, . : .
: 1) (1889 .); 2) ( , 1935 ).
, . , , :
1) EA;
2) .
exp(-Ea/RT), . P - , (. ).
: .
E1 ,
2 ,
DH , DH = E1 E2,
. . .
, .
:
+ → .
, .
W = ZA .
ZA = Z0×e- E /RT
E ; Z0 .
:
W = k×CA×CB
:
ZA = k×CACB; k×CA×CB = Z0×e- E /RT
= = 1,
k = Z0×e - E /RT,
Z .
, , , . , . , , :
k = PZ×e- E /RT
= 110-8
k = A×e Ea/RT.
:
E = Ea RT/2
RT/2 . :
= P×Z.
. , , 2- , . , 1- , 1- 2- .
|
|
1922 . .
. , :
A + A A* + A
W3
2- W1 *, , W3, , ( W2):
W1 = k1CA2,
W2 = k2CA*×CA,
W3 = k3CA*.
W1 = W2 + W3.
k1C2 = k2C*×C + k3C* = C*(k2C + k3),
C* = k1C2/(k2C + k3), C* - .
W3:
W3 = k3k1C2/(k2C + k3).
:
1) , :
k2<< k3, .. k2C 0, W3 = k1C2.
(), , 1- 2- .
2) , :
k2>> k3, .. W3 = (k3×k1/ k2)C, (k3×k1/ k2) = k,
W3 = kC.
, - * 1- . .
6.9.2. (
)
. :
+ [ ] ¹ + C
, . , . . , :
[ х]¹.
. , . , , .
, , -, , -, . , , . . , , , . .
|
|
:
k = χ(kT/h)K≠,
kB = 1.38.10-23 / - , h = 6.63.10-34 . - , K≠ - , ( /), χ , , .
.
: DG¹ = RTlnK¹,
K¹ = eDG¹ / RT,
DG¹ = DH¹ T×DS¹,
K¹ = eDH¹ / RT× eDS¹ / R,
k = χ×(kT/h)× eDH¹ / RT× eDS¹ / R,
DH¹ DS¹ - .
:
k = PZ ×eE/RT, : P = (χ×(kT/h)× eDS¹ / R) / Z, .. .