The microcosmic reaction mechanism of the thermal decomposition of potassium nitroformate（KNF） has been investigated by density functional theory within the generalized gradient approximation. The geometric structur...The microcosmic reaction mechanism of the thermal decomposition of potassium nitroformate（KNF） has been investigated by density functional theory within the generalized gradient approximation. The geometric structures of reactants, intermediates, transition states, and products are fully optimized. The frequency analysis approves the authenticity of intermediates and transition states. Our results show that there are four feasible reaction pathways. The main pathway of the reaction is KNF → B1 → TSB1 → B2 → TSB2 → B3 → TSB3 → B4 → KNO2 ＋ NO2 ＋ NO ＋ CO, and the energy barrier of the rate-limiting step is 216.30 k J·mol^-1. The dominant products predicted theoretically are KNO2, NO2, NO, and CO, which is in agreement with the experiment.展开更多
The thermal decomposition process of LiHC2O4·H2O from 30 to 600 ℃ was investigated by the thermogravimetric and differential scanning calorimetry (TG-DSC). The phases decomposited at different temperature were c...The thermal decomposition process of LiHC2O4·H2O from 30 to 600 ℃ was investigated by the thermogravimetric and differential scanning calorimetry (TG-DSC). The phases decomposited at different temperature were characterized by X-ray diffraction (XRD), which indicated the decompositions at 150, 170, and 420℃, relating to LiHC2O4, Li2C2O4, Li2C2O4, and Li2CO3, respectively. Reaction mechanisms in the whole sintering process were determined, and the model fitting kinetic approaches were applied to data for non-isothermal thermal decomposition of LiHC2O4?H2O; finally, the kinetic parameters of each reaction were also calculated herein.展开更多
Gd2O3∶Tb3+ luminescent nanoparticles were prepared by the thermal decomposition of the nanosized oxlate prepared in the reverse microemulsions based on triton X-100/n-hexyl alcohol, n-octane, and water. From TG-DTA, ...Gd2O3∶Tb3+ luminescent nanoparticles were prepared by the thermal decomposition of the nanosized oxlate prepared in the reverse microemulsions based on triton X-100/n-hexyl alcohol, n-octane, and water. From TG-DTA, XRD and FTIR analyses, the mechanism of thermal decomposition of the nanosized oxalate precursor is suggested as follows: Gd2(C2O4)3·10H2O → Gd2(C2O4)3 + 10H2O, Gd2(C2O4)3 → Gd2O2(CO3) + 3CO +2CO2, Gd2O2(CO3) → Gd2O3 + CO2. The kinetic parameters of thermal decomposition reaction-activation energy E of stage 2 and 3 are 194.6 kJ·mol-1, 110.9 kJ·mol-1, respectively, using Ozawa method. And the reaction order n is 2.9 and 0.43, respectively, according to the TG curves.展开更多
基金supported by the Scientific and Technological Research Program of Chongqing Municipal Education Commission(KJ131318,KJ1401227,KJ15012002)the Fuling Science and Technology Commission(FLKJ2015ABA1042)the Project of Chongqing Key Laboratory of Inorganic Special Functional Materials(KFKT201506)
文摘The microcosmic reaction mechanism of the thermal decomposition of potassium nitroformate（KNF） has been investigated by density functional theory within the generalized gradient approximation. The geometric structures of reactants, intermediates, transition states, and products are fully optimized. The frequency analysis approves the authenticity of intermediates and transition states. Our results show that there are four feasible reaction pathways. The main pathway of the reaction is KNF → B1 → TSB1 → B2 → TSB2 → B3 → TSB3 → B4 → KNO2 ＋ NO2 ＋ NO ＋ CO, and the energy barrier of the rate-limiting step is 216.30 k J·mol^-1. The dominant products predicted theoretically are KNO2, NO2, NO, and CO, which is in agreement with the experiment.
基金financially supported by the National"863"Program of China(No.2009AA03Z226)Project on the Integration of Industry,Education and Research of Guangdong Province(No.2011A090200012)the Fundamental Research Funds for the Central Universities(No.FRF-MP-12-005B)
文摘The thermal decomposition process of LiHC2O4·H2O from 30 to 600 ℃ was investigated by the thermogravimetric and differential scanning calorimetry (TG-DSC). The phases decomposited at different temperature were characterized by X-ray diffraction (XRD), which indicated the decompositions at 150, 170, and 420℃, relating to LiHC2O4, Li2C2O4, Li2C2O4, and Li2CO3, respectively. Reaction mechanisms in the whole sintering process were determined, and the model fitting kinetic approaches were applied to data for non-isothermal thermal decomposition of LiHC2O4?H2O; finally, the kinetic parameters of each reaction were also calculated herein.
文摘Gd2O3∶Tb3+ luminescent nanoparticles were prepared by the thermal decomposition of the nanosized oxlate prepared in the reverse microemulsions based on triton X-100/n-hexyl alcohol, n-octane, and water. From TG-DTA, XRD and FTIR analyses, the mechanism of thermal decomposition of the nanosized oxalate precursor is suggested as follows: Gd2(C2O4)3·10H2O → Gd2(C2O4)3 + 10H2O, Gd2(C2O4)3 → Gd2O2(CO3) + 3CO +2CO2, Gd2O2(CO3) → Gd2O3 + CO2. The kinetic parameters of thermal decomposition reaction-activation energy E of stage 2 and 3 are 194.6 kJ·mol-1, 110.9 kJ·mol-1, respectively, using Ozawa method. And the reaction order n is 2.9 and 0.43, respectively, according to the TG curves.
