Orkin Vladimir L, Martynova Larissa E, Kurylo Michael J
National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States.
J Phys Chem A. 2014 Jul 17;118(28):5263-71. doi: 10.1021/jp5018949. Epub 2014 Jul 2.
Measurements of the rate constant for the gas-phase reactions of OH radicals with trans-1-chloro-3,3,3-trifluoropropene (trans-CHCl═CHCF3) were performed using a flash photolysis resonance-fluorescence technique over the temperature range 220-370 K. The reaction rate constant exhibits a noticeable curvature of the temperature dependence in the Arrhenius plot, which can be represented by the following expression: kt-CFP (220-370 K) = 1.025 × 10(-13) × (T/298)(2.29) exp(+384/T) cm(3 )molecule(-1) s(-1). The room-temperature rate constant was determined to be kt-CFP (298 K) = (3.29 ± 0.10) × 10(-13) cm(3) molecule(-1) s(-1), where the uncertainty includes both two standard errors (statistical) and the estimated systematic error. For atmospheric modeling purposes, the rate constant below room temperature can be represented by the following expression: kt-CFP (220-298 K) = (7.20 ± 0.46) × 10(-13) exp[-(237 ± 16)/T] cm(3) molecule(-1) s(-1). There was no difference observed between the rate constants determined at 4 kPa (30 Torr) and 40 kPa (300 Torr) at both 298 and 370 K. The UV and IR absorption cross sections of this compound were measured at room temperature. The atmospheric lifetime, global warming potential, and ozone depletion potential of trans-CHCl═CHCF3 were estimated.
采用闪光光解共振荧光技术,在220 - 370 K的温度范围内,对OH自由基与反式-1-氯-3,3,3-三氟丙烯(反式-CHCl═CHCF3)的气相反应速率常数进行了测量。反应速率常数在阿累尼乌斯图中呈现出明显的温度依赖性曲线,可用以下表达式表示:kt-CFP(220 - 370 K) = 1.025 × 10(-13) × (T/298)(2.29) exp(+384/T) cm(3) molecule(-1) s(-1)。室温下的速率常数确定为kt-CFP(298 K) = (3.29 ± 0.10) × 10(-13) cm(3) molecule(-1) s(-1),其中不确定性包括两个标准误差(统计)和估计的系统误差。出于大气建模目的,室温以下的速率常数可用以下表达式表示:kt-CFP(220 - 298 K) = (7.20 ± 0.46) × 10(-13) exp[-(237 ± 16)/T] cm(3) molecule(-1) s(-1)。在298 K和370 K时,在4 kPa(30Torr)和40 kPa(300 Torr)下测定的速率常数之间未观察到差异。在室温下测量了该化合物的紫外和红外吸收截面。估计了反式-CHCl═CHCF3的大气寿命、全球变暖潜势和臭氧消耗潜势。