The reaction of C3H8＋O（^3p）→C3HT＋OH is investigated using ab initio calculation and dynamical methods. Electronic structure calculations for all stationary points are obtained using a dual-level strategy. The geo...The reaction of C3H8＋O（^3p）→C3HT＋OH is investigated using ab initio calculation and dynamical methods. Electronic structure calculations for all stationary points are obtained using a dual-level strategy. The geometry optimization is performed using the unrestricted second-order Moller-Plesset perturbation method and the single-point energy is computed us- ing the coupled-cluster singles and doubles augmented by a perturbative treatment of triple excitations method. Results indicate that the main reaction channel is C3Hs＋O（^3p）→i- C3HT＋OH. Based upon the ab initio data, thermal rate constants are calculated using the variational transition state theory method with the temperature ranging from 298 K to 1000 K. These calculated rate constants are in better agreement with experiments than those reported in previous theoretical studies, and the branching ratios of the reaction are also calculated in the present work. Furthermore, the isotope effects of the title reaction are calculated and discussed. The present work reveals the reaction mechanism of hydrogenabstraction from propane involving reaction channel competitions is helpful for the understanding of propane combustion.展开更多
An improved test rig providing both the heat and cold source was used to perform thermal response test （TRT）, and the line source model was used for data analysis. The principle of determining the temperature differ...An improved test rig providing both the heat and cold source was used to perform thermal response test （TRT）, and the line source model was used for data analysis. The principle of determining the temperature difference between the inlet and outlet of test well can keep the heating or cooling rate constant, along with a reduced size of test rig. Among the influencial factors of the line source model, the temperature difference was determined as the most important, which agreed with the test results. When the gravel was taken as the backfill material, the soil thermal conductivities of heating and cooling at the test place were 1.883 W/（m＆#183;K） and 1.754 W/（m＆#183;K）, respectively, and the deviation of TRT between heating and cooling soil was 6.8%. In the case of fine sand, the thermal conductivities of heating and cooling were 1.541 W/（m＆#183;K） and 1.486 W/（m＆#183;K）, respectively, and the corresponding deviation was 6%. It was also concluded that different velocities of water had less influence on TRT than the temperature difference.展开更多
We present nonadiabatic quantum dynamical calculations on the two coupled potential energy surfaces （12A＇ and 22A＇） [J. Theor. Comput. Chem. 8, 849 （2009）] for the reaction. Initial state-resolved reaction proba...We present nonadiabatic quantum dynamical calculations on the two coupled potential energy surfaces （12A＇ and 22A＇） [J. Theor. Comput. Chem. 8, 849 （2009）] for the reaction. Initial state-resolved reaction probabilities and cross sections for the N＋ND→N2＋D reaction and N＇＋ND→N＋N＇D reaction for collision energies of 5 meV to 1.0 eV are determined, respectively. It is found that the N＋ND→N2＋D reaction is dominated in the N＋ND reaction. In addition, we obtained the rate constants for the N＋ND→N2＋D reaction which demand further experimental investigations.展开更多
An isothermal operation is implemented by employing a thermogravimetric analyzer (TGA) for simulating the thermal decomposition behavior of 58μm pine sawdust in air atmosphere.An independent parallel reaction model i...An isothermal operation is implemented by employing a thermogravimetric analyzer (TGA) for simulating the thermal decomposition behavior of 58μm pine sawdust in air atmosphere.An independent parallel reaction model is adopted in this study to describe the thermal decomposition mechanism.The Weibull distribution function is used to record and analyze the weight loss during isothermal decomposition at different temperatures(500,600,700,and 800°C).The total weight loss of the pine sawdust is assumed as a linear combination of individual weight loss from three components,including the char and two volatile matters.The plot of the thermal decomposition rate curve leads to kinetic parameters such as the reaction rate constants and the reaction order.The results show that the Weibull distribution function successfully represents decomposition curves of three components,and fits the experimental data very well.Therefore,this study provides a simple way to evaluate the decomposition rate of biomass combustion in a real combustor.展开更多
A pentane-insoluble mixture of asphaltenes was processed by thermal hydrocracking and catalytic hydrocracking over Ni-Mo/γ-Al2O3 catalyst in a microbatch reactor at 430 ℃.The experimental data of asphaltene conversi...A pentane-insoluble mixture of asphaltenes was processed by thermal hydrocracking and catalytic hydrocracking over Ni-Mo/γ-Al2O3 catalyst in a microbatch reactor at 430 ℃.The experimental data of asphaltene conversion adequately fit second-order kinetics to give the apparent rate constants of 2.435×10-2 and 9.360×10-2 (wt frac)-1 min-1 for the two processes,respectively.A three-lump kinetic model is proposed to evaluate the rate constants for parallel reactions of asphaltenes producing liquid oil (k1) and gas+coke (k3),and consecutive reaction producing gas+coke (k2) from this liquid oil.The evaluated constants for asphaltenes hydrocracking,in the presence and absence of the catalyst,respectively,show that k1 is 2.430×10-2 and 9.355×10-2 (wt frac)-1 min-1,k2 is 2.426×10-2 and 6.347×10-3 min-1,and k3 is 5.416×10-5 and 4.803×10-5 (wt frac)-1 min-1.As compared with the thermal hydrocracking of asphaltenes,the catalytic hydrocracking of asphaltenes promotes liquid production and inhibits coke formation effectively.展开更多
The oxidation characteristics of boron particles, boron-A with the diameter of 2.545 μm and boron-B with the diameter of 10.638 μm, at low temperature（1500 K） have been investigated by thermogravimetry（TG） coupl...The oxidation characteristics of boron particles, boron-A with the diameter of 2.545 μm and boron-B with the diameter of 10.638 μm, at low temperature（1500 K） have been investigated by thermogravimetry（TG） coupled with simultaneous differential scanning calorimetry（DSC）, infrared and mass spectra. A rapid oxidation stage of boron particles, followed by a slow oxidation stage of sintered particles, is found from the TG and DSC curves. The onset temperatures of the oxidation process of boron-A particles are in the range of 806–889 K, which are at least 105 K lower than those of boron-B at the same condition. As the partial pressure of oxygen increases from 5% to 35%, the onset temperature of boron-A or boron-B particles decreases. However, when the partial pressure of oxygen is above 35%, the onset temperature becomes constant, implying a saturation effect of oxygen on the reaction rate. It indicates that the chemical adsorption of oxygen, i.e. chemical reaction, on the particle surface is the rate-limited step at the beginning of the rapid oxidation stage. Therefore, the first-order chemical reaction model is used to simulate the oxidation of boron particles, even that of the sinter. The average activation energies of the particles are 291.3 kJ/mol for boron-A and 338.4 k J/mol for boron-B. While the average activation energies of the sintered particles are 36.35 k J/mol for boron-A and 31.87 kJ/mol for boron-B. The pre-exponential factor of the particles is -10^4, while that of the sinter is 10^-1. The oxidation rate constant of boron is qualitatively mainly affected by the specific surface of the sample and the thickness of the oxide layer.展开更多
文摘The reaction of C3H8＋O（^3p）→C3HT＋OH is investigated using ab initio calculation and dynamical methods. Electronic structure calculations for all stationary points are obtained using a dual-level strategy. The geometry optimization is performed using the unrestricted second-order Moller-Plesset perturbation method and the single-point energy is computed us- ing the coupled-cluster singles and doubles augmented by a perturbative treatment of triple excitations method. Results indicate that the main reaction channel is C3Hs＋O（^3p）→i- C3HT＋OH. Based upon the ab initio data, thermal rate constants are calculated using the variational transition state theory method with the temperature ranging from 298 K to 1000 K. These calculated rate constants are in better agreement with experiments than those reported in previous theoretical studies, and the branching ratios of the reaction are also calculated in the present work. Furthermore, the isotope effects of the title reaction are calculated and discussed. The present work reveals the reaction mechanism of hydrogenabstraction from propane involving reaction channel competitions is helpful for the understanding of propane combustion.
基金Supported by the National Natural Science Foundation of China(No.41272263)
文摘An improved test rig providing both the heat and cold source was used to perform thermal response test （TRT）, and the line source model was used for data analysis. The principle of determining the temperature difference between the inlet and outlet of test well can keep the heating or cooling rate constant, along with a reduced size of test rig. Among the influencial factors of the line source model, the temperature difference was determined as the most important, which agreed with the test results. When the gravel was taken as the backfill material, the soil thermal conductivities of heating and cooling at the test place were 1.883 W/（m＆#183;K） and 1.754 W/（m＆#183;K）, respectively, and the deviation of TRT between heating and cooling soil was 6.8%. In the case of fine sand, the thermal conductivities of heating and cooling were 1.541 W/（m＆#183;K） and 1.486 W/（m＆#183;K）, respectively, and the corresponding deviation was 6%. It was also concluded that different velocities of water had less influence on TRT than the temperature difference.
基金This work was supported by the National Basic Research Program of China （No.2007CB815202） and the National Natural Science Foundation of China （No.20721004 and No.20833008）.
文摘We present nonadiabatic quantum dynamical calculations on the two coupled potential energy surfaces （12A＇ and 22A＇） [J. Theor. Comput. Chem. 8, 849 （2009）] for the reaction. Initial state-resolved reaction probabilities and cross sections for the N＋ND→N2＋D reaction and N＇＋ND→N＋N＇D reaction for collision energies of 5 meV to 1.0 eV are determined, respectively. It is found that the N＋ND→N2＋D reaction is dominated in the N＋ND reaction. In addition, we obtained the rate constants for the N＋ND→N2＋D reaction which demand further experimental investigations.
基金Supported by the Chung Yuan Christian University (CYCU-97-CR-CE)
文摘An isothermal operation is implemented by employing a thermogravimetric analyzer (TGA) for simulating the thermal decomposition behavior of 58μm pine sawdust in air atmosphere.An independent parallel reaction model is adopted in this study to describe the thermal decomposition mechanism.The Weibull distribution function is used to record and analyze the weight loss during isothermal decomposition at different temperatures(500,600,700,and 800°C).The total weight loss of the pine sawdust is assumed as a linear combination of individual weight loss from three components,including the char and two volatile matters.The plot of the thermal decomposition rate curve leads to kinetic parameters such as the reaction rate constants and the reaction order.The results show that the Weibull distribution function successfully represents decomposition curves of three components,and fits the experimental data very well.Therefore,this study provides a simple way to evaluate the decomposition rate of biomass combustion in a real combustor.
文摘A pentane-insoluble mixture of asphaltenes was processed by thermal hydrocracking and catalytic hydrocracking over Ni-Mo/γ-Al2O3 catalyst in a microbatch reactor at 430 ℃.The experimental data of asphaltene conversion adequately fit second-order kinetics to give the apparent rate constants of 2.435×10-2 and 9.360×10-2 (wt frac)-1 min-1 for the two processes,respectively.A three-lump kinetic model is proposed to evaluate the rate constants for parallel reactions of asphaltenes producing liquid oil (k1) and gas+coke (k3),and consecutive reaction producing gas+coke (k2) from this liquid oil.The evaluated constants for asphaltenes hydrocracking,in the presence and absence of the catalyst,respectively,show that k1 is 2.430×10-2 and 9.355×10-2 (wt frac)-1 min-1,k2 is 2.426×10-2 and 6.347×10-3 min-1,and k3 is 5.416×10-5 and 4.803×10-5 (wt frac)-1 min-1.As compared with the thermal hydrocracking of asphaltenes,the catalytic hydrocracking of asphaltenes promotes liquid production and inhibits coke formation effectively.
基金supported by the National Natural Science Foundation of China(Grant No.51206089)Postdoctoral Science Foundation of China(Grant No.2012M510438)the National Basic Research Program of China("973"Project)(Grant No.2013CB228502)
文摘The oxidation characteristics of boron particles, boron-A with the diameter of 2.545 μm and boron-B with the diameter of 10.638 μm, at low temperature（1500 K） have been investigated by thermogravimetry（TG） coupled with simultaneous differential scanning calorimetry（DSC）, infrared and mass spectra. A rapid oxidation stage of boron particles, followed by a slow oxidation stage of sintered particles, is found from the TG and DSC curves. The onset temperatures of the oxidation process of boron-A particles are in the range of 806–889 K, which are at least 105 K lower than those of boron-B at the same condition. As the partial pressure of oxygen increases from 5% to 35%, the onset temperature of boron-A or boron-B particles decreases. However, when the partial pressure of oxygen is above 35%, the onset temperature becomes constant, implying a saturation effect of oxygen on the reaction rate. It indicates that the chemical adsorption of oxygen, i.e. chemical reaction, on the particle surface is the rate-limited step at the beginning of the rapid oxidation stage. Therefore, the first-order chemical reaction model is used to simulate the oxidation of boron particles, even that of the sinter. The average activation energies of the particles are 291.3 kJ/mol for boron-A and 338.4 k J/mol for boron-B. While the average activation energies of the sintered particles are 36.35 k J/mol for boron-A and 31.87 kJ/mol for boron-B. The pre-exponential factor of the particles is -10^4, while that of the sinter is 10^-1. The oxidation rate constant of boron is qualitatively mainly affected by the specific surface of the sample and the thickness of the oxide layer.
