物理化学核心教程第二?沈文?课后习题答案5-8 - 百度文库

?rHm?rSmȻɵõ?rGm ?rHm???BB?fHm

???395.72?296.83?kJ?mol?1??98.89 kJ?mol?1 ?rSm???BBSm

?(256.76?248.22??205.14)J?K?1?mol?1

2??94.03 J?K?1?mol?1

?rGm??rHm?T?rSm

?3?1? ?? ?98.89?298?(?94.03)?10 kJ?mol??1 ??70.87 kJ?mol Kp?exp???1??rGm??70870?12?exp????2.65?10

?8.314?298??RT?2Hg(g)?O2(g)?rGm?44.3 kJ?mol?1

ӦƻǺܴġ

15 630 K ʱӦ2HgO(s)Լ㣺

(1) Ӧı׼ƽⳣKp (2) 630 K ʱ HgO(s)Ľѹ

O2(g)ѹΪ100 kPaĶУ (3) HgO(s)Ͷ뵽630 K630 K ʱ

ﵽƽ⣬HgO(s)ƽHg(g)ķѹ

??rGm⣺(1) Kp?exp???RT?44 300???4?exp??2.12?10 ???8.314?630???1p3 (2) HgO(s)ĽѹΪpһ໯ѧӦO2(g)ķѹΪ

Hg(g)ķѹΪ

2p 32?1??2? Kp??p/p???p/p??2.12?10?4

?3??3?ýѹ p?11.27 kPa

(3) Ϊ¶δ䣬Ա׼ƽⳣֵҲ䡣ʱHg(g)ķѹΪpHgֽO2(g)ķѹΪ

1pHgƽʱ 22p(O2)?pHg??? Kp?? p?p?(0.5pHg?100kPa)?pHg??4 ????2.12?10

p?p? pHg?1.45 kPa

ѾO2(g)ڣʹHg(g)ķѹ½

16 ijӦ1 100 K¶ÿ1 KKpԭ1%ڴ¶ȸ?rHm

2dlnKp1?1?0.01 K?1 ??0.01 K ⣺ ⣬

dTdTKp vant Hoff ʽ

2dKpdlnKpdT??1?rHm 2RT2?1???8.314?(1100)?0.01 J?mol ?? ?rHm?RT?0.01 K ?100.60 kJ?mol

17ڸºͱ׼ѹ£ˮͨȵú㣬ʽˮú

C (ʯī) + H2O(g) H2(g) + CO(g)

1 000 K1 200 KʱKpֱΪ2.47237.58Լڴ¶ȷΧڵĦӦʱ?rHm跴Ӧʱڸ¶Ϊ 1100 K ʱӦƽⳣ

?1Kp(1 100K)

⣺ vant Hoff Ķֹʽ lnKp(T2)Kp(T1)??rHmR?11???? ?T1T2?1??1???

1 000K1 200K???1 ln37.58?rHm?2.472R ?rHm?135.76 kJ?mol

lnKp(1 100K)2.472135 760 kJ?mol?1?11?????

R1 000K1 100K?? Kp(1 100K)?10.92

18֪N2O4(g)뷴Ӧı׼ƽⳣ298 KʱΪ0.143338 KʱΪ2.64Լ㣺

1N2O4(g)ı׼Ħʡ

2 318 K100 k Pa£N2O4(g)Ľȡ

⣺ (1) vant Hoff ʽ

?H?rm lnKp(T1)R lnKp(T2)?11???? ?T1T2?2.64?rHm?11????? 0.143R?298K338K??1ã ?rHm?61.04 kJ?mol

2318 K ʱƽⳣKp(318K)

lnKp(318K)0.14361 040 J?mol?1?11?????

R?298K318K?ã Kp(318K)?0.673

N2O4(g)ĽΪ?뷴ӦΪ

N2O4(g)2NO2(g)

t?0 1 0t?te 1?? 2??nBB?1??

2?2????4?21??????0.673 Kp(318K)?1??1??21??ã

??0.38

C2H5OH(l)ı׼ĦӦ?rGm19ϩˮϷӦC2H4(g)?H2O(l)¶ȵĹϵΪ?rGm/(J?mol)??34 585?26.4T/K?ln(T/K)?45.19T/K573 Kʱı׼ƽⳣKp

⣺573 K ʱ?rGmֵΪ

?rGm???34 585?26.4?573?ln573?45.19?573? J?mol

?1?1 ?87.38 kJ?mol

?1??GKp?exp??rm?RT?87 380???8?exp?????1.1?10

?8.314?573??20 298 KʱϩȡϩķӦΪC4H8(g)?C4H6(g)?H2(g)ѧݱԼ㣺

1298 KʱӦ?rHm?rSm?rGmͱ׼ƽⳣKpֵ 2830 Kʱ׼ƽⳣKpֵ?rHm¶޹ء

H2O(g)?1153ڷӦмˮ붡ϩıΪC4H8(g)Լ㷴Ӧ830 K200 kPa£ϩƽתʡ

֪298 Kʱ뷴ӦʵѧΪ C4H8(g) C4H6(g) H2(g) ?fHm/(kJ?mol?1) ?0.13 110.16 0 Sm/(J?K?1?mol?1) 305.71 278.85 130.68 ⣺ 1 298 Kʱ ?rHm???BB?fHm(B)

?1 ?[110.16?0?(?0.13)]kJ?mol ?rSm??110.29 kJ?mol?1

??BBSm(B)

?1?1 ?(130.68?278.85?305.71)J?K?mol ?103.82 J?K?mol

?rGm??rHm?T?rSm

?1?1

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