Feierabend Karl J, Zhu Lei, Talukdar R K, Burkholder James B
Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration, 325 Broadway, Boulder, Colorado 80305-3328, USA.
J Phys Chem A. 2008 Jan 10;112(1):73-82. doi: 10.1021/jp0768571. Epub 2007 Dec 1.
Rate coefficients, k1(T), over the temperature range of 210-390 K are reported for the gas-phase reaction OH + HC(O)C(O)H (glyoxal) --> products at pressures between 45 and 300 Torr (He, N2). Rate coefficients were determined under pseudo-first-order conditions in OH using pulsed laser photolysis production of OH radicals coupled with OH detection by laser-induced fluorescence. The rate coefficients obtained were independent of pressure and bath gas. The room-temperature rate coefficient, k1(296 K), was determined to be (9.15 +/- 0.8) x 10-12 cm3 molecule-1 s-1. k1(T) shows a negative temperature dependence with a slight deviation from Arrhenius behavior that is reproduced over the temperature range included in this study by k1(T) = [(6.6 +/- 0.6) x 10-18]T2[exp([820 +/- 30]/T)] cm3 molecule-1 s-1. For atmospheric modeling purposes, a fit to an Arrhenius expression over the temperature range included in this study that is most relevant to the atmosphere, 210-296 K, yields k1(T) = (2.8 +/- 0.7) x 10-12 exp[(340 +/- 50)/T] cm3 molecule-1 s-1 and reproduces the rate coefficient data very well. The quoted uncertainties in k1(T) are at the 95% confidence level (2sigma) and include estimated systematic errors. Comparison of the present results with the single previous determination of k1(296 K) and a discussion of the reaction mechanism and non-Arrhenius temperature dependence are presented.
报道了在45至300托（氦气、氮气）压力下，210 - 390 K温度范围内气相反应OH + HC(O)C(O)H（乙二醛）→产物的速率系数k1(T)。速率系数是在OH的准一级条件下测定的，采用脉冲激光光解产生OH自由基，并通过激光诱导荧光检测OH。得到的速率系数与压力和缓冲气体无关。室温速率系数k1(296 K)测定为(9.15 ± 0.8)×10⁻¹² cm³·分子⁻¹·s⁻¹。k1(T)呈现负温度依赖性，与阿仑尼乌斯行为略有偏差，在本研究涵盖的温度范围内，k1(T) = [(6.6 ± 0.6)×10⁻¹⁸]T²[exp([820 ± 30]/T)] cm³·分子⁻¹·s⁻¹可重现这种偏差。出于大气建模目的，在本研究中与大气最相关的210 - 296 K温度范围内，对阿仑尼乌斯表达式进行拟合，得到k1(T) = (2.8 ± 0.7)×10⁻¹² exp[(340 ± 50)/T] cm³·分子⁻¹·s⁻¹，能很好地重现速率系数数据。k1(T)中引用的不确定度为95%置信水平（2σ），包括估计的系统误差。将本研究结果与之前唯一一次对k1(296 K)的测定进行了比较，并讨论了反应机理和非阿仑尼乌斯温度依赖性。
Zotero 插件