Chen Donghua

Comparative method to evaluate reliable kinetic triplets of thermal decomposition reactions

Reliable kinetic information for thermal analysis kinetic triplets can be determined by the comparative method: (1) An iterative procedure or the KAS method had been established to obtain the reliable value of activation energy Ea of a reaction. (2) A combined method including Coats-Redfern integral equation and Achar differential equation was put forward to confirm the most probable mechanism of the reaction and calculate the pre-exponential factor A. By applying the comparative method above, the thermal analysis kinetic triplets of the dehydration of CaC2O4·H2O were determined, which apparent activation energy: 81±3 kJ mol-1, pre-exponential factor: 4.51·106-1.78·108 s-1, the most probable mechanism function: f(α)=1 or g(α)=α, which the kinetic equation of dehydration is dα/dt=Ae-Ea/RT.

Preparation and Kinetics of the Thermal Decomposition of Nanosized CuC2O4-ZnC2O4·2H2O

The physical mixture of nanosized CuC2O4−ZnC2O4·2H2O, as precursors of CuO−ZnO, have been prepared by the one-step solid state reaction method at room temperature. The thermal decomposition processes taking place in the solid state oxalate mixture of nanometer CuC2O4−ZnC2O4·2H2O have been studied in static air using TG, DSC, XRD and TEM techniques. TEM showed that the grain size of the decomposition product is 5–15 nm. The values of the activation energyEα were determined using the isoconversional procedure of KAS method and the Ozawa method. The most possible mechanism functionf(α) of the thermal decompositions of nanosized CuC2O4−ZnC2O4·2H2O are defined using the comparative method, function models of the decomposition of CuC2O4 and ZnC2O4 follow the same mechanism function “Avrami-Erofeev equation”. The pre-exponential factorA is obtained on the basis ofEα andf(α), thus the thermal analysis kinetic triplet of the decompositions of nanosized CuC2O4−ZnC2O4·2H2O are determined.

Studies of dehydration kinetics of Li2SO4·H2O by the master plots method

The kinetics of Li2SO4·H2O dehydration in static air atmosphere was studied on the basis of nonisothermal measurements by differential scanning calorimetry. Dehydration data were subjected to an integral composite procedure, which includes an isoconversional method, a master plots method and a model-fitting method. Avrami-Erofeev equation was found to describe all the experimental data in the range of conversion degrees from 0.1 to 0.9. The determined activation energy equals 65.45 kJ·mol−1 with standard deviation ±0.47 kJ·mol−1. The estimated value of parameter m in Avrami-Erofeev equation is 2.15 with standard deviation ±0.11. Also, the obtained pre-exponential factor is 7.79×105 s−1 with standard deviation ±0.55×105 s−1. The results show that the present integral composite procedure gives self-consistent kinetic parameters.

Description of mechanism function about dehydration of cobalt oxalate dihydrate by multiple rates isotemperature method

A new method of the multiple rates isotemperature is proposed to define the most probable mechanismg(α) of thermal anlaysis; the iterative isoconversional procedure has been employed to estimate apparent activation energyE; the pre-exponential factorA is obtained on the basis ofE andg(α). By this new method, the thermal analysis kinetics triplet of dehydration of cobalt oxalate dihydrate is determined, apparent activation energyE is 99.84 kJ·mol−1; pre-exponential factorA is 3.427×109–3.872×109 s−1 and the most probable mechanism belongs to nucleation and growth,Am model, the range ofm is from 1.50 to 1.70.