200300, 550700, 013100

2002

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XVIII . 1915 . ..
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(),
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(.1).
(, , )

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,

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, .
2

 ,

(.2).

.1.

.2.

, ,
G ( ),
, .

.
( 1 2)
- G .
S:
G = S
(1)
.

. ,
: d/dT < 0
.

,
.
,
. ,
/,

20 0.033 H/, / - 0.008 H/, /

, .

, ,
.

,
. , ,
,
,
. ,

.
.


.


.
.

,
, ,
/2, /2. > 0,
.
,
. < 0, ,

.
, = 0,

.


d/dC :
C d
=
,
(2)
RT dC
- ;
4

R - ;
T - ;
- .
(2) ,
,
d/dC < 0.
d/dC
, ,
, ().
,

.
= f(C) (.3). ,
,
.
,
. , - ,
. OH, COOH,
NH2 .
,
, ,
. .3 ,

-

= ()

:

.

= ()


().

d/dC < 0,

.3.

, ,
< 0. ,

 , . , , .
( ),
( )
- -
,
, -,
- .
, , ()
.
S0:
S0 = S/m,
S - ;
m .
S0 ,
:
= S/V,
V -
m = V,
:
S0 = /,
- .

1 .
, ,
.

.
() ()
.

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--,
. -
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,

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()

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,
. , ,
(H < 0),

.
.
,
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-
,
.
-.

 .
.
,
.

.
,
, .
l.
= max

. . ,
.

,
.
( ).

:
+ =

= /max -
. (1 ) -
.

,
.
C ,
- (1 ).
:
v = kC(1 ),
k - .

,
:
v = k,
k - .
v = v
kC(1 ) = k

kC(1 ) = ,
k = k/k -
T.
:
kpP
k cC
kcC
(3)
=
= max
; = max
1 + k cC
1 + k cC
1 + kpP
P - .

(.4).
kcC << 1 (
kpP << 1) :
= maxkcC = maxkpP
(4)
kcC >> 1 ( kpP >> 1)
=max,
.
,
().
,
, max,
( )
S = maxmaxNA,
(5)
NA - .
,

(3) .
S-.
-,
,

.
2

max
1

(.4):
= kCn
(6)
k - ,

= 1;
n - (n = 0 1)

.4. :
1 - , 2 -


, ,
C.

. - ,
,
.

, 1903 . ..
.

.

i- :
k c,i C i
,
i = max
N
1+

c,i C i

i =1

i, kc,i -
i- , .
,
, .

,
, ,
, .


.
.
.
.
.

.
,
.
.

, .

10


: , , , ,
, , 0.1 NaOH,
, , , .
I)
6 .
40 ,
20
. 20
. .
20 ,
.. 20
. ,
,
, .
II) N0
.
5
, 2-3 0.1 NaOH.
:
1) .
0.1 NaOH
.
,
.
, ,
. ,
( ) ,
.
.
2) .

5 .
.
, ,
. ,
,
,
.
11

3) .

.
,
.
.
-
, .
.
, .
(
0.1 ).
,
.
.
,
.
.
.
4) .
( 0.1
NaOH, )
0 :
(7)
C0 = NNaOHV0NaOH/V0,
NNaOH - NaOH (0.1 );
V0NaOH - (),
;
V0 - , (V0 = 5 ).

( 2, 3).

V0
,
C , / , /
, C0 , / V

1
2
3
4
5
6

12

NaOH

NaOH

III)
1 ( 0.01 ).

30 ,
.
IV) .
.
2 0.1
NaOH.
V)
:
C = NNaOHVNaOH/V,
(8)
VNaOH - (),
;
V - , (V = 2 ).

( 4, 5).
:
(9)
= (C0 C)V/m,
m - (m = 1 ).
( 5).
VI) .
C
= f(C) (.5) .
1)
.

(. ).
(6) :
lg = lgk + nlgC.
k n
lg , lgC (y lg, x lgC).

. 5

,
.

13

OA, , lgk,
- n (.6).
k n (6)
. ,

.
2) .
(3) max k .
:
1/ = 1/max + 1/(maxkcC).
1/ = 1/f(1/C) (y 1/,
x 1/C), AB, 1/max,
1/(maxkc) (.7).
max, kc.

.
lg

1/

lgk

1/max
lg
. 6

1/
. 7

C.
,
- .
= f(C)
, .



, ,

14

 , .
,

= f(C), lg = f(lgC)
(6) 1/ = f(1/C)
(3).

1) ?
? ?
2) .
?
3) - ()?
? .
4) ?
?
5) .
max kc ?
6) max
?
7) .
?
8) ?
?

1. .. . .: , 1975.
2. ..
. .: , 1973.
3. .., ..
. .: , 1978.
4. /
. .. , . 1982.
5. .. . .: , 1975.
6. ..
. .: , 1975.

15


1.

. k
:
k

1
< y >i =
k

i, j

i = 1, 2, 3, N,

(1)

j=1

k - ,
(k = 3);
yi,j - j- i- ;
N - (N = 6).

:
2i

1
=
k 1

(y

i, j

< y > i )2 .

(2)

j=1

,
:
2y

1
=
N

2
i

(3)

i =1

f = N(k 1).

:
max 2
Gp = N i .
(4)

2
i

i =1

.
G 1.
P = 0.95,
.
1
fG
N
1
2
3
4
5
6
7
8
5
0.841
0.684 0.598
0.544 0.507
0.478 0.456 0.439
6
0.781
0.616 0.532
0.480 0.445
0.418 0.398 0.382
7
0.727
0.561 0.480
0.431 0.397
0.373 0.354 0.338

16

 G
N f, ,
fG = k 1. Gp < G,
, - .
2,
.
2

yi,j

xi

yi,1

<yi>

yi,2

yi,3

y2

max i

2
i

Gp

i =1

1
2
3
4
5
6
2.


,
.
,
,
().
Y x:
Y = b1x + b0.
b0 b1 :
N

N
b1 =

x y x y
i

i =1

i =1

i =1

x i2

i =1

i =1
2

xi

(5)

y b x
i

b0 =

i =1

i =1

(6)

17

3.

. ,
, , ,
, :
2y
2
b =
.
(7)
N
, ,
:
| bj | > bt,
j = 0, 1,
t - ( 3), ft = (N B)
;
B - (B = 2).

ft
1
2
3
4
5

t
12.71
4.30
3.18
2.78
2.57

ft
6
7
8
9
10

t
2.45
2.36
2.31
2.26
2.23

ft
11
12
13
14
15

t
2.20
2.18
2.16
2.14
2.13

ft
16
17
18
19
20

3
t
2.12
2.11
2.10
2.09
2.09

,
.
4,
.
4
b2

bt

b0

b1

.
4.
, .
,
:
max( 2a , 2y )
Fp =
,
(8)
min( 2a , 2y )
2 - .
:

18

1
=
NB

(y Y )
i

(9)

i =1

yi, Yi - i-

:
f = N B. ,
F < F, F - 5.
5.

f
( )

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

ft ( )
1

18.51 19.00 19.16 19.25 19.30 19.33 19.35 19.37

10.13 9.55 9.28 9.12 9.01 8.94 8.89 8.85
7.71 6.94 6.59 6.39 6.26 6.16 6.09 6.04
6.61 5.79 5.41 5.19 5.05 4.95 4.88 4.82
5.99 5.14 4.76 4.53 4.39 4.28 4.21 4.15
5.59 4.74 4.36 4.12 3.97 3.87 3.79 3.73
5.32 4.46 4.07 3.84 3.69 3.58 3.50 3.44
5.12 4.26 3.86 3.63 3.48 3.37 3.29 3.24
4.97 4.10 3.71 3.48 3.33 3.22 3.14 3.07
4.84 3.98 3.59 3.36 3.20 3.10 3.01 2.95
4.75 3.89 3.49 3.26 3.11 3.00 2.91 2.85
4.67 3.81 3.41 3.18 3.03 2.92 2.83 2.77
4.60 3.74 3.34 3.11 2.96 2.85 2.76 2.70
4.54 3.68 3.29 3.06 2.90 2.79 2.71 2.64
4.49 3.63 3.24 3.01 2.85 2.74 2.66 2.59
4.45 3.59 3.20 2.97 2.81 2.70 2.71 2.55
4.41 3.56 3.16 2.93 2.77 2.66 2.58 2.51
4.38 3.52 3.13 2.90 2.74 2.63 2.54 2.48
4.35 3.49 3.10 2.87 2.71 2.60 2.51 2.45

,
.
6.
2

max(2, y2)

min(2, y2)

Fp

19

:


..
..
06268 14.11.01

6084
. .
.-. .
.-..
100 .

410054 . , . , 77
, 410054, . , . , 77

20