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14

14
.
. . 256-261

. . 156-158

kTAC

1
2

8kT
= P d
e

ETAC
RT

= PZ 0e

ETAC
RT

ETAC
RT

e
. ,
,
( , !).
, ,
. . ,
.
( *),

1 +2 +


( ), S 2
.
, ,
:

14
. .
( )
( ). ().
. ,
. , S= 2f +2, f -
.
,
.
.
:
, ( )
+ d
1
2

1
2
dw ( ) =
exp

d
kT
kT
1

(1)

, 1 1
- 2 2

+ d2

1
dw (1 )dw ( 2 ) =
kT

1
exp

kT

2
2

exp
1

kT
1

+ d1,
1

2
2 d 1d 2 (2)

1 +2 =

(3)

(2) (3)

1
dw (1 )dw ( ) =
kT

1
exp

kT

1
1

2
1
1 exp
( 1 ) 2 d 1d

kT

(4)
(4) 1 0 :

1
dw ( ) =
kT


exp

kT

1
1

2
2
1 ( 1 ) d 1 d
0

(5)
2

14

1
2

( )
1

1
2

d 1 =

( !)

1
dw ( ) =
kT


exp

kT

(6)

(6) - , +d,
.
, (
). (6) :

w ( K ) =

K kT


exp

kT

exp

0
+
exp

kT

K
kT


= exp

kT
(7)
S ,

S
1 2

exp
dw ( ) =

kT
kT

1
1
1
1

2
2
2
2
.....
...
...
..

d
d
d
( 1
1 2
S 1
S 1 )
S 1 d
1
2
0
0

(8)

1 +2 +

S =

(8) - , S

+d. (8) 0 1,2,S-1.


(8) .
(7)

14

S
1 2

exp
w ( K ) =

kT
kT

1
1
1
1

2
2
2
2 d d ..d
.....
...
...

(
)
1 2
S 1
S 1
S 1 d
1
1
2
0
0

(9)
(9) :

S
S
S S

1
2
1 2
1
1
K 2
K 2 2
K
w ( K ) =

+ S

...+ S S

S
kT
kT
kT

2 !
!
2 1!

2 2


exp K
kT
(10)
, >>kT

S
1

1 K 2
K

exp
w ( K ) =

S
kT
kT

2 1!

(11)


w ( K ) = exp K
kT

, S = 2, f = 0

(11) .

k1 .
4

14
--- .
.

. . 218-220

!

*
#
ETAK
kT QQQ RT
k = k =
e
*
h QQQ
k - .

(12)

(12).
,
, ,

kT
e
k =
h

ETAK
RT

(13)
12

6*10

300. 2*1013 -1

-1

h
i

kT
Qi = 1 e kT
h i

kTAK

h i
( ) ETAK

kT i = j +1 kT
=

e RT
h j
h
j kT ( AK )

(14)

.
(.. ). :

14

kTAK

kT h i
=

e
h kT

ETAK
RT

= i e

ETAK
RT

(15)
14

- 10

-1 .
13

14

( 10 -10 -1)

.
.

+ RT = ,
1000

+ 8,314 / =

kmono =

kT # kT # kT #
Kc =
Kp =
K
h
h
h

(16)

S p# = Sc#
kTAK

(17)

kT
=
e
h

GT#,0
RT

kT
=
e
h

H T#,0
RT

ST#,0
R

(18)

H T#,0 + RT = E A

kTAK
A=

kT
=
e
h
kT
e
h

ST#,0
R

GT#,0
RT

(19)
E

kT RTA
=
e e
h

ST#,0
R

e = Ae

EA
RT

e
(20)
6

14

K # , K c# , K p# , Sc# = S p# .

,
//.

N 2O5 2 NO2 +

10

1
J
O2 , S # = 8.4
2
mol * K

( COCl2 )2 2COCl ,

S # = 0.16
13

10
.

J
mol * K

-1.

. . 301-305
. . 180-183
:

2 NO + O2 2 NO2 ,
2 NO + X 2 2 NOX ,

X = Cl , Br , J

(22,)

A+ B +CP

kT Q #
ktr =
e
h QAQBQC

ETAK
RT

(23)


. .
,
.
.
.

14

2NO +O2 2NO2, (6/3/) *10-3

T, K
80
143
300
564
662

k (exp)
86
16
3
2
2

k ()
42
20
7
3
3

{AK#}

O
N

{}

N
O


-,

3
2

3
2

T T T T
3
2

3
2

3
2

1
2

T T T T T T

1
T3

(24)


.
(22) .
,
0.
,

14

ktri =

kT
e
h

H #
RT

S #p

RT dm6


2
=

1
s
p
bar
mol

p =1bar
S p# = Sc# + 2 R ln
mol
RT c =1 3
dm

S p#

(25)

( -

300

//) .

S #p

Pe

.
.
,
. ,
k1
k2

{NOCl2 } + NO
2 NO + Cl2
2 NOCl

k1

(26)

r = keff [ NO ]2 [Cl2 ] = k2 K c [ NO ]2 [Cl2 ],


keff = k2 K c

(27)

d ln keff
dT

d ln K c d ln k2
+
dT
dT

(28)


:
9

14

d ln K c
d ln K c
d ln k2
< 0,
>

dT
dT
dT
d ln keff
<0
dT

(29)

10