with the rates of chemical reactions in the solution phase.

Kenneth Connors is Professor in the School of Pharmacy at the University of Wisconsin at Madison.

Introduction to Chemical Kinetics

1

(16)

The Field of Chemical Kinetics

1

(2)

Time as a Variable

1

(1)

Uses of Chemical Kinetics

2

(1)

Literature of the Field

2

(1)

The Study of Reaction Mechanisms

3

(7)

The Definition of Reaction Mechanism

3

(3)

Methods for Studying Mechanisms

6

(1)

The Role of Kinetics

7

(1)

Classification of Mechanisms

8

(2)

Experimental Chemical Kinetics

10

(7)

The Rate of Reaction

10

(1)

Rate Equations and Stoichiometric Equations

11

(2)

Rate Constants and Reaction Orders

13

(1)

Temperature Dependence of Rate Constants

13

(4)

Simple Rate Equations

17

(42)

Integrated Rate Equations

17

(7)

Zero-Order Reactions

17

(1)

First-Order Reactions

18

(2)

Second-Order Reactions

20

(3)

Pseudo-Order Reactions

23

(1)

Determination of Reaction Order

24

(7)

Use of Integrated Equations

24

(2)

The Isolation and Pseudo-Order Techniques

26

(2)

Initial Rate Method

28

(1)

Fractional Time Methods

29

(2)

Methods of Data Analysis

31

(28)

Calculation of the Rate Constant from Concentrations

31

(3)

Treatment of Instrument Response Data

34

(2)

Methods When the Final Value is Unknown

36

(4)

Propagation of Errors

40

(1)

Linear Least-Squares Regression

41

(3)

Weighting in Least-Squares Regression

44

(1)

Weighting and the Transformation of Variables

45

(1)

Variances of the Parameters

46

(3)

Nonlinear Least-Squares Regression

49

(2)

Accuracy in Rate Constant Measurements

51

(8)

Complicated Rate Equations

59

(74)

Integration of the Rate Equations

60

(17)

Reversible Reactions

60

(2)

Parallel Reactions

62

(4)

Consecutive Reactions

66

(11)

Other Methods of Analysis

77

(38)

Measurement of Rates

77

(1)

Simplification of the Experimental Kinetics

78

(1)

Elimination of the Time Variable

79

(2)

Replacement of Time with an Area Variable

81

(1)

The Laplace Transformation

82

(8)

Secular Equations and Eigenvalues

90

(6)

The Preequilibrium Assumption

96

(4)

The Steady-State Approximation

100

(5)

Numerical Integration

105

(4)

Monte Carlo Simulation

109

(5)

Analog Simulation

114

(1)

The Kinetic Scheme

115

(18)

Model Building

115

(8)

Kinetic Equivalence of Rate Terms

123

(2)

Microscopic Reversibility and Detailed Balance

125

(8)

Fast Reactions

133

(54)

Diffusion-Controlled Reactions

134

(2)

Relaxation Kinetics

136

(17)

Linearization of Rate Equations

137

(2)

Complex Reactions

139

(4)

Experimental Methods

143

(3)

Applications

146

(7)

Nuclear Magnetic Resonance Spectroscopy

153

(23)

Magnetic Properties of Nuclei

153

(2)

The Resonance Condition

155

(2)

Spin-Lattice Relaxation

157

(2)

Spin-Spin Relaxation

159

(1)

The Bloch Equations

160

(4)

T1, T2, and the Correlation Time

164

(2)

Chemical Exchange

166

(4)

Pulse NMR Measurements

170

(3)

Applications

173

(3)

Rapid Mixing Methods

176

(4)

Batch Methods

176

(1)

Flow Methods

177

(3)

Other Methods

180

(7)

Fluorescence Quenching

180

(1)

Electrochemical Methods

181

(2)

Common Ion Inhibition

183

(4)

Theory of Chemical Kinetics

187

(58)

Theoretical Approaches

187

(13)

The Arrhenius Equation

187

(1)

Collision Theory

188

(3)

Potential Energy Surfaces

191

(9)

Transition State Theory

200

(9)

Assumptions of the Theory

201

(1)

The Partition Function

201

(4)

The Rate Equation

205

(2)

Thermodynamic Interpretation

207

(2)

Chemical Interpretations of the Transition State

209

(36)

Reaction Coordinate Diagrams

209

(4)

The Rate-Determining Step

213

(3)

Composition of the Transition State

216

(4)

Position and Height of the Energy Barrier

220

(10)

Concerted and Stepwise Reactions

230

(15)

Phenomena for Study

245

(66)

Temperature Dependence of Rates

245

(16)

The Arrhenius Equation

245

(6)

Curved Arrhenius Plots

251

(2)

Standard States

253

(3)

Complications in Buffered Solutions

256

(3)

Uses of Activation Parameters

259

(2)

The Effect of Pressure

261

(2)

Catalysis

263

(10)

Definitions and Examples

263

(5)

Determination of Catalytic Rate Constants

268

(3)

Distinction between General Base and Nucleophilic Catalysis

271

(2)

pH Effects

273

(19)

Preliminaries

273

(1)

Curves without Inflection Points

274

(3)

Sigmoid Curves

277

(8)

Bell-Shaped Curves

285

(7)

Kinetic Isotope Effects

292

(19)

Primary Isotope Effects

293

(5)

Secondary Isotope Effects

298

(2)

Solvent Isotope Effects

300

(11)

Structure-Reactivity Relationships

311

(74)

Extrathermodynamic Relationships

311

(4)

Substituent Effects in Aromatic Compounds

315

(23)

The Hammett Equation

315

(5)

Deviations and Variations

320

(3)

The Substituent Constant

323

(5)

The Reaction Constant

328

(6)

The Ortho Effect

334

(3)

Conclusions

337

(1)

Substituent Effects in Aliphatic Compounds

338

(6)

Electronic Effects

338

(4)

Steric Effects

342

(2)

Substituent Effects in Reagents

344

(24)

General Acid-Base Catalysis

344

(5)

Nucleophilicity in Acyl Transfers

349

(6)

The α Effect

355

(2)

Nucleophilicity at Saturated Carbon

357

(6)

Intramolecular Reactivity

363

(5)

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Chemical Kinetics The Study of Reaction Rates in Solution

Summary

Author Biography

Table of Contents

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