抄録
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
Sb(t,t+Δt)=Const.−ΔFs(t,t+Δt)⁄2T,
where ΔFs(t,t+Δt) is the amount of free energy increase in the system during the time interval Δt, 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(−βf), f’s are not energies but free energies.
