An instrument for measurement of peroxy radical by chemical amplification (PERCA) has been devel- oped at Peking University (PKU) and deployed in several field campaigns. PKU PERCA measures per- oxy radical via amplif...An instrument for measurement of peroxy radical by chemical amplification (PERCA) has been devel- oped at Peking University (PKU) and deployed in several field campaigns. PKU PERCA measures per- oxy radical via amplification of NO2 by peroxy radical in the presence of NO and CO through a chain reaction. The amount of amplified NO2 is detected by a NO2-luminal chemiluminescence detector. The chain length (CL) of 75±20 (1σ ) was determined routinely during field campaigns using a HO2 source from photolysis of water vapor at 185 nm in air. The detection limit for peroxy radical measurement was (1-5)×10?12 (volume ratio) with integration time of 1 min, mainly relying on the variation of the ambient O3 and NO2. The systematic uncertainty in the measurement of peroxy radical was estimated to be ±60%. The effect of water vapor on PKU PERCA was observed and determined in the laboratory. The meas- urements of peroxy radical during the Program of Regional Integrated Experiments of Air Quality over Pearl River Delta 2006 (PRIDE-PRD2006) campaign are presented to show the performance of the PERCA instrument and the behavior of the observed peroxy radical is discussed briefly.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
Carbonyl peroxy radicals (RC(O)O2) are the ubiquitous radical intermediates in the atmospheric oxidation of volatile organic compounds. In this work, theoretical studies are carried out to explore the role of the unim...Carbonyl peroxy radicals (RC(O)O2) are the ubiquitous radical intermediates in the atmospheric oxidation of volatile organic compounds. In this work, theoretical studies are carried out to explore the role of the unimolecular H-migration in the carbonyl peroxy radicals by using quantum chemistry and kinetics calculations. The results showed that H-migration could be significant in the atmosphere at least in CH3CH2CH2C(O)O2 and (CH3)2CHCH2C(O)O2 with rates of ∽0.012 and -0.58^-1 at 298 K. Subsequent reactions of CH3CHCH2C(O)OOH would lead to the products with multi-functional groups, which might affect the aerosol formation process;while (CH3)2CCH2C(O)OOH would transform to formaldehyde and acetone in a few steps. These processes would be important for the atmospheric modelling of volatile organic compounds under low-NOx conditions.展开更多
To determine the degree of oxidation in vegetable oil, a photochemical method using the electron spin resonance （ESR） spin trapping technique was developed, and the results were compared with those obtained using co...To determine the degree of oxidation in vegetable oil, a photochemical method using the electron spin resonance （ESR） spin trapping technique was developed, and the results were compared with those obtained using conventional peroxide-value （PV） and acid-value （AV） methods. Vegetable oil heat-treated were subjected to short UV illumination, and the produced alkyl-oxyl radicals were identified and quantified using the ESR spin trapping technique. ESR signal intensity was used as an indicator of oil oxidation, which monotonically increased as a function of the heat-treatment time. Commercially, available oils were selected and analyzed. The results were compared with those obtained using the PV and AV methods. The present method displayed some analogies with the PV method at least in the early stage of heating. Overall, the present method had highly sensitive and capable of detecting early-stage oxidation in vegetable oil.展开更多
基金Supported by Industry, University and Research Institute Cooperation Program of Beijing Municipal Commission of Education (Grant No. CXY100010401)National Basic Research Program of China (Grant No. 2002CB410801).
文摘An instrument for measurement of peroxy radical by chemical amplification (PERCA) has been devel- oped at Peking University (PKU) and deployed in several field campaigns. PKU PERCA measures per- oxy radical via amplification of NO2 by peroxy radical in the presence of NO and CO through a chain reaction. The amount of amplified NO2 is detected by a NO2-luminal chemiluminescence detector. The chain length (CL) of 75±20 (1σ ) was determined routinely during field campaigns using a HO2 source from photolysis of water vapor at 185 nm in air. The detection limit for peroxy radical measurement was (1-5)×10?12 (volume ratio) with integration time of 1 min, mainly relying on the variation of the ambient O3 and NO2. The systematic uncertainty in the measurement of peroxy radical was estimated to be ±60%. The effect of water vapor on PKU PERCA was observed and determined in the laboratory. The meas- urements of peroxy radical during the Program of Regional Integrated Experiments of Air Quality over Pearl River Delta 2006 (PRIDE-PRD2006) campaign are presented to show the performance of the PERCA instrument and the behavior of the observed peroxy radical is discussed briefly.
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).
基金supported by the National Key Research Development Program (No.2017YFC0212800)the National Natural Science Foundation of China (No.21477038 and No.21677051)the Natural Science Foundation of Guangdong Province (No.2016A030311005)
文摘Carbonyl peroxy radicals (RC(O)O2) are the ubiquitous radical intermediates in the atmospheric oxidation of volatile organic compounds. In this work, theoretical studies are carried out to explore the role of the unimolecular H-migration in the carbonyl peroxy radicals by using quantum chemistry and kinetics calculations. The results showed that H-migration could be significant in the atmosphere at least in CH3CH2CH2C(O)O2 and (CH3)2CHCH2C(O)O2 with rates of ∽0.012 and -0.58^-1 at 298 K. Subsequent reactions of CH3CHCH2C(O)OOH would lead to the products with multi-functional groups, which might affect the aerosol formation process;while (CH3)2CCH2C(O)OOH would transform to formaldehyde and acetone in a few steps. These processes would be important for the atmospheric modelling of volatile organic compounds under low-NOx conditions.
文摘To determine the degree of oxidation in vegetable oil, a photochemical method using the electron spin resonance （ESR） spin trapping technique was developed, and the results were compared with those obtained using conventional peroxide-value （PV） and acid-value （AV） methods. Vegetable oil heat-treated were subjected to short UV illumination, and the produced alkyl-oxyl radicals were identified and quantified using the ESR spin trapping technique. ESR signal intensity was used as an indicator of oil oxidation, which monotonically increased as a function of the heat-treatment time. Commercially, available oils were selected and analyzed. The results were compared with those obtained using the PV and AV methods. The present method displayed some analogies with the PV method at least in the early stage of heating. Overall, the present method had highly sensitive and capable of detecting early-stage oxidation in vegetable oil.
