화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.108, No.40, 8296-8306, 2004
Some observations concerning detailed balance in association/dissociation reactions
In this article we discuss the chemical kinetics of reversible association/dissociation reactions at great length. We find that, as long as the characteristic time for internal-energy relaxation is faster (not necessarily much faster) than that for chemical reaction, there will be a period of time, perhaps only late in the reaction but before equilibrium is reached, during which phenomenological rate laws will apply with rate coefficients that satisfy detailed balance. The nonequilibrium factor, f(ne), originally introduced by Smith, McEwan, and Gilbert (J. Chem. Phys. 1989, 90, 4265-4273) is not a measure of the degree to which detailed balance is satisfied by the association and dissociation rate coefficients. It is simply the fractional contribution to the "long-time" association rate coefficient, k(add), of the slowest-relaxing eigenmode of the system. That is, 1 - f(ne) is the fractional contribution to the same rate coefficient of the internal-energy relaxation modes. The standard practice of taking the dissociation rate coefficient, k(d), to be equal to that for irreversible dissociation is accurate as long as gamma equivalent to K(eq)n(m)(1 - f(ne)) much less than 1, where K-eq is the equilibrium constant for the association reaction, and n(m) is the concentration of the excess reactant under pseudo first-order conditions for the association reaction. Both rate coefficients, k(add) and k(d), show a very weak composition dependence, i.e., dependence on n(m).