Kinetics of the reaction of Cl atoms with methanol has been investigated at 2 Torr total pressure of helium and over a wide temperature range 225‐950 K, using a discharge flow reactor combined with an electron impact ionization quadrupole mass spectrometer. The rate constant of the reaction Cl + CH₃OH → products (1) was determined using both absolute measurements under pseudo‐first order conditions, monitoring the kinetics of Cl‐atom consumption in excess of methanol and relative rate method, k₁ = (5.1 ± 0.8) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹, and was found to be temperature independent over the range T = 225‐950 K. The rate constant of the reaction Cl + Br₂ → BrCl + Br (3) was measured in an absolute way monitoring Cl‐atom decays in excess of Br₂: k₃ = 1.64 × 10⁻¹⁰ exp(34/T) cm³ molecule⁻¹ s⁻¹ at T = 225‐960 K (with conservative 15% uncertainty). The experimental data for k₃ can also be adequately represented by the temperature independent value of k₃ = (1.8 ± 0.3) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹. The kinetic data from the present study are compared with previous measurements.

中文翻译：

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氯原子与甲醇和Br2反应的温度相关速率常数

使用放电流反应器结合电子碰撞电离四极质谱仪，研究了在2 Torr氦气总压力和225-950 K的宽温度范围内，Cl原子与甲醇的反应动力学。使用假一阶条件下的绝对测量，监测过量甲醇中Cl原子消耗的动力学和相对速率方法，确定了反应Cl + CH ₃ OH→产物（1）的速率常数，k ₁  =（ 5.1±0.8）×10 ^-11  cm ³ 分子^-1  s ^-1，发现在温度范围T内与温度无关 = 225-950K。 以绝对方式测量反应Cl + Br ₂ →BrCl + Br（3）的速率常数，监测Cl-原子的衰变超过Br ₂：k ₃  = 1.64×10 ^-10 exp（ 34 / T）cm ³ 分子^-1  s ^-1，T  = 225-960 K（保守15％不确定性）。k ₃的实验数据也可以用与温度无关的值k ₃  =（1.8±0.3）×10 ^-10  cm ³ 分子^-1  s ^-1来充分表示。。本研究的动力学数据与以前的测量结果进行了比较。