北京化工大学2004考研物理化学答案.pdf

器RTa0Vm一p其中用到麦克斯韦关系：2V2ws-pa(RT In2+aa2V v)2Vm-RTIn22V.aaVdV=V 2VaaQ=Un-Ww=2V.-(2V.。-RT2=RTn2aaHn=Um+pV2-pV=(pV=RT-Vm)dsdp）RROv)T=dS=Vm dV2V.Sm=RTIn Vm=RTIn21、3/2Po三、(15分)反应的3 P3p33 PIn k=-2 in p=-2nPa+21nl0=-2nPa+17.2731.464104=-269.32-T1K-5.651n(T/K)+17.272.26921041nK0=-86.71+T/K+8.34ln(T/K)H。a又lnK-I-RT+RnT比较式、得：I=-86.71H0=RX2.269210=1.8866X10a=R8.34=69.339，H.(UH,S)10mor=H_H0+4aTK=l.88610+69.39TK，C0m=Aa=6939J-K.mor四、(10分)613388()298.15K时N,分子振动配分函数：9-1-e7=1-e298.15=1.000011613388)当9=2=1-e7T=4888.89K五、(20分)298K时电池：Pt,H2(100kP)|稀NaOH|Ag2O(s),Ag(s)的电动势E=1.172V。(1)阳极反应：H2+20H=2H20+2e阴极反应：Ag2O+H2O+2e=2Ag+2OH电池反应：H2+Ag2O=2Ag+H2O(2)电动势E与0H的浓度无关，E=E=1.172V，G_，GH0.-，G(Ag,0s-2FE，G(Ag09，GH0.L+2FE=-237190+2X96485X1.172=-10291(3)Ag20(s)的分解反应：Ag20=2Ag+0+2O2此反应的，G2=-，G(Ag,0S=1029J=-RTnK=-RTnPo.-，G8-11029RT8.314298=exp=exp/=0.01166Po:-pX0.011662=13.6Pa六、(20分)威e层E。Ink=Inko-RT1Ea()以Ink对T作图，斜率m=一In(k/S)-14.71-11.759.25-7.00(K)/T0.003660.003410.003190.00300-7-10-15351/r104-7.00+15.00Eam=0.00300-0.00368=-11765=-REa=1756R=97812JmoE97812k=ke7-913106e834x392=913X105X2.16X105-1.97X102(2)安日T1=33.2Kk=913106sT2=373.2KEa=l1756R=97812Jmo解得k2=4.02102sIn 2 In 2h克=k2=0.0402=17.24s1kt=In 1-x转化率x=1-e=1-e00225=0.634=63.4%七、(15分)T/KIVAA-W%AB2BB二组分凝聚系统相图如下：(1)区域IIIV相数221稳定相态LA(s)+AB2(s)L+BB自由度数212B(表示固溶体)(2)C点，两相平衡：L+B图中标出各相组成（示意点）略LBbmg ac 22m=ab=3mg=3 m=2kgmL=1kg6