A new method is proposed to determine the amplification factor for 2-hydroxy ethylperoxy radicals （HOC2H4O2·） in chemical amplifier. The radical source comes from the reaction of excess ethene with HO· rad...A new method is proposed to determine the amplification factor for 2-hydroxy ethylperoxy radicals （HOC2H4O2·） in chemical amplifier. The radical source comes from the reaction of excess ethene with HO· radicals generated in the photolysis of water vapor at the wave length of 185 nm in air in a flow tube. This produces a radical source which contains equal amount of HO2·and HOC2H4O2·. The amplification factor is derived from the slopes of the lines between produced NO2 in chemical amplifier and total initial radical concentrations measured for the source of HO2· and that of the same amount of HO2· and HOC2H4O2· respectively. The amplification factor of HOC2H4O2· was similar to that of HO2·, indicating that HOC2H4O2· can be measured with the same sensitivity as HO2· by chemical amplifier.展开更多
The water effect on peroxy radical measurement by chemical amplification was determined experimentally for HO2 and HO2+OH, respectively at room temperature (298±2) K and atmospheric pressure (1×105 Pa). No s...The water effect on peroxy radical measurement by chemical amplification was determined experimentally for HO2 and HO2+OH, respectively at room temperature (298±2) K and atmospheric pressure (1×105 Pa). No significant difference in water effect was observed with the type of radicals. A theoretical study of the reaction of HO2·H2O adduct with NO was performed using density functional theory at CCSD(T)/6-311 G(2d, 2p)//B3LYP/6-311 G(2d, 2p) level of theory. It was found that the primary reaction channel for the reaction is HO2·H2O+NO→HNO3+H2O (R4a). On the basis of the theoretical study, the rate constant for (R4a) was calculated using Polyrate Version 8.02 program. The fitted Arrenhnius equation for (R4a) is k = 5.49×107 T 1.03exp(?14798/T) between 200 and 2000 K. A chemical model incorporated with (R4a) was used to simulate the water effect. The water effect curve obtained by the model is in accordance with that of the experiment, suggesting that the water effect is probably caused mainly by (R4a).展开更多
文摘A new method is proposed to determine the amplification factor for 2-hydroxy ethylperoxy radicals （HOC2H4O2·） in chemical amplifier. The radical source comes from the reaction of excess ethene with HO· radicals generated in the photolysis of water vapor at the wave length of 185 nm in air in a flow tube. This produces a radical source which contains equal amount of HO2·and HOC2H4O2·. The amplification factor is derived from the slopes of the lines between produced NO2 in chemical amplifier and total initial radical concentrations measured for the source of HO2· and that of the same amount of HO2· and HOC2H4O2· respectively. The amplification factor of HOC2H4O2· was similar to that of HO2·, indicating that HOC2H4O2· can be measured with the same sensitivity as HO2· by chemical amplifier.
文摘The water effect on peroxy radical measurement by chemical amplification was determined experimentally for HO2 and HO2+OH, respectively at room temperature (298±2) K and atmospheric pressure (1×105 Pa). No significant difference in water effect was observed with the type of radicals. A theoretical study of the reaction of HO2·H2O adduct with NO was performed using density functional theory at CCSD(T)/6-311 G(2d, 2p)//B3LYP/6-311 G(2d, 2p) level of theory. It was found that the primary reaction channel for the reaction is HO2·H2O+NO→HNO3+H2O (R4a). On the basis of the theoretical study, the rate constant for (R4a) was calculated using Polyrate Version 8.02 program. The fitted Arrenhnius equation for (R4a) is k = 5.49×107 T 1.03exp(?14798/T) between 200 and 2000 K. A chemical model incorporated with (R4a) was used to simulate the water effect. The water effect curve obtained by the model is in accordance with that of the experiment, suggesting that the water effect is probably caused mainly by (R4a).
