, , , , . 'm Am .
. , :
TdS = dU + δAmax = dU + pdV + δAmax. (114)
S V, (114)
-dU = δA'max
-ΔU= 'm, (115)
. . S V const δAm = δAmax, , .
S , (114)
(dU + pdV) = δAmax d (U + pV) = δA'max.
(U + pV) H,
-ΔH= 'max p (116)
. . S = const = const . , .
V .
TdS =dU + δmax,
-(dU - TdS)= ;
-d(U-TS)= .
(UTS) E
-ΔF = , (117)
,
- .
,
(dU + pdV T dS) =
-d(U + pV-TS) = .
(U + pV) H, (H TS) G,
dG =
-ΔH = , (118)
, - .
(102) (110) , 1
Vμ
pVμ = RT , , , :
(119) (120) , , . . ΔF = ΔG.
7.
(101) (109) 5 F G ,
|
|
(121)
(122)
(121), (122), V = const = const, .
ΔF ΔG , Qv ΔH Qp , :
. 3 .
3
V, S | U | ||||
p,S | H = U + pV | ||||
, V | (- ) F = U TS | ||||
p, | (-- ) G = H TS |
, . . ( ), , .
f , . , U =f (S, V, nl, n2,..., nk) G = f (p, , n1, n2,..., nk). , - dn1 -
.
dG, (110)
(125)
, (125), (1875 .) . , .
, (nt) , = const.
μh , i-
(126)
μ1dn1 + μ2dn2 + μkdnk
, (125)
() = const = const
(129)
(88), (95), (102) , , .
|
|
, V = const, 5 = const nl, n2,..., nk = const
(130)
= const, 5 = const, n2, n3,..., nk = const
(131)
V = const, T = const n2, n3,..., nk = const
(132)
, μi , , , . .
(133)
, (133) , (G, F, U, ) ( ) , . . ( ). :
(134)
Gi . , , (114) (125):
dU = TdS pdV - δA'max;
t=i
δA'max, , , (9). , , , δL == pdV, , ,
δQ = TdS, δA = Ede.
, , , , V, S .
(114). (125)
μi , ni , .
( ) , . , , . .
( ) , . ( ) .
t-ro , μi = f (p, T, n1 n2,..., nk).
, , const = const, , 1 , , . .
μi = Gi0 = const. (135)
(136)
,
(137)
(137) dG (110).
(138)
. = const
(139)