物理化学答案17课后答桉

1、课网，用心为你服务大-中-网课网，用心为你服务大-中-网最全最多的课后习题参，尽在课Khdaw团队一直秉承用心为大家服务，以关注学生的学习生活为出发点旨在为广大学生朋友学习提供一和交流。爱校园）课网）习题解1. 25Ag,Cl2(0.1MPa), 1.1362 V，电池反应电势的温度系数为5.9510V K 1 。试计算电池反Ag(s)1Cl (0.1MPa)习题解1. 25Ag,Cl2(0.1MPa), 1.1362 V，电池反应电势的温度系数为5.9510V K 1 。试计算电池反Ag(s)1Cl (0.1MPa)2225时的rGm、rSm 和rHmrGm 1964851.1362Jmol

2、1 109.63kJ1964855.95104JK1 zFE T r 57.4JK1 G T 109.63103 298.1557.4Jr 126.74kJ2. Ag,Hg2Cl2(s), 2525Ag1 Hg Cl AgCl2的 5.54 kJ mol1，各物质的标准摩尔熵为：Ag，42.55 J K1 Hmol1；AgCl，96.2 JK1 mol1 ；Hg，76.02JK1 mol1；Hg2Cl2 192.5JK1 mol1SSr B 1 196.2176.02142.55 192.5 J33.4JK1 2 G GHSr r r 5.54103 298.1533.4J4.42kJ G G

3、HSr r r 5.54103 298.1533.4J4.42kJ 4.42103 E r m V 0.04581Eo ES r m V1T 196485 0.346103VKHCl (0.1molkg1KOH (0.1molPt,H2(0.1Pt, H2(0.1Cl2(0.1MPa),O2(0.1MPa), ZnCl2 (0.1molkg Hg2Cl2 ,KOH (0.5molkg1Zn,HgO(s), 解：(1) H2 (0.1MPa)2H (0.1molkg ) Cl2 (0.1MPa)2e 2Cl (0.1molkg )H2 (0.1MPa)Cl2 (0.1MPa)2H (0.1mol

4、kg1) 2Cl (0.1molkg1(2) 负极2H2 (0.1MPa)4OH (0.1molkg ) 4H2OO2 (0.1MPa)2H2O4e 4OH (0.1molkg )2H2 (0.1MPa)O2 (0.1MPa)2H2(3) 负极ZnZn2 (0.1molkg1Hg2Cl2 2e 2Hg2Cl (0.2molkg )ZnHg2Cl2 2Hg Zn2 (0.1molkg1)2Cl (0.2molkg1) 2HgOH2O2e Hg2OH (0.5molkg )ZnHgOHg4. Br (a Fe3 (a 0.1),Fe2 (a Ag,25解：AgBr (a 0.34)AgBreFe3

5、 (a 0.1)e Fe2 (a AgBr (a 0.34)Fe3 (a 0.1) AgBr Fe2 (a 0.02)25解：AgBr (a 0.34)AgBreFe3 (a 0.1)e Fe2 (a AgBr (a 0.34)Fe3 (a 0.1) AgBr Fe2 (a 0.02) EoFe3,FeAgBr(s), E 0.7710.07116V 0.700a E Eo RT a Br 0.7000.05916 0.7145. 25ZnCl2 (0.005molkg Hg2Cl2(s),1.227V，0.005molkg1 ZnCl 2因子 0.78925解：负极Zn Zn2 (0.005

6、molkg1 Hg2Cl2 2e 2Hg2Cl (0.010molkg ZnHg2Cl2 2Hg Zn2 (0.005molkg1)2Cl (0.010molkg1b3 E E a EZnbo 40.005 0.789 1.2273321.0316. 25Pt 0.407 V ，其他数据可查17-3(1) 2Cr2(a 0.2)I 22Cr3(a 0.1)2I(a Pb(s)H2SO4(a 0.1)PbSO4 (s)H2 (0.1MPa) H2 (0.1MPa) Ag2O(s) 2Ag(s) H2O(l) 解：(1) 2Cr2 (a0.2)2Cr3 (a0.1)I2(s)2e 2I (aCr3

7、 (a 0.1),Cr2 (a 解：(1) 2Cr2 (a0.2)2Cr3 (a0.1)I2(s)2e 2I (aCr3 (a 0.1),Cr2 (a I (a I2(s),a2 aE Eo RT CraCr 0.5353 0.4070.05916lg 0.10.1 1.019PbSO2 ()PbSO SO44正极：2H )2e H (0.1H2SO4 (a 电池Pb,PbSO4H2(0.1MPa),/ p/ pE Eo ln Eo ln aa 00.3590 0.05916 10.27030.13 2) Ag2O(s)H2O2e 2Ag2OH (OH Pt,H2 (0.1Ag2O(s),E

8、Eo RT 10.342 0.8277pH1.170AgBra 0.2)AgBreAga 0.1)e Br (a Ag (aAg, E Eo RT 1 0.79940.071160.05916lg 10.10.62777. H2(0.1MPa)I2 (s)2HI(a 25时 (1) Eo；(2) 函数 GoE Eo RT 1 0.79940.071160.05916lg 10.10.62777. H2(0.1MPa)I2 (s)2HI(a 25时 (1) Eo；(2) 函数 Go标准平衡常K o r 1 (0.1MPa)1I (s)HI(a 2222 (Pt,H2 (0.1HI(a I2(s)

9、,EoI I (s),PtEo2H2,Pt 0.5353 zFEo 2964850.5353JGr 103.3kJ Gexp r mK8.3145298.151.250.5353E Go 51.65kJr KEoCuCu EoCuCu 8. 173 和25时EoCu2 Pt ，并计算反CuCu2 25解：(a) H2 (p )(a1)2H (a1)1 21 2(po)Cu(a1)H(a1)2(po)Cu2(a 1) H(a 1)Cu(a 2 G G a G oo1 21 2(po)Cu(a1)H(a1)2(po)Cu2(a 1) H(a 1)Cu(a 2 G G a G ooormr r FE

10、oCu2 Pt 2FEoCuCu 即 20.3417 0.5210.162(c)(b)E 0.1620.5210.359196485 zFEo K o 9. 17-3 2Hg2Fe3 Hg2 2在 25时的标准平衡常数。若所有物质均处于标准状态， 2964850.771 zFEo K o8.3145EEo 0.7710.7971V0.026V 10. 25Pt,H2(0.1HCl (0.1molkg1AgCl(s), 0.3522 V(1) 求反H (g)2AgCl(s)2H 2Cl 2在 25时的标准平衡常数。已知0.1mol kg1HCl 溶液的 0.798(2) 求金属银在1molkg1

11、HCl溶液中产生H 2时1molkg1HCl 溶液的 0.809aa解 E RT E/ pH0.35220.05916lg0.10.7982 0.2223zFEo 296485(2) 求金属银在1molkg1HCl溶液中产生H 2时1molkg1HCl 溶液的 0.809aa解 E RT E/ pH0.35220.05916lg0.10.7982 0.2223zFEo 2964850.2223K o8.31453.28b /boaaaKo Cl / p/ p/ pHHH1 100kPa 1.3110 6 3.2811. NaOH(0.01molkg1HCl(0.01molkg1 Pt,H2(0

12、.1H2(0.1MPa),250.587 V，同温度下0.01molkg1NaOH 0.01mol kg1HCl 溶液的oK都等于0.904，求水的离子w解：H2 (0.1MPa)2OH (aOH2H2O正极：2H )2e H (0.1电池：2H ) 2OH)2H E RT 1E 0.5870.05916V 0.82910.012RT ln FKwlgKo w0.98Kw12. CdI2AgI(s), 250.2860 V，求CdI2溶液的离子平均活度及电解质作为整体的活度aB 解：Cd(s)2AgI(s)2Ag(s)CdI2 E Eo RT a ln12. CdI2AgI(s), 250.2

13、860 V，求CdI2溶液的离子平均活度及电解质作为整体的活度aB 解：Cd(s)2AgI(s)2Ag(s)CdI2 E Eo RT a ln2o3EV 20.152410.4032lg33a a a3 13. ZnCl2(0.01molkg AgCl(s),在 25时的电池反应电势为 1.1566 V，其他数据可查表 17-3，求0.01molkg1 ZnCl 溶液的离子平均活度、离子平均活度因子及解：Zn(s)2AgCl(s)2Ag(s)ZnCl2(0.01molkg E Eo RT a2 o3Zn2Eo Elga 3 20.22216 0.76201.1566 3a a a3 1.48

14、b /b o4314. 25CuCl2AgCl(s),当CuCl2 溶液的浓度b 0.0001molkg E 0.191Vb 0.2molkg1E 0.074V。设0.0001molkg1 2溶液的 子平均活度因子 0.960，试求0.2molkg1 解：2Cu(s) 2AgCl(s) 2Ag(s)CuCl2当CuCl2 溶液的浓度b 0.0001molkg E 0.191Vb 0.2molkg1E 0.074V。设0.0001molkg1 2溶液的 子平均活度因子 0.960，试求0.2molkg1 解：2Cu(s) 2AgCl(s) 2Ag(s)CuCl24b 3 E Eo 1 ,1 1b

15、o4b 3 E Eo 2 ,2 2bob2,2 lnE1 E2 b1 20.1913b2,2 lg b1 b29680.00010.96015. Pt, H2(0.1KCl(0.1 moldm3 SHg2Cl2(s),S pH 6.86 25时电池反应的电势为 0.7409 VS pH 0.6097 VpHEx Es F 6.86 0.6097sRT 16. 25Pt,H2(0.1稀的NaOH水溶HgO (s),的电池反应电势为 0.9265 VH2O的 标 准摩尔生成焓为285.830 kJ mol1。各物质的标准摩尔熵为：HgO , 70.29 JK1 mol1； Hg(l) , 76.0

16、2 JK1mol1 O2(g) , 205.138 JK1mol1 H2(g) ,130.684JK1 mol1；H2O(l), 69.91JK1 mol1。25时HgO 的解：H2 HgOH2OH 1O H 2222HgOHg122 G ormr 2964850.9265J G 2H 解：H2 HgOH2OH 1O H 2222HgOHg122 G ormr 2964850.9265J G 2H 2T S ooor r 285.83010 298.1531205.138J 2237.13kJ oooGG2rmr r 178.79237.13kJ 58.34kJ G olnK o r 6.0K

17、1/ OKp Ko2 po 6.010112 100kPa 3.6101917. 试计算Ag2O(s)Ag O(s)2Ag(s)1O 222101.3 kPa，空气中O20.21Ag2O(s)标准摩尔生成焓为3.05kJmol1OH解：Pt,O2Ag2O(s), zFE 2964850.3420.401olnK o298.15 8.3145 Ko298.15K1/ KoT O pH11 m Ko298.15 298.15zFE 2964850.3420.401olnK o298.15 8.3145 Ko298.15K1/ KoT O pH11 m Ko298.15 298.15T 311T /

18、KT 42818. Pt,H2(HCl (0.1molkg1Hg2Cl2(s), 在 25测得 p 0.1013MPa E 0.3990V p 11.16MPa 时， E 0.4596VH22511.16 MPa 0.1013MPa时H2可当作理想气体。 H2 (p1)H2 (p2 G 3G 1 G 2zFE or r r 12f p G RTln 2 RTln 2 又r f p11 20.39900.4596 lg p2 p1 1120.10131218Zn2(a 1Zn2(a 2HCl(0.1molPt,H (p 0.1H (p 0.01MPa),101.3解：(1) Zn2a 0.5Zn

19、2a 8.3145291.15ln 0.1E RT ln 0.02022H2p1 0.1MPaH2p2 0.01 8.3145291.15ln 0.01解：(1) Zn2a 0.5Zn2a 8.3145291.15ln 0.1E RT ln 0.02022H2p1 0.1MPaH2p2 0.01 8.3145291.15ln 0.01E RT 0.1 20.028920. 25KCl (0.5molkg1KCl (0.05 molkg1Ag,AgClAgCl(s),的电池反应电势0.0536 V0.5 mol kg1和0.05 molkg1KCl 溶液的离子平均活度因子分别为 0.649 和

20、0.812。试计算K 的迁移数及该电池解：96485 C AgCl(a ) AgCle1K(a) 2 )1 2Cl(a ) 1Cl(a) 2RT ln (a )2 (a )2t RT ln (a ) r (a (a (a RT ln b1E rGm RT ln (a)b (a 2 0.50.649 0.0536V 2t 0.05916即t E RT ln (a )1 2t 1RT ln b1b 液(a 2 0.50.649 20.50210.059160.20.050.81221. 10.263 g 硝酸亚 ，1dm3S 6.30 g 2.63 g 硝酸亚 2试确定在溶液中的亚 离子是Hg还是

21、Hg22解：设亚 离子为Hg E21. 10.263 g 硝酸亚 ，1dm3S 6.30 g 2.63 g 硝酸亚 2试确定在溶液中的亚 离子是Hg还是Hg22解：设亚 离子为Hg E RT ln a,1 RT ln FF8.3145291.15ln 2.63 0.2630.0578设亚 离子为Hg22Hg2 ) Hg2E RT ln a,1 RT ln b,1 0.0289a,2因后一假设求得的反应电势与实验值相符，故亚 离子应为Hg2222. 25时用铅作电极电解pH 4.76的硫酸溶液。当阴极电流密度为1 A cm2 时，测得铅阴极的电极电势为1.8416 V ，阴极电流密度为0.01A

22、 cm2 时，铅阴极的电极电势为1.6216 V 。求当阴极电流密为0.1 A cm2 时，氢在铅阴极上的超电势H(pH4.76)e 1H (po解：2211Ec0E 00.05916 oaH 0.05916pHV 0.059164.76 0.282c Ec jEc 1.84160.282V1.560j 1Acm2cj0.01Acm2， 1.62160.282V1.340c ab1.560V abln11031.340V abln0.01103解得 a 1.230b0.0478j 0.1Acm21.230 0.04781.560V abln11031.340V abln0.01103解得 a

23、1.230b0.0478j 0.1Acm21.230 0.0478ln0.1103V 1.450cc 1.45023. 25时，以 为阴极电解含有浓度为0.01moldm3的NaCl溶液，阴极反应 Na e Na 受传质控制，极限电流密度为25.0 mA cm2 ，求阴极上Na 的传质系数以及扩散层厚度。已知溶液中Na D 1.33105cm2 s1。dz25.0103 104A 2.5910 ms196485 Cmol1 0.01103 molm31.33105 104 km 5.1410 2.59NiCl2(0.01molkg 24. 25 时以铂电极电解含有和CuCl2 (0.02mol

24、kg ) 铂电极上的超电势可忽略不计，并设活度可用浓度代替，问： (1) 极上何种金属先析出？ (2) 第二种金属析出时，第一种金属在溶液中173。ENi2NiEoNi2NiRT ln 0.257 lg0.0120.316ECu2CuEoCu2CuRT ln 0.3417 0.2912Cu0.3417 0.05916lg Cu25.8a aCub b molbo25. 250.3417 0.05916lg Cu25.8a aCub b molbo25. 25.1molkg1的 ZnCl2溶液，若电流密度为10mAcm2，问在阴极上首先析出什么物质？在阳极上又析出什么物质？已知此电流密度下H2在铜电极上的超电势为0584V，O20.896 ，并假定Cl2在石墨电极上的超电势可略而不计，活度可用浓度代替。解： Z