Cooperative Chemical Kinetics

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Abstract
Kikuchi's theory of irreversible cooperative phenomena is extended so as to treat cooperative chemical kinetics. A state distinguished chemically from others (a chemical state) is made up of a number of physically distinguishable states. When probabilities of transitions between states belonging to a same chemical state are large compared with those between states belonging to different chemical states, the path entropy of a heat bath is shown to be \begin{aligned} S_{b}(t,t+\varDelta t){=}\text{Const.}-\varDelta F_{s}(t,t+\varDelta t)/2T, \end{aligned} where Δ F s ( t , t + Δ t ) is the amount of free energy increase in the system during the time interval Δ t , and T is the temperature of the heat bath. This expression of the path entropy of a heat bath can be used in chemical kinetics, since statistical weight parameters of a chemical system are given in a form exp (-β f ), f 's are not energies but free energies.

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