2018 年 60 巻 192 号 p. 112-121
After the interpretation of the kinetic mechanism of hydrogen-oxygen combustion in the early twentieth century, the elementary reaction kinetics has been considered to be one of the essential issues in the science and technology of combustion. Recent developments in the quantum chemical methodology and computational technology have provided powerful tools for the construction and improvement the reaction mechanisms of combustion. However, the underlying theories of the reaction rate constants have not been well understood nor documented, especially in the sense that they are essentially based on the molecular statistical thermodynamics. In this article, the key points in the reaction kinetics will be described with a focus on the theoretical evaluation of the rate constants. The rate law of the gas-phase elementary reaction is briefly introduced and then the statistical theory of the rate constant, transition state theory, will be described. The molecular statistical thermodynamics will be discussed as it plays a central role in the actual evaluation of the rate constants. The theory of unimolecular reactions will be also introduced.
