A Combined Experimental and Theoretical Study on the Gas Phase Reaction of OH Radicals with Ethyl Propyl Ether.,The Journal of Physical Chemistry A

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A Combined Experimental and Theoretical Study on the Gas Phase Reaction of OH Radicals with Ethyl Propyl Ether.
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-01-09 , DOI: 10.1021/acs.jpca.9b10742
Cici Fan _{1,

2} , Weigang Wang _{1,

3} , Bo Shi _{1,

2} , Yan Chen _{1,

3} , Ke Wang _{1,

3} , Wenyu Zhang _{1,

3} , Zheng Sun ₂ , Maofa Ge _{1,

3,

4}

Affiliation

The reaction of ethyl propyl ether (EnPE) with OH radicals was studied using proton-transfer-reaction mass spectrum (PTR-MS), and the rate constant was measured at 298 K and atmospheric pressure using the relative rate method: kexp(OH+EnPE) = (1.13 ± 0.09) × 10-11 cm3 molecules-1 s-1. In addition, a parallel theoretical study was performed using the traditional transition state theory (TST) with a tunnelling effect correction in combination at M05-2X method with two basis sets, 6-311++G(d,p) and aug-cc-pVTZ. According to these calculations, H atom abstraction occurs more favorably from the methylene group adjacent to the -O- bond than from the other groups. The theoretical calculation of the total rate constant of the reaction of EnPE with OH radicals was consistent with the experimental values. The gas-phase products indicated that the major products observed were ethyl formate, ethyl propionate, propionic acid. Combined with the experimental and theoretical results, the possible reaction mechanisms were proposed and discussed. The atmospheric implications of the studied reaction are presented, and the lifetime of EnPE in the presence of OH radicals was evaluated to be approximately 1 day.

中文翻译：

OH自由基与乙基丙醚的气相反应的理论与实验研究相结合。

使用质子转移反应质谱（PTR-MS）研究了乙基丙基醚（EnPE）与OH自由基的反应，并使用相对速率方法在298 K和大气压下测量了速率常数：kexp（OH + EnPE）=（1.13±0.09）×10-11 cm3分子-1 s-1。此外，使用传统的过渡态理论（TST）与隧穿效应校正相结合的平行理论研究是在M05-2X方法下结合使用的，这两个基础是6-311 ++ G（d，p）和aug-cc -pVTZ。根据这些计算，与-O-键相邻的亚甲基比从其他基团更有利地发生H原子抽象。EnPE与OH自由基反应的总速率常数的理论计算与实验值一致。气相产物表明，观察到的主要产物是甲酸乙酯，丙酸乙酯，丙酸。结合实验和理论结果，提出并讨论了可能的反应机理。介绍了所研究反应的大气影响，并评估了在存在OH自由基的情况下EnPE的寿命约为1天。

更新日期：2020-01-17

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