- (ΔG), (Δ) (ΔS)
ΔG = ΔH T ΔS
TΔS . , . , . , . . ,
-. Δ, , , . . zFE. :
ΔG = ΔA = zFE
:
, .
,
, ,
= const,
:
Δ , zF , . . .
, , , .
ΔGV = ΔHV TΔS ΔS = (∂ ΔG/∂T)V
, , , . (dE/dT)P = 0,
E = ΔH/zF
. . .
(dE/dT)P < 0 , , , . ( ), .
(dE/dT)P > 0, , , . , , .
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(. 6.4).
6.4.
. | ||
1. 2. 3. 4. 5. | () Zn | ZnCl2 (aq), AgCl (.) | Ag (+) 0,535 /3 () Pb | (CH3COO)2Pb (aq) || || (CH3COO)2Cu (aq) | Cu (+) () Hg | HgO, KOH || KCl, Hg2Cl2 | Hg (+) 0,01 /3 0,01 /3 () Pb | PbBr2 () | Br2 (C) (+) () Ag | AgCl () | Cl2 (C) (+) | Zn + 2AgCl (.) = = ZnCl2 + 2Ag Pb + (CH3COO)2Cu = = (CH3COO)2Pb + Cu Hg2Cl2 + 2KOH = = Hg2O + H2O + 2KCl Pb + Br2 = PbBr2 Ag + ½ Cl2 = AgCl |
1 , ( ), 218,0 /. , , , Δ. , . 90% , 10% . 4, 5. , 73 82% .
2 . , , ( 33%), . , , .
, 3 , . , , .
, . 6.4, , (298,15 25). :
, | z | E, B | , / | ΔG, | , | Δ, / | |
- - | --- | ||||||
1,015 0,476 0,164 1,100 0,913 | 4,02∙104 3,85∙104 0,84∙103 0,67∙103 0,29∙103 | 196,0 92,0 31,6 212,6 88,1 | 21,0 21,8 46,7 79,0 20,4 | 217,0 70,2 15,1 291,6 108,5 | 218,0 69,1 15,7 289,1 106,8 |
Ű, ΔͰ, Ұ, dE/dT , .
- , , Δ dE/dT . , , ,
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, , . .
:
,
, (∂2/∂∂2) =0
.
, , , . . Δ = 0. .
, , (), .
,
= 0 + k ( 0)
k .
, . (Δ) :
- (Δ. ), . .
Δ , . :
= º + + bT2 + cT3 +
Δ
Δ = Δº + Δ + ΔbT2 + ΔcT3 +
Δ T0 , :
, Δ, .
,
,
Δ , :
ΔST zF, T. , T , .
, , , . ()
(∂ΔG/∂P)T = V
V .
ΔGV = zFE,
(∂ΔGV/∂P)T = zF(∂E/∂P)T
(∂E/∂P)T = V/zF
dE = V dP/zF
:
,
P , , .
, , .
.
|
|
,
Sn () | SnSO4 | Sn ()
ΔH . , , ΔG = 0 , , = 0,
ΔH = zFT(dE/dT)P
. . .
() | | ()
( ),
b (.) | b12 | Pb (.)
. , , , , . , ΔG = 0 , , . , .
, . U , ΔH = 0
E=T(dE/dT)P
, .
dE/E = dT/T
d ln E = dlnT
ln E = ln + const E = kT
, , .
(∂U/∂V)P ≠ 0 ΔH . ,
() | || | (+)
a1 2
ΔH 2 1, . . (2 > a1).
. , 1, a2, , :
() (Pt) H2 | HCl, AgCl (.) | Ag Ag | AgCl (.), 1 | H2 (Pt) (+)
a1 a2
Ep = E1 E2 , ,
, 2 1.