9

9.
: .
. .
. . 66-74,

.-. . 73-77,
. . 89-95

:

d ln k
E
= A2
dT
RT

(1)

EA - (.. !)
. :

lnk = lnA - EA/RT

(2)

k = A e- EA/RT

(3)

(2) (3) ,
A . ln

k = f (1/T) :

-EA /R.
.
:

k = A(T )e

EA
RT

= A0T e
n

EA
RT

(4)

A0 , n .
. , (1) (4)
.

EA +

d ln A(T )
RT 2
dT
RT 2

d ln k d ln A(T ) E A
=
+
=
dT
dT
RT 2
E A*
d ln A(T )
*
2
;
E
E
RT
=
=
+

A
A
RT 2
dT

(5)

E A* . E A

.
2

 9
-
/:

K + Br2 = KBr + Br, EA = 0

C2H4 + H2 = C2H6, EA = 180 /

(6)

.

. ,
:

d [ A]
= ( k1 + k2 )[ A] = keff [ A]
dt
d ln keff d ln ( k1 + k2 ) E A
=
=
dT
dT
RT 2

d ln ( k1 + k2 )
1
dk1 dk2
=
+

=
dT
( k1 + k2 ) dT dT
k1 dk1 k2 dk2
d ln k2
1
1
d ln k1
+
+ k2

=
k1
=
k
k
k
dT
k
dT
k
k
dT
dT
+
+
( 1 2) 1

2
( 1 2)
EA
k1 E1, A
k2 E2, A
;
=
+
RT 2 k1 + k2 RT 2 k1 + k2 RT 2

k1
k2
EA =
E1, A +
E2, A
k1 + k2
k1 + k2

(7)

K=

k1 d ln K d ln k1 d ln k1
=

;
;
k1
dT
dT
dT

(8)

H 0 = E1, A E2, A
.
3

 9
(1) .
().
.
:.

A+BC+D
-d[A]/dt = k [A]*[B]

(9)

.
:
nA-B , . nA-B

N, :

d nA-B /dt = { // };

r=

1 dnA B
d [ A]
=
N A dt
dt

(10)

.
V. , V ,
.
? :

. d = r + r , r, r. . - V.

 9

. , .
:
.

d2 V nB

(11)

nA .

d2 V nB nA

(12)

r=

d [ A] 1 dnA B
1
=
=
d 2VnAnB =
dt
N A dt
NA

(13)

= N A d 2V [ A][ B]
(13)

r=

d [ A]
= k[ A][ B] = N A d 2V [ A][ B];
dt
k = N A d 2V

(14)

<V> = (8kT/ m)1/2

(15)

?. . . !
1

1
1
mB mA
=
+
=

m
m
mA + mB
B
A

(16)

 9
1
2

1
2

1
2

1
2

1
1
8kT 1
2 8kT
+
k = N A d
(17)
= N A d

m
m

A
B
2

, .
, .
, :

.

(A, B).

(A, B) = dnB /B

(18)

dnB , {/ }, B . ,
, , , ,
c A. ,
. , ,
, , .
, - .
,
!
1
2

EA
RT

1
2

E
E
A
8kT 1 RTA
= Ae RT
k = N A d
e

2

(19)

(19) -. ,
.
- ().

. . 232-247
. . 122-125, 136-146
-, . 102-110.
.
V, ..

mV 2
=
2

(20)

, V
, ( -)
( ) V . ,
V
.
.

b -

( !) :

OO1 = d = (rA + rB);

b = d sin

V 2 VK2
VK2
K
sin =
1
1
=

V2
V2

(21)

b 2 = d 2 1 K

(22)

d 2 1

2
= b

(23)