Microscopic reversibility, and

Light J C, Ross J and Shuler K E 1969 Rate coefficients, reaction cross sections and microscopic reversibility Kinetic Processes in Gases and Piasmas ed A R Hochstim (New York Academic) pp 281-320... 

Definition of Critical and Rate-Limiting Bottlenecks" The hypothesis of local equilibrium within the reservoirs means that the set of transitions from reservoir to reservoir can be described as a Markov process without memory, with the transition probabilities given by eq. 4. Assuming the canonical ensemble and microscopic reversibility, the rate constant Wji, for transitions from reservoir i to reservoir j can be written... 

Superficially this appears to be a violation of microscopic reversibility. However, since the reaction is not adiabatic, we are not dealing with the interconversion of two species. Each reaction proceeds from excited state of reactant to ground state of product and microscopic reversibility is not relevant. 

Rate equations and their coefficients in networks are not entirely independent. They are subject to two constraints thermodynamic consistency and so-called microscopic reversibility. For reversible reactions, the algebraic form of the rate equation of the forward reaction imposes a constraint on that of the rate equation of the reverse reaction. In addition, the requirements of thermodynamic consistency and microscopic reversibility can be used to verify that the postulated values of the coefficients constitute a self-consistent set, or to obtain a still missing coefficient value from those of the others. 

It has been said that only termination, but not dissociation, involves a collision partner M and that the ratio klm, ikcB, in the rate equation does not equal the dissociation equilibrium constant because the two coefficients are "not linked by detailed balancing" [16], However, this argument is without merit. In the absence of H2 (or any other species with which Br- can react), thermodynamic consistency and microscopic reversibility clearly require M to participate in dissociation if it does so in recombination. The addition of any species such as H2 that takes no part in the dissociation step may cause the system to deviate from thermodynamic dissociation equilibrium, but can obviously not alter the mechanism of dissociation. 

Shreve G. A. and Lewis N. S. (1995), An analytical description of the consequences of abandoning the principles of detailed balance and microscopic reversibility in semiconductor photoelectrochemistry , J. Electrochem. Soc. 142, 112-119. 

The most common initiation or homolysis reaction is the breaking of a covalent C-C bond with the formation of two radicals. This initiation process is highly sensitive to the stability of the formed radicals. Its activation energy is equal to the bond dissociation enthalpy because the reverse, radical-radical recombination reaction is so exothermic that it does not require activation energy. C-C bonds are usually weaker than the C-H bonds. Thus, the initial formation of H radicals can be ignored. The total radical concentration in the reacting system is controlled both by these radical initiation reactions and by the termination or radical recombination reactions. In accordance with Benson (1960), the rate constant expressions of these unimolecular decompositions are calculated from the reverse reaction, the recombination of two radical species to form the stable parent compound, and microscopic reversibility (Curran et al., 1998). The reference kinetic parameters for the unimolecular decomposition reactions of K-alkanes for each single fission of a C-C bond between secondary... 

Although an unfolding simulation can provide information on the folding pathway and microscopic reversibility has been confirmed for some systems, it should be remembered that this assumption is valid and unfolding is... 

Most kineticists are familiar with the principles of detailed balance and microscopic reversibility, as stated in equations (1.9) and (1.10). The successive stages of averaging over initial state distributions and summing over final state distributions by which one can proceed rigorously from (1.10) to (1.9) are less well-known. This procedure is important, not only for its own sake, but also because it yields equations that relate the parameters describing the kinetics of forward and reverse processes at all levels of detail. It is now outlined for a reaction of the type... 

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