Experimental investigation of incremental reactivity of di-tert-butyl peroxide

Large quantities of di-tert-butyl peroxide (DTBP) have been emitted into the troposphere due to human activities. Its role in the atmospheric photochemical reaction has not been understood. This study presents the results of the photochemical reactions of DTBP and NOx, which have been simulated in a self-made smog chamber under the temperature of (29±1)℃. Both the wall decays of ozone and NO2 could be neglected, compared to the results in simulative experiments. The effective intensity of UV light used in the experiments was 1.28×10-3 s-1, which was expressed by the rate constant of NO2 photolysis in purified air. The reaction mechanism was proposed according to our results and reports of other researchers. The maximum values of incremental reactivity (IR) in the three simulative ex- periments were 9.53×10-2, 5.23×10-2 and 3.78×10-2, respectively. The incremental reactivity decreased with the increase of initial concentrations of DTBP. The IR value of DTBP obtained in this study was comparable to that of acetylene reported in our previous research.

Experimental investigation of incremental reactivity of di-<Emphasis Type="Italic">tert</Emphasis>-butyl peroxide

Large quantities of di-tert-butyl peroxide (DTBP) have been emitted into the troposphere due to human activities. Its role in the atmospheric photochemical reaction has not been understood. This study presents the results of the photochemical reactions of DTBP and NO_x, which have been simulated in a self-made smog chamber under the temperature of (29±1)°C. Both the wall decays of ozone and NO₂ could be neglected, compared to the results in simulative experiments. The effective intensity of UV light used in the experiments was 1.28×10⁻³ s⁻¹, which was expressed by the rate constant of NO₂ photolysis in purified air. The reaction mechanism was proposed according to our results and reports of other researchers. The maximum values of incremental reactivity (IR) in the three simulative experiments were 9.53×10⁻², 5.23×10⁻² and 3.78×10⁻², respectively. The incremental reactivity decreased with the increase of initial concentrations of DTBP. The IR value of DTBP obtained in this study was comparable to that of acetylene reported in our previous research. Supported by the Knowledge Innovation Program of the Chinese Academy of Sciences as part of “A Preliminary Study of the Formation and Evolution Mechanism of Photochemical Smog in the Beijing Region and Its Control Experiments” (Grant No. KJCX2-SW-H8), Hundred Talents Fund and the National Natural Science Foundation of China (Grant Nos. 20577052, 20673123, 20473094 and 20503035)