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Ag,AgCl(s)HCl(aq)Cl2(0.1MPa),1.1362V，電池反應電勢的溫度系數(shù)為5.9510Ag(s)1

(0.1MPa)25℃時的rGm、rSm和rHm .1362Jmol1109.63kJr

EmzFEr rr r

1964855.95104JK1

GTS109.6310298.1557.4J 126.74kJAg,AgCl(s)KCl(aq)Hg2Cl2(s),Ag1Hg

的Ho5.54kJmol1，各物質(zhì)的標準摩爾熵為：Ag，42.55JK1 mol1；AgCl，96.2JK1mol1；Hg，76.02JK1mol1；Hg2Cl2192.5JK1mol1mB mB196.2176.02142.55

JK1

r r rGGoHor r r4.42kJ 4.42103E rm V0.0458 o1964o85E E rm T T 1964850.346103VK

HCl(0.1molkg1)

O2(0.1MPa),Pt

ZnCl2(0.1molkg1

((1)H2(0.1MPa)Cl2(0.1MPa)2H(0.1molkg12Cl(0.1molkg1kg12H2(0.1MPaO2(0.1MPa)2H2O((2HgZn2(0.1molkg1)2Cl(0.2molkg1Zn2OH(0.5molkg1)ZnO2HO2eHgO2HO2eHg2OH(0.5Ag,AgBr(s)Br(a Fe3(a0.1),Fe2(a0.02)AgBrFe2(a0.02) aEE ln aaBr0.7000.05916 0.714

ZnZnCl(0.005molkg12

HgCl(s), 1.227V，0.005molkg1ZnCl2因子0.78925((2HgZn2(0.005molkg1)2Cl(0.010molkg1 b EoE a2E ln4 3 2Cr2(a0.2)I2 2Cr3(a0.1)2I(a

H2(0.1MPa)Ag2O(s)2Ag(s)H2O(l)(4)Ag(a0.1)Br(a0.2)電池：PtCr3(a0.1),Cr2(a I(a0.1)I2(s),

a2aE

lnCra a Cr

0.10.53530.4070.05916 1.01944

SO

2H(

HH

H2SO4(a/p

H2(0.1MPa), /pEEo Eo aH aH

00.3590 lg10.2703

H2(0.1MPa2OHa2H2O2ePt,H2(0.1MPa)OH(a)Ag2O(sAgEEoRT 1.170

Aga0.1)e電池：Ag,AgBr(s)Br(a Ag(a0.1)EEoRT

a 0.79940.071160.05916lg

0.6277

25(1)Eo；(2)標準摩爾反應吉布斯函數(shù)Go(3)Ko；(4)r12H

(0.1MPa)12

Pt,H2(0.1MPa)HIa1)I2(s EoEoII(s),PtEoHH,Pt0.5353 GozFEo2964850.5353Jr103.3kJ Go 103.3103Koexprmexp RT 8.3145298.151.25Eo0.5353Go51.65kJrKo1.1217–3EoCu2Cu和EoCuCuCuCu2

12H12H

GocGoaGor r r FEoCu2,CuPt2FEoCu2Cu Cu∴EoCu2,CuPt2EoCu2CuEoCu0.162(c)(b)得CuCu2a12Cua0.359

zFEo K

22在25℃時的標準平衡常數(shù)。若所有物質(zhì)均處于標準狀態(tài)，反應進解： zFEo 2964850.771Kexp exp RT 8.3145 EEo0.7710.7971V0.026V∴Pt,H2(0.1MPa)HCl(0.1molkg1)AgCl(s),25℃時的標準平衡常數(shù)。已知0.1molkg1HCl溶液的0.798℃時1molkg1HCl溶液的0.809 a2a解：(1)

E ln /p0.2223 zFEo 2964850.2223KexpRTexp8.3145 3.28a2a a

/b

(2)Ko Cl pH/p

/p

/p1 pH3.28107100kPa1.31106 Pt,H2(0.1

HCl(0.01molkg1

H2(0.1MPa),250.587V，同溫度下0.01molkg1NaOH0.01molkg1HCl溶液的0.904Ko

HH )2OHHH

EoERT

1HaH0.5870.05916 V0.829EoRTln

KFKFlgKo0.829 wKo0.98wCdCdI2(aq)AgI(s),250.2860V，求CdI2溶液的離子平均活度a及電解質(zhì)作為整體的活度aB。EEoRT a2EoRTln lga

3

20.152410.40320.286030.05916aaBa3ZnZnCl2(0.01molkg1)AgCl(s),在25℃時的電池反應電勢為1.1566V，其他數(shù)據(jù)可查表17-30.01molkg1ZnCl2溶液的離子平均活度、離子平均活度因子及ZnClEEoRT a2EoRTlna lga320.222160.76201.15661.943230.05916aaa31.48 a a

0.0114b/

33CuCuCl2(aq)AgCl(s),22b0.2molkg1E0.074V。設0.0001molkg1CuCl溶液的離子平均活度因子0.960，試求0.2molkg1CuCl2溶液的。22 4b33EEo ln1,1

bo E

RT

4b332,2 zFb zFb E1

3RTlnb2,2

21,1 21,1

3 1,1

∴

9680.00010.960Pt,H2(0.1MPa) SpH6.8625℃時電池反應的電勢為0.7409VSpH未知的溶液，同溫度下測得電池反應的電勢為0.6097V，求該溶液的pH。pHpHExEsF6.860.6097

RT

的電池反應電勢為0.9265VH2O(l)的標準摩爾生成焓為,Hg(l),76.02JK1mol1O2(g),205.138JK1mol1H2(g),130.684JK1mol1；H2O(l),69.91JK1mol125℃時HgO的分 H1

Go1G1r r .9265JGo2Ho2TSor

r3285.830

298.1512

205.138JGo3Go1Gor r r Go lnKrKo6.0p op

8.3145

∴

Ko2po6.010112100kPa3.61019試計算Ag2O(s)

101.3kPa，空氣中O20.21Ag2O(s的 Pt,O2(g)OH(aq)Ag2O(s),

2964850.3420.4018.3145298.15

101.3101.3p p KoT

Ho

1 m T31.05103 1 T428

T/K

25℃測得p0.1013MPaE0.3990Vp11.16MPa時，時H2可當作理想氣體。 2 Go3G1G2zFEEr r r f p3 r3

RTlnf

RTln2p 1 lgp2220.39900.4596p22p1

1120.10131 ZnZn2(a1 Zn2(a20.5)Pt,H(p0.1MPa)HCl(0.1molkg1)H(p0.01MPa), ERTlna18.3145

2

ln0.50.0202ERTlnp28.3145291.15ln0.01 2 0.10.0289Ag,AgCl(s)KCl(0.5molkg1)KCl(0.05molkg1)AgCl(s),0.0536V0.5molkg1和0.05molkg1KCl溶液的11 GtRTln(a)2(a)22tRTln(a)r

ErGm2tRTln(a)22t

(a

0.0536V 解 t

0.05916lg0.50.649 ERTln(a)12t1RTlnb12液 (a2

20.50210.05916lg0.50.6490.2

0.050.812

HgS1S220.263g硝酸亞，1dm3S2溶液中含有6.30g硝酸和2.63g硝酸亞。試確定在溶液中的亞離子是Hg還是Hg2。2解：設亞離子為Hg，則電池反應為ERTlna,1RTln 8.3145

2.63ln 0.057822設亞離子為Hg2，則電池反應為222Hg22

,1ERTlna,1RTlnb,10.0289V 2因后一假設求得的反應電勢與實驗值相符，故亞離子應為Hg2225℃時用鉛作電極電解pH4.76的硫酸溶液。當陰極電流密度為1Acm2時，測得鉛陰極的電極電勢為1.8416V，陰極電流密度為0.1Acm2解：H(pH4.76)e1

E0EoRTln100.05916lg1c a c

aH0.282cEcjEcj1Acm2 1.84160.282V1.560ccj0.01Acm2，1.62160.282V1.340c ab解得a1.230cb0.0478c

j0.1Acm2∴c1.450

25℃時，以為陰極電解含有濃度為0.01moldm3的NaCl溶液，陰極反應NaeNa受傳質(zhì)控制，極限電流密度為25.0mAcm2，求陰極上Na的傳質(zhì)系數(shù)以及擴散層厚度。已知溶液Na的擴散系數(shù)D1.33105cm2s1。

z 25.0103104A 2.5910m196485Cmol10.01103 1.33105104 m5.1410 25NiCl20.01molkg1)CuCl2(0.02molkg1鉑電極上的超電勢可忽略不計，并設活度可用濃度代替，問：(1)極上何種金屬先析出？(2)第二種金屬析出時，第一種金屬在溶液中的濃度是多少？所需的標準電極反應電勢可查表17–3。 0.257

0.316

ECu2CuEoCu2CuRTln 0.3417

Cu

0.291

lg0.02 0.34170.05916lg

2a5.8a

Cu

abo5.81023molb 1 1ZnCl2溶液，若電流密度為10mAcm2，問在陰極上首先析出什么物質(zhì)？在陽極上又析出什么物質(zhì)？已知此電流密度下H2電勢為0.584V，O20.896V，并假定Cl2在①Zn2(a0.1)2