物理化学偏摩尔量.pptVIP

物理化学(Ⅰ)PHYSICALCHEMISTRY（9）过程方向和限度判据：孤立系统DS，熵增加原理封闭系统DS，熵增加原理绝热过程DA，赫姆霍兹函数减小原 理等温无功（等V,W’=0）DG，吉布斯函数减小原理等温等压W’＝0？（有物质交换发生）开放系统DS，考虑环境、构建孤立系其它过程Compositionandtheamountsofsubstancesarechangeableinsystemsinvolvingphasetransitionsandchemicalreactions.(对其中的一相而言,可看作开放系统)04Characteristicsofmulti-componentandheterogeneoussystems03第三章溶液热力学基础ThermodynamicsofMulti-componentSystems(SolutionChemistry)013.1Partialmolarquantities(偏摩尔量)02VolumeChangeuponMixingofC2H5OH(A)andH2O(B)wA%VA*/cm3VB*/cm3(VA*+VB*)/cm3V/cm3DV/cm32025.3480.32105.66103.242.424050.6860.24110.92106.933.996076.0240.16116.18112.223.9680101.3620.08121.44118.562.88(2)Nonadditivityofextensiveproperties,suchasvolume。(3)Morethan3independentvariablesareneededtodefinethestateofasystem.2.PartialmolarquantitiesTakingvolumeasanexample.Forasystematthermalandmechanicalequilibrium,wehaveDefine:aspartialmolarvolumeofsubstanceBPartialmolarinternalenergyPartialmolarenthalpyPartialmolarentropyPartialmolarvolumesofH2OandCH3CH2OHat25oCDiscussion:①Partialmolarquantitiesareintensivepropertiesofasystem.（强度性质）②PerspectivesofphysicalsignificanceVxBnBChangingrateofVagainstnBatagivenstate(T,p,andconcentrationxB).偏摩尔体积也可看作是在等温等压的条件下，在无限大的系统中加入1molB所引起系统体积的变化量。Conditions:ConstantTandp.Foramono-componentsystem,3.Twoimportantequationsofpartialmolarquantities(1)Additivityofpartialmolarproperties(偏摩尔量的集合公式，或加和公式)在指定T，p均不变的条件下V是nB的一次齐函数。根据齐函数的Euler定理即：(2)Gibbs-DuhemequationAtconstantTandp,FromBycomparison,wehaveVA是nA的零次齐函数，Forbinarysystems,(A+B),根据齐函数的Eul