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1 [] [] [] Cu 2+ 2e=Cu Zn 2+ 2e=Zn 2H + 2eH 2 Cu2e=Cu 2+ Ni2e=Ni 2+ 2OH 2e=H 2 O 1/2O 2 2Cl 2e=Cl 2 1

2 z+ ze l H 3 O + e 2 1 H 2 O 2a H 2 O e 2 1 OH 2b O 2 2H 2 O 4e4OH 3 z+ ze 4 z+ (zh)e h+ 5 l 2 HH + e H + H 2 O(H 3 O) + (H 3 O) + (H 3 O) + (H 3 O) + (H 3 O) + [(H 3 O) xh 2 O] + (H 3 O) + xh 2 O (H 3 O) + (H 3 O) + H 2 OH + H + eh () HHH 2() 2

3 xh 2() xh 2 xh 2 xh 2 η (15-1) H = a + bln D 2 k ηh 2 D k V D k m -2 a b2 2.3RTF b mV b >140mV a a 1 a V PbCdHgTiZnGaBiSn 2 a V FeCoNiCuWu 3 a V Pt Pd 15-l ab ηh 2 D k b=22.3rtf b ηh 2 a a b a

4 a b a b g l u Be Bi Cd Co Cu Fe Ge Hg Mn Mo Nb Ni Pb Pd Pt Sb Sn Ti Tl W Zn m u Cd Cu Pt Pt l g Sn V Fe Zn Bi Ni Pb

5 ~-2.0V V 15-3 Na Mg l Si P S Cl r Ca Se Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge s Se Br r Rb Sr Y Zr Nb Mo Te Ru Rh Pd g Cd In Sn Sb Te I Xe Cs Ba Hf Ta W Re Os Ir Pt u Hg Ti Pb Bi Po t Rn 15-3 Ti 2+ V

6 1. ε = ε e(k) η ε (k) = ε 0 RT zf z+ ze α ln α z+ η (k) 15-2 ε ε = ε RT = ε 1 2 α 0 1 ln η 1 1 (k) zf α z+ 1 RT α 0 2 ln η 2 2 (k) zf α z

7 (4) ph 7

8 ze z+ 1 2 zh 2 O ze = (OH) z zh + 2 =O z/2 zh + z/2h 2 O 3 2H 2 O 4e=O 2 4H + 3a 4OH 4e=O 2 2H 2 O 3b 4 z+ ne (z+n)+ (4) 5 2Cl 2eCl 2 5 ze z+ ε = ε 0 z S V η V RT α z+ + + ln + η 15-4 zf α 15-4 ε 0 z+ α z + α η 8

9 ε 0 α z α + z+ η l B BC CD DE 2. OH O 2 ph 9

10 HCl Sn-Bi 15-2 Sn-Bi Sn-Bi 0.05mol HCl Sn-Bi l 2 Cu-u Cu-u 10

11 98 Ni-Cu PbSO 4 2 2e=PbSO 4 0 ε =0.356V 2 PbSO 4 2H 2 O2ePbO 2 H 2 SO 4 2H + ε 0 =+1.685V 3 4 Pb2H 2 O 4e=PbO 2 4H + ε 0 =+0.655V 4OH 4e=O 2 2H 2 O 0 ε =+0.401V 5SO SO 4 2e=S 2 O 8 ε =+2.01V m 2 D 0.2 m -2 ε 11

12 l9mol 15-4 lmol H 2 SO m mol V 12

13 4OH 4e=2H 2 O O mol mol SO 4 2 S 2 O 8 2SO eS 2 O V u Cu g Pt Pt Ni Ni ε e

14 15-4 CuSO 4 Cu 2+ SO 2-4 Cu 2+ SO ε e ε e ε ε I I 15-5 CuSO 4 I I 15-5 ph ε e SO 2-4 OH - 14

15 ε e 15-5 η η E f = ε ε H + OH - SO 2-4 η η E f ε ε E Ω E Ω E f = ( ε ε ) + E E Ω = E f + Ω CuSO 4 I ε ε I = E f E ' f' ' ε '' I I ' 15

16 ε I ' ε ' η I ' I ' E ' f ' ε ε I '' '' η ε I I '' '' '' '' E '' f OH ε ε E f E f = E + E = [ ε ε ] + ( η + η η ) E ef E f ef e() e() E η = η + η E E R Ω E T = E f E E R Ω 15-5 E f E ef E η η E Ω η 16

17 1 1 = + R r r n + = r 1 d 1 2 R r 1 r 2 r 1 =r 2 ==r n d n d = 2n = 2 n 1 n n l r l r = ρr ρ r l R = r n d = 1 n d ρ r l R dr R t = R 0[1 (t t 0 )] dt dr dt 1 l E Ω = IR = I ρr (15-6) n d I D I = 2n = I n D d 17

18 D k E Ω = ρr l D k m 2 ρr cm lcm ρ r 0.02V 0.03V 0.02V 0.03V 2535 mol 96500C b η i (%) = qit η i bg I h gg ( h) C mg 1 h g l Bi

19 Fe u Cd Co Mg Mn Cu Ni Sn Pb g Cr Zn W W W' ω (%) = W = W =I E ef WIE T 10-8 I' = ηi I I' E ef ω (%) = 100 (15-10) I E T E ef ω '(%) = ηi E T %

20 15-11 W W W" E f ω "(%) = 100 = η i W E T g L g L m 2 OH ε 0 =0.401V ε 0 =0.763V 0.76V 0.02V 3. 24h 240kg V12 Zn 2+ H 2 O=Zn 1/2O 2 2H + G = kJ mol CuSO 4 1CuCu 2+ +2e 22H 2 OO 2 +4H + +4e h 1.50g11 2 Cu 3 Cu O cm 2 0.4V cm % g 2 1g molCuCl 2 10m cm V 7. Fe 2+ 1mol Zn 2+ 1mol 0.4V H + H 2 Zn 2+ Zn ph? 8. 1 Zn 2+ Fe V FeH 2 Zn ε + = 0.44V 0.763V Fe 2 Fe ε + = Zn 2 Zn 20