Вы находитесь на странице: 1из 11

18

18.
- ().
.-. . 336-342
,

[ SH + ] = K c [ S ] [ H + ]
.
:

{SH+/SH+}Kc* [S]* [H+] = [SH+]

(1)

S,

H+,SH+ ,

, S, S ,
[S]=1().
.

h = {SH+/SH+}*[H+] = {S/SH+} aH+

(2)

h . ,

{S/SH+}

(3)
+

H S .
H0, :

H 0 = lg h = lg

S
S
lg aH = lg H
lg[ H + ] =
SH
SH
+

lg K SH + lg

[ SH ]
[S ]

(4)

(4)

S + H +
SH +

18
, ,

S , SH +

H + , ,

. .

.
12 (-12). , ,
+
. - SbF5 HF 1:1, [H ]
[SbF6-] 28 (-28).

[ SH + ]
H 0 = lg K ( SH ) lg
[S ]
H 0 .
+

S , SH + , H 0 .

. .

-12

-10

H0

-8

-6

-4

-2

0
0

20

40

60

80

100

H2SO4 % weight

:
1) .
2) .
:
.

18

H 2 SO4

).
h
, :

k = k2*Kc [H+] /{1+ Kc * [H+]}


k = k2*Kc h /{1+ Kc* h}

(5)

r = keff [ S ]0 =

k2 K c h [ S ]0
1 + Kch

(6)

k = f (h) ,
.
:

1
k

1
1 1
+
K c k2 h k2

(7)

k2 Kc

h,

1 >> Kc*h

(8)

(. (6)) :

k = k2*Kc h;

lg k = lg (k2*Kc) H0

(9)

- .

.-. . 336-342
:
K

k2
+
c
ZZZ
X
S + HA YZZ
P + HA
Z SH A

(10)

18

H + ( H 3O + ) , HA . ()

() .
: .

r =k2 ( HA)[ SH + ][ A ] = k2 ( HA) K c ( HA)[ S ][ HA] = keff ( HA)[ S ]


keff ( HA) = k2 ( HA) K c ( HA)[ HA]

(11)

.
.
,
K c ( HA )
k2 ( HA )
+
ZZZZZ
X
S + HA YZZZZ
P + HA
Z SH A

K c ( H 2O )
k2 ( H 2 O )
+

ZZZZZ
X
S + H 2O YZZZZ
P + H 2O
Z SH OH

(12)

K c ( H 3O )
k2 ( H 2 O )
+
ZZZZZX
Z
S + H 3O YZZZZZ
P + H 3O +
Z SH H 2O

- .
, :
K c ( AlCl3 )
k2 ( AlCl3 )
ZZZZZX
Z
S + AlCl3 YZZZZZ

P + AlCl3
Z SAlCl3

(13)

, .

keff = keff ( HAi ) =


Ai

= [ k2 ( HA) K c ( HA)[ HA] + k2 ( H 2O ) K c ( H 2O)[ H 2O ]...]

(14)

keff

ln keff ( HA) = + ln K HA

(15)

18

HA U H + + A , K HA =

aH + a A
aHA

(16)

- .

( ) .
. .

- .
.
.
- :
. - .
.
.
. - .
.
.
.
. - .
.
,
.
. -
. .
.
.
.
.
,
[0].

[ Asurf ];

[ Asurf ] [ A0 ] .

.
. , , l
:

18

cm 2
d [ A]
mol
rdif = D( A)
, D ( A)
, rdif 2

dl
sec
cm
sec

(17)

cm
mol
rchem = kchem [ Asurf ], kchem , rchem 2
,

sec
sec
cm

(18)

() ,
. ,

1
1
2 3
cm
cm
.
(17) (18)

rchem = rdif ,
(19)

d [ A]
= kchem [ Asurf ]
D ( A)
dl
(19)

L . [ A] = [ A0 ] :

18
L

d [ A] =

surf

kchem[ Asurf ]
D ( A)

surf

[ A0 ] [ Asurf ] =

dl ,

kchem[ Asurf ]L
D( A)

; kdif =

(19)

D( A) cm

L
sec

[ Asurf ] =

kdif [ A0 ]

(20)

kdif + kchem

rchem =

kchem kdif
kdif + kchem

kchem  kdif

[ A0 ] = keff [ A0 ]

(21)

, .

[ Asurf ] =

kdif [ A0 ]

(22)

kchem

rchem = kdif [ A0 ]
,

[ Asurf ] =

(23)

kchem  kdif , .

kdif [ A0 ]
kdif

= [ A0 ]; rchem = kchem [ A0 ]

(24)

(24)
:

18

-EA/R
lnkeff

ln kdif

ln kchem

1/T

. ,
,
- .
.

. .125-133

A B,
.
K
k2

Aads
Agas
Bgas

(25)

. -
.
,
:

A =

K pA
= ( K p A ) (1 A )
1 + ( K pA )

18

A =

[ Asurf ]

(26)

[ A0 ]

[ Asurf

] - , [ A0 ] -
15 molec
, 10
, - , K -
2
cm

, pA A , (1-A)

r = k2 [ Asurf ] = k2 A [ A0 ] = k2 K p A (1 A )[ A0 ] =
p
= keff p A = keff ( RT ) A = keff' [ Agas ]
RT
keff'

(27)

{/(**- )}
r (27)
, ..

{/(*)} = {- ./}
k2
..

,
{1/}

{1/}
, (25) :
KA
KB
k2

Agas
A

B
sf
sf Bgas

(28)

18

A = K A p A (1 A B ),
B = K B pB (1 A B )

(29)

B =

K B pB
A ;
K A pA

A =

K A pA
1 + K B pB + K A p A

(30)

r = k2 A[ A0 ] =

k2 K A p A [ A0 ]
1 + K B pB + K A p A

(31)

.
- .
(31)
)

r = k2 A[ A0 ] =

k2 K A p A [ A0 ]
= k2 K A p A [ A0 ] = keff p A ,
1
K A p A , K B pB  1, 1 A 1

(32)
,
.
)

r = k2 A[ A0 ] =

k2 K A p A [ A0 ]
p
= ke''ff A ,
K B pB
pB

(33)

( K B pB )  1 + ( K A p A )

, .

()

10

18

keff = k2 K A [ A0 ],
d ln keff

d ln k2 d ln K A
+
,
dT
dT
dT
Eeff = E2 + H ads ( A) = E2 H des ( A)

Eeff

(34)

- ( ) ,

H ads , H des - .

():

keff'' =

k2 K A [ A0 ]
,
KB

d ln keff''

d ln k2 d ln K A d ln K B
+

,
dT
dT
dT
dT
Eeff = E2 + H ads ( A) H ads ( B )
=

(35)

11