. dS ≥ 0. , , .
dS = 0 , . .
(102) :
dF ≤ dV S dT. (159)
- ( V = const = const) (159)
dF ≤ 0. (160)
(160) , - , .
. ,
dF =0. (161)
- - . (110),
dG ≤ V dp S dT. (162)
- p = const T = const)
dG ≤ 0. (163)
, (- ) - , .
4
dQ = O | dS > 0 | S = max; |
(U = const, | dS = 0 | |
V = const) | ||
- | ||
- | ||
( = const, | dF<0 | F = min: |
V = const) | dF = 0 | |
- | ||
- | ||
( = const, | dG<0 | G = min: |
= const) | dG= 0 |
( ) .
dG = 0. (164)
, , , , , , , (, ) F ( V = const = const) G ( = const
|
|
= const), , , - - , .
(160) (163) , (74), .
. 4 .
, , , . , , (130)
dU ≤ Tds p dV + . (165)
S = const V = const
dU ≤ (166)
, , U ,
dU < 0 < 0,
. . .
= 0 (167)
.
, , (, , , ). . . , , , , , . . , f - , λ.
, , .
.
, , .
, , , . .
= .
, q:
= q.
( , ). , 2, 2 2, , . , , . , () NaCl 2. , . , i-o dni .
|
|
dG' = μi' dni',
dG" = μi" dni",
dG = dG' + dG" = μi' dni' + μi" dni".
, dni' dni" , , :
dG = (μi' - μi") dni. (168)
dni , dG = 0. (μi' - μi") dni = 0. , dni ≠ 0 μ'i = μ"i. , , , . , , , ( = const = const).
, (, , ), = const = const . dn G"dn G"dn.
dG = (G' G") dn
, ,
G' > G",
. . , . , , . .
G1' = G1",
:
dG = 0 (169)
(169) .
, , , .
, , . , .
, . , 2 . , , , ( 1) .
, , (ʗ1) + 2. . : . , :
(170)
, . , , ԗ1,
(ԗ1).
, , , ( ), . . μ .
|
|
(170) , , (ԗ1). , , , , . f :
f (ʗ1) + 2 (ԗ1).
f = ʗ + 2, (171)
(171) : , , .
f , f ≥ 0 ( ), (171)
≤ + 2. (172)
f = 0, ; f = 1 ; f =2 . .
10
, , .
, . μp (G/p)T = V (. 25). . 25 , μi' = f () μi" = f () = const , μ μ , . , . , , μ, , , , .
> ( ) ( ). < . , , .
. 25. = const
, , . μi' = f () μi" = f (), μiT μi = (dG/dT)p = S (. 26) . . μ, , . , μ, , , , μ, .
= const = const , , . - . : , , , .
|
|
, , ( ), , . , , .
-, V- җs- .
- , , , -
. (. 27). I () , II () , III () . , . . , . . . . =610,6 , = = 273,16 .
, V-, , ( -), , , . . 28 Vμ -. I , II , III . IV . , , , , , . V , VI .
, .
IV . . ,
( = 1). , , .
. ( = 1). , ,, . . , . , , . (, , Vμ). T .
: = = 221,29105 , T =647,3 , Vμ=0,05768 3/. . 29 , җs-. , , , vμ - (. . 28).