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339
1. .
, ,
, .
,
, ,
, .
.
,
, ()
. .
,
,
.
.
, ,
.
.
( )
, .
,
.
,
+
1.
2.
3.
4.
5.
6.
7.
8.
.., .. . .: , 2001.
/ . . .. .: , 2001.
.. . .: , 2002.
.., .. . .: . , 1993.
. . .: , 1980.
., . . .: , 1978.
., . . , 1976.
.., .., .., .., ..
. .: , 2003.
9. .., .., ..
. .: , 1976.
H 2 O NaCl , Na Cl
.
,
, .
,
.
K .
,
,
.
, .
,
.
, H 2 I 2 ,
H 2 + I 2 = 2 HI HI
.
Kp =
2
pHI
,
pH p I
, K = 3 1 = 2 .
HI ,
2HI = H 2 + I 2 .
... .
3. .
338
33
).
m2
m1 m2
V2
m m2 V1
= 1
m2
m2 V2
V1
n
c ( 2)
K = 2(1) =
c2
V1
V1
m2 = m1
= m0
V1 + KV2
V1 + KV2
V1
mn = m0
+
V
KV
1
2
(
), 2HI = H 2 + I 2
2
, nV2 ,
,
m = m0
V1
V1 + KnV2
, V1 = V2 K = 9 n = 1
m
= 270 . ,
mn
m
mn
m
= 1 , n = 4
mn
, n -
,
. ,
.
.
, ,
,
.
.
,
, .
.
H 2 I 2 .
K = 3 2 = 1 .
.
,
.
[418]
, :
, , .
.
,
.
C .
() C = 0 , ()
C = 1 , ( ) C = 2 , C = 3
..
2. .
,
d G p ,T = 0
,
,
i d ni = 0
i
p T ( ) ( ) dni
i - , , i -
:
i d ni = i( ) d ni( ) + i( ) d ni( ) = 0
i
i - ( ) ,
( ) ,
d ni( ) = d ni( )
i( ) d ni( ) = i( ) d ni( )
i( ) = i( )
p T
.
... .
3. .
34
337
( p T )
:
i( ) + d i( ) = i( ) + d i( )
( )
d i( ) = d i( )
,
.
( p T )
,
i - ( ) ( )
i( )
d i( )
>
>
( )
, ( ,
) ,
.
( 2) (1) (2) :
a2
( 2)
a2
( 2)
0 (1)
= i( )
f i () ,
i( ) = i( , ) ,
i( ) = i( , )
K =
i( , ) = i( , )
i =
i*
+ RT ln f i ,
i* + RT ln f i ( ) = i* + RT ln f i ( )
f i ( ) = f i ( )
,
f i
pi
() .
i -
,
( ) ( ) :
... .
( 2)
a2( 2) 2( 2) c2( 2)
= (1) (1) = K 2(1) ,
(1)
2 c2
2
a2
c2( 2)
c2(1)
.
K K .
(),
.
,
.
m0 ( 2)
, m1 , .
pi( ) = pi( )
f i ( ) > f i ( )
20(1) 20( 2)
a2( 2)
=
,
exp
K
RT
a2(1)
K =
i( ) = i( , )
a2( 2)
1
=
20(1) 20( 2)
a2(1) RT
: ,
,
,
.
i( ) = i( , ) .
i( ) = i( )
0 ( 2)
(1) (2), 2
2
.
i( )
d i( )
( ) ( ) : i
29. .
c ( 2)
K = 2(1) =
c2
m0 m1
m m1 V1
V2
= 0
m1
m1 V2
V1
m1 = m0
V1
V1 + KV2
V1 () , V2
( ,
3. .
336
35
1 ( x1 , ) =
1*
3. .
*
, d 1 = 0
d x1 + 1 d = 0
x1 ,T
x1 ,T
G
= V )
( d G = S d T + V d p ,
p T
V1
1
= V1
x1 ,T
d x1 + V1 d = 0
x1 ,T
d
1
= 1
d x1
V1 x1 ,T
d 1 = RT d ln x1 , p1 = p10 x1
( ), V1 V1 ,
RT
d = 0 d ln x1
V1
0 1 x1
RT
= 0 ln x1
V1
RT p1 RT p10
ln
=
ln
p1
V10 p10 V10
x2 << 1 ( ,
x2
x3
ln x1 = ln(1 x2 ) = x2 2 2 L x2 ,
2 23
0
( V = 1V1 ) -
RT
RT 2
RT 2
= RT 2 = RTc 2
= 0 x2 = 0
V
V1
V1 1 + 2 V10 1
c2 = 2 .
V
-
, .
,
.
.
( )
,
, .
... .
,
.
, K
.
, ,
p , T .
, , ( p T ).
, K ,
(K 1) .
(K 1) .
,
(K 1) + 2 .
, K
1(1) = 1( 2) = 1(3) = L = 1( ) , .. ( 1)
2(1) = 2( 2) = 2(3) = L = 2( ) , .. ( 1)
.................................................
K(1) = K( 2) = K(3) = L = K( ) , .. ( 1)
K( 1) .
,
()
C = (K 1) + 2 K( 1) = K + 2
: ,
,
:
C=K+2
.
, :
.
C = 0 ( )
= K + 2.
K + 2.
(,
),
C = K +1
, p T
(,
,
,
3. .
36
335
), .. n
,
C=K+n
C =1 + 2 = 3
..
.
.
,
.
,
,
.
,
,
.
.
,
G
G
V =
T p
p T
S =
G (T )
. G (T )
.
,
: C p ,
,
1 2G
=
V Tp
1 2G
= 2
T p T
G (T ) C Cp 6H6 (T ) .
... .
H 1
H T
1
=
R T ,1 T
R T T ,1
, ,
K+n
4. .
2G
C p = T 2
T p
ln x1 =
S KCl (T )
x2 << 1,
mM 1
T T,1 , ln x1 x2 , x2
1000
RT2
RT2 M 1
T =
x2
m = K m
H
H 1000
K =
RT2 M 1
H 1000
( 1
).
.
,
, .
g1 g 2
T
M2:
M 2 = K
1000 g 2
T g1
,
1 .
,
T
T
m 0 :
m
m
K = lim
m0
T
,
m
K = lim
m0
T
.
m
28. .
, ,
,
.
,
,
, .
, .
,
,
1
*
1 :
3. .
334
37
g1 g 2
M2.
g1
g
g M
, 2 = 2 , x2 2 = 2 1 ;
1 g1 M 2
M1
M2
T 1000 g 2 M 1
x 1000
=
m= 2
K
M 1 g1M 2
M1
1 =
T = K m
M 2 = K
m=
T
K
1000 g 2
T g1
, ..
.
,
: .
, ,
.
5. -.
27. .
T
T T,1 .
.
( )
T = T T,1
(
)
= * + RT ln x1
*
, x1
.
+ RT ln x1
= RT ln x1
.
G
G = H + T
T p
ln x1
( RT ln x1 ) = H RT ln x1 RT 2
RT ln x1 = H + T
T
p
T p
H
ln x1
=
RT 2
T p
H .
, H = const ,
x1
ln x
1 T d x =
T ,1
H
dT
RT 2
... .
d ( 2) = S ( 2) d T + V ( 2) d p
(1)
( 2)
(1)
( 2)
S , S ,V ,V
.
d
(1)
= d ( 2 )
S (1) d T + V (1) d p = S ( 2 ) d T + V ( 2 ) d p
S ( 2) d T S (1) d T = V ( 2 ) d p V (1) d p
( S ( 2 ) S (1) ) d T = (V ( 2) V (1) ) d p
S .. d p
=
V.. d T
,
.
S .. =
H ..
T
, H ..
, T .
-
d p H ..
=
dT
TV
dT
TV
=
d p H ..
6. .
- ( )
d T T (V V )
=
dp
H .
( H . > 0) ,
.
3. .
38
(1)
(2)
333
T
(1)
p
(2)
p
(1)
(2)
T
7. .
-
d T T (V V )
=
dp
H
H , .
ln x1
RT ln x1 = H + T
( RT ln x1 ) = H + RT ln x1 + RT 2
T
p
T p
H
ln x1
T
RT 2
p
H .
, H = const ,
H
ln x
1 T d x = T RT2 d T
H 1
H T
1
=
ln x1 =
R T,1 T
R T T,1
x2 << 1 ( ) T T ,1 ,
V >> V .
(, 273 V =22400 3, V =18 3.)
V = V V V .
RT
d p 1 H
dT
RT 2
=
=
V =
,
p
dT p
d p pH
RT 2
d ln p H
=
dT
RT 2
d ln p
,
> 0 , ..
dT
.
,
H = const .
H d T
R T2
ln p 1 T
H 1
ln p = C
R T
C .
d ln p =
ln x1 = ln(1 x2 ) = x2
... .
x22
x3
2 L x2
2 23
H T
H T
=
R T T,1
R T 2
T =
RT2
x2
H
m+
1000 1000
( m
M1
M1
1000
, M 1 )
x2 =
T =
H
(): tg =
.
R
H 1
H 1
ln p1 = C
ln p2 = C
.
R T1
R T2
T ,1
x1
K =
mM 1
m
.
1000 1000
m+
M1
RT2 M 1
m = K m
H 1000
RT2 M 1
H 1000
( 1
).
.
,
, .
3. .
332
39
,
.
:
,
,
,
.
,
( ,
)
p10 p1
= x2
p10
, p 2 << p1
p10 x1 .
p = p1 =
p p10 p
=
= x2
p10
p10
,
.
26. .
T,1 T .
T = T,1 T
( )
(
)
= * + RT ln x1
*
, x1
.
= * + RT ln x1
= RT ln x1
.
G
G = H + T
T p
... .
H 1 1 H 1 1
p2
=
=
p1
R T2 T1
R T1 T2
H T2 T1
p
ln 2 =
p1
R
T1T2
, ln
,
T1 ,
T2 .
,
.
,
() , H = const .
8. .
, p T , V = V ( p, T ) .
( )
,
.
p, T ,V .
CO 2 .
( p, T ) ,
( p,V ) (V , T ) .
,
,
.
( p, T ) - .
:
C =1 + 2 = 3
,
.
, C = 2
2 ( )
( )
3. .
310
331
( ) (
).
( p, T ) -
.
( p, T ) , C = 1
( ).
, T ,
, p = p (T ) .
p = p(T )
() .
, , ( = 3) C = 0
(),
( p, T ) - ,
.
.
9. .
( p, T ) - .
d ln p H
=
dT
RT 2
.
-
d T T (V V )
=
dp
H .
.
p = 6,1 (4,6 ), T =273,1576 (0,0076 ).
( )
, , V = V V < 0
.
,
, ,
, .
,
,
.
,
, ,
... .
X = xi X i ,
xi d X i = 0
( p, T = const )
x1 d X 1 + x 2 d X 2 = 0
.. -
,
,
.
, X 1 X 2 .
X
X = x1X 1 + x2 X 2
X 1 ,
X 2 .
x1 d 1 + x2 d 2 = 0
i , = i , = i0 + RT ln f i
d ln f1 =
x2
d ln f 2
x1
d ln p1 =
x2
d ln p2
x1
i = i* + RT ln ai
*
i i -
, ai = i xi ( i ),
( dx1 = dx 2 )
ln a1
ln a2
= x2
xi
x1 p ,T
x2 p ,T
,
,
.
25. .
,
, .
3. .
330
311
) X (, G ,
H , S , V , C p , .)
n1 , n2
, p T :
X = f (T , p, n1 , n2 )
p T
X
()
d X =
d n1 +
d n2 = X 1 d n1 + X 2 d n2
n
n
1 p ,T ,n2
2 p ,T ,n1
X i ( ) i -
i -
( i -
).
,
i -
.
,
.
,
, .
.
d X
( )
X = X 1n1 + X 2 n2
.. n1 = 0
n2 = 0 X .
X = X 1n1 + X 2 n2 :
d X = X 1 d n1 + X 2 d n2 + n1 d X 1 + n2 d X 2
()
() ()
n1 d X 1 + n2 d X 2 = 0
n1 + n2
10.
. 95,4
. .
( )
( )
.
,
,
.
(C 6 H 5 ) 2 CO .
, 4 ,
,
(. ).
,
:
DA : ; AB : ;
BE : ; BC : ;
CF : ; AC : .
= 1 , C = 3 1 = 2
.
= 2 , C = 3 2 = 1 .
( A, B, C ) , = 3 , C = 3 3 = 0
.
11. -
n1 d X 1 + n2 d X 2 = 0
.
,
( ),
.
X = X 1n1 + X 2 n2
()
x1 x 2
x1 d X 1 + x 2 d X 2 = 0
X = x1 X 1 + x2 X 2 ,
X
n1
n2
x1 =
, x2 =
, X =
.
n1 + n2
n1 + n2
n1 + n2
i i
... .
-
,
.
(, , , .)
.
: ().
-
,
, ,
.
3. .
312
329
()
().
p = const
K = 2, C = 2 +1= 3 .
,
= 3 ( C = 0 ),
C = 2 ( = 1 ).
.
:
,
,
.
12.
,
.
TA , TB .
TA E TB E
.
( )
( ),
.
,
TE .
( ) FG .
.
:
1) TA ETB ( ) = 1 ,
C = 3 = 2 ,
, ,
2) TA EF ( ) (
) = 2 , C = 3 = 1 ,
... .
: , ()
()
( ), V (V)
() (
).
24. .
, .
, (1)
(2) , (
3. .
328
313
23. .
.
,
( E AA , E BB ) ( E AB )
( E AA = E AB = E BB ), .
.
E AA > E AB E BB > E AB ,
B ,
A , A , B .
,
.
, E AA < E AB E BB < E AB ,
,
.
,
.
.
,
.
.
( TA E ),
3) TB EG ,
4) AFGB .
, .
( Ma0 )
.
m ( A) f1 f 0
=
m ( B) f 0 f 2
m ( A) ( f 0 f 2 ) = m ( B ) ( f1 f 0 )
,
M ( f 0 ) ,
( f 2 f1 ) f 0 ,
m ( A) m (B ) .
a0
f2
f0
f1
m ( A)
m (B)
,
().
b2
b0
b1
.
m ( A + B)
mTB (A)
TA EF , ,
,
.
b0 ,
() b2 b1 , .
: b2 (
), b1 .
:
,
,
.. ( ),
0
p1 , p 2 .
: {
} ( {
} ,
.
.
.
, a
, .
, ,
,
.
... .
( mTB ( A)) ( m ( A + B ))
:
m = m ( A + B) + mTB ( A)
TE
d 0 ,
( E ).
( d 0 )
{1) , 2)
3) } ,
, (
) : TE ,
( AE : BE ) E .
d 0 ,
3. .
314
327
( ) .
,
a0 d 0 ,
( .)
Ma0 b1 E ,
( ) ( ).
13.
( congruentis
),
, , ..
.
.
m c
( xm ) ,
.
() (
xd ).
,
, , ,
.
.
,
1 .
T x
.
, "" ,
.
AB (
A m B n ).
,
.
1.
( )
, , =11+1=1
.
. , =12+1=0
TC , .
CF1GyC .
CuMg 2 Cu 2 Mg .
p x T x
p T x . BD
. AC
.
,
p, T .
.
a b ,
.
c , d ,
. a b c d e f g
.
,
, ()
.
.
,
.
... .
3. .
326
315
: Cu Cu 2 Mg , Cu 2 Mg CuMg 2
CuMg 2 Mg .
incongruentis ),
p1 p10 x1
=
p2 p20 x2
x1 =
p1
,
p1 + p2
x2 =
,
.
,
.
AB
TC .
,
( R )
,
( ).
.
p2
p1 + p2
p1 + p 2 = p , ,
x1 p10 x1
=
x2 p20 x2
,
,
0
p1 = p 2 .
0
, , p1 > p 2 ,
x1 x1
>
, ..
x2 x2
.
:
,
(
).
22. .
,
(, ,
, .). ,
.
.
( 1) ( 2) .
0
( 1), p1 > p 2 , 2
1 ( ).
1 . 2
. dc d c ,
... .
TC
:
y ( ).
(
), TC .
=21+1=2 .
a0 ,
,
Ba0 C . g 2
g1 g 2 : ( g 2 ),
g1 .
3. .
316
325
mTB ( B) ( g 2 g 0 ) = m ( A + B ) ( g 0 g1 )
b0 TC
y 2 ( +
+ ) =23+1=0 TC ,
y ( ) y 2
.
, y
(
).
(
), ,
.
bb' .
, ,
, .
, ,
.
T f
mTB ( AB ) ( f 2 f 0 ) = m ( A + B ) ( f 0 f1 )
A AB .
Ma0 CE .
N
, n0
.
TB TC
.
mTB ( B) (b2 2) = m ( A + B) (2 C )
,
.
, .
( ),
.
""
.
Nn0 C .
14. ,
.
.
.
20. .
( T = const )
:
x2 =
1
p2
K
p2 = K x2
( K )
.
.
:
.
21.
, .
1887 . ..
:
p1 = p10 x1
0
p1 .
p1
= x1 ,
p10
p1
= 1 x1 ,
p10
p10 p1
= x2
p10
.
,
p1 = p10 x1 ,
p 2 = p20 x2
,
,
.
.
.
... .
3. .
324
317
,
, ,
,
.
, ,
.
, ,
.
.
.
.
,
.
, ,
.
.
:
1) ,
:
gi
, g i i - .
gi
wi =
i
, i i - .
xi =
i
i
ci = i , i i -
V
2)
(103 3) .
,
:
mi =
i
1000
g1
i -
,
.
, .
.
.
.
,
.
.
,
.
,
.
Ta
a0
( y0
( y3 ).
Tc < T < Ta
=22+1
.
,
, b1b2
1000 .
"1".
( 2 ):
m=
1000 c
1000 c M 2
xi =
mi
1000
mi +
M1
, M i i - .
.
( b1 ) ,
... .
3. .
( b2 ).
318
323
m ( y0 y1 ) = m ( y 2 y1 )
( m0 )
m0 = m + m
m0
y0
y
y
= m 1 + m 2
100
100
100
m0
m
m
( y0 y1 )
( y 2 y1 )
.
Tc ,
y0 ( c0 ) y0
.
,
( ),
(. )
.
Ma0 b1c1 .
(
, , Mn C ),
,
, Co Cr ).
.
.
, 100%.
,
100%.
,
AM , MN , NB
AB , , 20,
30 50%.
,
,
.
, CN
, CL , 3:7.
,
,
.
, P, E , FD ,
AB , ,
30%.
19.
Tb , y 2 ,
"" .
"" ( y0 ), ""
.
,
.
:
( ), ( ) .
.
, ,
.
,
.
, .
,
.
,
.
... .
3. .
15.
, Tb
,
() (),
.
y0 , "",
y3 .
322
319
.
,
B ( TK =440,6
).
TK
,
.
a1a2 b1b2
.
ABC .
, ,
(, (C 2 H 5 ) 3 N ),
TK
.
(, C10 H14 N 2 )
(. ).
.
,
.
,
.
,
.
:
, ,
,
.
, (
) , (
"" ), "" ,
.
.
, (
) (),
.
, ,
( ,
).
,
,
(
).
( ) ,
""
.
, 1
109 () [1-332] (
5 ).
16. ,
, .
.
, ,
.
.
, , . ,
.
.
1-
2- .
1-
, .
2- ,
,
.
1- .
(),
( ).
D
( ),
().
ADF
... .
3. .
18.
320
321
, BCG .
Ta TE , ,
=22+1 .
, b0
y1 ( b1 ), y 2 ( b2 ).
TE d 0
: 1) y E ( E ), 2)
yC ( C ), 3)
y D ( D ).
=23+1=0
,
.
.
DF CG .
, e0 Te
e1 e2 .
Ma0 E .
2- .
( y H )
.
, .
Cg1 , Hg 0 .
g 0 g 0 k 0
.
CF .
TC .
IHFL
.
HI FL .
M 2 ,
TC ( d 0 , , ) -
-, ,
. d 0
HI FL .
17.
TC ,
TC
()
.
M 1 a0
.
.
a0 C , a 2 F .
TC ( )
TC
y H ( H ) .
(
=23+1=0 ) TC
yC , y H , y F ( C , H , F ).
yC
... .
1) ( C 2 H 5 OH ),
2) ( ),
3) ( C 6 H 5 NH 2 ,
C 6 H 5 OH , (C 2 H 5 ) 3 N ,
C10 H14 N 2 .)
,
( ).
,
.
C 6 H 5 NH 2 .
ABC
, =22+1=1
.
,
AB
BC
.
3. .