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. . , . .

"
"

. --
2004

I.


:
,
;

- - (..
).
, ,
() (- ).

(dG < 0, dF < 0). ,
(, "" )
. Y
= f(x)
: dY = 0; d2Y > 0. ,

:
- (P = const, T = const):
G = 0

dG = 0, d2G > 0

- (V = const, T = const):
F = 0

dF = 0, d2F > 0

,
2

,
- .
- .

- . ,
, .. . ,
.
,
; , ..

.
,

. , , ,
,
.

, i,
Pi Xi .

1A1 + 2A2 + ... '1A'1 + '2A'2 + ...
:
KC =

'

'2

C1' 1 C '2
C1 C 2

...

KP =

(1)

...
KX =

'

'2

X 1' 1 X '2
X1 X2

...

'

'2

P1' 1P2'
P1 P2

...

(2)

...

(3)

...


;
.

, Pi = CiRT, i = ni/V,
, P = Pi ,
Pi,
i Xi i- :
P i = C iRT = X iP =

ni
P
ni

(4)

Kc, Kp Kx:
K p = K c (RT ) = K x P

(5)


( = - 1 - 2 - ... + '1 + '2 + ). Kx,
Kc Kp, .

.
,
. V1
, V2 :

'

'2

V1 = k1 C1 1 C 2

V2 = k2 C1' 1 C '2

(6)

(7)


; , ,
. ,
,

..

.
, V1 = V2, :

k1 C1 1 C 2

'

= k2 C1' 1 C '2

'2

(8)

'

'

k 1 C 1' 1 C '2 2 ...


=
= KC
k 2 C 1 C 2 ...
1
2

(9)

..,
. :
,
, 1 /.
, ,
,
,
, . ,

.

. ,
, ,
. , ,
:

G = f(T, P, n1, n2, , nk)

(10)

- :

F = f(T, V, n1, n2, , nk)

(11)

dni i
G
i

n
i

dn . G
i

:
k G
G
G
dG =
dP + i
dni
dT +

n =1 ni
T p, n i
T T, n i
P,T,n

j i

(12)

F :
k F
F
F
dF =
dT +
dV + i
dni

n =1 ni
T V, n i
T T, n i
V,T,n

j i

(13)


i-
i :
G
i

ni P,T,n

i =

F
i

ni V,T,n

i =

(14)
j i

(15)
j i

, i-

().
" " ,
.
.
, (12 - 13) :
k

dG = SdT + VdP +

idni

dF = SdT PdV +

idni

(16)

n =1
k

(17)

n =1

( )
(16) (17) . :
k

dG = 1dn1 + 2dn2 + ... + kdnk =

idni
n =1

(20)

dF = 1dn1 + 2dn2 + ... + kdnk =

idni
n =1

(21)


(dG = 0, dF = 0), :

idni = 0

(22)


.
:
1A1 + 2A2 + ... '1A'1 + '2A'2 + ...

,
("-" , "+" ); ..,
:

dn1

dn 2

= ... =

dn' 1 dn' 2
=
= ... = d
'1
' 2

(23)

.. ,
. dni = id, G
:

dG = SdT + VdP 11d 22d + ... + '1'1d + '2'2d + ...

(24)

:
G

P ,T

ii

(25)

,
G

= 0

P ,T

ii

= 0

(26)

(26) -.

.
, dF = SdT PdV

dF = PdV. :
dF = RT

dV
V

F = RT lnV + g(T)

(27)

g(T) ,
1
.
=
V
( ), :

F = RT lnC + g(T)

(28)

, = F. :

= RT lnC + g(T)

(29)

i = RT lnCi + gi(T)

(30)

(i = 1 /) gi(T) = oi (
).

i = i + RT lnCi

(31)

i = i + RTlnPi

(32)


(26), :

ii = ii + RT i lnPi = 0

(33)

, - ,

ii = ii + RT i lnCi = 0
(33) - (34) Pi Ci

(34)

. ii = const, :

i lnCi =

i i
= const
RT

(35)

i lnPi =

i i
= const
RT

(36)


1A1 + 2A2 + ... '1A'1 + '2A'2 + ...
(35) (36)
'1

'
' 2

'

ln C1 C2
C1

C2

'1

'
' 2

'

ln P1 P2
P1

P2

...

...

...
...

= const = ln K C

(37)

= const = ln K P

(38)

, ,
,
, ,
.

( -)

(G < 0, F < 0). ..,
:
F

=

V ,T

ii

= RT

i ln Ci + i i 0

(39)

=

P ,T

ii

= RT

i ln Pi + i i 0

(40)

, ,
i i
,

V ,T

V ,T

= 1,
F = RT

i ln Ci + i i

(41)

, (35,37), i o i = RT ln K C ,
, ( -):
F = RT

i ln Ci RT ln K C

A max = RT ln K C RT

i ln Ci

(42)
(43)

- :
G = RT

i ln Pi RT ln K P

A ' max = RT ln K P RT

i lnPi

(44)
(45)

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