《物理化学上》期末试题A卷[001] 下载本文

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1.(3分)条件自由度为0的点:M、N、Q、R;条件自由度为0的线:ENC、PQS 2.

de:Ф=1,f*=2-1+1=2

ef:Ф=2,f*=2-2+1=1 ff’:Ф=3,f*=2-3+1=0 f’g:Ф=2,f*=2-2+1=1 gg’:Ф=3,f*=2-3+1=0

(2分) (5分) 五、证明题(5分)

∵dH=TdS+Vdp ∴(?H?S)T?T()T?V ?p?p?V?S)T=?()p

?T?p又∵(∴(?V?H)T =?T()p?V

?T?p六、计算题(34分) 1.(16分) (1)等温可逆压缩:

ΔU=0

ΔH=0

6p?W =nRTln?=1×8.314×298.15ln6=4.44kJ?mol-1

pQ=-W=-4.44kJ?mol-1 ΔS=

QR?4440?=-14.89J?K-1 T298.15ΔA=ΔU-TΔS=-298.15×14.89=4.44kJ ΔG=ΔH-TΔS=-298.15×14.89=4.44kJ

(2)绝热可逆压缩:

Q=0

ΔS=

QR?0 T1??∵p1T1?p2T2

?1???5 / 7

∴1001?75298.15?600T2

751?7575T2=497.47K ∵ ΔU=Q+W

∴ΔU= W=nCv,m(T2-T1) =1×2.5×8.314×(497.47-298.15) =4.14kJ

ΔH=nCp,m(T2-T1) =1×3.5×8.314×(497.47-298.15) =5.79kJ

ΔA=ΔU-SΔT =4140-205.03×(497.47-298.15) =-36.73kJ

ΔG=ΔH-SΔT =5790-205.03×(497.47-298.15) =-35.08kJ 2.(18分) 298K;ΔrHkJ?mol-1M2ub6vSTnP ΔrS?m,1=

?m,1=

??BB??fHm(B,298K)=-30.585+(-393.51)-(-501.66)=77.565

??BB?Sm(298K)=121.8+213.8-167.4=168.2 J?K-1?mol-1

??ΔrG?m,1=ΔrHm,1-T1ΔrSm,1=77565-298×168.2=27.441kJ?mol-1

ΔrGm,1=-RTlnK?p,1

?lnK?p,1=?27441=-11.076

8.314?298K?104 p,1=6.46× ΔrCp=

???BBCp,m(298K)=65.7+37.6-109.6=-6.3J?mol-1?K-1

? 398K:ΔrHm,2=ΔrHm,1+ ΔrSm,2=ΔrSm,1+

???398298?rCpdT=77565+(-6.3) ×100=76.935kJ?mol-1

dT=168.2+(-6.3) ×ln

398=166.377 J?K-1?mol-1 298???398?rCpT?298 ΔrGm,2=ΔrHm,2-T2ΔrSm,2=76935-398×166.377=10.717kJ?mol-1 ΔrGm,2=-RTlnKp,2 ∴lnKp,2=?????10717=-3.239

8.314?398Kp,2=0.0392

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