Gaona-Colmán Elizabeth, Blanco María B, Barnes Ian, Wiesen Peter, Teruel Mariano A
Instituto de Investigaciones en Fisicoquímicas de Córdoba (INFIQC), Dpto. de Fisicoquímica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria 5000 Córdoba Argentina
Physikalische Chemie/FBC, Bergische Universitaet Wuppertal 42119 Wuppertal Germany.
RSC Adv. 2018 Jul 31;8(48):27054-27063. doi: 10.1039/c8ra04931a. eCollection 2018 Jul 30.
Rate coefficients for the gas-phase reactions of Cl atoms with β-ocimene and camphene were determined to be (in units of 10 cm per molecule per s) 5.5 ± 0.7 and 3.3 ± 0.4, respectively. The experiments were performed by the relative technique in an environmental chamber with FTIR detection of the reactants at 298 K and 760 torr. Product identification experiments were carried out by gas chromatography with mass spectrometry detection (GC-MS) using the solid-phase microextraction (SPME) method employing on-fiber carbonyl compound derivatization with -(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride. An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and cyclic and acyclic terpenes with a conjugated double bond at 298 K is presented. The atmospheric persistence of these compounds was calculated taking into account the measured rate coefficients. In addition, tropospheric chemical mechanisms for the title reactions are postulated.
已确定氯原子与β-罗勒烯和莰烯的气相反应速率系数分别为（单位：10⁻¹⁵ cm³每分子每秒）5.5±0.7和3.3±0.4。实验采用相对技术在环境舱中进行，在298 K和760托的条件下用傅里叶变换红外光谱法检测反应物。产物鉴定实验通过气相色谱-质谱联用检测（GC-MS）进行，采用固相微萃取（SPME）方法，利用-(2,3,4,5,6-五氟苄基)盐酸羟胺对纤维上的羰基化合物进行衍生化。本文给出了在298 K下氯原子和羟基自由基加成到具有共轭双键的烯烃、环状和非环状萜烯双键上的可用速率分析。考虑到测得的速率系数，计算了这些化合物在大气中的持久性。此外，还假定了标题反应的对流层化学机制。
