Experimental and modeling studies of the pressure and temperature dependences of the kinetics and the OH yields in the acetyl + O2 reaction.
Experimental and modeling studies of the pressure and temperature dependences of the kinetics and the OH yields in the acetyl + O2 reaction.
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DOI：
10.1021/jp1099199
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发表时间：
2011-01
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影响因子：
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通讯作者：
Scott A. Carr;D. Glowacki;Chi-Hsiu Liang;M. Baeza_Romero;M. Blitz;M. Pilling;P. Seakins
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文献类型：
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作者：
Scott A. Carr;D. Glowacki;Chi-Hsiu Liang;M. Baeza_Romero;M. Blitz;M. Pilling;P. Seakins
用激光诱导荧光（LIF）和电子结构/主方程分析研究了乙酰基+ O（2）反应。分析实验的OH时间曲线以获得乙酰基+ O（2）反应的动力学和在213-500 K温度范围内在5-600 Torr压力范围内的氦气中的相对OH产率。对N（2）和CD（3）CO + O（2）进行了更有限的测量。通过假设零压力下的OH产率为1，将相对OH产率转换为绝对产率。势能面驻点的电子结构计算与主方程分析相结合，以反应的高压极限速率系数k（∞）（T）和能量传递参数ΔE（d）为变量，拟合He中的实验数据。得到的最佳拟合参数为k（∞）= 6.2 × 10（-12）cm（-3）molecule（-1）s（-1），在实验范围内与温度无关，（ΔE（d））（He）= 160（T/298 K）cm（-1）.在N（2）中使用相同的k（∞）（T）进行拟合，得到（ΔE（d））（N（2））= 270（T/298 K）cm（-1）。根据修正的Troe表达式，从最佳拟合主方程计算中，以参数化形式给出了在1 ≤ p/Torr ≤ 1.5 × 10（5）和200 ≤ T/K ≤ 1000的压力和温度范围内，以He和N（2）作为浴气时，OH和CH（3）C（O）O（2）的生成速率系数。导致HO（2）+ CH（2）CO和CH（2）C（O）OOH的次要通道在此范围内的产率通常<1%。
The acetyl + O(2) reaction has been studied by observing the time dependence of OH by laser-induced fluorescence (LIF) and by electronic structure/master equation analysis. The experimental OH time profiles were analyzed to obtain the kinetics of the acetyl + O(2) reaction and the relative OH yields over the temperature range of 213-500 K in helium at pressures in the range of 5-600 Torr. More limited measurements were made in N(2) and for CD(3)CO + O(2). The relative OH yields were converted into absolute yields by assuming that the OH yield at zero pressure is unity. Electronic structure calculations of the stationary points of the potential energy surface were used with a master equation analysis to fit the experimental data in He using the high-pressure limiting rate coefficient for the reaction, k(∞)(T), and the energy transfer parameter, (ΔE(d)), as variable parameters. The best-fit parameters obtained are k(∞) = 6.2 × 10(-12) cm(-3) molecule(-1) s(-1), independent of temperature over the experimental range, and (ΔE(d))(He) = 160(T/298 K) cm(-1). The fits in N(2), using the same k(∞)(T), gave (ΔE(d))(N(2)) = 270(T/298 K) cm(-1). The rate coefficients for formation of OH and CH(3)C(O)O(2) are provided in parametrized form, based on modified Troe expressions, from the best-fit master equation calculations, over the pressure and temperature ranges of 1 ≤ p/Torr ≤ 1.5 × 10(5) and 200 ≤ T/K ≤ 1000 for He and N(2) as the bath gas. The minor channels, leading to HO(2) + CH(2)CO and CH(2)C(O)OOH, generally have yields <1% over this range.