17

17.
().

.-. . 171-172
. . 281-282
.
,
, ()
. .
,

(1) , (2) (3) :

*

A2 [A A]

r = k = I 0 ( A2)

(1)

[A-A] A + A

kD

(2)

[A-A] A2

k-1

(3)

[A-A] :
*

I 0 = kD [A-A] + k-1[A-A]

[ A A] =

(4)

I 0*
k1 + k D

(2) :

k D I 0*
rD = k D [ A A] =
k1 + k D

(5)

rD
kD
=

I 0*
k D + k1

(6)

 17
.

kD ~ 1/
.
.

H2 + Br2 = 2HBr

{0}

h
Br2
2 Br

{1)

k1
Br + H 2
HBr + H

{2}

k2
H + Br2
HBr + Br
k3
H + HBr
H 2 + Br
k5
Br + Br + M
Br2 + M

{3}
{5}

,
- Br2 .
500

-580 . 290

/. 194
/, .. . ,
:

 17

{0} :
*

r = I 0

I , I =
*
0

*
0

S I 0 1 e L[ Br2 ]
V

).

{5}.
,
:
*

r = I 0 = r4 = k5[Br]2[M]

(7)

Br :

I
[ Br ] =

[
]
k
M
5

*
0

1
2

(8)

( ) , :

 17

1
d [ HBr ] 2k1 K [ Br2 ] 2 [ H 2 ]

=
k
[
]
HBr
dt
1+ 3

k2 [ Br2 ]

(9)

(9) , ,
1

2
K [ Br2 ] , (8).

:
1

*
2

2k
0
[H2 ]

k5 [ M ]
d [ HBr ]

k
HBr
[
]
dt
1+ 3

k2 [ Br2 ]

(10)

, .. HBr
1

2k

H
[
]

1
2

k5 [ M ]I 0*
1 d [ HBr ]
'

=
= *

k
HBr
[
]
I 0 dt

1+ 3

k2 [ Br2 ]

(11)

CO +Cl2 = COCl2
1000.
.
. . pdf

 17
.
- , .
.

r , rf , rr

G
k f [Re]

1 e RT
r = rf rr =
R

- , ,

kf

- , [Re] -

, G - ( !) .
.
, .. ,
. ,
, .
,
. IUPAC, ,
, .
, .
1)

+ = # =>

(12)

+ + Cat = Cat # => Cat +

(13)

(12) :

kT
Q#

e
k=
h QAQ

ETAK
RT

(14)

(13)

QCat #
kT
kCat =

e
h QAQQCat

ETAK ,Cat
RT

[Cat ]

(15)

 17

rCat kCat
QCat #
=
= #
[Cat ] e
r
k
Q QCat

( ETAK ,Cat ETAK )

RT

(16)

, , , .
:
Catalase
H 2O 2 (l )
H 2O(l ) +

1
O 2 ( gas )
2

( = 300)

d [ H 2O2 ]
)
dt

Ea (kJ/mole)

(M/sec)

HBr
Fe2+/Fe3+
Catalase (enzyme)

10-8
10-4
10-3
107

71
50
42
8

.
.

:

 17
.

. 3
. (!)
,
.

CH3

CH3
C

CH3

CH3
C

CH3

C
H+

H
C

H+

C
H+

CH3
H

CH3
C
H

H+

CH3

. .
.
.
.
IUPAC ,
(phase-transfer), .
.
,
. .

. -
. ,
. IUPAC
, .
~ 1 100 .
.

.
. (

 17
!) .
,
.
TOF (turnover frequency, -
). ,
( ) .
, TOF ,
, .
TOF . TOF
. k2 -.

TOF = 106 -1. TON (turnover number)

( ) ( ), ,
.
TON .
.
.

rHet
k Het QHet #QHomo [ Het ]
=
= #

rHomo k Homo QHomoQHet [ Homo]

(17)

, ,

-

rHet
k
[ Het ]
= Het
rHomo k Homo [ Homo]

(18)

. ,
,
. (, )
(, ).
-6
10 ,

[ Het ]
5 103
[ Homo]
-
.
.

 17
. , ,

, /

(A) ,
Au
100

90

80

70
60
50

~
Au = 6

40
30
20
10
0
2

2,5 2,7 3,4

7,5

13 15 18 27 34 39 52 84

d(Aun),

= 6. .
, , =6, .

+2 2CO2
, Mo Ti. ,
TOF .
1.5 . -,
( ,
). . ,
, . , , . , ,
, 2.5 .

 17

, ,
. . - 1
(). .
(. ). (
) , - ,
,
. ( ) - , , -,
. -, ,
.

- .

10

 17

.- . . 333-336
.
.

S
P

(19)
+

, H :

SH +
P+ H+
S + H +

(20)

, :

k
+

S + H +
SH
1

(21)

,
k P+ H+
SH +

(22)

H 3

K c [ S ] [ H + ] = [ SH + ]
r = k2 [ SH + ] = k2 K c [ S ] [ H + ]

(23)

- .

, ,
, . P
[S]:

[ S ]0 = [ S ] + [ SH + ]; [ S ]0 [ S ] = [ SH + ]
[ S ]0 [ S ] = K c [ S ] [ H + ];

(24)

[ H + ] [ SH + ]; [ S ]0 [ P]

11

 17

[S ] =

[ S ]0
1 + Kc[H + ]

(25)

k2 K c [ H + ][ S ]0
= keff [ S ]0
r = k2 [ SH ] =
1 + Kc [ H + ]
+

keff

k2 K c [ H + ]
=
1 + Kc [ H + ]

(26)

(27)
+

k2:

(k2 , K c )
1

k
eff
1

[H + ]

12

 17

- .

13