Cl-Initiated Photo-oxidation Studies of Methyl Valerate and Methyl Isovalerate under Tropospherically Relevant Conditions

被引：0

作者：

Kaipara, Revathy ^{[1
]}

Rajakumar, B. ^{[1
]}

机构：

[1] Indian Inst Technol Madras, Dept Chem, Chennai 600036, Tamil Nadu, India

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2020年 / 124卷 / 13期

关键词：

GAS-PHASE REACTIONS; RATE CONSTANTS; ATMOSPHERIC CHEMISTRY; ORGANIC-COMPOUNDS; CHLORINE; KINETICS; OXIDATION; ATOMS; HYDROCARBONS; MECHANISMS;

D O I：

10.1021/acs.jpca.9b10740

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Rate coefficients for the reactions of methyl valerate (MV) and methyl isovalerate (MIV) were investigated using the relative rate (RR) technique in the temperature range of 268-363 K and at 760 Torr of N-2. The rate coefficients at 298 +/- 2 K were measured to be k(MV+Cl) = (1.69 +/- 0.40) x 10(-10) cm(3) molecule(-1) s(-1) and k(MIV+ Cl) = (1.06 +/- 0.23) x 10(-10) cm(3) molecule-(1) s(-1). To comprehend the experimentally measured rate coefficients, kinetic parameters for the title reactions were computed at the CCSD(T)/cc-pVTZ//BHandHLYP/6-311+G(d,p) level of theory over the temperature range of 200-400 K using canonical variational transition (CVT) state theory in conjunction with small curvature tunneling (SCT) corrections and the interpolated single-point energy (ISPE) method. Additionally, the degradation mechanisms were proposed based on the analyzed products. Moreover, to further understand the atmospheric fate of these molecules in the troposphere, atmospheric lifetimes, radiative forcings (RFs), and global warming potentials (GWPs) were calculated.

引用

页码：2515 / 2529

页数：15

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