Moise Tamar, Rudich Yinon, Rousse Davy, George Christian
Department of Environmental Sciences, Weizmann Institute, Rehovot 76100, Israel.
Environ Sci Technol. 2005 Jul 15;39(14):5203-8. doi: 10.1021/es048488h.
Prior to the massive use of new oxygenated solvents, data on their multiphase reactivity must be obtained to assess their environmental fate and impact on water and air quality. For this, the kinetics and mechanisms of the photochemical and photocatalytic degradation of selected oxygenated solvents by common tropospheric oxidants (such as OH and ozone) must be characterized. We studied the oxidation kinetics of new oxygenated solvents as pure organic liquids and in an aqueous medium by ozone and bythe OH radical, respectively. The studied chemicals are all unsaturated compounds, having none, one, or two ether groups. The results indicate that the OH reaction proceeds atthe diffusion limit by addition to the double bond. The reactive uptake coefficients associated with the reaction initiated by ozone are of the order of 10(-3). The reactions of compounds with two double bonds are very fast and probably occur at the surface. This kinetic information demonstrates that organic solvents in an organic medium or in an aqueous droplet will be oxidized rapidly by these oxidation reactions. These reactions, however, are not significant sinks for ozone and OH radicals.
在大量使用新型含氧溶剂之前,必须获取有关其多相反应性的数据,以评估它们在环境中的归宿及其对水质和空气质量的影响。为此,必须表征选定的含氧溶剂被常见对流层氧化剂(如羟基自由基和臭氧)进行光化学和光催化降解的动力学及机理。我们分别研究了新型含氧溶剂作为纯有机液体以及在水介质中被臭氧和羟基自由基氧化的动力学。所研究的化学物质均为不饱和化合物,含有零个、一个或两个醚基。结果表明,羟基自由基反应通过加成到双键上在扩散极限下进行。与臭氧引发的反应相关的反应吸收系数约为10⁻³。含有两个双键的化合物的反应非常快,可能发生在表面。这些动力学信息表明,有机介质或水滴中的有机溶剂将通过这些氧化反应被迅速氧化。然而,这些反应对于臭氧和羟基自由基而言并非重要的汇。