_7
(d)

(b)
(2) DGT, P > 0
2HCl2H+ + 2Cl−= H2 + Cl2
(3) G




(2) W' = QVQV
(3) G




(2)




7.1
Faraday 1 mol Faraday 1 F
1 F = Nae = 6.02 1023 mol−1 1.6022 10−19 C
= 96485 C·mol−1 96500 C·mol−1





Cu2+ + 2e− = Cu
1 F 1 mol 1 mol 0.5 mol Ag Cu




1 mol A / n mol
Q = nF


















c+ c−
z+ z−
u+ u− V/l V l




Q+ = c+ u+ z+ F
Q− = c− u− z− F
Q = Q+ + Q− = c+ u+ z+ F + c− u− z− F
c+ z+ = c− z−
Q = c+ z+ F(u+ + u−) = c− z− F(u+ + u−)




(2)




(4)
(1) V = IRV I
(2) R l A r
r 1 m 1 m2




7.2
R G S W−1
r k S·m−1
k 1 m 1 m2





7.2
1 m 1 mol Lm S·m2·mol−1





7.2
l 1 m 1 mol Vm Lm









(2)
KCl l/A




7.2
1 25C 0.01 mol·dm3 KCl 150.00 W 0.01 mol·dm3 HCl 51.40 W 0.01 mol·dm3 HCl
KCl l/A HCl




7.2
7.3 25C 0.01 mol·dm3 KCl k 0.140877 S·m1
HCl
(1)
(a)




(1)
(b)








(a)
(ii) 1 mol m m
(i) m









(i) m Lm
(ii) 1 mol m




(1) Mv+Av




(2)
H+ HCl H2SO4 H2O 0.034982 S·m2·mol1





m





c m c





c MA m KcKc c




Ostwald
m ~ c 1/m vs. cm Kc




7.3
225C 0.1000 mol·dm3 HAc m 5.201 104 S·m2·mol1 HAc Kc
HAc HAc Kc
HAc H+ Ac




25C HAc





H2O = H+ + OH
k = 5.5 106 S·m1 r = 18 M·m

~ 1 103 S·m1
< 1 104 S·m1 KMnO4 KOH CO2 1 ~ 2
< 1 104 S·m1




k (H2O) = k (H+) + k (OH)
H+ OH




H2O c





7.3
325C AgCl 3.41 104 1.60 104 S·m1 AgCl 25C




AgCl Ksp
NaCl
→
HCl → NaCl
+
NaCl + NaOH
NaAc
→
HAc → NaCl
+
NaAc + NaOH
(3)




m1 mol·kg1




7.4
+ a a+a




Mv+Av a




Mv+Av a a+a

a
7.4
Mv+Av v = v+ + v a m
a







m a m a




7.4
Mv+Av m m+ m
m Mv+Av m
a a




m
1-2 Na2SO4 m








mol·kg1
Lewis I
A' A'
A' I I








(b)












(a)
(b)
(c)
I
A A(298 K) = 1.172 kg1/2mol1/2A(273 K) = 1.123 kg1/2mol1/2






lng








1 mol
(a) (DrGm)T, p Wr
(b) Wr E nF nFE




Zn Zn 2e = Zn2+
Cu Cu2+ + 2e = Cu

Zn Zn2+ + 2e = Zn
Cu Cu 2e = Cu2+

Zn Zn 2e = Zn2+
Cu 2H+ + 2e = H2

Zn 2H+ + 2e = H2
Cu Cu 2e = Cu2+





(3)
(1)
M Mz+ MMz+
Mz+ + ze = M




7.6
H2O2 Cl2 Pt H+OH Cl
Pt








(ii)






Ag-AgClCl Hg-Hg2Cl2Cl





Ag Ag+ Ag+ Cl AgCl





Hg Hg22+ Hg22+ Cl Hg2Cl2




7.6
H+ OH
Hg-HgOH+ Hg-HgOOH Ag-Ag2OH+ Ag-Ag2OOH




(ii)




(b)





(Pt)Fe2+, Fe3+(Pt)Sn2+, Sn4+(Pt)[Fe(CN)6]4, [Fe(CN)6]3
Fe3+ + e = Fe2+
(2)

K
G

(1) K S AB G c1 Ac1 S Es
(2) K X AB G c2 Ac2 X Ex























CdSO48/3H2O(s)Hg2SO4(s)-Hg(l)
CuSO4(m2)
HCl(m1)
Pt




(1) E
E = + =




(i)




(iii)
(3) (Pt)H2(g)NaOH(m)O2(g)(Pt)
Hg2SO4 + 2e- 2Hg + SO42-
H2(g) + Hg2SO4(s) 2Hg(l) + H2SO4(m)
(2) (Pt)Sn4+, Sn2+Tl3+, Tl+(Pt)
Sn2+ – 2e- Sn4+
Tl3+ + 2e- Tl+
Sn2+ + Tl3+ Sn4+ + Tl+




H2 + 2OH- – 2e- 2H2O
H2 – 2e- 2H+
H2(g) + 1/2O2(g) H2O(l)
(d)
(3) H+ + OH H2O(l)
(4) H2(g) + 1/2O2(g) H2O(l)
(1) Zn(s) + Cd2+ Zn2+ + Cd(s)
Zn(s) Zn2+ Zn(s)Zn2+ Cd2+ Cd(s) Cd(s)Cd2+
Zn(s)Zn2+Cd2+Cd(s)
Cd2+ + 2e- Cd





(2) Pb(s) + HgO(s) Hg(l) + PbO(s)
Pb(s) PbO(s) Pb(s)-PbO(s) HgO(s) Hg(l) Hg(l)-HgO(s)
Pb(s)-PbO(s)OHHgO(s)-Hg(l)
HgO + H2O + 2e- Hg + 2OH-
Pb(s) + HgO(s) Hg(l) + PbO(s)




(3) H+ + OH H2O(l)
(a) H+ OH- H+ OH-
(b) (i) H+ H2(g) (Pt)H2H+
(ii) H2(g) H2O (Pt)H2OH- H2(g)




(Pt)H2OH- (Pt)H2H+
(Pt)H2(g)OH-H+H2(g)(Pt)
2H+ + 2e- H2
2H+ + 2OH- 2H2O
(b) O2(g) H2O (Pt)O2(g)H+ O2(g)




O2 + 4H+ + 4e- 2H2O
4H+ + 4OH- 4H2O
(4) H2(g) + 1/2O2(g) H2O(l)
(a) H2(g) H2O (Pt)H2OH-
(b) O2(g) OH (Pt)O2OH-
(Pt)H2(g)OH- O2(g)(Pt)
1/2O2 + H2O + 2e- 2OH-
H2 + 1/2O2 H2O
(a) O2(g) H2O (Pt)O2H+
(b) H2(g) H+ (Pt)H2H+
(Pt)H2(g)H+O2(g)(Pt)
H2 + 1/2O2 H2O
(b) Pb(s) PbSO4(s) SO42 Pb-PbSO4(s)SO42




Pb2+ + 2e- Pb
Pb2+ + SO42 = PbSO4(s)
aA + bB = gG + hH
7.7
Cu2+ Zn2+ 1 Cu2+ Zn2+

Eq





Pb(s) + HgO(s) = PbO(s) + Hg(l)
1 Eq








1/2H2 – e H+






7.7
aAg = 1 aAgCl = 1 H2 aH2 = pH2/pq = 1










7.7
HCl m E [E + 2RT/Fln(m/mq)] vs. m1/2 Eq




m HCl m E
Eq
(Pt)H2(pq)HBr(m)AgBr(s)-Ag(s)
m
7.7
[E + 2RT/Fln(m/mq)] vs. m1/2 Eq
m1/2 [E + 2RT/Fln(m/mq)]
0.07145 V Eq = 0.07145 V
m1/2 / (10-4 molkg-1)1/2
Eq




I





4 -0.07145 V




E
(a)















(i) Qr Qp Qr = Qp(b)
(ii) Qp(b) (a) Qp(a) DrHm
Qr = Qp(b) DrHm = Qp(a)

Ag-AgCl(s)KCl(m)Hg2Cl2(s)-Hg




DrGmDrSmDrHm Qr




2 n 2
DrHmDrSmDrGm E








H+ DfGmq DfHmq Smq
DfGmqDfHmq Smq









PbSO4(s)
Pb2+
SO42
Pb-PbSO4(s)SO42Pb2+Pb(s)

(c) Eq
Pb + SO42 2e PbSO4
Pb2+ + 2e Pb
Pb2+ + SO42 PbSO4(s)




(b)




(d) e M l
e y1 y2


















7.8
(b)

U KCl




(i) KCl K+ Cl
(ii) K+ Cl




e = 0
j l(1) = j l(2)

E = e+ + e = [jCu j l(2)] + [jZn j l(1)] = jCu jZn
= j+ j




E = j+ j
7.8
(1)
Pt a(H+) = 1 pq Pt










ZnZn2+ (a = 0.1)
(Pt)H2(pq)H+(a = 1)Zn2+(a = 0.1)Zn
E = 0.792 V
H2(pq) + Zn2+(a = 0.1) 2H+(a = 1) + Zn
E = − 0.792 V ZnZn2+ (a = 0.1) (Zn/Zn2+) = 0.792 V




CuCu2+ (a = 0.1)
(Pt)H2(pq)H+(a = 1)Cu2+(a = 0.1)Cu
E = 0.342 V
H2(pq) + Cu2+(a = 0.1) 2H+(a = 1) + Cu
E = 0.342 V CuCu2+ (a = 0.1) (Cu/Cu2+) = 0.342 V




(Pt)H2(pq)H+(a = 1)Cu2+(a)Cu
H2 2e 2H+
Cu2+ + 2e Cu
E

q 7.6
(b) H2 O2





E E
= E + ()






25C q(Hg2Cl2) = 0.2681 V KCl Cl−
KCl 25C = 0.2444 V




1/2Cl2(p2) + e Cl
1/2H2(p1) e H+
1/2H2(p1) + 1/2Cl2(p2) HCl(a)
7.9
E a a
a




Cd2+ + 2e Cd
Zn 2e Zn2+




7.9
E ai i ai i
+ = − = + −

2H+ + 2e H2(p2)
H2(p1) 2e 2H+




Ag+(m2) + e Ag
Ag e Ag+(m1)
Ag+(m2) Ag+(m1)




+ −




E
E
(1)
(2) E ai i a




(1) E a
(2) E ai i








1.






q (Cu/Cu2+) = 0.337 Vq (Zn/Zn2+) = − 0.763 V Zn Cu2+ Cu Cu Zn2+ Zn




7.10
q(Fe3+/Fe2+) = 0.771 Vq(Sn4+/Sn2+) = 0.150 V
Sn4+ + Fe2+ = Sn2+ + Fe3+
q(Fe3+/Fe2+) = 0.771 V > q(Sn4+/Sn2+) = 0.150 V
Fe2+ Sn2+ Fe2+ Sn4+ Sn2+




(1) q a q
(2)
7.10
925C (1) a(Sn2+) = 1.0a(Pb2+) = 1.0(2) a(Sn2+) = 1.0a(Pb2+) = 0.1 Pb Sn
Pb Sn2+ Sn Pb/Pb2+ Sn/Sn2+
(1) (Pb) > (Sn)
(2) (Pb) < (Sn)




q(Pb) = − 0.126 Vq(Sn) = − 0.136 V
(1) (1) a(Sn2+) = a(Pb2+)
q(Pb) = − 0.126 V > q(Sn) = − 0.136 V Pb Sn




(2) (2) a(Sn2+) a(Pb2+) (2)
(Pb) = − 0.156 V < (Sn) = − 0.136 V Pb Sn








Zn + Cu2+ Zn2+ + Cu




ZnZn2+Cu2+Cu
7.6
Eq
Mv+Av(s) = v+Mz+ + vAz
Ksp




7.10
11 q 25C AgBr Ksp




(Ag/AgBr) = 0.0711 V





(2) Ag − e− Ag+
(2) n2 = −1





E a E a




(Pt)H2(pq)HCl(m = 0.1 molkg1)AgCl-Ag(s)
E = 0.3524 V HCl




AgCl + e− Ag + Cl−
q(Ag/AgCl) = 0.2224 V




pH = − lga(H+)




7.10
pH H+ E H+ E pH




(2) pH
pH pH pH pH pH




7.10
0.1 molkg−1 HCl Ag-AgCl
pH




[a(H+)]
E
()
7.10
pH pHs pHx Es Ex
pHx

(b)
E = a + bln[Mz+]
E





I r





E





(b) I




7.11
R IR DE
DE = () + ()
E
E r
E = r() − r() = r() − r()




VI = E + DV
DV
(b) I




7.11
R IR DV
DV = () + ()
I() = r +
I() = r −




CuCu2+
Cu2+
(a) CuCu2+
Cu2+ + 2e− Cu
Cu2+ Cu2+ Cu2+ c(Cu2+) Cu2+ c(Cu2+)




(b) CuCu2+
Cu − 2e− Cu2+
Cu2+ Cu2+ Cu2+ c(Cu2+) Cu2+ c(Cu2+)













(c)




(a) (Pt)H2H+








I r




(b)




b















V() () ()
V() = () − () = () − ()






V() () ()
V() = () − () = () − ()





V() V()
() ()
() ()
V()
V() = () − ()
V() () () V() V()
V() = V()
(1)




(i) () = (Cu) = q (Cu) = 0.337 V Cu
(ii) Cu Cu2+ Cu
Cu2+ 0.1 molkg−1 0.307 V




7.12
Ag+Cu2+ Cd2+ 1 molkg−1
(Ag) = q (Ag) = 0.799 V
> (Cu) = q (Cu) = 0.337 V
> (Cd) = q (Cd) = − 0.403 V
Ag Cu Cd








7.12
Ag+Cu2+ Cd2+ 1 molkg−1 AgCu Cd
(i) () = (Ag) = q (Ag) = 0.799 V Ag
(ii) Ag
(iii) () = (Cu) = q (Cu) = 0.337 V Cu Ag+
Ag+ 1.5 10−8 molkg−1




7.12
(iv) () = (Cd) = q (Cd) = − 0.403 V Cd Cu2+
Cu2+ 10−25 molkg−1
AgCuCd





1Pb-Sn
(Sn) = − 0.136 V (Pb) = − 0.126 V Sn2+ Pb2+ Sn Pb Pb-Sn Pb-Sn




2Cu-Zn
(Cu) = 0.337 V(Zn) = − 0.763 V Cu2+ Zn2+ Cu-Zn
CN− Cu2+ Zn2+ Cu(CN)3− Zn(CN)42− Cu-Zn








7.12
(i) H2 − 0.414 V H2
− 0.414 V
(ii) H2 ZnCuAgFe H2 − 0.414 V − 0.414 V




7.12
H2 Zn 0.6 ~ 0.8 V H2 Zn (H2)
(H2) = r(H2) − (H2) − 1.0 ~ − 1.2 V
Zn Zn2+ Zn Zn




7.12
13 25C 0.5 molkg−1 CuSO4 H2 Cu 0.230 V H2 Cu2+
H2 () H2 (H2)
(H2) = (H2) − h (H2)
(H2) Cu2+




(H2)





(1) Pt
Cl− Br− I− OH− Cl2 Br2 I2 O2
SO42− NO3− PO43−





7.12
Cu 1 molkg−1 CuSO4
(i) Cu (Cu) = 0.337 V
(ii) O2 OH− O2
Cu O2




7.12
14 KClKBrKI 0.1000 molkg−1 0.1000 molkg−1 ZnCl2 25C V
(1) 99%




() () V
(2) ZnZn2+ ZnCl2 Zn2+ ()




X− ()




2X− − 2e− X2




X− ()
(1) 99% I− I− 1% 0.0010 molkg−1 (, 1)




X− ()
(2) Br− 0.0001 molkg−1 (, 2)




X− ()
(3) Cl− 0.0001 molkg−1 (, 3)




V(1) = (, 1) − () = 0.714 − (−0.793)
= 1.507 V
= 2.094 V
= 2.389 V
(2)
(a)
(a)
(b)

(c)
Fe + 2H+ = Fe2+ + H2


CO2 SO2




O2 O2
O2 + H2O + 4e− = 4OH−
H2





Cu









O2 O2







(b) > 65%
K2Cr2O4H2O2HClO3KMnO4








(c) CD
(d) DE





(5) CrMoAlNiFeTiTaNd











Zn Fe Zn Fe
Sn Fe Fe Fe





Sn2+ Sn Fe




Pt Pt




1 FeCrNi
Cr Fe Cr Cr
Ni
Al Al Al





NSO




7.13
1 Zn Mg Fe Zn Mg Fe





(ii)