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A classic kinetic methodology including the treatment of the steady-state method and a multivariate modeling kinetic treatment were applied to the kinetics and mechanism of the isomerization reaction of 5-cholesten-3-one to 4-cholesten-3-one catalyzed by EtO − in ethanol absolute. The rate constants, thermodynamic parameters of activation, equilibrium constant, and the isomerization enthalpy were determined. The multivariate modeling kinetic treatment allows us to calculate the concentrations of the species, in which the 3,5-dienolate is included as a highly reactive intermediate species and was able to discriminate among several applicable mechanisms validating the one comprising two reversible steps. C 2005 Wiley Periodicals, Inc. Int J Chem Kinet 38: [38][39][40][41][42][43][44][45][46][47] 2006