前回の問題の解説 - apchem2.kanagawa-u.ac.jp

1 E3. Ag AgCl(s), M HCl KCl , Hg2Cl2 Hg E1 = E0 +RT/(nF) log [Ag+][Cl-] E4 = E0 +RT/(nF) log [Hg2+][Cl-]2. E2. V. H+ .. Hg/Hg2Cl2. SiOH SiO H .. H+. 11 . ~ ~. 2010-12-6. K = [Ag+][Cl-]/[AgCl( )]. [Ag+][Cl-] = K[AgCl( )] = Ksp Ksp : . AgCl BaSO4 .. - - +. +. +. - - . + + + . + - + - + - +- +. -+ - -+ - +. AgCl ( ) Ag+ + Cl- . 5-1. Ag2SO4 x 10-2 mol/L . Ag2SO4 . Ag2SO4 . Ag2SO4 2Ag+ + SO42- x 10-2 mol Ag2SO4 x 10-2 mol Ag+ x 10-2 mol SO42- .. Ksp = [Ag+]2[SO42-] = ( x 10-2)2 x ( x 10-2). = x 10-5 (mol/L)3. 5-2. Ksp= x 10-5. (mol/L)2 100 g .. CaCO3 Ca2+ + CO32- . [Ca2+][CO32-] = x 10-5 (mol/L)2.. [Ca2+] = [CO32-] = ( x 10-5). = x 10-3 (mol/L). 5-3. Fe2+, Pb2+, Cu2+, Zn2+ mol/L .. S2- x 10-22 mol/L.

2 (mol/L)2 FeS: x 10-18, PbS: x 10-28, CuS: x 10-30, ZnS: x 10-18 . mol/L [S2-] . mol/L x x 10-22 mol/L = x 10-23 (mol/L)2.. FeS: x 10-18 > x 10-23 . PbS: x 10-28 < x 10-23 . CuS: x 10-30 < x 10-23 . ZnS: x 10-18 > x 10-23 .. I-5 . I-6 . II-2 .. II-2 .. 1.. 7.. [ ]. Cu2+ .. [ ]. Mn+ . Mn+ ( ) + ne- M ( ).. M. Mn+ ne- Mn+ ne- M Mn+ (a) .. E = E 0 + RT/(nF) ln a(Mn+) (E 0 : (1). C . a= yC (2). (1) . E = E0 + RT/(nF) ln y + RT/(nF) ln C (Mn+) (3). E1 = E0 + RT/(nF) ln y1 + RT/(nF) ln C1 (Mn+) (4). E2 = E0 + RT/(nF) ln y2 + RT/(nF) ln C2 (Mn+) (5). E2-E1 = E0+RT/(nF) ln(y2/y1)+RT/(nF) ln(C2(Mn+)/C1(Mn+)) (6). mol/L (6).. a ( ) = m .. 1.. a+, a- . a . a = a+a- = a 2. B +A - v+B+ + v-A- . a = a+ +a- - = a ( + + -).)

3 R = a /m = a /m( + + - - )1/ = + + - ( ). I = 1/2 (mizi ). 2. mi i zi .. Debye-Huckel . Log = z+z- I. mol/L .. M.. Mn+ ne- Mn+ ne- V.. M N.. Mn+ ne- Nn+ ne- Mn+ ne- Nn+ ne- . V.. M Pt .. Mn+ ne- H+ e- Mn+ ne- 2H + + 2e- H. H+ e- 2. 0 V. 1M H+. atm H2.. (1) . AgCl + e- Ag + Cl- E = E 0 + RT/(nF) ln ([AgCl]/([Ag][Cl-])). = E 0 RT/(nF) ln[Cl-]. KCl . + (vs. 25 ) . / .. + 0 - . (2) . 1/2Hg2Cl2 + e- Hg + Cl- E = E 0 + RT/(nF) ln ([Hg2Cl2]/([Hg]2[Cl-]2)). = E 0 RT/(nF) ln[Cl-]. + (vs.. 25 ) .. Hg . Hg2Cl2. + 0 - . ( . b a X r . 2. X = r b a 1 .. R = x (l/A) . : ( . :A. l : ( = 1/ . = //(RA) = / 4 . K .. b a X r ?? V1 V3 . 2.. V1 = V2 V3 = V4. 1 . V2 V4.. i1 = i3. i3. i1. i2 i4. i2 = i4. V1 = i1 x b i1 = i3.)))

4 V2 = i2 x a i3. i1. V3 = i3 x X. V4 = i4 x r V1 V3. V4. V2. i2 i4. i2 = i4. V = I R .. V1 = V2 i1 = i3 V1 = i1 x b V3 = V4 i2 = i4 V2 = i2 x a V3 = i3 x X. V4 = i4 x r X = r b a . I x r1 = Es R. I x r2 = Ex .. Ex = Es x r2 / r1.. 1. S P1 . 2. S . 1. (X) . X = r (b/a).