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反应F + CH:反应速率常数及反应产物产率与298 - 950K温度的函数关系

Reaction F + CH: Rate Constant and Yields of the Reaction Products as a Function of Temperature over 298-950 K.

作者信息

Bedjanian Yuri

机构信息

Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), CNRS, 45071 Orléans Cedex 2, France.

出版信息

J Phys Chem A. 2018 Mar 29;122(12):3156-3162. doi: 10.1021/acs.jpca.8b01371. Epub 2018 Mar 15.

Abstract

The kinetics and products of the reaction of F + CH have been studied in a discharge flow reactor combined with an electron impact ionization mass spectrometer at nearly 2 Torr total pressure of helium in the temperature range 298-950 K. The total rate constant of the reaction, k = (1.78 ± 0.30) × 10 cm molecule s, determined under pseudo-first-order conditions, monitoring the kinetics of F atom consumption in excess of CH, was found to be temperature independent in the temperature range used. H, CHF, and HF were identified as the reaction products. Absolute measurements of the yields of these species allowed to determine the branching ratios, k/ k = (0.73 ± 0.07) exp(-(425 ± 45)/ T) and k/ k = 1 - (0.73 ± 0.07) exp(-(425 ± 45)/ T) and partial rate constants for addition-elimination (H + CHF) and H atom abstraction (HF + CH) pathways of the title reaction: k = (0.80 ± 0.07) × 10exp(189 ± 37/ T) and k = (1.26 ± 0.13) × 10exp(-414 ± 45/ T) cm molecule s, respectively, at T = 298-950 K and with 2σ quoted uncertainties. The overall reaction rate constant can be adequately described by both the temperature independent value and as a sum of k and k. The kinetic and mechanistic data from the present study are discussed in comparison with previous absolute and relative measurements and theoretical calculations.

摘要

在一个与电子碰撞电离质谱仪联用的放电流动反应器中,于总压力接近2托的氦气环境下,在298 - 950 K的温度范围内研究了F + CH反应的动力学和产物。在准一级条件下,通过监测过量CH存在时F原子消耗的动力学,确定该反应的总速率常数k = (1.78 ± 0.30) × 10 cm³分子⁻¹ s⁻¹,发现在所用温度范围内其与温度无关。H、CHF和HF被鉴定为反应产物。对这些物种产率的绝对测量使得能够确定分支比k₁/k = (0.73 ± 0.07) exp(-(425 ± 45)/T) 和k₂/k = 1 - (0.73 ± 0.07) exp(-(425 ± 45)/T) 以及标题反应的加成 - 消除(H + CHF)和H原子夺取(HF + CH)途径的部分速率常数:在T = 298 - 950 K且引用2σ不确定度时,k₁ = (0.80 ± 0.07) × 10 exp(189 ± 37/T) 和k₂ = (1.26 ± 0.13) × 10 exp(-414 ± 45/T) cm³分子⁻¹ s⁻¹。总反应速率常数既可以用与温度无关的值充分描述,也可以表示为k₁和k₂之和。将本研究的动力学和机理数据与先前的绝对和相对测量以及理论计算进行了比较讨论。

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