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物化词汇部分：Chemicalthermodynamics化学热力学Chemicalkinetics化学动力学物理化学的分支：quantumchemistry量子化学；structurechemistry结构化学；catalysis催化；electrochemistry电化学；colloidchemistry胶体化学。热力学体系：closedsystem封闭体系：asystemthatdoesnotallowtransferofsubstancebutenergyisolatedsystem孤立体系：asystemthatdoesnotallowtransferofsubstanceandenergyopensystem开放体系：asystemthatallowtransferofsubstanceandenergyInternalenergy内能：motions分子运动；interaction相互作用；bondingofitsconstituentmolecules分子成键（ionicbond离子键,covalentbond共价键,coordinationbond配位键,hydrogenbond氢键,metallicbond.金属键）externalenergy外能：（velocity速度；locationofitscenterofmass位置）=kinetic动力+potentialenergy势能Thermalenergy(internalenergy+heat)Mechanicalenergy(externalenergy+mechanical/electricalwork)Heat:energytransferasaresultsofonlytemperaturedifferenceWork:energytransferbyanymechanismthatinvolvesmechanicalmotionacrossthesystemboundaries.Microscopicproperties:moleculekineticenergy分子动能(translationalenergy跃迁能,rotationalenergy转动能,vibrationalenergy振动能)Intermolecularforces分子间力(electrostaticforces静电力,inductionforces感应能,forcesofattraction(ordispersionforces)分散能andrepulsion排斥能,specific(chemical)forceslikehydrogenbonds)Intermolecularpotentials分子势(Lennard-Jonespotential)Macroscopicproperties:pressure,volume,temperatureextensivevariables广度性质(volume,mass)intensivevariables强度性质(T,P,molarvolume,molarmass)ThermodynamicEquilibriums热力学平衡:thermalequilibrium,热平衡forceequilibrium,力平衡phaseequilibrium,相平衡chemicalequilibrium化学平衡PVTrelationscompressibilityfactor压缩因子expansioncoefficient体积膨胀系数compressibilitycoefficient等温压缩系数热力学定律Thefirstlawofthermodynamics*Energyisneithercreatednordestroyed,butmaychangeinformsenthalpy焓heatcapacity热容isochoric等容isobaric等压reversible可逆,irreversible不可逆isothermal等温,adiabatic绝热(diabatic),cyclic循环,freeexpansion自由膨胀throttling节流(isenthalpy等焓,Joule-Thomsoncoefficient)ThesecondlawofthermodynamicsClausiusstatement:Itisnotpossibletoconstructadevicethatoperatesinacycleandwhosesoleeffectistotransferheatfromacolderbodytoahotterbody.TheefficiencyoftheCarnotheatengineisdefinedtobe:η＝(QH-QC)/QH=W/QH=1-TC/THendothermic吸热exothermic放热entropy熵,isentropicprocess等熵过程spontaneoussystem自发系统,entropybalance熵平衡热化学：Heatofreaction反应热,isothermal、isobaric、onlyvolumetricwork，thereaction’heatchangeheatofcombustion燃烧热,25℃，100kPatheheatchangeof1molpuresubstancefullycombustionheatofformation生成热fixedtemperatureandpressure，theheatchangeof1molpuresubstanceproducedbythemoststableelementGibbsfreeenergy:G=H-TSHelmholtzfreeenergy:F=U-TS相平衡：vaporpressure蒸汽压thepressureexertedbyavaporinthermodynamicequilibriumwithitscondensedphases(solidorliquid)atagiventemperatureinaclosedsystem.boilingpoint沸点thetemperatureatwhichthevaporpressureoftheliquidequalsthepressuresurroundingtheliquidandtheliquidchangesintoavapor.meltingpoint熔点thetemperatureatwhichitchangesstatefromsolidtoliquidatatmosphericpressuresolidifyingpoint凝固点thetemperatureatwhichitchangesstatefromliquidtosoildatatmosphericpressurePartialmolarquantity偏摩尔量Apartialmolarpropertyisathermodynamicquantitywhichindicateshowanextensivepropertyofasolutionormixturevarieswithchangesinthemolarcompositionofthemixtureatconstanttemperatureandpressure.Chemicalpotential化学势,isaformofpotentialenergythatcanbeabsorbedorreleasedduringachemicalreactionorphasetransition.activity活度activity(symbola)isameasureofthe“effectiveconcentration”ofaspeciesinamixture,inthesensethatthespecies'chemicalpotentialdependsontheactivityofarealsolutioninthesamewaythatitwoulddependonconcentrationforanidealsolution.fugacity逸度,thefugacityofarealgasisaneffectivepartialpressurewhichreplacesthemechanicalpartialpressureinanaccuratecomputationofthechemicalequilibriumconstant.activitycoefficient活度系数,fugacitycoefficient逸度系数thedegreeoffreedom自由度f=C-Π+2thenumberofdegreesoffreedomisthenumberofvaluesinthefinalcalculationofastatisticthatarefreetovaryPhasediagram相图:single-phase/binary/ternaryx-ydiagram,p-x-ydiagram,t-x-ydiagramfully/partlymisciblesolution可混溶的溶液,immisciblesolution不可混容的溶液minimum/maximumazeotrope共沸（正偏差，最低共沸点；负偏差，最高共沸点）,dewpoint露点thetemperatureatwhichairbornewatervaporwillcondensetoformliquiddew.,bubblepoint泡点,thetemperature(atagivenpressure)wherethefirstbubbleofvaporisformedwhenheatingaliquidconsistingoftwoormorecomponents.eutecticpoint共熔点thepointatwhichtheliquidphaseLbordersdirectlyonthesolidphaseα+β(ahomogeneouscomposedofbothAandB),representingtheminimummeltingtemperatureofanypossiblealloyofAandB.multi-componentsystem多组成体系化学平衡：Chemicalequilibriuminasingle-phasesystem:freeenergyofformation组成自由能equilibriumconstant平衡常数endothermicreaction放热反应exothermicreaction吸热反应ionizationconstant电离常数dissociationconstant解离常数associationconstant结合常数化学动力学chemicalreactionkinetics:rateofreaction反应速率,orderofreaction反应要求activationenergy活化能,activatedmolecules活化分子activation活化collision碰撞,activecenters活性中心activationenthalpy活化焓parallelreaction平行反应：substancereactsordecomposesinmorethanonewayseriesreaction串联反应,twoormorereactioninsameenvironmentwithoutnewoperationchainreaction链式反应：Achainreactionisasequenceofreactionswhereareactiveproductorby-productcausesadditionalreactionstotakepla