Predictive Combustion Kinetics of OH Radical Reactions with a C5 Unsaturated Alcohol: The Competitive H-Abstraction and OH-Addition Reactions of 2-Methyl-3-buten-2-ol,The Journal of Physical Chemistry A

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Predictive Combustion Kinetics of OH Radical Reactions with a C5 Unsaturated Alcohol: The Competitive H-Abstraction and OH-Addition Reactions of 2-Methyl-3-buten-2-ol
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2021-11-23 , DOI: 10.1021/acs.jpca.1c07623
Yanbo Li ₁ , Jiwen Guan ₁ , Huanhuan Wang ₁ , Long Zhu ₁ , Lili Ye ₂ , Zhandong Wang _{1,

3}

Affiliation

2-Methyl-3-buten-2-ol (MBO232) is a potential biofuel and renewable fuel additive. In a combustion environment, the consumption of MBO232 is mainly through the reaction with a OH radical, one of the most important oxidants. Here, we predict the intricate reactions of MBO232 and OH radicals under a broad range of combustion conditions, that is, 230–2500 K and 0.01–1000 atm. The potential energy surfaces of H-abstraction and OH-addition have been investigated at the CCSD(T)/CBS//M06-2X/def2-TZVP level, and the rate constants were calculated via Rice–Ramsperger–Kassel–Marcus/master equation (RRKM/ME) theory. The decomposition reactions of the critical intermediates from the OH-addition reactions have also been studied. Our results show that OH-addition reactions are dominant below 850 K, while H-abstraction reactions, especially the channel-abstracting H atoms from the methyl groups, are more competitive at higher temperatures. We found that it is necessary to discriminate H atoms attached to the same C atom, as their abstraction rates can differ by up to 1 order of magnitude. The calculated results show good agreement with the reported experimental data. We have provided the modified Arrhenius expressions for rate constants of the dominant channels. The kinetic data determined in this work are of much value for constructing the combustion models of MBO232 and understanding the combustion kinetics and mechanism of other unsaturated alcohols.

中文翻译：

与 C5 不饱和醇的 OH 自由基反应的预测燃烧动力学：2-Methyl-3-buten-2-ol 的竞争性 H-抽象和 OH-加成反应

2-Methyl-3-buten-2-ol (MBO232) 是一种潜在的生物燃料和可再生燃料添加剂。在燃烧环境中，MBO232 的消耗主要是通过与 OH 自由基（最重要的氧化剂之一）发生反应。在这里，我们预测了 MBO232 和 OH 自由基在广泛的燃烧条件下（即 230-2500 K 和 0.01-1000 atm）的复杂反应。已在 CCSD(T)/CBS//M06-2X/def2-TZVP 水平上研究了 H-抽象和 OH-加成的势能面，并通过 Rice-Ramsperger-Kassel-Marcus/master 计算了速率常数方程（RRKM/ME）理论。还研究了来自 OH 加成反应的关键中间体的分解反应。我们的结果表明 OH-加成反应在 850 K 以下占主导地位，而 H-抽象反应，特别是从甲基中提取通道的 H 原子，在更高的温度下更具竞争力。我们发现有必要区分连接到同一个 C 原子上的 H 原子，因为它们的提取率可能相差 1 个数量级。计算结果与报道的实验数据吻合良好。我们已经为主要通道的速率常数提供了修改后的 Arrhenius 表达式。本工作确定的动力学数据对于构建MBO232的燃烧模型和理解其他不饱和醇的燃烧动力学和机理具有重要价值。因为它们的提取率可以相差 1 个数量级。计算结果与报道的实验数据吻合良好。我们已经为主要通道的速率常数提供了修改后的 Arrhenius 表达式。本工作确定的动力学数据对于构建MBO232的燃烧模型和理解其他不饱和醇的燃烧动力学和机理具有重要价值。因为它们的提取率可以相差 1 个数量级。计算结果与报道的实验数据吻合良好。我们已经为主要通道的速率常数提供了修改后的 Arrhenius 表达式。本工作确定的动力学数据对于构建MBO232的燃烧模型和理解其他不饱和醇的燃烧动力学和机理具有重要价值。

更新日期：2021-12-09

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