Section10.1:discussesthedistributionofenergiesinSection10.1:discussesthedistributionofenergiesincollisions,andderivesthemolecularcollisioncollisions,andderivesthemolecularcollisionfrequency.frequency.Section10.2:BothcanleadtoasimplecollisiontheorySection10.2:Bothcanleadtoasimplecollisiontheoryexpressionforthereactionrateconstantk.expressionforthereactionrateconstantk.Section10.3:Transition-statetheoryisderived.Section10.3:Transition-statetheoryisderived.Section10.4:moderntheoriesofunimolecular(Section10.4:moderntheoriesofunimolecular(单分单分子子)reaction.)reaction.Section10.5:analogouspressureeffectsofbimolecularSection10.5:analogouspressureeffectsofbimolecular((双分子双分子)reaction.)reaction.10.4Unimolecularreactions11.LindemannTheory.LindemannTheoryThecreationrateofproductsAandThecreationrateofproductsAandB:B:Thehighpressure:Thehighpressure:IsIsindependentindependentofpressure.ofpressure.Thelowpressure:Thelowpressure:FallsoffFallsofflinearlylinearlywithpressure.withpressure.BetweenlowpressureandhighBetweenlowpressureandhighpressure:pressure:22.Hinshelwood’s(.Hinshelwood’s(欣谢尔伍德)Theory)TheoryThefirstshortcomingsoftheLindemannThefirstshortcomingsoftheLindemanntheoryistheoryisunderstimatingunderstimatingtheexcitationratetheexcitationrateconstantkeconstantkeWhenWhentheenergytransferintothetheenergytransferintotheinternal(i.einternal(i.e.,vibrational).,vibrational)degreesoffreedomdegreesoffreedomisistakenintoaccount,thekeismuchlargerthantakenintoaccount,thekeismuchlargerthanpredictedbysimplecollisiontheory.predictedbysimplecollisiontheory.SomeoftheSomeoftheassumptionsassumptionsintroducedinintroducedinHinshelwood’smodelarestilloverlyHinshelwood’smodelarestilloverlysimplisticsimplistic..HinshelwoodassumedthatthemoleculeCHinshelwoodassumedthatthemoleculeCisiscomposedofsidenticalharmonicoscillatorscomposedofsidenticalharmonicoscillatorsofoffrequencyv,andnisthetotalnumberoffrequencyv,andnisthetotalnumberofvibrationalquanta.vibrationalquanta.thenextassumptioni...
