Kinetic study of the gas-phase reaction of O3 with three unsaturated alcohols. 2018

Weiran Li, and Yi Chen, and Shengrui Tong, and Yucong Guo, and Yunhong Zhang, and Maofa Ge
The Institute of Chemical Physics, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China; State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

Rate constants for the reactions of ozone with 1-octen-3-ol, 1-nonen-3-ol and 1-nonen-4-ol have been determined at 298±1K and atmospheric pressure for the first time. The experiments were performed in a 100-L FEP Teflon film bag using absolute rate method; the rate constants were (1.91±0.19)×10-17, (1.89±0.20)×10-17, and (0.83±0.08)×10-17cm3/(molecule·sec) for 1-octen-3-ol, 1-nonen-3-ol, and 1-nonen-4-ol, respectively. The rate constants have been compared with those of unsaturated alcohols structural homologs, and used to estimate the reaction reactivity. The electronegativity of carbon-carbon double bond was calculated by atomic charges analysis. The calculated results show that the electronic effect of the lone pair electrons of hydroxyl oxygen is the main cause of the difference in rate coefficient. According to the obtained rate constants, the atmospheric lifetimes of studied unsaturated alcohols were also estimated, which indicates that the reaction with ozone is an important loss pathway in the atmosphere, especially in polluted areas.

UI MeSH Term Description Entries
D007700 Kinetics The rate dynamics in chemical or physical systems.
D008956 Models, Chemical Theoretical representations that simulate the behavior or activity of chemical processes or phenomena; includes the use of mathematical equations, computers, and other electronic equipment. Chemical Models,Chemical Model,Model, Chemical
D010126 Ozone The unstable triatomic form of oxygen, O3. It is a powerful oxidant that is produced for various chemical and industrial uses. Its production is also catalyzed in the ATMOSPHERE by ULTRAVIOLET RAY irradiation of oxygen or other ozone precursors such as VOLATILE ORGANIC COMPOUNDS and NITROGEN OXIDES. About 90% of the ozone in the atmosphere exists in the stratosphere (STRATOSPHERIC OZONE). Ground Level Ozone,Low Level Ozone,Tropospheric Ozone,Level Ozone, Ground,Level Ozone, Low,Ozone, Ground Level,Ozone, Low Level,Ozone, Tropospheric
D000438 Alcohols Alkyl compounds containing a hydroxyl group. They are classified according to relation of the carbon atom: primary alcohols, R-CH2OH; secondary alcohols, R2-CHOH; tertiary alcohols, R3-COH. (From Grant & Hackh's Chemical Dictionary, 5th ed)
D001272 Atmosphere The gaseous envelope surrounding a planet or similar body. (From Random House Unabridged Dictionary, 2d ed) Atmospheres
D001274 Atmospheric Pressure The pressure at any point in an atmosphere due solely to the weight of the atmospheric gases above the point concerned. Atmospheric Pressures,Pressure, Atmospheric,Pressures, Atmospheric
D017665 Hydroxyl Radical The univalent radical OH. Hydroxyl radical is a potent oxidizing agent.

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