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13

13
.

. . 199-203
. .285-292
.-. .94-96

:

kbi =

kT # kT #
kT # RT
Kc =
K p RT =
K

=
h
h
h
p
bar
1

K C#

{}-1,

(1)

K p# -

{}-1, K - .

+ = #
(1) ,
( )
.

GT#,0 = RT ln K # = H T#,0 T ST#,0


#,0

K # = e HT
kbi =

kT
e
h

kT
e
h

H T#,0
RT

H T#,0 +T ST#,0
RT

ST#,0
R

(2)
+T ST#,0

RT

=
1
p
bar
=

RT

p = 1bar

(3)

13
(2) ,

GT#,0 , , H T#,0

ST#,0 , .

= 1 .
,
:

E A = H T#,0 + 2 RT

(4)

H T#,0 ST#,0

kTAC

1
2

EA
8kT 12 RT
= PN A d
e e
= kTAK

kT
= e
h

ST#,0
R

ee

EA
RT

(5)

RT
p = 1bar

:
3
2

P = LT e

ST#,0
R

(6)
0

=1 ,

= 1 /.
, 1
p = (c=1/)*RT

* = 1 /

mol

1
=

c
R
T

L
*
0

= + RT ln
p =1bar

(7)
2

13
C

#,*
GT#,* = AK

mol

1
=
RT
c

*A B* = GT#,0 RT ln
p =1bar

(8)

H T#,0 = H T#,*

(9)

GT#,* GT#,0

mol

1
c
=

R
T

L
#
#

= T (S p Sc ) = RT ln
p =1bar

mol

1
c
=

R
T

L
#
#

Sc = S p + R ln
p =1bar
1mol

S #p
c
=
RT

L
e R
p = 1bar

(10)

#
RSc
=e

(9) (10), (3) :

1mol

c
=
RT
kT
L =
e
e R

kbi =


mol
1
=
h
p
bar
1

c=

L
1mol

S #p
H T#,0
c
RT
=

kT
1
L
RT
R
=
=
e
e

1mol
h
p
1
bar
=

c=


H T#,0
RT

S #p

13

kT
e
h

HT#,0
RT

Sc#
R

1mol
c=

kbi =

kT
e
h

kT
e
h

kbi =

EA
RT

e2 e

kT
e
h

kT
e
h

H T#,0
RT

EA
RT

H T#,0
RT

S #p

S p# Sc# :

RT

=
p = 1bar

RT

p = 1bar

e2 e

S #p

(11)

Sc#
R

Sc#
R

1mol
c=
L

1mol
c=
L

(12)

, ..

, ( ),
, ( ),
( ) (
).

EAr,

, (-1, /)10-9
. ,
,

13

NO+O3=NO2+O2
NO2+CO=NO+CO2
NO+Cl2=NOCl+Cl
2ClO=Cl2+O2

10
130
85
0.5

0.8
12
4
0.063

=
0.44
6
1.2
0.001

=
0.68
110

47
74
93
42

,
.
.

. . 251-261
. .146-158

A P
, , ,
:

,
, >. ,
, , , .
. ?
, ,
.
, *
.
.
:
5

13

A + M A* + M

(k1)

(13)

A* + M A + M

(k2)

(14)

A*

(k3)

(15)

. , ,

,
[A] [M]
A* ,
,

d[A*]/dt = k1[A]2 - k3 [A*] - k2[A] [A*] = 0;

k1[ A]2
[A*] =
k3 + k2 [ A]

(16)

d [ B] k3k1[ A]2
r=
=
= keff [ A]
dt
k3 + k2 [ A]

(17)

, ,
[A]

keff =

k3k1[ A]
k3 + k2 [ A]

(18)

13

.
:

k = k = k3k1/k2

[A]

(19)

.
-:

k1[ A]2
k [ A]
[A ] =
1
= K c [ A]
k3 + k2 [ A]
k2
*

(20)

.. .
:

keff =

k3k1[ A]
= k1[ A] ; r = k1[ A]2 , [ A] 0
k3

(21)

k1 , .

k1

keff =

k3k1[ A]
k
=
k
k3 + k2 [ A]
+1
k1[ A]

(22)

13

1
keff

( ) :

1
1 1
1
=
+
keff k1 [ A] k

(23)

, 1/2 , ,

[ A] 1 . ()
2

k:

keff =

k
=
2

k
k1[ A]1

k
k
+ 1 = 2,
=1
k
A
k
A
[
]
[
]
1
1
+1 1 1
;

k3k1
k
k
k
[ A]1 = , [ A]1 = 2 = 3
k1
k1
k2
2
2

(24)

(13)
8

13
1
2

8kT
1
k1 = d 2
e

ETAC
RT

,
, :

keff =

k3k1[ A]
k3
=
k1[ A] < k1[ A]
k3 + k2 [ A] k3 + k2 [ A]

(25)

k3
<1
k3 + k2 [ A]
, (14) (15)
. ,
(13).

(25).
. ,
,
. , (.
(23)) .
, (25).

C2H5Cl CH2=CH2 +HCl


rexp / rtheor = 106
k ,

k1, (25).

, (13).
, , ,
(13). , ,
,
. -,
, ..
.
.
9