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1、ReactionKinetics(1)XuanChengXiamenUniversityPhysicalChemistry1PhysicalChemistryReactionKineticsForexample-16.63-237.19Thermodynamics:spontaneousreactions(possibletotakeplace)Thermodynamics:can’tanswer(1)howtomakethemhappen(2)howfasttheywilltakeplace(3)th
2、ereactionmechanismReactionKinetics2PhysicalChemistryReactionKineticsT,P,catalystT,catalystChemicalKinetics:ChemicalKineticsThestudyoftheratesandmechanismsofchemicalreactionsAreactingsystemisnotinequilibriumReactionKinetics3PhysicalChemistryRateofReaction
3、Considerthehomogeneousreaction(occursentirelyinonephase)(17.1)TherateofconversionJ(17.2)Atequilibrium,J=0ReactionKinetics4PhysicalChemistryRateofReaction(17.3)(17.4)*AtconstantVTherateofreactionrmoldm-3s-1molcm-3s-1ReactionKinetics5PhysicalChemistryRateL
4、awsFormanyreactions(17.5)*k:rateconstant(ratecoefficient),k=f(T,P),,:orderorpartialorder+++n:overallorderTheexpressionforrasafunctionofconcentrationsatafixedtemperatureiscalledtheratelaw.ReactionKinetics6PhysicalChemistryReactionOrdersZero-order
5、First-orderSecond-orderThird-orderNegativeFirst-order1.5-orderNosimpleorderReactionKinetics7PhysicalChemistryRateLawsReactionRateLawReactionKinetics8PhysicalChemistryReactionMechanisms(17.7)intermediate(17.8)Step(a)Step(b)Step(c)ElementaryreactionReactio
6、nactuallyoccursReactionKinetics9PhysicalChemistryMeasurementofReactionRatesChemicalMethodTheconcentrationofareactantorproductasafunctionoftimeReactionvesselsAtconstantTAtintervalsSlowsdownorstopthereactionRapidlyanalyzechemicalcompositionsofthemixtureCoo
7、lingthesampleremovingacatalystDilutingthemixtureAddingaspeciesReactionKinetics10PhysicalChemistry反应速率的测定方法化学方法不同时刻取出一定量反应物,设法用骤冷、冲稀、加阻化剂、除去催化剂等方法使反应立即停止,然后进行化学分析。ReactionKinetics11PhysicalChemistryMeasurementofReactionRatesPhysicalMethodMeasuresaphysical
8、propertyofthereactionsystemasafunctionoftime.Thisallowsthereactiontobefollowedcontinuouslyasitproceeds.Moreaccurateandlesstedious物理方法用各种物理性质测定方法(旋光、折射率、电导率、电动势、粘度等)或现代谱仪(IR、UV-VIS、ESR、NMR、ESCA等)监测与浓度有定量关系的物理量的变化,从而求得浓度变化。物
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