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Accumulation and Decay of Macroscopic Correlations in Elementary Reactions Kinetics
Doktorov, Alexander B.,Kipriyanov, Alexander A.,Kipriyanov, Alexey A. Korean Chemical Society 2012 Bulletin of the Korean Chemical Society Vol.33 No.3
In the present contribution the Encounter Theory (ET) (the prototype of the classical Collision Theory in rarefied gases) concepts for widely occurring diffusion assisted irreversible bulk reactions A + A ${\rightarrow}$ C and A + B ${\rightarrow}$ C in liquid solutions examined by the authors in the literature are analyzed and compared with each other for these different types of reactions. It is shown that for a particular case of equal initial concentrations $[A]_0=[B]_0$ in the reaction A + B ${\rightarrow}$ C, when the kinetics of both reactions A + A ${\rightarrow}$ C and A + B ${\rightarrow}$ C in the framework of formal chemical kinetics and ET are the same, the accumulation of macroscopic correlations breaking the concepts of independent encounters and leading to the Generalized Encounter Theory (GET) are drastically different. The influence of the force interaction and the decay of nonstable reactants on the time behavior the macroscopic correlations is also briefly discussed.
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Accumulation and Decay of Macroscopic Correlations in Elementary Reactions Kinetics
Alexander B. Doktorov,Alexander A. Kipriyanov,Alexey A. Kipriyanov 대한화학회 2012 Bulletin of the Korean Chemical Society Vol.33 No.3
In the present contribution the Encounter Theory (ET) (the prototype of the classical Collision Theory in rarefied gases) concepts for widely occurring diffusion assisted irreversible bulk reactions A + A → C and A + B → C in liquid solutions examined by the authors in the literature are analyzed and compared with each other for these different types of reactions. It is shown that for a particular case of equal initial concentrations [A]0 = [B]0 in the reaction A + B → C, when the kinetics of both reactions A + A → C and A + B → C in the framework of formal chemical kinetics and ET are the same, the accumulation of macroscopic correlations breaking the concepts of independent encounters and leading to the Generalized Encounter Theory (GET) are drastically different. The influence of the force interaction and the decay of nonstable reactants on the time behavior the macroscopic correlations is also briefly discussed.
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