△nSn=△nHm/T=9300Jmol1/2153K 43.2J-K- I 4.10分(2176) 2176 答](a)以纯液体为标准态:xB=1yg=1a=1 aP: p,=p(I-y2)p =34291Pa(1-0.7446/13706Pa=0.6390 (2分) a2=P2/P2=06490 (1分) Y=a1x1=063900.6=1.065 (1分) Y2=a2/x2=0649004=1.6225 (1分) (b)以极稀溶液为标准态:当xB→0 B aBIB ka=(/xB)B取x2=0.0100实验值 k-p/x2=py2/x2 =(14l59Pa×0.0414)0.0100=58618Pa (3分) a2=p2/k=34291Pa×0.7446/58618Pa=0.4356 (1分) Y2=a2x2=043560.40=1.09 (1分) 3346 答]△G(NO298K)=△G3+△G(NO298K)=51.76kJmo (1分) 2NO2(g)=N2O4(g) △H(298K)=△(N2O4298K)-2△(NO2298K =.58.04kI-mor- (1分) nK(298K)=nK(291K)[△H(298KR298K-1/291K) △Gn(298K)=-RnK(28K)=-5106Jmo 分) △G3(NO4298K)=△GB(298K)+2△G5(NO2,298K) =9842k] l 四、问答题(共2题15分) 6.10分(1095) ](1)(aUan=Tap/aTr-P=(nRT/V)P=a∆fusSm= ∆fusHm/T = 9300 J·mol -1/ 215.3 K = 43.2 J·K-1 ·mol-1 (1 分) 14. 10 分 (2176) 2176 [答] (a) 以纯液体为标准态：xB= 1 γ B= 1 aB= 1 a1= p1/ * p1 = p(1-y2)/p* = 34 291 Pa(1-0.7446)/13 706 Pa = 0.6390 (2 分) a2= p2/ * p2 = 0.6490 (1 分) γ 1= a1/x1= 0.6390/0.6 = 1.065 (1 分) γ 2= a2/x2= 0.6490/0.4 = 1.6225 (1 分) (b) 以极稀溶液为标准态：当 xB→ 0 γ B= aB/xB → 1 kB= (pB/xB)xB 取 x2= 0.0100 实验值 k=p2/x2=py2/x2 =(14159Pa×0.0414)/0.0100 = 58618 Pa (3 分) 当 x2= 0.4 时 a2= p2/k = 34 291 Pa×0.7446/58 618 Pa = 0.4356 (1 分) γ 2= a2/x2= 0.4356/0.40 = 1.09 (1 分) 15. 5 分 (3346) 3346 [答] ΔfG m $ (NO2,298 K)=ΔrG m $ +ΔfG m $ (NO,298 K)=51.76 kJ·mol-1 (1 分) 2NO2(g) = N2O4(g) ΔrH m (298 K) =Δ $ fH m (N $ 2O4,298 K) - 2ΔfH m (NO $ 2,298 K) = - 58.04 kJ·mol -1 (1 分) lnK(298 K)=lnK (291 K)-[ΔrH m $ (298 K)/R](1/298 K - 1/291 K) =2.061 (1 分) ΔrG m $ (298 K) = -RTlnK(298 K) = - 5106 J·mol-1 (1 分) ΔfG m $ (N2O4,298 K) =ΔrG m $ (298 K) + 2ΔfG m $ (NO2,298 K) = 98.42 kJ·mol -1 (1 分) 四、问答题 ( 共 2 题 15 分 ) 16. 10 分 (1095) 1095 [答] (1) ( ∂ U/ ∂ V)T = T( ∂ p/ ∂ T)V -p = (nRT/V)-p = a (5 分)