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ProfessionalEnglishinChemicalEngineeringDepartmentofChemicalandBiochemicalEngineeringDepartmentofChemicalandBiochemicalEngineeringXiamenXiamenUniversityUniversityLiJunLiJun20072007Contentsn1Introductionn2FundamentalsinChEn3SpecializedtopicsinChEMathematicsPhysicsChemistryPhysicalChemistryUnitoperationLaboratory3.SpecializedTopicsinChE3.1PhysicalChemistrynContentsofphysicalchemistryChemicalthermodynamics:Itconcernswithenergychange:theroutineofenergychange,thechangetrendofequilibrium,andtheequilibriumstate.Chemicalkinetics:Itfocusesontherateofmatterchange:reactionrate,reactionmechanisms,reactor,andreactorscale-up.Structurechemistry:Itconcernsabouttherelationbetweenmatterpropertiesanditsmicrostructures.PreliminaryknowledgeA(closed/isolated/open)systemanditssurroundingsPhase:thestateofagglomerationofthesystemInternalenergy(motions,interactions,andbondingofitsconstituentmolecules)Externalenergy(velocity,locationofitscenterofmass)=kinetic+potentialenergyThermalenergy(internalenergy+heat)Mechanicalenergy(externalenergy+mechanical/electricalwork)Heat:energytransferasaresultsofonlytemperaturedifferenceWork:energytransferbyanymechanismthatinvolvesmechanicalmotionoforacrossthesystemboundaries..Microscopicproperties:moleculekineticenergy(translationalenergy,rotationalenergy,vibrationalenergy)Intermolecularforces(electrostaticforces,inductionforces,forcesofattraction(ordispersionforces)andrepulsion,specific(chemical)forceslikehydrogenbonds)Intermolecularpotentials(Lennard-Jonespotential).Macroscopicproperties:pressure,volume,temperatureextensivevariables(volume,mass)intensivevariables(T,P,molarvolume,molarmass)ThermodynamicEquilibriums:thermalequilibrium,forceequilibrium,phaseequilibrium,chemicalequilibriumPVTrelationsIdeal-gasequationofstate:PV=RTvanderWaalsequationofstate(twoparameters):P=RT/(V-b)-a/V2Virialequation(Virialcoefficients,…)ThePrincipleofCorrespondingState(reducedT,PandV)Moreconcepts:compressibilityfactor(Z=PV/RT)expansioncoefficientcompressibilitycoefficientPTVV)(1∂∂TPVV)(1∂∂-Z1?Z=1?andZ1?MolarvolumeThefirstlawofthermodynamics*Energyisneithercreatednordestroyed,butmaychangeinforms.*Internalenergy,workandheatinaclosedsystemOtherconcepts:enthalpy,heatcapacity,isochoric,isobaric,…Processes:reversible,irreversibleisothermal,adiabatic,cyclic,freeexpansionthrottling(isoenthalpy,Joule-Thomsoncoefficient)QWdUdd+=ThelawsofthermodynamicsThezerothlawofthermodynamics?ThesecondlawofthermodynamicsThesecondlawofthermodynamicsClausiusClausiusstatement:Itisnotpossibletoconstructadevicestatement:Itisnotpossibletoconstructadevicethatthatoperatesinacycleoperatesinacycleandwhosesoleeffectistotransferandwhosesoleeffectistotransferheatfromacolderbodytoahotterbody.heatfromacolderbodytoahotterbody.KevinKevin--Planckstatement:ItisimpossibletoconstructaPlanckstatement:Itisimpossibletoconstructadevicedeviceoperatinginacycleoperatinginacyclethatresultsinnoeffectotherthatresultsinnoeffectotherthantheproductionofworkbytransferringheatfromathantheproductionofworkbytransferringheatfromasinglebody.singlebody.Otherconcepts:Otherconcepts:CarnotCarnotcycle,heatengine,theefficiencyofheatengine,cycle,heatengine,theefficiencyofheatengine,endothermic,exothermic,endothermic,exothermic,entropy,entropy,isoentropicisoentropicprocessprocess,,spontaneoussystemspontaneoussystem,,entropybalanceentropybalance……222121gen11;QQSSSSSTTdd-≥-=+∫∫PPVV1(Q1(Q11,T,T11))223(Q3(Q22,T,T22))44Thethirdlawofthermodynamics*Theentropiesofallsubstancesintheperfectcrystallineortheperfectliquidstatearezeroattheabsolutezerooftemperature(0K).*Itisimpossibletoattainatemperatureofabsolutezero.Concepts:Perfectstate:withoutanydisturbanceinthearrangementoftheatoms.Heatofreaction,heatofcombustion,heatofformationGibbsfreeenergy:G=H-TSHelmholtzfreeenergy:F=U-TSFundamentalequationsofthermodynamics:VdpSdTdG+-=pdVSdTdF--=pdVTdSdU-=VdpTdSdH+=Conditions?:closedsystem;volumetricworkonly(withoutshaftwork)ThermalchemistryClapeyronequations:providetherelationofequilibriumPandequilibriumTforpuresubstances(vaporpressure,boilingpoint,meltingpoint,solidifyingpoint).Idealsolution:Raoulttheorem,HenrytheoremVapor-liquidequilibriumofidealbinarysolution.Realsolution:Partialmolarquantity,Chemicalpotential,activity,fugacity,activitycoefficient,fugacitycoefficient,…Phaseequilibrium0/;;iiiiiiiiiiiaffaxfPyPgjj====)(,,jinPTiiijnGG≠⎟⎟⎠⎞⎜⎜⎝⎛∂∂==mPhaserule:thedegreeoffreedom,f=C-Π+2Phasediagram:single-phase/binary/ternaryx-ydiagram,p-x-ydiagram,t-x-ydiagramfully/partlymisciblesolution,immisciblesolutionminimum/maximumazeotrope,dewpoint,bubblepoint,eutecticpoint,…multi-componentsystem,…y1x1y-xdiagramatTfixedP-x-ydiagramatTfixedT-x-ydiagramatPfixedPx1,y1Tx1,y1tielineliquidvapordewpointbubblepointliquidvaporatPfixednContentsofchemicalequilibriumChemicalequilibriuminasingle-phasesystem:freeenergyofformationequilibriumconstantendothermicreactionexothermicreactionionizationconstantdissociationconstantassociationconstantnContentsofchemicalkineticschemicalreactionkinetics:rateofreaction,orderofreactionactivationener