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10

10
-. ()

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

.

3
2

mV 2
m
dw(V ) =
dV = (V ) dV
exp
2

kT
2
kT

V , .

(1)

3
2

mV 2
m
(V ) =

exp
2

kT
2
kT

.
, V V

VB VB +dVB

+dV ,

d w (V) d wB (VB)= (V) (VB) dVdVB =


3
2

3
2

m V mB
mBVB2
mA

dVAdVB

exp
exp
2 kT
2kT 2 kT
2kT
2
A A

(2)


2
( mA + mB )V. .
mAVA2 mBVB2 V
+
=
+
2
2
2
2
m m
= A B
mA + mB
2

(3)

10

V.. ,
V.. =

mAVA + mBVB
mA + mB

(4)

V
V = (VA-VB)

(5)

(3),

(V) (VB) = (V..) (V)

(6)

dVBdVA = dVdV..

(7)

(6) (7)

dw(V.) dw(V) = . dV. dV = dw(VA) dw(VB) =


= (V) (VB) dVA dVB

(8)

V VB V V. (4) (5).
,
(8) V.:

dw (V ) = . .dV . . dV = dV

(9)

(9) ,
V V

+ dV . .

, .
.
V . (9)

dVx,.dVy, dVz, = V2 dV sin d d


2

10

dw(V, , ) = (V, , )* V2 dV sin d d

d w(V) = (V )V dV sin d
2

(10)

. (V ) ,
(1) .

(10)

0 2 0 .

3
2

V 2 2

dw(V ) =
V 4 dV
exp

2
kT
2
kT

(11)

.
V V+dV ?
3
2

V 2 2
K

dr = d (1 ) V
V 4 nB dV (12)
exp

kT
kT
2
2

(12) .
nB V dV

. ,
. ( . (10)).
,

. (12)

1
2

2
=V

1
1
1

1 12
dV = 2 d = 2 2 2 2 d
2

1
2

1
2

10

K
4 d

2

3
2

3
2

1
1
1
2
2 2 2

exp
2 nB d

kT
kT
2

3
1
3
3
1
3
3
1

K 2 2
2
2
2
2
2
2
= d
4(2) (2) (2)

3


2
( kT ) exp
nB d =
kT
2

= d
2

1
2

3
2

( K )

1
2


(8) ( kT ) exp
kT
1
2

3
2

1
2

3
8

d ( K )
kT
exp

( )
kT

2

nB d =

nB d

(13)


(13)

n. ,

B , A, .
1
2

3
8
dnB


2
2 exp
= d ( K )

kT
(
)

dt

kT

d nAnB (14)

x :

x=

K
kT

d = kTdx;

kT

= x +

K
kT


exp
kT

x
exp
=

kT

K
exp

kT
4

10

dnB
=
dt
1
2

3
8

K
2

d
x
(
kT
)
kT
exp(
x
)
exp
(
)


0
kT

dnB
8kT
= d 2 nA nB exp K

dt
kT

1
2

x exp( x)dx

dx nAnB

(15)

x exp ( x ) dx = x exp ( x ) | exp ( x )dx =

x exp ( x ) exp ( x ) = ( 0 + 0 ) (0 1) = 1
0

(16)

(15):
1
2

8kT
dnB
K
=d2
exp

dt
kT

1
2

nAnB

d [ B]
8kT
K
r =
= N A d 2
exp

[ A][ B ]

dt
kT

(17)

(18)


1
2

8kT
K
k = N A d 2
exp

kT

(19)
5

10
(19) - -.
.

.
:

d ln k
E
= 2 ;
dT
RT
E
d TAC
d ln T
RT
=

2dT
dT

1 E
=
+ TAC2 ;
2T RT

d ln kTAC
dT
1
RT + ETAC
1
E
2
;
E
RT + ETAC
=
=

2
2
2
RT
RT
1000

(20)

RT = 4 /. -

/.
, -:
1) .
.
.

10

!
2) , , .

, .
.
. . =300.

,
//
3

1010
6.3 107
1012
1.3 106
1.2 1011

2NOCl2NO+Cl
2ClOCl2 + O2
K+Br2KBr + Br
H2 + C2H4 C2H6
Cl+HIHCl + I

,
//
3

6.3 1010
4.0 1010
2 1011
7.3 1011
1.3 1011

,
/
103
0
0
180
0

1.6 10-1
2.5 10-3
4.8
1.7 10-6
1

.
10

11

10 10 // . ,
. , .
.
1) :

dT = d 0 (1 +

RT

), > 0, < 0

(21)

10
2) . ,

().

. . 202-210
-. . 79-84
. .183-187
. .pdf
.
() -
.
.
. , ..
. , ,
, .

H(+- +-+-) = E

(22)

.
E . ,
, E
, E

(0).

(0), E (1) ..

U(T=0K) = E (0) = E () + U- + U- +U- = f (q1q2q3..)


, ,
, ,
, , .
0 K.
, .
. .

( ).
, .:

10

.
,
. , ,
.
, .
,
.

, ( )
. ,
r(-) r(-). z.
. .
.
9

10
- , , - -

.
+ = +
( )
( ).
,
, - ,
.
. :

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

10