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32

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) :

20(1) + RT ln a2(1) = 20( 2) + RT ln a2( 2)


(1)

a2

( 2)

a2

( 2)
0 (1)

20(1) 20( 2) = RT ln a2( 2) RT ln a2(1)


ln
K =

= 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. .

pi( ) > pi( )

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 .

.
( )

d (1) = S (1) d T + V (1) d p

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

( V > V , V > 0 ), dT dp > 0



.
.

( V < V , V < 0 ), dT dp < 0



.
, ,
, , .

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 ( A + B) (b1 b0 ) = mTB ( A) (b0 b2 )

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

p = p1 + p2 = p10 x1 + p 20 x2 = p10 (1 x2 ) + p20 x2 = p20 ( p10 p20 ) x1

,
,
.

.
.

... .

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%.
,

=50%, =20%, =30%.




,
.

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. .