Study on Atmospheric Photo-oxidation of Methyl Hydroperoxide Initiated by Cl-atom
SHI Fei，CHEN Zhong-ming
The State Key Joint Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences, Peking University, Beijing 100871, China
Abstract：Organic peroxides play an important role in chemistry of the atmosphere and in controlling urban air quality; however, accurate knowledge about their atmospheric reactions is lacking. In this paper, the experimental simulation was employed to study the atmospheric photo-oxidation of methyl hydroperoxide (CH3OOH, MHP), a key organic peroxide in the atmosphere. At the temperature of (292±2)K and pressure of 9.3×104 Pa (20% O2+80% N2), the MHP photo-oxidation was initiated by Cl-atom and the process of reaction was in-situ observed by long path Fourier transform infrared (Long Path FTIR) spectrometry. From FTIR spectra, the main products observed were formaldehyde (HCHO), formic acid (HCOOH), carbon monoxide (CO) and carbon dioxide (CO2), and minor methanol (CH3OH) was found as well. Within the reaction period of 60 min, yields were determined: 24% for HCOOH and 6% for CO; 50% for HCHO at its maximum concentration although its yield was varying with the reaction time. Finally, reaction mechanisms were discussed, which implied that MHP is a reservoir of odd-hydrogen radicals (HOx) and plays an important role in atmospheric photo-reactions.
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