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

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作者
Yu. A. Chaikina
机构
[1] Russian Academy of Sciences,Semenov Institute of Chemical Physics
关键词
thermodynamics; equilibrium fluctuations; kinetic theory of gases; chemical kinetics; reaction rate; rate constant;
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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:7
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