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15

15.
. .
.

-. . 120-122.

. . 334-337, 345-346.
, .

(. ).
/nA0/
r.
V :

S = 4 r 2 / nA0 / V
( /nA0/, ,

(1)

1
2
,
S

).
3

dnB
= J
dr

(DA+DB)*

2
(DA+DB)

J 2

( ),

(2)

dnB
,

dr

dnB

> 0, r
dr

15

, Vchem
,

dn
V Vchem = 4 r 2 / nA0 / ( DA + DB ) B V
dr

(3)

Vchem
dnB
=
4 r 2 ( DA + DB ) / nA0 / dr

(4)

(4) :
nB0

Vchem
r 4 r 2 ( DA + DB ) / nA0 / dr = n ( r ) dnB ,
B

(5)

Vchem
= nB0 nB ( r )
0
4 r ( DA + DB ) / nA / r

nB0. ,

nB0

Vchem
= nB (r )
4 r ( DA + DB ) / nA0 /

(6)
2

15
:

Vchem = kchem nA0 nB (r )

(7)

, ,
-- :

r = (rA + rB)
(6) (7) :

Vchem = k

n n (r ) = k

0
chem A B

Vchem
n nB
0

+
+

4
(
)
/
/
r
r
D
D
n
(
)
A
B
A
B
A

0
chem A

(8)

kchemVchem nA0
= kchem nA0 nB0 ,
Vchem +
0
4 ( rA + rB ) ( DA + DB ) / nA /

kchem
= kchem nA0 nB0
Vchem 1 +

4 ( r + r ) ( D + D )
A
B
A
B

Vchem =

kchem nA0 nB0

kchem { }
+
1

+
+

r
r
D
D
4
(
)
(
)
A
B
A
B

(9)

(9)

()

keff =

kchem

kchem
+
1

+
+

4
(
)
r
r
D
D
(
)
A
B
A
B

(10)

15

kdif = 4 ( rA + rB ) ( DA + DB )

(11)

keff =

(k

kchem kdif
chem

+ kdif )

kchem  kdif ,

kchem
1
4 ( rA + rB ) ( DA + DB )

keff = kdif = 4 ( rA + rB ) ( DA + DB )
(12)
,

kchem  kdif ,

kchem
1
4 ( rA + rB ) ( DA + DB )

(13)

keff = kchem
,
(. (6)) :

nB ( r ) nB0 =

Vchem
1
4 (rA + rB )( DA + DB ) / nA0 /

-:

DA =

kT
1

6 s rA

DA + DB =

kT
r +r
A B
6 s
rArB

(14)

(14) , ,
s. (12) (14) :
4

15

kdif

kT
rA + rB 2 kT ( rA + rB )
= 4 ( rA + rB )

=
rArB
rArB
6 s
3 s

(15)

,
, .
()
:

d ln keff
dT

d ln kdif 1 d ln s RT Es
EA
=
=
=
=
RT 2
dT
T
dT
RT 2

(16)

. ,

Es -

.
, ,
( 15),
( 16).
k ,
, -
.

.
.

-. . 161-163
. . 351-352

:
k2

AB #
P
A + B
Kc

[ AB # ]
Kc =
, r = k2 K c [ A][ B ]
[ A][ B ]
5

15

, .
-,

K c ( )

K , . -,
, K c ( ) .

K c ( ) K , ,
.

K c ( )

[ AB # ]

= K A B
K c ( ) =
[ A][ B]
AB #

(17)

K
, .

pA = kA xA

p A = [ A] RT
,

x A = [ A] d

(18)

[ A] = LA [ A]

(19)

LA .
:

15

K C ( ) =
=

LAB#
LA LB

LAB#
LA LB

[ AB # ] p p
[ A] p p [ B ] p p

LAB#
LA LB

Kc ( ) =
(20)

(20) .

K c ( p p) = K

A B

L L
= K c ( ) A B A B
AB
AB
LAB
#

K c ( p p ) :

QAB #
K c ( gas ) = * * e
QA QA

(21)

ETAK
RT

QAB #
KC ( p p) = * * e
QA QA

ETAK
RT

A B LA LB
#
#
AB
LAB

(22)

k ( ) :

0
k
( )

0
k ( ) = k
( )

A B
AB

(23a)

(21).

k ( ) = k ( )

A B LA LB

AB
LAB
#

(23)

(23) (23) -.
7

15
,

LA , LB , LAB# , A , B , AB#

- ,

.
.
.(=298 ) . .

-1 -1

109 - 1010

3.7*109 - 1010

:
+ + ( )

1.4 1011

+ + S-

0.8 1011

( )

2 1011

( , . )

( . )

40*1011

102-104

, +
( 40 /) . ,
.
,
, 40%
( ),
(=1).
. , ..
.
.
.

. .
.

N2O5 N2O4 + O2
8

15

k105 25, -1

logA0 {-1}

EA, /

3,38

13,6

103

CCl4

4,09

13,8

107

CHCl3

3,72

13,6

103

C2H2Cl2

4,79

13,6

102

C2HCl5

4,30

14,0

105

CH3 NO2

3,13

13,5

103

Br2

4,27

13,3

100

N2O4

7,05

14,2

105

C3H4Cl2

0,510

14,6

113

. .
.
, =
398.

(25)I + (C2H5)3N (25)I *(C2H5)3N

k105, 11

2.5

log 0

EA, /

0,5

4,07

66,9

25,3

4,02

54,4

39,8

3,28

47,7

1,66102

4,54

52,3

2,65102

4,40

49,8

1,13103

5,02

49,8

1,38103

4,93

48,5

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