, . . , , , , , . , , , : , , . .
,
ν+ ν , ; ν+ + ν = ν , .
:
, (. III. M. ., , 1965), , , ( 1 ). (/3 ), , .
γ a , , , γ + = γ a+ = , , . .
γ = γ+ = γ a = a+ = a
, :
, ,
a+ = m+γ+; a = mγ
m+ = ν+m m = νm ( m ),
p , , . . 3.1 .
3.1.
ν+ | ν | ν | a = pmγ | |||
11; 2-2; 3 3 | 1, ZnSO4, La[Fe(CN)8] | (11∙11)1/2 = 1 | mγ | |||
2 1 | 12 | (11∙22)1/3 = 1,59 | 1,59mγ | |||
1 2 | Na2SO4 | (22∙11)1/3 = 1,59 | 1,59mγ | |||
3 1 | LaCl3 | (11∙33)1/4 = 2,28 | 2,28mγ | |||
1 3 | K3[Fe(CN)6] | (33∙11)1/4 = 2,28 | 2,28mγ | |||
4 1 | Th(NO3)4 | (11∙44)1/5 = 3,04 | 3,04mγ | |||
1 4 | K4 [Fe(CN)6] | (44∙11)1/5 = 3,04 | 3,04mγ | |||
3 2 | A12(SO4)3 | (22∙33)1/5 = 2,55 | 2,55mγ | |||
2 3 | Cu3(PO4)2 | (33∙22)1/5 = 2,55 | 2,55mγ |
|
|
,
a = f N
f ; N , (ni) (np) , . .
N = ni / (ni + np)
, f → 1, .
f γ . - μ =μ0 + + RT ln a :
μ = μ0 + RT ln mγ; μ = μ0 + RT ln N f
- μ0 μ0 .
( ∞), , :
;
m 1000 ,
p . , 1000 >> m∞Mp
, m → 0; f → γ, . . . , .
( , ) .
μ i = μ0 i + RT ln C
μ μ i = RT ln C RT ln γC = RT ln γ
, - .
. , , , . . , - . ,
μ i = μ0 i + RT ln (ai / a0i)
, . , - , (0i = 1). . , , , .
|
|
, , , . , , , , CuSO4∙5H2O . , , , .
, , - . , . , . . . , . , . . → 0. () γ → 1. a → C.
. , , , = 1 γ = 1. = , , .
, , . , , :
N1 d ln a 1 + N2 d ln a 2 ++ N id ln ai = 0
:
= const = const,
dG = 0 dni = 0, . ∑ nid μ i = 0. μ i = μ0 i + RT ln ai ,
n 1 d ln a 1 + n 2 d ln a 2 ++ nid ln ai = 0
∑ n. n / ∑n N .
:
/, :
a 01 = a 02 ( 2 ) (a 1).
. , = 298 = = 1,013∙105 , 1 760 . .
, ( ) . . , , (. III), , , .
. 3.1. , . ,
|
|
. 3.1. m ( 25 ).
. 3.2. ( 25 ).
. , γ , 12 .
. . , 20 1 γ= 485. , , .
, , , .
, (. 3.2). .
(. 3.3). γ , . γ . , , , , .
.
. . 3.4, , , . , , , . . , . , , , .
, . . , , , , . , , . 3.4, m = 1,25 /, = 2,0 / = 4,6 /.
|
|
. 3.3. ( 25 ):
1 NaI ; 2 NaI ; 3 NaI ; 4 l .
. 3.4. ( 25 ).
. 3.5. ( 25 ).
. , (. 3.5).
, . , , .
, . - . - , , , . , , , .
. , , , . 1923 . . , , , .