5 mol single atomic perfect gas，from the initial state of 300K, 50kPa is firstly adiabatical reversible compressed to 100 kPa, then isobaricly cooled to decrease the volume to 85dm3 .Calculate W, Q,△U, △H and △S of the whole process.
答案：Q＝-19.892kJ,W=13.935kJ,△U=-5.958kJ，△H=-9.930kJ,△S=-68.66J/K 5. 甲醇在101.325kPa下的沸点（正常沸点）为64.65℃，在此条件下的摩尔蒸发焓
?vapHm?35.32kJ?mol?1。求在上述温度压力下，1kg甲醇全部成为甲醇蒸气时的
Q,W,△U，△H，△S,△A及△G
At 101.325kPa, the boiling point of CH3OH is 64.65℃, ?vapHm?35.32kJ?mol at this condition. Calculate Q,W,△U,△H，△S,△A and △G of the following process: 1kg CH3OH (l, 64.65℃,101.325kPa)→CH3OH (g, 64.65℃,101.325kPa)
答案：Q＝△H＝1102.65kJ,W=-87.65kJ,△U=1014.65kJ，△S=3.263kJ/K，△A=-86.58kJ，△G=0
6. 已知水的沸点是100℃，摩尔定压热容Cp,m?H2O,l??75.20J?mol?K,汽化
?1?1?1焓?vapHm?40.67kJ?mol，水气摩尔定压热容
?1Cp,m?H2O,g??33.57J?mol?1?K?1(摩尔定压热容可视为与温度无关)，求过程：
1molH2O(l,60℃,101325Pa) →1molH2O(g,60℃,101325Pa)的Q,W,△U，△H，△S,△A及△G Given the boiling point of water is 100℃, Cp,m?H2O,l??75.20J?mol?K,
?1?1?vapHm?40.67kJ?mol?1, Cp,m?H2O,g??33.57J?mol?1?K?1( don’t change with
temperature),
Calculate Q,W,△U，△H，△S,△A and △G of the following process: 1molH2O(l,60℃,101325Pa) →1molH2O(g,60℃,101325Pa)
答案：Q＝△H＝42.34kJ,W=-2.77kJ,△U=39.57kJ，△S=113.7J/K,△A=1.69kJ，△G=4.06kJ
7. 已知1mol、-5℃、100kPa的过冷液体苯完全凝固为－5℃、100kPa固态苯的熵变化为-35.5J/K,固态苯在－5℃时的蒸气压为2280Pa,摩尔熔化焓为9874J/mol。计算过冷液态苯在－5℃时的蒸气压。
Given that △S of the process 1molC6H6(l,-5℃,100kPa) →1molC6H6 (s,-5℃, 100kPa), 答案：2680Pa
8. 4mol理想气体从300K、p?恒压加热到600K,求此过程的Q、W、△U、△H、△S、
?△A、△G。已知此理想气体的Sm(300K)=150.0J·K-1·mol-1，Cp,m =30.00J·K-1·mol-1
4 mol perfect gas from the initial state of 300K, p? isobaricly heated to 600K. Calculate Q,W,△U,△H,△S,△A and △G of the process. Given for the perfect gas ?(300K)=150.0J·K-1·mol-1，Cp,m =30.00J·K-1·mol-1.Sm答案：△U=26.02kJ; △H=Q=36.0kJ;W=-9.978kJ; △S=83.18J/K;△A=-203.9kJ; △G=-193.9kJ
9. 8mol某双原子理想气体由始态(400K,0.20MPa)分别经下列三个不同过程变到该过程指定的终态，分别计算各过程的Q,W,△U;△H;△S;△A;△G. 过程Ⅰ：恒温可逆膨胀到0.10MPa; Ⅱ: 自由膨胀到0.10MPa;
Ⅲ: 恒温下对抗恒外压0.10MPa膨胀到平衡
8 mol double atomic perfect gas from the initial state of 400K,0.20MPa through the following three different paths to given final state. Calculate Q,W,△U;△H;△S;△A;△Gof each paths.
(1) Isothermal reversible expands to 0.10MPa. (2) Free expands to 0.10MPa.
(3) Isothermal expands against an external constant pressure of 0.10MPa to equilibrium. 答案： 过程 Ⅰ Ⅱ Ⅲ W/kJ -18.41 0 -6.65 Q/kJ 18.41 0 6.65 △U/kJ 0 0 0 △H/kJ 0 0 0 △S/kJ 46. 10 46.10 46.10 △A/kJ -18.44 -18.44 -18.44 △G/kJ -18.44 -18.44 -18.44 3
10. 将装有0.1mol乙醚液体的微小玻璃瓶放入容积为10dm的恒容密闭的真空容器中,并在35.51℃的恒温槽中恒温。35.51℃为在101.325kPa下乙醚的沸点。已知在此条件下乙醚的摩尔蒸发焓为25.10kJ/mol。今将小玻璃瓶打破，乙醚蒸发至平衡态，求：（1）乙醚蒸气的压力；（2）过程的W,Q,△U,△H,△S,△G,△A。
答案：P=25.664kPa;W=0J;Q=△U=2.254kJ;△H=2.51kJ;△S=9.275J/K;
△A=-0.61kJ;△G=-0.353kJ
3
11.将装有0.1mol乙醚液体的微小玻璃泡放入35℃、101325Pa、10dm的保温瓶中,其中充满N2(g),将小玻璃泡打碎后,乙醚全部汽化,形成的混合气体可视为理想气体。已知乙醚在101325Pa时的正常沸点为35℃,其汽化焓为25.10kJ/mol。计算（1）混合气中乙醚的分压；（2）氮气的△H,△S,△G；（3）乙醚的△H,△S,△G 答案：(1)P=25.664kPa;(2)△U=0kJ;△H=0kJ;△G=0kJ；
(3)△S=9.275J/K;△H=2510kJ;△G=-0.353kJ
12.已知298K时石墨和金刚石的标准摩尔燃烧焓分别为-393.511kJ/mol和-395.407kJ/mol，标准摩尔熵分别为5.694J?K?1?mol?1和2.439J?K?1?mol?1，体积
?质量分别为2.260和3.520g/cm3。（1）计算C(石墨) →C(金刚石)的?rGm?298K?; (2)25℃时需多大压力能使上述转变成为可能（石墨和金刚石的压缩系数均可近似视为零）
??Given at 298K, ?cHm(C, graphite)= -393.51kJ/mol, ?cHm (C, diamond)= ?-395.407kJ/mol, Sm( C, graphite)= 5.694J?K?1??mol?1,Sm( C, diamond)=
2.439J?K?1?mol?1,
ρ( C, graphite)= 2.260g/cm3, ρ( C, diamond)= 3.520g/cm3.
(1) Calculate ?rGm?298K? of this process: C(graphite) →C(diamond);
?(2) How to control pressure to make the above change realized.
答案：(1) 2.867kJ/mol; (2) p>1.51×109Pa 13． 已知水在77℃时的饱和蒸气压为41.891kPa,水在101.325kPa下的正常沸点为100℃,求:
(1) 下面表示水的蒸气压与温度关系的方程式中的A和B值;
lg?pPa???AT?B
(2) 在此温度范围内水的摩尔蒸发焓; (3) 在多大压力下水的沸点为105℃．
Given that saturated vapor pressure of water is 41.891kPa at 77℃.Normal boiling point of water is 100℃ under 101.325kPa. Please calculate:
(1) The value A and B below expressing the relationship of water vapor pressure with
temperature.
lg?pPa???AT?B
(2) Molar vapor enthalpy in this temperature scope.
(3) How much the pressure when boiling point of water is 105℃． 答案 (1) A=2179.133K,B=10.8455; (2) 41.719kJ/mol;(3) 121.042kPa
14.水和氯仿在101.325kPa下的正常沸点分别为100℃和61.5℃,摩尔蒸发焓分别为
?vapHm?H2O??40.668kJ?mol?1和?vapHm?CHCl3??29.50kJ?mol?1,求两液体
具有相同饱和蒸气压时的温度.
The normal boiling point of H2O and CH3Cl are 100℃ and 61.5℃ respectively,
?vapHm?H2O??40.668kJ?mol?1 and
?vapHm?CHCl3??29.50kJ?mol?1,
Calculate the temperature when the two liquid has the same saturated pressure. 答案:262.9℃
第四章 多组分热力学
一、选择题
**1. 在一定的温度T下,由纯液态A和B形成理想液态混合物,已知pA,当气-液两?pB相达到平衡时,气相组成yB总是( )液相组成xB。
(A) > (B) < (C) = (D)无法确定
2.在?、?两相中都含有A和B两种物质，当达到相平衡时，下列三种情况正确的是： （ ）
α (A?)A??αB ? α(B)β?AA? C B ) (D) 无法确定 α ? A ? β(?3.在恒温、恒压下,由A和B形成理想液态化合物的过程的?mixU和?mixA（ ）
(A)?mixU=0，?mixA<0 (B)?mixU<0，?mixA=0 (C) ?mixU>0， ?mixA>0 (D) ?mixU=0，?mixA>0 4.150℃，101 325Pa的液态H2O(l)的化学势?l， 150℃，101325Pa的气态H2O(g)的化学势?g ，二者的关系为（ ）
(A) ?l > ?g (B) ?l < ?g (C) ?l = ?g (D) 无法确定
5.某物质溶于互不相溶的两液相?和?中，该物质在?相以A2的形式存在，在?相以A形式存在，则定温定压下，两相平衡时（ ）
(A)?α(A2)??β(A) (B)?α(A2)?2?β(A) (C)2?α(A2)??β(A) (D) 无法确定