The G3 and CBS-QB3 theoretical methods are employed to study the decomposition of CF3OH into FCFO and HF by water, water dimmer, and ammonia. The decomposition of CF3OH into FCFO and HF is unlikely to occur in the atm...The G3 and CBS-QB3 theoretical methods are employed to study the decomposition of CF3OH into FCFO and HF by water, water dimmer, and ammonia. The decomposition of CF3OH into FCFO and HF is unlikely to occur in the atmosphere due to the high activated energy of 88.7 k J/mol at the G3 level of theory. However, the computed results predict that the barrier for unimolecular decomposition of CF3OH is decreased to 25.1 kJ/mol from 188.7 k J/mol with the aid of NH3 at the G3 level of theory, which shows that the ammonia play a strong catalytic effect on the split of CF3OH. In addition, the calculated rate constants show that the decomposition of CF3OH by NH3 is faster than those of H2O and the water dimmer by 10^9 and 10^5 times respectively. The rate constants combined with the corresponding concentrations of these species demonstrate that the reaction CF3OH with NH3 via TS4 is of great importance for the decomposition of CF3OH in the atmosphere.展开更多
CF3I gas mixtures have attracted considerable attention as potential environmentally-friendly alternatives to SF6 gas,owing to their excellent insulating performance.This paper attempts to study the CF3I ternary gas m...CF3I gas mixtures have attracted considerable attention as potential environmentally-friendly alternatives to SF6 gas,owing to their excellent insulating performance.This paper attempts to study the CF3I ternary gas mixtures with c-C4F8 and buffer gases N2 and CO2 by considering dielectric strength from electron transport parameters based on the Boltzmann method and synergistic effect analysis,compared with SF6 gas mixtures.The results confirm that the critical electric field strength of CF3I/c-C4F8/70%CO2 is greater than that of 30%SF6/70%CO2 when the CF3I content is greater than 17%.Moreover,a higher content of c-C4F8 decreases the sensitivity of gas mixtures to an electric field,and this phenomenon is more obvious in CF3I/c-C4F8/CO2 gas mixtures.The synergistic effects for CF3I/c-C4F8/70%N2 were most obvious when the c-C4F8 content was approximately 20%,and for CF3I/c-C4F8/70%CO2 when the c-C4F8 content was approximately 10%.On the basis of this research,CF3I/c-C4F8/70%N2 shows better insulation performance when the c-C4F8 content is in the15%–20%range.For CF3I/c-C4F8/70%CO2,when the c-C4F8 content is in the 10%–15%range,the gas mixtures have excellent performance.Hence,these gas systems might be used as alternative gas mixtures to SF6 in high-voltage equipment.展开更多
CF3I is a potential SF6 alternative gas.In order to study the insulation properties and synergistic effects of CF3I/N2 and CF3I/CO2 gas mixtures,two-term approximate Boltzmann equations were used to obtain the ionizat...CF3I is a potential SF6 alternative gas.In order to study the insulation properties and synergistic effects of CF3I/N2 and CF3I/CO2 gas mixtures,two-term approximate Boltzmann equations were used to obtain the ionization coefficient α,attachment coefficient η and the critical equivalent electrical field strength（E/N）（cr）.The results show that the（E/N）（cr）of CF3I gas at 300 K is 1.2 times that of SF6 gas,and CF3I/N2 and CF3I/CO2 gas mixtures both have synergistic effect occurred.The synergistic effect coefficient of CF3I/CO2 gas mixture was higher than that of CF3I/N2 gas mixture.But the（E/N）（cr）of CF3I/N2 is higher than that of CF3I/CO2 under the same conditions.When the content of CF3I exceeds 20%,the （E/N）（cr） of CF3I/N2 and CF3I/CO2 gas mixture increase linearly with the increasing of CF3I gas content.The breakdown voltage of CF3I/N2 gas mixture is also higher than that of CF3I/CO2 gas mixture in slightly non-uniform electrical field under power frequency voltage,but the synergistic effect coefficients of the two gas mixtures are basically the same.展开更多
The application of mass spectrometry to investigations o{ gas-phase photochemistry and kinetics by flash photolysis was first reported in 1957. Mass spectrometry is advantageous and versatile for kinetics and mechani...The application of mass spectrometry to investigations o{ gas-phase photochemistry and kinetics by flash photolysis was first reported in 1957. Mass spectrometry is advantageous and versatile for kinetics and mechanism studies since it is capable of detecting many different chemical species during the course of the reaction and one can determine kinetic rates of reactant decay and product growth. When the mass spectrometer is used to determine kinetic decays and growths following pulsed photolysis, it may be called flash photolysis with time-resolved mass spectrometry(FPTRMS). While experiments using FPTRMS can obtain direct and valuable information on kinetics and mechanism o[ chemical reactions, they are limited in some cases. For example, experiments can be conducted only at limited temperature and pressure ranges. Moreover,the experimental investigation alone does not always provide sufficient information for the reaction mecha-nism study, especially for a complex reaction system. The theoretical investigations including Ab Initio cal-culations, RRKM calculations and numerial simulations are useful and supplemental tools to the experimen-tal studies. Ab initio and RRKM calculations can be used to predict rate coefficients of chemical reactions ina much wider ranges of temperature and pressure. Important information on the mechanism can also be obtained from the theoretical studies. However, the validation and accuracy of the results from the theoreticalinvestigations need to be verified or adjusted by experimental results. As an example, a study of kinetics and mechanism of CF3CHC10 radical reactions using FPTRMS combining with the theoretical calculations is reported.展开更多
基金This work was supported by the National Natural Science Foundation of China （No.10865003） and the Guizhou University for Nationalities （2010）. The authors thank professors W. T. Duncan, R. L. Bell, and T. N. Truong or providing the rate program through the internet.
文摘The G3 and CBS-QB3 theoretical methods are employed to study the decomposition of CF3OH into FCFO and HF by water, water dimmer, and ammonia. The decomposition of CF3OH into FCFO and HF is unlikely to occur in the atmosphere due to the high activated energy of 88.7 k J/mol at the G3 level of theory. However, the computed results predict that the barrier for unimolecular decomposition of CF3OH is decreased to 25.1 kJ/mol from 188.7 k J/mol with the aid of NH3 at the G3 level of theory, which shows that the ammonia play a strong catalytic effect on the split of CF3OH. In addition, the calculated rate constants show that the decomposition of CF3OH by NH3 is faster than those of H2O and the water dimmer by 10^9 and 10^5 times respectively. The rate constants combined with the corresponding concentrations of these species demonstrate that the reaction CF3OH with NH3 via TS4 is of great importance for the decomposition of CF3OH in the atmosphere.
基金supported by National Natural Science Foundation of China(No.51337006)。
文摘CF3I gas mixtures have attracted considerable attention as potential environmentally-friendly alternatives to SF6 gas,owing to their excellent insulating performance.This paper attempts to study the CF3I ternary gas mixtures with c-C4F8 and buffer gases N2 and CO2 by considering dielectric strength from electron transport parameters based on the Boltzmann method and synergistic effect analysis,compared with SF6 gas mixtures.The results confirm that the critical electric field strength of CF3I/c-C4F8/70%CO2 is greater than that of 30%SF6/70%CO2 when the CF3I content is greater than 17%.Moreover,a higher content of c-C4F8 decreases the sensitivity of gas mixtures to an electric field,and this phenomenon is more obvious in CF3I/c-C4F8/CO2 gas mixtures.The synergistic effects for CF3I/c-C4F8/70%N2 were most obvious when the c-C4F8 content was approximately 20%,and for CF3I/c-C4F8/70%CO2 when the c-C4F8 content was approximately 10%.On the basis of this research,CF3I/c-C4F8/70%N2 shows better insulation performance when the c-C4F8 content is in the15%–20%range.For CF3I/c-C4F8/70%CO2,when the c-C4F8 content is in the 10%–15%range,the gas mixtures have excellent performance.Hence,these gas systems might be used as alternative gas mixtures to SF6 in high-voltage equipment.
基金supported by National Natural Science Foundation of China (Grant No.51337006)China Postdoctoral Science Foundation (2016M602728)the Science and Technology Project of SGCC ‘Research on SF_6 Alternative Gas for Insulation and Arc Quenching Application’
文摘CF3I is a potential SF6 alternative gas.In order to study the insulation properties and synergistic effects of CF3I/N2 and CF3I/CO2 gas mixtures,two-term approximate Boltzmann equations were used to obtain the ionization coefficient α,attachment coefficient η and the critical equivalent electrical field strength（E/N）（cr）.The results show that the（E/N）（cr）of CF3I gas at 300 K is 1.2 times that of SF6 gas,and CF3I/N2 and CF3I/CO2 gas mixtures both have synergistic effect occurred.The synergistic effect coefficient of CF3I/CO2 gas mixture was higher than that of CF3I/N2 gas mixture.But the（E/N）（cr）of CF3I/N2 is higher than that of CF3I/CO2 under the same conditions.When the content of CF3I exceeds 20%,the （E/N）（cr） of CF3I/N2 and CF3I/CO2 gas mixture increase linearly with the increasing of CF3I gas content.The breakdown voltage of CF3I/N2 gas mixture is also higher than that of CF3I/CO2 gas mixture in slightly non-uniform electrical field under power frequency voltage,but the synergistic effect coefficients of the two gas mixtures are basically the same.
文摘The application of mass spectrometry to investigations o{ gas-phase photochemistry and kinetics by flash photolysis was first reported in 1957. Mass spectrometry is advantageous and versatile for kinetics and mechanism studies since it is capable of detecting many different chemical species during the course of the reaction and one can determine kinetic rates of reactant decay and product growth. When the mass spectrometer is used to determine kinetic decays and growths following pulsed photolysis, it may be called flash photolysis with time-resolved mass spectrometry(FPTRMS). While experiments using FPTRMS can obtain direct and valuable information on kinetics and mechanism o[ chemical reactions, they are limited in some cases. For example, experiments can be conducted only at limited temperature and pressure ranges. Moreover,the experimental investigation alone does not always provide sufficient information for the reaction mecha-nism study, especially for a complex reaction system. The theoretical investigations including Ab Initio cal-culations, RRKM calculations and numerial simulations are useful and supplemental tools to the experimen-tal studies. Ab initio and RRKM calculations can be used to predict rate coefficients of chemical reactions ina much wider ranges of temperature and pressure. Important information on the mechanism can also be obtained from the theoretical studies. However, the validation and accuracy of the results from the theoreticalinvestigations need to be verified or adjusted by experimental results. As an example, a study of kinetics and mechanism of CF3CHC10 radical reactions using FPTRMS combining with the theoretical calculations is reported.
