基础化学动力学

　　When teaching chemical kinetics to successive cohorts of undergraduates I have often wished that there existed an inexpensive textbook possessing all the conceivable virtues. It should， as far as possible， treat all aspects of kinetics， rather than leave important topics unmentioned. It should do justice to both experiment and theory， putting the role of each in context. It should explain concepts in ways that students might be expected to understand， aiming for the merits of lucidity and simplicity rather than for excessive erudition.In December 1993， I was invited to prepare my own undergraduate text on kinetics. In doing this I have started at the beginning since I believe that many difficulties about kinetics are derived from an incomplete understanding of the basics. Technological advances have resulted in the widespread use of many kinetic techniques， not merely by physical chemists， but by organic （and not simply physical organic） chemists， inorganic chemists and biochemists. A growing proportion of the ever-expanding chemicalN literature contains some kinetic component. For all such workers， the fundamentals of the subject are vitally important. To avoid too large a compendium， in regard to various aspects I have had to make my selection. In so doing， my central aim has been to illustrate the principles involved.

暂缺《基础化学动力学》作者简介

Preface.xi
Acknowledgementsxiii
1THEEMPIRICALFRAMEWORKOFCHEMICALKINETICS1
1.1IntroductionI
1.2Therateequation3
1.3Integratedrateequations5
1.4Reactionhalf-lifeandmeanlifetime9
1.5Thedeterminationofreactionorder12
1.6Effectoftemperatureonreactionrates17
Suggestedreading21
Problems21
2THEEXPERIMENTALSTUDYOFREACTIONKINETICS
2.1Minimumrequirementsforthestudyofchemicalkinetics24
2.2Theevolutionoftechniquesformonitoringreactionprogress25
2.3Theapplicationofspectrophotometrytochemicalkinetics27
2.4Electricalconductivityanddilatometry30
2.5Techniquesforthegasphase31
2.6Modernexperimentaltechniques33
2.7Theevaluationoftherateconstant35
Suggestedreading38
Problems38
3REACTIONMECHANISMANDREACTIONORDER40
3.1Anelementaryreactionandthemolecularity40
3.2Consecutivereactionprocesses42
3.3Formationofanintermediatecomplex45
3.4The"thirdbody"effectinatomrecombination47
3.5Parallelreactions50
3.6Reactantparticipatinginequilibria53
3.7Opposingreactions55
3.8Isotopicexchangereactions58
Suggestedreading61
Problems62
4THEORIESOFBIMOLECULARREACTIONS65
4.1TheCollisionTheory65
4.2TransitionStateTheory70
4.3Thetheoryofdiffusion-controlledreactionsinsolution78
Suggestedreading84
Problems85
5THEINTERPRETATIONOFBIMOLECULARREACTIONSINSOLUTION86
5.1Solventeffectsonreactionrates86
5.2Appliedhydrostaticpressure87
5.3Dielectricpermittivity90
5.4Ionicstrength91
5.5Linearfreeenergyrelationships94
5.6Kineticisotopeeffects96
5.7Electrontransferreactionsinsolution101
Suggestedreading105
Problems106
6UNIMOLECULARGASPHASEREACTIONS109
6.1Thekineticresults..109
6.2TheLindemannmechanism111
6.3TheRRK(orKassel)theory114
6.4TheRRKMtheory118
Suggestedreading121
Problems121
7CHAINREACTIONS123
7.1Linearchainreactions123
7.2Pyrolysisreactionsinvolvingchainmechanisms126
7.3Chainpolymerisation:freeradicalprocesses129
7.4Chainpolymerisation:ionicprocesses131
7.5Lesssimplelinearchainreactions135
7.6Branchingchainsandexplosionphenomena138
Suggestedreading143
Problems143
8HETEROGENEOUSCATALYSIS146
8.1Introduction146
8.2Chemisorptionandthechemisorbedstate146
8.3TheLangmuiradsorptionisotherm148
8.4Reactionsonacatalystsurface151
8.5Catalyticexchangeofalkaneswithdeuterium153
8.6Thecatalyticoxidationofcarbonmonoxide156
8.7Catalyticsynthesisanddecompositionofammonia158
8.8Thecriterionforagoodcatalyst161
8.9Catalysisinindustry162
Suggestedreading164
Problems165
9HOMOGENEOUSCATALYSIS167
9.1Gasphasecatalysis167
9.2Catalysisinsolution169
9.3Catalysisbyacids171
9.4Catalysisbybases174
9.5Autocatalysis177
9.6Oscillatingreactions179
9.7Catalysisbyenzymes184
9.8Enzymeinhibitors187
Suggestedreading189
Problems190
10RELAXATIONANDOTHERADVANCEDTECHNIQUES192
10.1Introduction192
10.2Relaxationtechniques:experimentalaspects196
10.3Morecomplexreactionsystems199
10.4NMRspectroscopy202
10.5Electrochemicalmethods206
Suggestedreading209
Problems210
11PHOTOCHEMISTRYANDRADIATIONCHEMISTRY212
11.1Initialeffectsoflightabsorption212
11.2Photochemicalkinetics215
11.3Flashphotolysis224
11.4Primaryeffectsofionisingradiations228
11.5Radiationchemistryofaqueoussolutions229
11.6Pulseradiolysis232
Suggestedreading236
Problems236
12REACTIONDYNAMICS239
12.1Introduction239
12.2Studiesusingcrossedmolecularbeams240
12.3Energydistributionwithinthereactionproducts242
12.4Ion-moleculereactions245
12.5Dynamicsofion-moleculereactions248
Suggestedreading251
APPENDIXA252
APPENDIXB254
ANSWERSTOTHEPROBLEMS256
INDEX...258
INDEXOFCHEMICALREACTIONS263