[] [] [] 15.1 1 2 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
1. 2. 15.2 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
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 100 140mV b >140mV a a 1 a 1.01.5V PbCdHgTiZnGaBiSn 2 a 0.50.7V FeCoNiCuWu 3 a 0.10.3V Pt Pd 15-l ab 293 1 ηh 2 D k 15-2 298 2 b=22.3rtf b ηh 2 a a b a 15-1 3
a b a b g 0.95 0.10 0.73 0.12 l 1.00 0.10 0.64 0.14 u 0.40 0.12 - - Be 1.08 0.12 - - Bi 0.84 0.12 - - Cd 1.40 0.12 1.05 0.16 Co 0.62 0.14 0.60 0.14 Cu 0.87 0.12 0.96 0.12 Fe 0.70 0.12 0.76 0.11 Ge 0.97 0.12 - - Hg 1.41 0.114 1.54 0.11 Mn 0.80 0.10 0.90 0.12 Mo 0.66 0.08 0.67 0.14 Nb 0.80 0.10 - - Ni 0.63 0.11 0.65 0.10 Pb 1.56 0.11 1.36 0.25 Pd 0.24 0.03 0.53 0.13 Pt 0.10 0.03 0.31 0.10 Sb 1.00 0.11 - - Sn 1.20 0.13 1.28 0.23 Ti 0.82 0.14 0.83 0.14 Tl 1.55 0.14 - - W 0.43 0.10 - - Zn 1.24 0.12 1.20 0.12 15-2 298 m -2 1 10 20 50 100 500 1000 2000 5000 10000 15000 u 0.122 0.24-0.322 0.390 0.507 0.588 0.688 0.770 0.798 0.807 Cd 0.651 0.981-1.086 1.134 1.211 1.216 1.228 1.246 1.254 1.257 Cu 0.351 0.479-0.548 0.584-0.801 0.988 1.186 1.254 1.269 Pt 0.0034 0.0154 0.0208 0.0272 0.0300 0.0376 0.0405 0.0420 0.0448 0.0483 0.0495 Pt - 0.024 0.034 0.051 0.068 0.186 0.288 0.355 0.573 0.676 0.768 l 0.499 0.565 0.625 0.745 0.826 0.968 1.066 1.176 1.237 1.286 1.292 0.3166 0.5995 0.6520 0.7250 0.7788 0.9032 0.9774 1.0794 1.1710 1.2200 1.2208 g 0.2981 0.4751 0.5987 0.6922 0.7618 0.8300 0.8749 0.9379 1.0300 1.0890 1.0841 Sn 0.3995 0.8561 0.9469 1.0258 1.0767 1.1851 1.2230 1.2342 1.2380 1.2380 1.2286 V Fe 0.2183 0.4036 0.4474 0.5024 0.5571 0.7000 0.8134 0.9854 1.2561 1.2915 1.2908 Zn - 0.716 0.726 0.726 0.746 0.926 1.064 1.168 1.201 1.229 1.243 Bi - 0.78 - - 1.05 1.15 1.14 1.20 1.21 1.23 1.29 Ni - 0.563 0.633 0.633 0.747 0.890 1.084 1.130 1.280 1.244 1.254 Pb - 0.52 - - 1.090 1.168 1.179 1.217 1.235 1.262 1.290 4
3 4-1.8~-2.0V -1.8-2.0V 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 2+ 1 2 3 5
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+ 2 15-3 15-3 2. 1 2 3 6
4 1 2 3 (4) ph 7
5 15.3 1 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
ε 0 α z α + z+ η l 15-1 15-1 15-1 B BC CD DE 2. OH O 2 ph 9
HCl 1 2 3 Sn-Bi 15-2 Sn-Bi 95 15-2 Sn-Bi 0.05mol HCl Sn-Bi l 2 Cu-u Cu-u 10
98 Ni-Cu 1 2 3 1 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 4 2 2 2 0 2SO 4 2e=S 2 O 8 ε =+2.01V 15-3 0.2 m 2 D 0.2 m -2 ε 11
15-3 0.0l9mol 15-4 lmol H 2 SO 4 15-4 m -2 298 322 348 298 322 348 0.019mol 50 1.99 1.90 1.83 1.91 1.86 1.82 100 2.02 1.95 1.86 1.94 1.89 1.85 200 2.04 1.98 1.90 1.99 1.92 1.88 400 2.07 2.01 1.95 2.02 1.96 1.90 600 2.09 2.02 1.96 2.03 1.97 1.92 1000 2.12 2.05 1.98 2.05 2.00 1.94 2000 2.15 2.09 2.01 2.10 2.05 1.96 3000 2.18 2.12 2.03 2.15 2.09 1.96 4000 2.23 2.18 2.06 - - - 5000 2.27 2.20 2.09 2.19 2.17 1.99 15-4 0.010.1V 12
4OH 4e=2H 2 O O 2 2.10mol 4.968.76mol SO 4 2 S 2 O 8 2SO 2 2 4 2eS 2 O 8 15-5 15-5 298 V u Cu g Pt Pt Ni Ni 10 0.525 0.673 0.442 0.58 0.721 0.398 0.353 0.414 50 0.705 0.927 0.546 0.674 0.80 0.480 0.461 0.511 100 0.896 0.963 0.580 0.729 0.85 0.521 0.519 0.563 200 0.963 0.996 0.605 0.813 0.92 0.561 - - 500-1.064 0.637 0.912 1.16 0.605 0.670 0.653 1000 1.091 1.224 0.660 0.984 1.28 0.638 0.726 0.687 2000 1.142-0.687 1.038 1.34-0.775 0.714 5000 1.186 1.527 0.735 1.080 1.43 0.705 0.821 0.740 10000 1.240 1.63 0.793 1.131 1.49 0.766 0.853 0.762 15000 1.282 1.68 0.836 1.14 1.38 0.786 0.871 0.759 15.4 15-4 ε e 15-4 13
15-4 CuSO 4 Cu 2+ SO 2-4 Cu 2+ SO 2-4 15-5 ε e ε e ε ε I I 15-5 CuSO 4 I I 15-5 ph ε e SO 2-4 OH - 14
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 15-6 15-6 CuSO 4 I ε ε I = E f E ' f' ' ε '' I I ' 15
ε I ' ε ' η I ' I ' E ' f ' ε ε I '' '' η ε I I '' '' '' '' E '' f OH - 15.5 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
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 2 8-818-80 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 -2 15-6 d 17
D k E Ω = ρr l 157 10000 D k m 2 ρr cm lcm ρ r 0.02V 0.03V 0.02V 0.03V 2535 mol 96500C 9095 100 b η i (%) = 100 15-8 qit η i bg I h gg ( h) 1 15-6 15-6 1C mg 1 h g l 3 26.89 0.0932 0.3356 Bi 3 208.98 0.7219 2.5995 18
Fe 2 55.85 0.2894 1.0420 3 0.1929 0.6947 u 1 197.00 2.0415 7.3507 3 0.6805 2.4502 Cd 2 112.41 0.5824 2.0972 Co 2 58.94 0.3054 1.0996 Mg 2 24.32 0.1260 0.4537 Mn 2 54.94 0.2847 1.0250 Cu 1 63.54 0.6584 2.3709 2 0.3292 1.1854 Ni 2 58.71 0.3042 1.0953 Sn 2 118.70 0.6150 2.2416 4 0.3075 1.1013 Pb 2 207.21 1.07360 3.8659 g 1 107.88 1.1179 4.0254 Cr 3 52.01 0.1797 0.6469 6 0.0898 0.3234 Zn 2 65.38 0.3388 1.2198 W W W' ω (%) = 100 15-9 W = W =I E ef WIE T 10-8 I' = ηi I 15-10 I' E ef ω (%) = 100 (15-10) I E T E ef ω '(%) = ηi 100 15-11 E T 9095 95% 100 19
15-11 W W W" E f ω "(%) = 100 = η i 100 15-12 W E T 1. 2. 56g L -1 150 g L -1 313 500 m 2 OH ε 0 =0.401V ε 0 =0.763V 0.76V 0.02V 3. 24h 240kg 28 9000 92V12 Zn 2+ H 2 O=Zn 1/2O 2 2H + G =384.380kJ mol -1 4. CuSO 4 1CuCu 2+ +2e 22H 2 OO 2 +4H + +4e 1.00 2h 1.50g11 2 Cu 3 Cu O 2 5. 5577.18cm 2 0.4V 199.14 cm -2 1 85% 190.51g 2 1g 6. 25 0.1molCuCl 2 10m cm -2 20 0.896V 7. Fe 2+ 1mol Zn 2+ 1mol 0.4V H + H 2 Zn 2+ Zn ph? 8. 1 Zn 2+ Fe 2+ 0.40V FeH 2 Zn 25 0 0 ε + = 0.44V 0.763V Fe 2 Fe ε + = Zn 2 Zn 20