, .
|| | || :
- ;
- ;
- ;
- .
(U, ) , , ( ).
| (V = const|)
∆ U = QV
∆U - || ;
QV - , ( ) .
(∆, ) - , (∆V) .
( = const|)
∆ = - Q = - (∆U + ∆V)
∆ || ;
Q , ( ) .
∆ , || .
∆.. (..), .
, (∆ > 0).
, (∆ < 0).
1 , (∆., / ).
, 1,01 105 , , 298 (∆0298).
1 , (∆., / ).
, . ∆. = - ∆ .
(2, 2, Fe, S) .
1 ( ) (∆ ., / ).
- , 1 (∆., / ).
+ 2() → +42(), ∆ .
, , (∆0298, ).
(.. , 1840.). () .
|
|
|
. .
∆0.. = ∑ ∆0 - ∑∆0
, || :
()+ 2()= ()+ 3(), ∆0..
,
,
||
.
(∆0..) .
∆0.. = (∆0(). + 3 ∆0().) (∆0(). +2 ∆0().)
∆0.. . , . , ∆0..< 0.
,
(∆0..> 0), .
(S, / ) .
S = R ∙ ln ω ∕ NA, ∕
S
R
N
ω || ||, || || .
ω, :
) || ;
) || || , || ;
) .
||.
, , (S0298 (), ) . , ∆0.
(S ≠ 0).
|| | :
∆S0.. = ∑ S0 - ∑ S0
|| || ||. , || , ∆S > 0.
| || , || .
(G, ) , , .
(G), (), , || || (∆G).
|
|
|
∆G0. (∆G0. ).
|| , || , :
∆G0.. = ∑ ∆G0 - ∑∆G0
, , :
G = H T S (1)
∆G = ∆H T ∆S (2)
,| || ∆ < 0 ∆S > 0, || (2) || : ∆G < 0.
, , .
, , .
( ) :
υ. = ∆ ∕ ∆τ; ∕ ∙ (, )
υ ;
;
τ - .
, . : , .
- , () . : , , .
( ) :
υ. = ∆n ∕ ∆τ ∙ S; ∕ ∙ 2
υ -
n | | |
τ
S , || .
, ||
.
, , , ||, .
2K + 2 H2O = 2KOH + H2, υ1 -
Mg + 2H2O = Mg(OH)2 + H2 , υ2
Cu + H2O υ3
υ1 > υ2; υ2 > υ3 ; υ3 = 0
|| , , |.
, ., - , , . , , .
() + 2() = 2(), ∆G 0298 <0
|| |. || | . (, ) γ ().
|| || .
, .
, .
+ > , .1
+ > , .2 -
+ > + , .3 -
;
|
|
|
.2 < .1; .3 <
( ) || , || .
100 (10) 2 4
υt2 / υt1 = γ t 2 - t 1 ∕ 10
υt2, υt1 - t1 t2 .
γ - - , 100 (10).
( ) , .
() + () = () + dD()
υ.. = [ ] ∙ [ ], ∕
υ.. -
. [ ] = [ ] = 1 / υ.. =
[ ], [ ]
, | , .
|| , || ||.
() + () = () + dD()
υ.. = [ ]
|| || , || | .
(↔) , (→), (←) .
| + | ↔ | + dD|
-
[ ].., [ ]. [ ].. = [ D ]. = 0
- [ ]., [ ]., [ ]., [ D ].
→ ← → ←
υ = υ [ ] ∙ [ ] = [ ] ∙ [ D ]d
→
[ ] ∙ [ D ]d
--- = = ----------------
[ ] ∙ [ ]
- + ↔ + dD
. ., .
|| , || || .
. , (, , , ).
(1884)
, || , ||, , || || .
, . .
|
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