Key words: thermodynamics, equilibrium fluctuations, kinetic theory of gases, chemical kinetics, rate of reaction, rate constant
The contribution of local fluctuations to the rates of thermal chemical reactions is evaluated for the first time. In the framework of the «ideal gas» model the fluctuation supplement to the rate constant is proportional to the specific volume of the particles and can reach 1—10 % at densities not exceeding a 20-fold normal atmosphere density. This is the reason why the accounting of local fluctuations in chemical kinetics should be made before the accounting of specific volumes in the equation of state.
doi:10.1134/S1990793110070031