TO CALCULATION OF SPEEDS CONSTANTS OF BIMOLECULARE
REACTIONS IN THE GAS PHASE ON THERMODYNAMIC DATA
V.V. Dudorov, T.A. Melchakova, A.R. Mishanov
Nizhniy Novgorod state Agricultural academy
Agriecology and Agrichemitrsy faculty
603107, Nizhny Novgorod, Ju. Gargarin Prospect 97, Russia
fax: (8312) 660684, e-mail: root@agri.sci-nnov.ru
The basis of modern ways of theoretical calculation of chemical reactions
velocity constants is made with a method of the activated complex (transition
condition). In the updating of a method offered by us for calculation of velocity
constants of bimolecular reactions in a gas phase the transition condition of
reaction is considered in the form of a real complex, formatted from cooperating
molecules with maximal energy of the chemical bands which are taking part the
certificate of transformation. The scheme of reaction АВ + СД = AC +ВД in
this case can be presented in the form of to:
К
АВ + М  АВ*
К
СД + М  СД*
k1
k*
АВ* + СД*  (АВСД)*  АС + ВД
k--1
Then, in assumption quasistationary concentrations of reagents and with idea of
a method of a transitive condition the complex constant of reaction speed will
become the form:

k  k*
K1  K 2  k1 kT 

K .
k1  k *
2
(1)
According to the data received by us earlier [1] formation of an
intermediate complex in reaction can lead to transition of reaction in oscillation
(pulsing) condition. However, according to our calculation of velocity constants
to reversible gas reactions H2 + I2 =2HI the speed constant (1), not dependent
on concentration of reagents, changes droningly in wide temperature interval.
Literature
1. Dudorov V.V. // Metalloorganic Chemistry. 1988. V. 1. № 3. P. 580-585.
161