Термодинамика элементарных химических реакций

.
.
I,
12
12
.
-
,
.
.
,
:
i
=
0
i
pi -
+ RTlnpi =
0
i
+ RTlnxip =
i–
;
0
i
;
0’
i
+ RTlnxi (12.1)
–
; xi –
–
,
,
0’
i
;
-
–
,
.
,
,
,
-
.
.
G = ni
:
(12.2)
i
.
-
:
G
= n1
,
1
+ n2
2
= n1
1
0’
+ n2
2
0’
(12.3)
,
.
xi
-
,
(12.1) (12.2):
G
= n1
1
+ n2
2
= n1
1
0’
+ n2
2
0’
+ RT(n1 lnx1 +n2lnx2 ) (12.4)
,
:
G
= RT(n1 lnx1 +n2lnx2 )
,
G
(12.5)
,
<0.
,
.
1
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.
.
I,
12
:
G
T
S ....(12.6)
p
G
S
R (n1 ln x1
T
n 2 ln x 2 )....(12.7)
p
–
G
= H
-T S
H
(12.8)
=0
(12.9)
,
.
,
,
.
,
,
-
,
,
.«
,
»,
.
.
,
-
.
,
.
.
dG = -SdT + Vdp
,
(12.5),
V
,
(12.10)
,
G
p
0....(12.11)
T
.
2
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.
.
I,
12
.
)=
)
(12.12)
,
.
.
G = nA
nA ,
+ nB
A
(12.13)
B
; nB .
;
1
A,
B
-
,
,
-
:
nA = 1 -
(12.14)
n =
-
(
(12.15)
)
G= (1 - )
.
+
,
B
:
(12.16)
:
xA
xB
nA
nA
(12.17)
nB
nB
nA
(12.18)
nB
:
=
B
=
0
+ RTlnpA =
0
B
+ RTlnpB =
0
+ RTlnp + RTlnxA =
0
B
+ RTlnp + RTlnxB =
0
+ RTlnp + RTln(1 - )
0
B
+ RTlnp + RTln( )
(12.19)
(12.20)
3
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.
(12.13)
G = (1 - )
((1 - )
0
+( )
0
B )
0
.
I,
12
:
+ (1 - ) RTlnp + RT(1 - ) ln(1 - ) + ( )
0
B
+ ( ) RTlnp + RT( ) ln( ) =
+ RTlnp + RT((1 - ) ln(1 - ) + ( ) ln( ))
(12.21)
.
G
,
(1 - )
12.5).
.
,
,
,
.
,
G
0
A +
0
B
,
(1-
)
.
,
.
,
,
.
-
:
G
0
(12.22)
p ,T
(12.21)
:
4
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.
G = ((1 - )
0
+( )
G
-
0
B )
0
.
+ RTlnp + RT((1 - ) ln(1 - ) + ( ) ln( ))
+
0
B +
I,
12
(12.21)
RT (-ln(1 - ) + (1- ) (1/ (1 - ))(-1)+ ln( )+( ) (1/ )) = 0;
p ,T
0
0
+ RTln(1 - ) =
,
.
+ RTln( )
=
,
.
(12.22)
(12.23)
,
.
(12.22)
:
0
A
x2
x1
K
0
B
RT
e
(12.24)
,
2
.
1
,
-
,
.
.
.
.
.
-
,
,
.
,
,
-
.
.
,
.
-
:
.
pi = pi* xi
(12.25)
,
.
,
,
,
5
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.
,
.
I,
12
.
,
.
,
-
.
,
:
x1
p1
p1
,
p2
......(12.26)
,
.
,
,
.
-
.
,
,
,
,
,
;
.
pi = Kixi
(12.27)
.
.
,
.
.
-
.
,
,
-
i
:
=
(12.28)
i
-
:
i
=
0
i
+ RTlnpi
(12.29)
6
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.
.
,
I,
,
12
i
:
0
i
=
*
i
=
0
i
+ RTlnxi pi* =
+ RT lnpi*
(12.30)
:
+ RT lnpi* + RTlnxi =
0
i
*
i
+ RTlnxi (12.30)
.
(12.28)
-
=
*
i
+ RTlnxi
(12.31)
*
i
,
( =1).
(12.31)
.
.
,
G = ni
(12.32)
i
:
G
= n1
1
+ n2
2
+ n2
2
= n1
1
= n1
*
+ n2
*
2
+ RT(n1 lnx1 +n2lnx2 ) (12.34)
1
2
*
(12.33)
:
G
G
= n1
1
*
+ n2
= RT(n1 lnx1 +n2lnx2 )= RTn( x1 lnx1 +x2 lnx2 )
(12.35)
.
:
S
= - Rn( x1 lnx1 +x2 lnx2 )
(12.36)
,
.
7
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