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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Kinetic Study of the Unimolecular Keto–Enol Tautomerism Propen-2-ol ? Acetone. Pressure Effects and Implications in the Pyrolysis of tert- and 2-Butanol
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Theoretical Kinetic Study of the Unimolecular Keto–Enol Tautomerism Propen-2-ol ? Acetone. Pressure Effects and Implications in the Pyrolysis of tert- and 2-Butanol

机译：单分子酮烯醇互变异构体的理论动力学研究填补-2-OL？ 丙酮。 Tert的热解性和影响 - 和2-丁醇的压力效应和影响

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摘要

The need for renewable and cleaner sources of energy has made biofuels an interesting alternative to fossil fuels, especially in the case of butanol isomers, with its favorable blend properties and low hygroscopicity. Although C_(4) alcohols are prospective fuels, some key reactions governing their pyrolysis and combustion have not been adequately studied, leading to incomplete kinetic models. Enols are important intermediates in the combustion of C_(4) alcohols, as well as in atmospheric processes. Butanol reactions kinetics is poorly understood. Specifically, the unimolecular tautomerism of propen-2-ol ? acetone, which is included in butanol combustion kinetic models, is assigned rate parameters based on the tautomerism vinyl alcohol ? acetaldehyde as an analogy. In an attempt to update current kinetic models for tert - and 2-butanol, a theoretical kinetic study of the titled reaction was carried out by means of CCSD(T,FULL)/aug-cc-pVTZ//CCSD(T)/6-31+G(d,p) ab initio calculations, with multistructural torsional anharmonicity and variational transition state theory considerations in a wide temperature and pressure range (200–3000 K; 0.1–10~(8) kPa). Results differ from vinyl alcohol ? acetaldehyde analogue reaction, which shows lower rate constant values. It was observed that decreasing pressure leads to a decrease in rate constants, describing the expected falloff behavior. Tunneling turned out to be important, especially at low temperatures. Accordingly, pyrolysis simulations in a batch reactor for tert - and 2-butanol with computed rate constants showed important differences in comparison with previous results, such as larger acetone yield and quicker propen-2-ol consumption.
机译：对可再生和更清洁的能量来源的需求使生物燃料成为化石燃料的有趣替代品，特别是在丁醇异构体的情况下，其有利的共混物性能和低吸湿性。虽然C_（4）醇是前瞻性燃料，但有一些关键的反应尚未得到充分研究其热解和燃烧，导致不完全的动力学模型。烯醇是C_（4）醇的燃烧中的重要中间体，以及大气过程。丁醇反应动力学明白很差。具体而言，Propen-2-OL的单分子互变异物？包含在丁醇燃烧动力学模型中的丙酮是基于互变异构体乙烯醇的速率参数分配？乙醛作为类比。在尝试更新叔丁醇和2-丁醇的当前动力学模型中，通过CCSD（T，Full）/ Aug-CC-PVTZ // CCSD进行标题反应的理论动力学研究（T ）/ 6-31 + g（d，p） ab initio计算，具有多体扭转Anharmonicity和变分过渡状态理论在宽温度和压力范围内的考虑（200-3000 k; 0.1-10〜（8）KPA ）。结果与乙烯醇有所不同吗？乙醛模拟反应，显示出较低的速率恒定值。观察到，降低压力导致速率常数的降低，描述预期的衰减行为。隧道突出是重要的，特别是在低温下。因此，与先前的结果相比，分批反应器中的分批反应器中的热解模拟和具有计算速率常数的重要差异，例如较大的丙酮产率和更快的Propen-2-OL消费。

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