According to the theoretical bases of thermokinetics and analog thermogram method, a general analog thermogram method for several types of reversible reactions, with which the rate constants of forward and backward re...According to the theoretical bases of thermokinetics and analog thermogram method, a general analog thermogram method for several types of reversible reactions, with which the rate constants of forward and backward reactions and equilibrium constant can be calculted from the same thermogram simultaneously, has been proposed in this paper. The thermokinetics of the reactions of nitroethane with ammonia at 15℃ and 25℃ and with tris (hydroxymethyl)aminomethane at 15℃ and 30℃ have been studied with this method,re-spectively. The results of rate constants and equilibrium constants calculated with this method are in agreement with those in literatures. Therefore, the analog thermogram method for the reversible reactions is believed to be correct.展开更多
Based on the thermokinetic theory, a novel thermokinetic research methodself-function regression method, which could be used to determine the kinetic parameters k1, k2 and k-1 of the complex reaction: B+ ...Based on the thermokinetic theory, a novel thermokinetic research methodself-function regression method, which could be used to determine the kinetic parameters k1, k2 and k-1 of the complex reaction: B+ , ,was proposed in this paper. The kinetics of the reaction of ascorbic acid (H2A) with hydrogen peroxide was investigated at pH=57 and T=298.15 K, and the kinetic parameters k1, k 2 and k-1 were obtained with this method. The kinetics of the reaction was investigated in detail. The kinetic parameters of the oxidation of ascorbic monoanion (HA-) and ascorbic dianion (A2-) with hydrogen peroxide were 3.33×10-3 s-1and 25.48 s-1 at 298.15 K, respectively. The molar enthalpy change for the reaction was -554.64 kJ·mol-1 in phosphate buffer solution at pH 7 and at 298.15 K.展开更多
文摘According to the theoretical bases of thermokinetics and analog thermogram method, a general analog thermogram method for several types of reversible reactions, with which the rate constants of forward and backward reactions and equilibrium constant can be calculted from the same thermogram simultaneously, has been proposed in this paper. The thermokinetics of the reactions of nitroethane with ammonia at 15℃ and 25℃ and with tris (hydroxymethyl)aminomethane at 15℃ and 30℃ have been studied with this method,re-spectively. The results of rate constants and equilibrium constants calculated with this method are in agreement with those in literatures. Therefore, the analog thermogram method for the reversible reactions is believed to be correct.
基金Project supported by the National Natural Science Foundation of China (Nos. 20107004 & 20173038).
文摘Based on the thermokinetic theory, a novel thermokinetic research methodself-function regression method, which could be used to determine the kinetic parameters k1, k2 and k-1 of the complex reaction: B+ , ,was proposed in this paper. The kinetics of the reaction of ascorbic acid (H2A) with hydrogen peroxide was investigated at pH=57 and T=298.15 K, and the kinetic parameters k1, k 2 and k-1 were obtained with this method. The kinetics of the reaction was investigated in detail. The kinetic parameters of the oxidation of ascorbic monoanion (HA-) and ascorbic dianion (A2-) with hydrogen peroxide were 3.33×10-3 s-1and 25.48 s-1 at 298.15 K, respectively. The molar enthalpy change for the reaction was -554.64 kJ·mol-1 in phosphate buffer solution at pH 7 and at 298.15 K.
