Thermodynamics of irreversible processes ‘When the system reaches equilibrium, the concentrations no longer change (ie. defd1=0) and the kinetic equations reduce to O= (hy thal + heicg + keh, Om ky = (ka thal pha, (0.24) O= hase + hac = (hes tale ‘Solving for cf in the first equation and inserting it into the second equation yields kak mlb thet At oki? or (9.25) where K“) js the equilibrium constant for the reaction AZ B. ‘We now consider the same set of reactions from the point of view of the thermodynamics of irreversible processes. First, we express the eon- centrations in Eq. (9.23) through the chemical thermodynamic forces Equation (9.15) implies that cm __(),,¢) = erp intie —rrinti APs — (ue pf) =-RT I = RP In Near equilibrium, the ratio ¢,/cF isclose to unity and hence we may expand the logarithm to abtain such that (9.26) Inserting Eq. (9.26) into Eq. (9.23) and using Eq. (9.24), we find er = SB pen = Bytom lea, Gtk Te Ti ag 27)