. , . , , : - ( ) - ( ).
, , , . (Δ = 0) ΔS, , , (S = 0 S = const) Δ, , , . :
, ; , .
, - - - - (.. ). , , (-) (- ).
, . , Amax ( , , ), (I.53, I.54):
(I.68)
(I.69)
(I.69), :
(I.70)
:
(I.71)
:
(I.72) (I.73)
- ( ), , - .
, - , - G:
|
ΔF = Amax, :
(I.76)
'max ( ). , .
|
|
:
- (P = const, T = const):
ΔG < 0, dG < 0
- (V = const, T = const):
ΔF < 0, dF < 0
, , . - , ( ) . ΔG , ΔH ΔS , (I.75), ΔG; ΔG ΔͰ (I.77):
(I.77)
- ΔG298 . (I.75), ΔG , Δ ΔS.
1. ; ΔH < 0.
) ΔS > 0, ΔG ; , , .
) ΔS < 0, Δ > TΔS ( ).
2. ; ΔH > 0.
) ΔS > 0, Δ < TΔS ( ).
) ΔS < 0, ΔG ; , , .
, (dG < 0, dF < 0). , (, "" ) . Y = f(x) : dY = 0; d2Y > 0. , :
- (P = const, T = const):
ΔG = 0 dG = 0, d2G > 0
- (V = const, T = const):
ΔF = 0 dF = 0, d2F > 0
:
, , - .
. . , , .. . , . , ; , .. . ; . , . , , , , .
|
|
, , P X .
:
(I.78) (I.79) (I.80)
; . .
, . V1 , V2 :
(I.81)
(I.82)
; , , . , , , .. .
, V1 = V2, :
(I.83)
(I.84)
.., . : , , 1 /.
( ) . . , (T, P V), , . , (.. ), . dni i- ; . , , μi :
(I.85) (I.86)
:
(I.87) (I.88)
μ i (Pi = 1 ., i = 1 /.). , :
|
|
(I.89) (I.90)
(dG = 0, dF = 0), :
(I.91)
; .., :
(I.92)
:
(I.93)
:
(I.94)
(I.94) . , :
(I.95)
Σn i μ i = ΔF, Σn i μ i = ΔF, :
(I.96)
- :
(I.97)
I.96 I.97 . , ; :
(I.98) (I.99)
i i ( i i I.96 I.97).
ΔF ΔG , (), , ( ) , . (I.98, I.99) . () , . ΔG (ΔF) . ΔG (ΔF) (Pi = 1 ., i = 1 /) . ΔG (ΔF) , .. , i ( i) :
(I.100)
(I.101)
, .