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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Experimental and theoretical studies of the kinetics of the reactions of OH and OD with 2-methyl-3-buten-2-ol between 300 and 415 K at low pressure
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Experimental and theoretical studies of the kinetics of the reactions of OH and OD with 2-methyl-3-buten-2-ol between 300 and 415 K at low pressure

机译：OH和OD与2-甲基-3-丁烯-2-醇在300至415 K低压下反应动力学的实验和理论研究

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摘要

The rate constants for the reactions of OH and OD with 2-methyl-3-buten-2-ol (MBO) have been measured at 2, 3, and 5 Torr total pressure over the temperature range 300-415 K using a discharge-flow system coupled with laser induced fluorescence detection of OH. The measured rate constants at room temperature and 5 Torr for the OH + MBO reaction in the presence of O-2 and the OD + MBO reaction are (6.32 +/- 0.27) and (6.61 +/- 0.66) x 10(-11) cm(3) molecule(-1) s(-1), respectively, in agreement with previous measurements at higher pressures. However, the rate constants begin to show a pressure dependence at temperatures above 335 K. An Arrhenius expression of k(0) = (2.5 +/- 7.4) x 10(-32) exp[(4150 +/- 1150)/T] cm(6) molecule(-2) s(-1) was obtained for the low-pressure-limiting rate constant for the OH + MBO reaction in the presence of oxygen. Theoretical calculations of the energetics of the OH + MBO reaction suggest that the stability of the different HO-MBO adducts are similar, with predicted stabilization energies between 27.0 and 33.4 kcal mol(-1) relative to the reactants, with OH addition to the internal carbon predicted to be 1-4 kcal mol(-1) more stable than addition to the terminal carbon. These stabilization energies result in estimated termolecular rate constants for the OH + MBO reaction using simplified calculations based on RRKM theory that are in reasonable agreement with the experimental values.
机译：OH和OD与2-甲基-3-丁烯-2-醇（MBO）的反应速率常数已在300-415 K的温度范围内使用放电-流动系统结合激光诱导的OH荧光检测。在存在O-2和OD + MBO反应的情况下，OH + MBO反应在室温和5 Torr下测得的速率常数为（6.32 +/- 0.27）和（6.61 +/- 0.66）x 10（-11） ）cm（3）分子（-1）s（-1），分别与先前在较高压力下的测量结果一致。但是，速率常数开始在335 K以上的温度下显示出压力依赖性。k（0）=（2.5 +/- 7.4）x 10（-32）exp [（4150 +/- 1150）/ T的Arrhenius表达式] cm（6）分子（-2）s（-1）是在氧气存在下OH + MBO反应的低压限制速率常数。 OH + MBO反应能量的理论计算表明，不同的HO-MBO加合物的稳定性相似，相对于反应物的预测稳定能在27.0至33.4 kcal mol（-1）之间，内部还添加了OH碳预测比添加到末端碳更稳定1-4 kcal mol（-1）。这些稳定化能量使用基于RRKM理论的简化计算得出了OH + MBO反应的估计分子速率常数，与实验值合理地吻合。

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