Bergische Universitaet Wuppertal, Physikalische Chemie/FBC, Gauss Strasse 20, D-42119 Wuppertal, Germany.
J Phys Chem A. 2012 Sep 6;116(35):8885-92. doi: 10.1021/jp305992a. Epub 2012 Aug 28.
Using a relative rate technique, kinetic studies on the gas-phase reactions of OH radicals, ozone, and NO(3) radicals with iso-butyl vinyl ether (iBVE) and tert-butyl vinyl ether (tBVE) have been performed in a 405 L Duran glass chamber at (298 ± 3) K and atmospheric pressure (750 ± 10 Torr) in synthetic air using in situ FTIR spectroscopy to monitor the reactants. The following rate coefficients (in units of cm(3) molecule(-1) s(-1)) have been obtained: (1.08 ± 0.23) × 10(-10) and (1.25 ± 0.32) × 10(-10) for the reactions of OH with iBVE and tBVE, respectively; (2.85 ± 0.62) × 10(-16) and (5.30 ± 1.07) × 10(-16) for the ozonolysis of iBVE and tBVE, respectively; and (1.99 ± 0.56) × 10(-12) and (4.81 ± 1.01) × 10(-12) for the reactions of NO(3) with iBVE and tBVE, respectively. The rate coefficients for the NO(3) reactions are first-time determinations. The measured rate coefficients are compared with estimates using current structure activity relationship (SAR) methods and the effects of the alkoxy group on the gas-phase reactivity of the alkyl vinyl ethers toward the oxidants are compared and discussed. In addition, estimates of the tropospheric lifetimes of iBVE and tBVE with respect to their reactions with OH, ozone, and NO(3) for typical OH radical, ozone, and NO(3) radical concentrations are made, and their relevance for the environmental fate of compounds is considered.
利用相对速率技术，在（298±3）K 和大气压力（750±10 Torr）下，在一个 405 L 的 Duran 玻璃室中，使用原位 FTIR 光谱法监测反应物，对 OH 自由基、臭氧和 NO3 自由基与异丁基乙烯基醚（iBVE）和叔丁基乙烯基醚（tBVE）的气相反应进行了动力学研究。得到了以下速率系数（单位为 cm3 分子-1 s-1）：OH 与 iBVE 和 tBVE 的反应分别为（1.08±0.23）×10-10 和（1.25±0.32）×10-10；iBVE 和 tBVE 的臭氧分解分别为（2.85±0.62）×10-16 和（5.30±1.07）×10-16；NO3 与 iBVE 和 tBVE 的反应分别为（1.99±0.56）×10-12 和（4.81±1.01）×10-12。NO3 反应的速率系数是首次测定的。将测量的速率系数与使用当前结构活性关系（SAR）方法的估计值进行了比较，并比较和讨论了烷氧基对烷基乙烯基醚与氧化剂在气相中反应性的影响。此外，还对 iBVE 和 tBVE 与 OH、臭氧和 NO3 反应的大气寿命进行了估计，考虑了它们与化合物环境命运的相关性。
