The rates of bimolecular thermal reactions taking into account local medium fluctuations

被引：0
|
作者：
Chaikina, Yu A. [1 ]
机构：
[1] Russian Acad Sci, NN Semenov Chem Phys Inst, Moscow, Russia
来源：
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B | 2010年 / 4卷 / 07期
关键词：
thermodynamics; equilibrium fluctuations; kinetic theory of gases; chemical kinetics; reaction rate; rate constant;
D O I：
10.1134/S1990793110070031
中图分类号：
O64 [物理化学（理论化学）、化学物理学]; O56 [分子物理学、原子物理学];
学科分类号：
070203 ; 070304 ; 081704 ; 1406 ;
摘要：
The contribution of local medium fluctuations to the rates of thermal chemical reactions was calculated for the first time. It was shown for the "ideal gas" model that the fluctuation contribution to a rate constant was proportional to the specific volume of particles and amounted to 1-10% already at densities of about 20 atmosphere densities. For this reason, chemical kinetics calculations of reaction rates should be performed taking into account local medium fluctuations before taking into account specific volume in the equation of state.
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页码：1061 / 1068
页数：8
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