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717应用表741的数据计算下列电池在25℃时的电动势。CuCuSO4(b1001molkg1)‖CuSO4(b201molkg1)Cu解:该电池为浓差电池,电池反应为CuSO4(b201molkg1)→CuSO4(b1001molkg1)查表知,γ±(CuSO4,b1001molkg1)041γ±(CuSO4,b201molkg1)016
EE
RTa1CuSO4l
zFa2CuSO4
1b1RTb831429815l
041001001749Vl
zF2b2296500016010b
718在25℃时,电池PtH2(100kPa)HCl(b010molkg1)Cl2(100kPa)Pt电动势为14881V,试计算HCl溶液中HCl的平均离子活度因子。解:该电池的电池反应为H2(g,100kPa)Cl2(g,100kPa)2HCl(b010molkg1)
a2HClRTRTEEl
El
a2HClzFzFpH2ppCl2p

根据Ner
st方程
1488113579
831429815l
a2HCl296500aHCl629103
b1baHCla,即aHCl62910307931b010b
222
71925℃时,实验测定电池PbPbSO4(s)H2SO4(001molkg1)H2(g,p)Pt
的电动势为01705V。已知25℃时,(H2SO4,aq)fGm(SO2aq)74453kJmol1,fGm4,(PbSO4,s)8130kJmol1。fGm
(1)写出上述电池的电极反应和电池反应;(2)求25℃时的E(SO2;4PbSO4Pb)(3)计算001molkg1H2SO4溶液的a±和γ±。解:(1)上述电池的电极反应和电池反应如下
f正极:2H2eH2(g,p)
负极:Pb(s)SO242ePbSO4(s)
电池反应:H2SO4(001molkg1)Pb(s)PbSO4(s)H2(g,p)
(2)rGm

B
B
fGmB
fG,,Hs2GmPbSO4fm2

gGf
m
H,SO24
aGqf,m

Pb
s
813007445306847kJ1mol
因为:rGmzEFzE(H



2H2Pt)E(SO4PbSO4Pb)F


E(SO

24
G6847103PbSO4Pb)rm03548VzF296500
pH2ppH2pRTRTl
El
3(3)EEzFaH2SO4zFaH2SO4

01705003548
831429815100100l
3296500aH2SO4
aH2SO48369103
bH2SO4bHbSO2_
2
4


13
0022001
13
15874102molkg1
baH2SO4,bb1即ar
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