4.6 Article

Peroxy Radical Processes and Product Formation in the OH Radical-Initiated Oxidation of α-Pinene for Near-Atmospheric Conditions

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JOURNAL OF PHYSICAL CHEMISTRY A
卷 125, 期 41, 页码 9151-9160

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AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.1c05576

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This study investigates the formation of RO2 radicals and their closed-shell products from the OH + alpha-pinene reaction under close to atmospheric conditions. The main closed-shell products are substances with the composition C10H16O2 and C10H16O4, obtained with molar yields in specific ranges. The findings also reveal the suppression of highly oxygenated organic molecules by a factor of 2-2.2 for the highest NO concentration used.
alpha-Pinene, C10H16, represents one of the most important biogenic emissions into the atmosphere. The formation of RO2 radicals HO-C10H16Ox = 2-6, and their closed-shell products from the OH + alpha-pinene reaction has been measured for close to atmospheric reaction conditions in the presence of NO with concentrations of (1.7-490) x 10(9) molecules cm(-3). Main closed-shell products are substances with the composition C10H16O2 and C10H16O4, most likely carbonyls, obtained with molar yields in the range 0.42-0.45 and 0.17-0.19, respectively, for NO concentrations >5 x 10(10) molecules cm(-3). The corresponding total product yields amount to 0.75-0.81, indicating efficient product detection by the mass spectrometric method applied. All stated molar yields represent lower limit values affected with an uncertainty of (+104)(-58)%. Kinetic and product analysis consistently revealed the suppression of the formation of highly oxygenated organic molecules (HOMs) by a factor of 2-2.2 for the highest NO concentration used. The findings of this study provide insights into the RO2 radical processes of the OH + alpha-pinene reaction for atmospheric conditions and give an overview about the first-generation products.

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