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Relation between rate constants of opposite reaction directions

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Combustion, Explosion and Shock Waves Aims and scope

Conclusions

  1. 1.

    The concept of rate constants (coefficients) of mutually reversible reaction directions in an ideal gas (or in an ideal solution) and the question of their connection with the equilibrium constant are quite meaningful upon compliance with the following two respective conditions: a) the progress of the reaction in each of the two directions is such that the rate of change in the concentration of intermediate products is low in comparison to the reaction rate, and b) the reaction occurs in a medium whose state is either in or sufficiently close to thermodynamic equilibrium. Under the conditions mentioned, the ratio between the rate constants (coefficients) of the two reaction directions equals its equilibrium constant calculated at the temperature of the medium. This regularity is intrinsic not only to the single-stage but also to complex multistage reactions.

  2. 2.

    The ratio between the rate constants (coefficients) of mutually reverse reaction directions in a spatially homogeneous medium whose state is characterized by two different subsystem temperatures (T1 and T2), equals the “constant” K(T1T2) characterizing the equilibrium of the reaction in such a not completely equilibrium medium.

  3. 3.

    If the equilibrium of the medium is substantially spoiled during the reaction itself, then the state of the medium depends (not only in quantitative but also in qualitative respects) on the direction of the reaction in the general case. Hence, the ratio between the reaction rate constants (coefficients) is already not a thermodynamic characteristic of the medium.

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Authors
  1. N. M. Kuznetsov
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Moscow. Translated from Fizika Goreniya i Vzryva, Vol. 9, No. 5, pp. 683–699, September–October, 1973.

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Kuznetsov, N.M. Relation between rate constants of opposite reaction directions. Combust Explos Shock Waves 9, 595–609 (1973). https://doi.org/10.1007/BF00742887

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  • DOI: https://doi.org/10.1007/BF00742887

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