基础化学动力学 英文版 作者:S. R. Logan 出版时间:2004年版 内容简介 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. 目录 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