7

7.
. .

.-. . 380-383, 389-390.

. .pdf
:

d [ A]
= r0 + ( f ( p ) g ( p ) )[ A]
dt

(1)

r0 , f ( p )[ A]
, g ( p )[ A]
. f g ,
p .
:

d [ A]
r0
+ [ A]
f ( p) g ( p)

= ( f ( p ) g ( p ) ) dt

r0
r0
ln
+ [ A] ln
=
f
(
p
)

g
(
p
)
f
(
p
)

g
(
p
)

( f ( p) g ( p) ) t

(2)

( f ( p ) g ( p ) )t
r0
r0
A
+

=
[
]
f ( p) g ( p)
f ( p) g ( p) e

( f ( p ) g ( p ) )t
r0
1
[ A] =
e
f
p
g
p

(
)
(
)

) f > g; ) f < g ) f=g.

(3)

) . ) . )

 7
, ,
!

.
:
:

1
1
H 2 + O2 OH i
2
2

(4)

O2 + H 2 O2 H i + H i

{0}

{1}

H i + O2 OH i + O

r1, k1

{2}

OH i + H 2 H i + H 2O

r2, k2

{3}

O + H 2 OH i + H i

r3, k3

{4}

H i + =>

r4 = k4 [ H i ]

H i
O2 H i :
,

H i + O2 + M HO2 i + M

{5}

r5 = k5 [ H i ][ O2 ][M]

:

d [ H i]
= r2 + r3 r1
dt
d [OH i ]
= r1 + r3 r2
dt

d O
=r r
1
3
dt

(5)

, ,

O OH i ,

d [OH i ]
= r1 + r3 r2 = 0
dt

d O
=r r =0
1
3
dt
r1 = r3 ; r1 + r3 = r2

(6)

2r1 = r2

(7)

 7

:

H i

d[ H i ]/dt = r2 + r3 - r1 = r2 = 2 r1 = 2k1[ H i ][O2]

(8)

(, !)
,
{0}, {4},{5}:.

d[ H i ]/dt = r0 + 2k1[ H i ][O2] - k4 [ H i ] - k5 [ H i ][ O2 ][M]

(9)

H i .
.
(9),

d[ H i ]/dt = r0 + [ H i ] {f(p) g(p)}

(10)

g(p) = k4 + k5[O2][M] = k4 + k5 p2
(11)

f (p) = 2k1[O2] = 2k1 p;

p02

p02
[O2 ] RT
1
=
=

, =
p
p
RT
p

- ,

.
(10):

( f ( p ) g ( p ) )t
r0
1
[ H ] =
e

(
)
(
)
f
p
g
p

f() > g(), [ H i] ;

f() < g(p),

(12)

r0
[ H ]

g ( p) f ( p)
(13)

fg

, ,

. (f-g) ,
.
H i .
- ,
.

 7
2

p*10 atm
2.5

p(2)

p(1)

0.5

720

750

T,K

750

(1) .
(1), (1) (2)
.
. , (2)
.
- ,
. H i
, , , :

f(p) g(p) >0 , f(p) g(p) < 0

f(p)

(14)

g(p) =0

2k1 p - k4 - k5 p2 =0

(15)

(1) (2) , :
p1,2 = k1/k5 {(k1/k5)2 - k4/(k5 )}1/2

(16)

,
.

p1= k4/(2k1 ), k5=0,

p2 = 2k1/k5, k4=0

(17)

(1) (f-g)<0
. (2) .

 7
k1,k4 ,k5. k4
, .. .

.
.
, - .
, -
, .
,

v ,
l :

 7
. l
, - l + dl .
, :

( A)l

( A)l + dl
2

[ / / ].
, :

( A)l S

( A)l + dl S

S- .
,
l :

v A[ A]l S

v A [ A]l + dl S

? n

, (), V(
),

dm3
mol
nA
= vAS
= AS ; V
sec
sec

n
S
[ A]l = A = A = A
V
vAS
vA

(18)

,
:

d [ A]

= r
dt

(19)

d [ A]
dl S= l ( A) S l + dl ( A) S r Sdl
dt

(20)

 7


:

d [ A] l ( A) l + dl ( A)
=
r
dt
dl
d [ A]
d ( A) d [ A]
= l
+
, dl 0
dt
dl
dt

(21)

, ..

d l ( A) d [ A]
+
= 0,
dl
dt
d ( A)
d [ A]
l
=

dl
dt

(22)

(18)

d [ A]
d [ A]
=

dl
dt

(23)

,
. , , ,
.
.
l .

.
.

(23) :

d [ A]
= k[ A]
dl

(24)

d [ A]
k
[ A]l
k
= dl ; ln
= l;
[ A]
[ A]0
A
A
[ A]l = [ A]0 e

k
l
vA

(25)

[ A]L = [ A]0 e

L
vA

k
L
vA

= [ A]0 e k

(26)

- .

, :

ln

[ A]L
[ A]0

= k

(27)

.
:

d [ A]L
LS = v A S[ A]0 v A S [ A]L r LS ;
dt

(28)

d [ A]L
LS = 0 = v A S [ A]0 v A S [ A]L r LS ;
dt
L
[ A]0 [ A]L = r
vA

(29)

( )

 7
,

[ A]0 [ A]L = k[ A]L

L
vA

(30)

,
.
:

{[ A]0 [ A]L } = k
[ A]L

(31)

, :
:

ln

[ A]0 1
[ A]L 1
= ln
=k
[ A]0
[ A]L

1
[ A]0 [ A]L 1 [ A]0
=
1 = k
[ A]L
[ A]L

(32)

[ A]0
[ A]0
[ A]0
1, ln

1
[ A]L
[ A]L
[ A]L
( ln x x 1, x 1)

10

[ A]0 . ,
[ A]L 0 .
[ A]L

,
. , , ,
:

[ A]L ,
[ A]L ,

[ A]0 e k
=
= e k (1 + k ) (1 k )(1 + k ) =
[ A]0
1 + k

(33)

1 ( k ) < 1
2

.
.
, :

d [ A]
= k1[ A] k1[ B ]
dt

. :

d [ B]
SL = ( k1[ A]L k1[ B]L ) SL [ B]L v A S ;
dt
1
d [ B]
= 0 = ( k1[ A]L k1[ B ]L ) [ B ]L

dt
[ B ]L = [ A]0 [ A]L = ( k1[ A]L k1[ B ]L )
[ B ]L
[ B ]L
= k1 k1

[ A]L
[ A]L
[ B ]L
[ A]L
1
1
=
+
(1 + k1 ) = k1 ;
[ A]L
[ B]L k1 K

(34)

11

 7

, ,

[ A]L
1
.
[ B ]L

, - . ,
.

12