The High Pressure Range of the Addition of OH to C2H2 and C2H4

D. Fulle, H.F. Hamann, H. Hippler, C.P. Jänsch
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引用次数: 29

Abstract

The kinetics of the bimolecular reactions OH+C2H2+M ⟺ C2H2OH+M (1) and OH+C2H4+M ⟺ C2H4OH+M (2) have been investigated over an extended pressure (1–130 bar) and temperature (300–800 K) range. The OH radicals have been generated by laser flash photolysis of suited precursors and their decays have been measured by saturated laser-induced fluorescence (SLIF) under pseudo-first-order conditions. The pressure dependences have been analyzed by constructing falloff curves at fixed temperatures leading to reliable extrapolations towards the high pressure limiting rate constants k. In the given temperature range these rate constants are represented as k1,∞ = 3.8×10−11 exp (–910 K/T) cm3 molecule−1 s−1 and as k2,∞ = 1.0×10−11 cm3 molecule−1 s−1. At temperatures above 700 K biexponential decay curves have been obtained. The chemical equilibria of reactions (1) and (2) could be determined. By a third law analysis the equilibrium constants have been evaluated with reaction enthalpies for the addition complex C2H2OH of δIHo1 (O K) = -(146 ± 10) kJ/mol and for C2H4OH of δIHo2 (O K) = -(123 ± 6) kJ/mol, respectively. The two equilibrium constants are given by K1,eq = (5.4±2.2)×10−2 (T/K)−1.7±0.2 exp ((17560±1200) K/T) bar−1 and K2,eq = 2.1 × 10−2 (T/K)−95±0.1 × exp ((14780±720) K/T) bar−1, respectively.

氢氧加成C2H2和C2H4的高压范围
研究了双分子反应OH+C2H2+M→C2H2OH+M(1)和OH+C2H4+M→C2H4OH+M(2)在压力(1 ~ 130 bar)和温度(300 ~ 800 K)范围内的动力学。在准一阶条件下,用饱和激光诱导荧光(SLIF)测量了OH自由基的衰变。通过构建固定温度下的衰减曲线来分析压力依赖性,从而可靠地推断出高压极限速率常数k∞。在给定温度范围内,这些速率常数表示为k1,∞= 3.8×10−11 exp (-910 K/T) cm3分子−1 s−1,k2,∞= 1.0×10−11 cm3分子−1 s−1。在700 K以上的温度下,得到了双指数衰减曲线。反应(1)和(2)的化学平衡可以确定。用第三定律计算了δIHo1 (O K)的C2H2OH加成络合物的反应焓,分别为-(146±10)kJ/mol和δIHo2 (O K)的C2H4OH = -(123±6)kJ/mol。两个平衡常数K1和K2分别为eq =(5.4±2.2)×10−2 (T/K)−1.7±0.2 exp((17560±1200)K/T) bar−1和eq = 2.1 ×10−2 (T/K)−95±0.1 × exp((14780±720)K/T) bar−1。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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