Liu Z R, Hu D
Environmental Science Center, Peking University, Beijing 100871, China.
Guang Pu Xue Yu Guang Pu Fen Xi. 2001 Oct;21(5):585-7.
alpha-pinene and beta-pinene are the most dominating species among natural terpenes. Terpenes are mainly emitted from forest trees, flowers and grass. In the lower troposphere terpenes can react fast with OH radical, ozone, NO3 radical and ground state oxygen atom. These reactions may contribute to the occurring of aerosols, peroxides (hydrogen peroxide and organic peroxide), carbon cycle (mainly CO), acid rain (organic acids, NO3- and SO4(2-), ozone and active radicals such as OH radical. Reactions with ozone occur both in the daytime and in the night. The study in this field in China began in the late 1980. The main work focus on the source emission and the experimental simulation has just started. It is most of our group's work. In this paper preliminary experimental simulation of the gas-phase reactions of alpha-pinene and beta-pinene with ozone were carried out in the quartz chamber. The rate constants of these reactions were measured using long-path Fourier transform infra-red combined with relative rate constant method. And the rate constants for the gas-phase reactions of alpha-pinene, beta-pinene with ozone were determined as 2.83 x 10(17) cm3.molecule-1.s-1 and 1.48 x 10(17) cm3.molecule-1.s-1 at 1.0 x 10(5) Pa and 296 +/- 3 K. The results are quite similar to the data from Atkinson group. No cyclohexane was added to the reaction system during the measurement to restrain the formation of OH radical. The formation of OH radical could not be quantified, so that the effect of subsidiary reactions induced by OH radical has not been calculated. In the later simulation study and model this effect should be considered.
α-蒎烯和β-蒎烯是天然萜类化合物中最主要的种类。萜类化合物主要由森林树木、花卉和草类释放。在对流层下部,萜类化合物能与羟基自由基、臭氧、硝酸根自由基和基态氧原子快速反应。这些反应可能导致气溶胶、过氧化物(过氧化氢和有机过氧化物)、碳循环(主要是一氧化碳)、酸雨(有机酸、硝酸根和硫酸根)、臭氧以及诸如羟基自由基等活性自由基的产生。与臭氧的反应在白天和夜晚都会发生。中国在该领域的研究始于20世纪80年代末。主要工作集中在源排放方面,实验模拟才刚刚起步。这主要是我们团队的工作。本文在石英反应室中对α-蒎烯和β-蒎烯与臭氧的气相反应进行了初步实验模拟。采用长路径傅里叶变换红外光谱结合相对速率常数法测量了这些反应的速率常数。在1.0×10⁵帕和296±3开尔文的条件下,α-蒎烯、β-蒎烯与臭氧气相反应的速率常数分别确定为2.83×10¹⁷立方厘米·分子⁻¹·秒⁻¹和1.48×10¹⁷立方厘米·分子⁻¹·秒⁻¹。结果与阿特金森团队的数据非常相似。测量过程中未向反应体系中添加环己烷以抑制羟基自由基的形成。羟基自由基的形成无法定量,因此未计算羟基自由基引发的副反应的影响。在后续的模拟研究和模型中应考虑这一影响。