Ab initio chemical kinetics of Isopropyl acetate oxidation with OH radicals

IF 5.8 3区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry Letters and Reviews Pub Date : 2023-01-02 DOI:10.1080/17518253.2023.2233539

M. Abdel-Rahman, M. Shibl, A. Shiroudi, Mohamed A. M. Mahmoud

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Abstract

ABSTRACT Global reactivity descriptors of isopropyl acetate (IPA) and thermo-kinetic aspects of its oxidation via OH radicals have been studied. Transition state theory (TST) was utilized to estimate the bimolecular rate constants. Ten oxidation pathways have been investigated, and all of them are exothermic. The potential energy diagram has been sketched using different pre- and post-reactive complexes for all reaction pathways. Rate coefficient calculations were obtained directly by connecting the separated reactants with different transition states. The results indicate that the reaction of IPA with OH radicals occurs in the ground state rather than the excited state, and the rate constants obtained directly and from the effective approach are the same, which confirmed the accuracy of the estimated pre-reactive complexes and the reaction mechanism. Rate constants and branching ratios show that hydrogen atom abstraction from the iso C − H (C2 atom) bond is the most kinetically preferable route up to 1000 K, while at higher temperatures, H-atom abstraction from the out-of-plane CH3 group (C3 atom) became the most dominant route with high competition with that of the in-plane CH3 group (C4 atom). GRAPHICAL ABSTRACT

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来源期刊

Green Chemistry Letters and Reviews CHEMISTRY, MULTIDISCIPLINARY-GREEN & SUSTAINABLE SCIENCE & TECHNOLOGY

CiteScore

9.10

自引率

3.00%

发文量

期刊介绍： Green Chemistry Letters and Reviews is an Open Access, peer-reviewed journal focused on rapid publication of innovative new syntheses and procedures that reduce or eliminate the use and generation of hazardous materials. Reviews of state-of-the-art green chemistry technologies are also included within the journal''s scope. Green Chemistry Letters and Reviews is divided into three overlapping topic areas: research, education, and industrial implementation. The journal publishes both letters, which concisely communicate the most time-sensitive results, and reviews, which aid researchers in understanding the state of science on important green chemistry topics. Submissions are encouraged which apply the 12 principles of green chemistry to: -Green Chemistry Education- Synthetic Reaction Pathways- Research and Process Analytical Techniques- Separation and Purification Technologies- Renewable Feedstocks- Degradable Products