A novel thermokinetic research method for determination of rate constants of simple-order reaction in batch conduction calorimeter
under isothermal condition, the characteristic parameter method, is proposed in this paper. Only needing the characteristic
time parameter tm obtained from the measured thermoanalytical curve, the kinetic parameters of reactions studied can be calculated
conveniently with this method. The saponifications of ethyl propionate and ethyl acetate in aqueous ethanol solvent, the polymerization
of acrylamide in aqueous solution, the ring opening reaction of epichlorohydrin with hydrobromic acid have been studied. The
experimental results indicate that the characteristic parameter method for simple-order reaction is correct.
According to the theoretical basis of thermokinetics, the integral and differential thermokinetic equations of opposing reactions have been derived, and a novel thermokinetic research method, the characteristic parameter method for opposing reactions which taking place in a batch conduction calorimeter under isothermal condition, has been proposed in this paper. Only needing the characteristic thermoanalytical data corresponding to tm and 2tm from the same curve, the rate constants of forward and backward reactions and equilibrium constant can be calculated simultaneously with this method. In order to test the validity of this method, the proton-transfer reactions of nitroethane with ammonia at 15 and 25°C, and with trihydroxymethyl aminomethane (Tris) at 15 and 30°C have been studied, respectively. The results of rate constants and equilibrium constants calculated with this method are in agreement with those in the literature. Therefore, the characteristic parameter method for opposing reaction is believed to be correct.
Authors:Y.-Q. Zhang, X.-C. Zeng, Y. Chen, X.-G. Meng, and A.-M. Tian
On the basis of the theory of thermokinetics proposed in the literature, a novel thermokinetic method for determination of the reaction rate, the characteristic parameter method, is proposed in this paper. Mathematical models were established to determine the kinetic parameters and rate constants. In order to test the validity of this method, the saponifications of ethyl benzoate, ethyl acetate and ethyl propionate, and the formation of hexamethylenetetramine were studied with this method. The rate constants calculated with this method are in agreement with those in the literature, and the characteristic parameter method is therefore believed to be correct.In the light of the characteristic parameter method, we have developed further two thermo-kinetic methods, the thermoanalytical single and multi-curve methods, which are convenient for simultaneous determination of the reaction order and the rate constant. The reaction orders and rate constants of the saponifications of ethyl acetate and ethyl butyrate and the ring-opening reaction of epichlorohydrin with hydrobromic acid were determined with these methods, and their validity was verified by the experimental results.