ݷʱ : 2024/11/9 1:39:50һ µȫĶ
?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) ӦıƽⳣKp (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)ĽѹΪpһѧӦO2(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ԱƽⳣֵҲ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
17ڸºͱѹ£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)뷴Ӧıƽⳣ298 KʱΪ0.143338 KʱΪ2.64Լ㣺
1N2O4(g)ıĦʡ
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)ıĦӦ?rGm19ϩˮϷӦC2H4(g)?H2O(l)¶ȵĹϵΪ?rGm/(J?mol)??34 585?26.4T/K?ln(T/K)?45.19T/K573 KʱıƽⳣKp
⣺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?rGmͱƽⳣKpֵ 2830 KʱƽⳣKpֵ?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