Davis Maxine E, Talukdar Ranajit K, Notte Gregory, Ellison G Barney, Burkholder James B
Earth System Research Laboratory, National Oceanic and Atmospheric Administration, 325 Broadway, Boulder, Colorado 80305-3328, USA.
Environ Sci Technol. 2007 Jun 1;41(11):3959-65. doi: 10.1021/es070048d.
The rate coefficientforthe reaction of OH with pinonaldehyde (C10H16O2, 3-acetyl-2,2-dimethyl-cyclobutyl-ethanal), a product of the atmospheric oxidation of alpha-pinene, was measured under pseudo-first-order conditions in OH at temperatures between 297 and 374 K at 55 and 96 Torr (He). Laser induced fluorescence (LIF) was used to monitor OH in the presence of pinonaldehyde following its production by 248 nm pulsed laser photolysis of H2O2. The reaction exhibits a negative temperature dependence with an Arrhenius expression of k1(T) = (4.5 +/- 1.3) x 10(-12) exp((600 +/- 100)/ 7) cm3 molecule(-1) s(-1); k1(297 K) = (3.46 +/- 0.4) x 10(-11) cm3 molecule(-1) s(-1). There was no observed dependence of the rate coefficient on pressure. Our results are compared with previous relative rate determinations of k1 near 297 K and the discrepancies are discussed. The state of knowledge for the atmospheric processing of pinonaldehyde is reviewed, and its role as a marker for alpha-pinene (monoterpene) chemistry in the atmosphere is discussed.
在55和96托(氦气)压力下,于297至374 K的温度范围内,在准一级条件下测量了OH与蒎烯醛(C10H16O2,3 - 乙酰基 - 2,2 - 二甲基 - 环丁基 - 乙醛)反应的速率系数,蒎烯醛是α - 蒎烯大气氧化的产物。在通过248 nm脉冲激光光解H2O2产生蒎烯醛后,利用激光诱导荧光(LIF)监测其存在下的OH。该反应呈现负温度依赖性,阿仑尼乌斯表达式为k1(T) = (4.5 ± 1.3) x 10(-12) exp((600 ± 100)/T) cm3 molecule(-1) s(-1);k1(297 K) = (3.46 ± 0.4) x 10(-11) cm3 molecule(-1) s(-1)。未观察到速率系数对压力的依赖性。将我们的结果与之前在297 K附近对k1的相对速率测定进行了比较,并讨论了差异。综述了蒎烯醛大气处理的知识状态,并讨论了其作为大气中α - 蒎烯(单萜)化学标志物的作用。