. , , , , . , .
, , , , . . ∆H ≈ 0 ∆V ≈ 0. , .
, . , . , . . (∆ = 0) (∆V = 0) . (∆S > 0). ; . , , , . , ∆H ≈ 0 ∆V ≈ 0. , , .
1. .
, .
, (. 7). : . (∆G = 0). - .
. 7.
, - * ( ). - , 1 ; - . , , . . . . , , p1 , p1.
|
|
, , . . p1 X1:
p1 = K X1.
. , X1 = 1, . . , p1= p1, . . = p1.
, :
p1 = p1 X1
. . ( , 1887 .).
.
X1 = 1 X2 ( X2 - ),
p1 = p1(1 - X2) = p1 - p1 X2 p1 - p1= p1 X2
p1,
(p1 - p1)/ p1 = X2
, ( , ).
, ,
pi = pi Xi,
pi ; Xi i- ; pi i- .
, - . . 1 2,
p1 = p1 X1, p2 = p2 X2. (1')
( ):
p = p1+ p2= p1.X1 + p2 X2
, ,
p = p2.+ (p1 - p2)X1
1 2 . 8.
. 8. pi i , .
, , 2 X2. 1 X1 = 1 X2. : X1 = 1, X2 = 1. p1 p2 . . () . , .
, , ; .
|
|
, . , . . . , , . . 9 , (. 9) (. 9) . , (-, -, -) , (-, -...).
, . , . , , , (∆H < 0).
) )
9. : ) ; ) ; n
. 9 , , - ( ), .. ( 0.01).
2.
.
, , . , (, 101 100, 80).
- . , . , .
. 10, , : mo= 0 < m1 < m2 T, o < T, 1 < T, 2 , ,
ΔT = T, i.- T, o > 0
, ( , ) (. 10). - ( ). . , , .
. 10. (mo) (m1 m2)
|
|
, , . . ( A0B . 10) ( A0 , A1 A2 m1 m2 ). . 10, .
, . m (/1 ):
ΔT = Em
ΔT = ʷm
. E = ∆ K = ∆T m = 1 /, m = 1 ( 342 1 !), . , , 1 / 2O. , .
, . ,
= RT2 /1000 λ; K = RT2 /1000 λ,
T T λ λ . . 5.
5.
() ()
E | K | E | K | ||
0,516 | 1,86 | 3,1 | 3,9 | ||
2,57 | 5,12 | 5,27 | 6,9 | ||
5.30 | 29.80 |
∆ ∆ , (6,0221023), . , ( ).
: .
3.
, (. 11) . , , ( )*. . , : = 1, < 1. . ( ) , ( ).
|
|
. 11. ,
:
1 ;
2 ;
3 ;
4
, , , .
1887 . , :
) (/).
) -
.. - - -, . , , , :
πc = RT πcV = nRT,
, R ( n V).
-: , , , , , .
, .
. .
. . ( ), .
, , . . .
, -, , , , .
. . ( ) ∆T. , ∆.
. - , .
πc = gRT / M + A g2 πc/g = RT / M + A g,
g ( ). (A g2) .
πc/g . (. 12).
πc/g , , RT/M, .
. 12. πc / g = RT / M + A g