-1stPhysicalThermodynamicsandRelated教(Prof.Dr.Shi-Gang 教 DepartmentofChemistry,Xiamen 輔導(dǎo)老師電子：：2教學(xué)前教學(xué)兩次習(xí)第9考核：平時(shí)作業(yè)20%（每周二提交作業(yè)中期測(cè)試期末測(cè)試3等，《物理化學(xué)》(上、下)，廈門(mén)大育“十一五”國(guó)家級(jí)規(guī)

，2008（普通高andCompany,1999or2006(Since1940-IraN.Levine,《PhysicalChemistry》（5thEdition&中譯本McGraw-HillHigherEducation,2002(since1978-1998.(Since1972-，高執(zhí)棣，高盤(pán)良，《物理化學(xué)》，高等教 ，2001 ,《物理化學(xué)》第四版，高等教 （1961年第一版）高執(zhí)棣，《化學(xué)熱力學(xué)基礎(chǔ)》 ，2006，高執(zhí)棣，《化學(xué)熱力學(xué)》，高等教 ，1997 ，1981趙凱華 ,《熱學(xué)》，高等教 ，1999，《熱學(xué)》（第二版 ，1999 物理化學(xué)熱力學(xué)課用Ftp工具登陸（cutftp，leafftp等）化院服務(wù)（0）， ing文件 課地址：FTP://：ing/0-SGSun_物：ing/0-SGSun_物理化（請(qǐng)保留到2012年8月 英語(yǔ)中 中文 中文課5物理化學(xué)學(xué)習(xí)方法物理化學(xué)學(xué)習(xí)方法 預(yù)習(xí)，復(fù)習(xí)和筆記（注意力集中、手腦并用6重視習(xí)題和注意思維方法和邏如何學(xué)習(xí)雙語(yǔ)課程（HowtofollowthebilingualThefirstistostudyandunderstandthecontentsofphysicalchemistry(readtheChinesetextbook); ThesecondistolearntheEnglishtermsandexpressions(readtheEnglishtextbook)Thethirdistocombinethetwo WhatisPhysicalPhysicalchemistryisadisciplinethatstudiestheprincipleandmethodsofchemistry,andthemostgenerallawandtheoryofchemicalsystems.Physicalchemistryinvestigatestheessenceofchemistry,utilizesmathematicalandphysicalmethods,andintroducesdifferentexperimentaltechniquestorevealthebasiclawsthaternthechemicalreactions.8ThecontentsofphysicalThefundamentalofphysicalchemistryconsistsofmainly4parts:Thermodynamics(熱力學(xué)） Itstudiesthetransformationofenergyinthechangeofmatters（p、V、T、phaseandchemicalchanges),andthedirectionandlimitofenergeticeffects(work,heat).Thermo-dynamicsconcernsthelawofenergyconservationandthelawofmatterequilibrium.Quantummechanics（量子力學(xué)） Itstudiesthemovingstatesofmicro-systems.Inelementaryapplication,theSchr?dingerequationissetupforthesystem,andthensolvedeither yticallyor,inmanypracticalsystems,numerically,withduenoteoftheboundaryconditions (3)Statisticalmechanics（統(tǒng)計(jì)力學(xué)）?Itstudiestheaveragebehavioroflargeassembliesofparticles.Statisticalmechanicsisthetheoryinwhich(3)Statisticalmechanics（統(tǒng)計(jì)力學(xué)）?Itstudiestheaveragebehavioroflargeassembliesofparticles.Statisticalmechanicsisthetheoryinwhichthepropertiesofmacroscopicsystemarepredictedbythestatisticalbehavioroftheirconsti Branches hsicalchemistrQuantumchemistry（量子化學(xué)）Structuralchemistry(結(jié)構(gòu)化學(xué))Catalyticchemistry(催化化學(xué))Electrochemistry(電化學(xué))Photochemistry(Branches hsicalchemistrColloidandinterfacialchemistry膠體與界面化學(xué)Thermochemistry(熱化學(xué))Chemistryofhighenergy高能化學(xué))Computingchemistry(計(jì)算化學(xué))Physicalchemistryisoneofbasesinfrontierresearchoftoday’sscienceandtechnologyHigh-ThedevelopmenttrendofphysicalchemistryFrommacrosystemstomicroFrombulktoFromstationarytoFromqualitative Frommono-disciplinetomulti-ThestudymethodsofphysicalMacroscopicItisthethermodynamicmethod.Thermodynamicsconcernsmacroscopicsystemthatconsistsoflargeamountofparticles.Th themethoddoesnotcarethemicroscopicstructureof nsidematters,butdealswithonlythemacroscopicpropertiesbeforeandafterthechangeofItisthequantummechanicalmethod.Quantummechanicsconcernsmicroscopicsystemthatconsistsofindividualelectronandatom.Themethodstudiesthemovingstatesofindividual ThebridgebetweenmicroscopicandmacroscopicItisthestatisticalmethodthatbridgesthequantummechanicsmethodandthermodynamicmethod.Statisticalmechanicsisabridelinkin microandmacrosystems4.ThetasksofphysicalchemistryInitiatingknowledge：Basic4.ThetasksofphysicalchemistryInitiatingknowledge：Basicconcepts,basicprocesses,basictheories,andbasiccalculations ：GeneralscientificImportanceofthemethodology：Itwouldbemuchbeneficialtofishes(Cultivatingtheability：Theabilityofapplyingtheprinciplesofphysicalchemistrytosolvepracticalproblems.Knowledge＋methodology＝Innovation5.Theimportanceandtheobjectivestudying5.TheimportanceandtheobjectivestudyingphysicalTrainingtheabilityofthinkingandMasteringexperimentalskillsandmethodsthroughTheThemaincontentsofthisTheapplicationofthermodynamicsinponentsystemsEquilibrium（Phase，ChemicalStatisticalChapter1ThezerothlawofChapter1ThezerothlawofandthestateSystem體系Theobjectofinterestthatisdistinguishedfromitssurroundingsbyaboundary(邊界),i.e.theinterfacethatseparatesthemAmacroassemblythatcontainslargenumberofSurroundings環(huán)境(=Heater(熱源)+Engine(做功的機(jī)器))Theuniversethatseparatesfromthesystembyaphysical(oranimainar)boundar,andhascloserelationwiththesImportantTherelationbetweensystemandsurroundingsconsistsmainlyinImportantThermodynamicsystemistheobjectcomposedofnumerousparticles(atoms,molecules,phonons,electrons,etc.)underspecifiedconfinement,whichmeansthatthesystemsatisfiestherestrictionofmacroconditions,thusitcanbedescribedbymacroparameters（V，A，l，T,etc.）；ThelargenumbermeansthethermodynamiclimitN=6.021023,cm3~m3； bereal,orimaginary,suchasrigidwall,movableadiabaticwall,semi-transparentwall,Differentsystemhasdifferentsurroundings,itisoftendescribedbytheconceptofheatsource(Thematterthathasunlimitedmass,andunlimitedheatcapacity.Thetemperaturewillnotchangewhenlimitedheatisinjectedintoorpumpedoutfromthematter)；Thesystemmaybemultivariable,suchas ponent,solid,liquid,gas,chemicalreactions,singlephase,doublephase,multiphase,etc.Thedefinitionofaphase：thepartthathasuniformphysicalandchemicalpropertiesinaThreekindAnopencanexchangematterandenergywithitssurroundings.Aclosedcanexchangeenergywithitssurroundings,butitcannotexchangematter.Anisolated(orinsulated)systemcanexchangeneitherenergynormatterwithitssurroundings.22(開(kāi)放體系 (封閉體系 體系MassMassbetweensystemEnergytransferring(intheformofheatandwork)Note:Therightchoi asyste isthekeytosolvethermodynamicproblems玻璃 瓶糖糖絲Class絲Classdiscussion:Decidewhatkindsystemwillbeunderdifferentconsiderationsbelow？電電OpenOpenClosed電阻 Closed+電ClosedEquilibriumstate:Asystemisequilibriumwithitssurroundingswhenithasnotendencytoundergospontaneouschanges.ThemacropropertiesofsystemdonotchangewithItdoesnotexistanyinnerandoutsideinteractionsthatmakehappeningthemacro-flow(matterandenergy)betweensystemandsurroundings,aswellaschemicalreactions.Thermodynamic1.2Equilibriumstate1.2Equilibriumstateand 2Mechanic3Chemical4Phase

T1=T2=p1=p2=A+BC+H2O(l) StationaryStationarystate(定態(tài)Themacropropertiesofsystemnotchangewithtime,butitexistsflowofmatterandStationarystate≠EquilibriumAxiomofequilibriumstate(平衡態(tài)公理):Anisolatedwilltendtowardsauniueeuilibriumstateforenouh Macropropertiesofasystem:Thecollectiveactionsofanaggregatethatcontainslotsofparticles,suchasp,V,T,U,H,S,A,G,arenamedasmacrocharactersofsystem(thermodynamicroerties).TwotypesofmacroIntensiveproperties(強(qiáng)度性質(zhì)):Theyarenotdependentoftheamountofsubstance,andhavenoaddingnature(e.g. p,T,etc.)；Extensiveproperties(廣度性質(zhì))：Theydependontheamountofsubstance,andhaveaddingnature(e.g., anextensivepropertyanotherextensiveproperty V，m,

有加和有加和 無(wú)加和ImportantImportantthermodynamicExtensiveIntensiveV壓p面積A表面電量ElectricQ電動(dòng)E熵S熱力學(xué)T物質(zhì)B物質(zhì)B的化學(xué)內(nèi)能InternU摩爾焓HelmholtzHA摩爾體膨脹GibbsG等壓熱等容C摩爾等容C1.3MacrodescriptionmethodofMethodsdescribing1.3MacrodescriptionmethodofClassicmechanics:CoordinatesandmomentumorgeneralizedcoordinatesandmomentumQuantummechanics:Wavefunctions,themicromethodofStatisticalmechanics:Distributingprobability,thestatisticaldescriptionmethodofstatesThermodynamics:Asetofindependentmacroproperties,thermodnamicdescritionmethodormacrodescritionof Axiomofstate(狀態(tài)公理Foranuniformphasesystematequilibrium,thenumber(F)ofindependentmacropropertiesequalthesumofthenumber(R)ofvariablesubstances,thenumber(Axiomofstate(狀態(tài)公理F=R+W+F=1+1+1=3,L=L(F=1+1+1=3,L=L(T,pe.g.2：systemofuniformmulti-substance

L=L(T,p,e.g.3：systemofuniformmulti-phase,liquid|gas

L=L(Tl,pl,nl,Tg,pg,ng,Ts,ps, Equationofstate(物態(tài)方程、狀態(tài)方程):MathematicalbetweenmacropropertiesforanuniformsystemEquationofstate(物態(tài)方程、狀態(tài)方程):MathematicalbetweenmacropropertiesforanuniformsystematStatevariable(狀態(tài)變量):Theindependentmacropropertiesthatdescribethestatesofsystemitisalsocalledthermodynamicvariables(coordinates)Statefunction(狀態(tài)函數(shù))Astatefunctionisthethermodynamicpropertythatdependsonlyonthecurrentstateofthesystem,andisindependentoftheprevioushistoryofthesystem.Thatis,astatefunctionisthefunctionofasetofvariablesthatdefinethecurrentstateofthe TheThechoiceofstatevariablemaybeartificial,sothevariableandthestatefunctionarecomparative,andtheymaybereplacedeachother,forexampleVf(T,p,n)pTg(p,V,n)Fromstate1toWhenthesystemisvariedthouhaseriesofchanesandreturnedtostate1,if

ZZ21ZdZdZ1

Z1thedifferentialofZisthenatotal(orexact)differential(全微分Thatis，if

dZfdxf 1.4ThermodynamicAnystatechangeoccurringtothesystem1.4ThermodynamicIsothermalprocesses(等溫過(guò)程Tinitial=Tfinal=Theater=Constanttemperatureprocesses(恒溫過(guò)程)TIsobaricprocesses(等壓過(guò)程pi=pf=pex=Constantpressureprocesses(恒壓過(guò)程)p=5Isochoricprocesses(等容過(guò)程Vi=Vf5Isochoricprocesses(等容過(guò)程Constant-volumeprocesses(恒容過(guò)程)V=Quasistaticprocesses(準(zhǔn)靜態(tài)過(guò)程)AtanymomentoftheprocessthesystemisinAdiabaticprocesses(絕熱過(guò)程)ThereisnoexchangeinenergyasheatbetweenthesstemanditssurroundinsTheTheconditionsatconstantp,VandExpansion Gasisexpandedtovacuum(Freeexpansionprocess)1（自由膨脹真1（自由膨脹真氣(IsobaricpTP始,pTP始,VpT23.Gas3.Gasisexpandedagainstapressurethatdecreasesfrompinitialtopfinal(Quasistaticp(一個(gè)重物TTP始始準(zhǔn)準(zhǔn)靜態(tài)過(guò){ppp定10.Processesof10.Processesoftemperature1molN2,

溫差無(wú)限小熱源 等壓323K物體（熱源等壓323K物體（熱源直接

11.ProcessesofphaseH2O(1mol,H2O(1mol,11.ProcessesofphaseH2O(1mol,H2O(1mol,始態(tài)水與373K熱源接觸，對(duì)抗恒外壓p緩慢蒸發(fā)(準(zhǔn)靜態(tài)蒸發(fā)12.12.Mixing隔N(g)1mol,O(g)1mol22p,NN2(g)1mol,O2(g)1molp,等溫等準(zhǔn)等溫等準(zhǔn)靜態(tài)只透N2(g)只透 13.13.ChemicalreactionN2(g,1mol,723K,30MPa)+Nonquasistaticstate(b)Quasistaticprocess（利用van’t(b)Quasistaticprocess（利用van’tHoff平衡箱進(jìn)行態(tài)過(guò)程將NH3

N2(g)+3H2(g)= 1.5Zerothlawofthermodynamics(熱力學(xué)第零定律)(Thetemperature)TheZerothLawofthermodynamicsisthejustificationoftheconceptoftemperature,whichisusedtodetermi