An experimental kinetic study and products research of the reactions of O-3 with a series of unsaturated alcohols
An experimental kinetic study and products research of the reactions of O-3 with a series of unsaturated alcohols
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O-3与一系列不饱和醇反应的实验动力学研究及产物研究
DOI：
10.1016/j.atmosenv.2016.09.057
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发表时间：
2016
影响因子：
5
通讯作者：
Ge Maofa
中科院分区：
文献类型：
--
作者：
Chen Yi;Wang Jing;Zhao Sanping;Tong Shengrui;Ge Maofa
在298 K和760 ℃的大气压下，在FEP聚四氟乙烯膜室中研究了不饱和醇与O3的气相反应。用绝对速率法和相对速率法测定了C6-C8烯醇与O3反应的速率常数，（Z）-3-己烯-1-醇为（5.96 ± 0.35）× 10− 17 cm 3 molecule − 1 s − 1，（Z）-3-庚烯-1-醇和（Z）-3-辛烯-1-醇的分子量分别为（5.12 ± 0.30）× 10− 17 cm 3 molecule − 1 s − 1和（5.66 ± 0.52）× 10− 17 cm 3 molecule − 1 s − 1。用质子转移反应质谱（PTR-MS）检测了上述反应的气相产物。（Z）-3-己烯-1-醇的主要气体产物为HOCH_2CH_2CHO、CH_2CH_2CHO、HCHO和CH_3CHO。（Z）-3-庚烯-1-醇的气相产物主要为HOCH_2CH_2CHO和CH_3（CH_2）_2CHO。（Z）-3-辛烯-1-醇的主要气相产物为CH 3（CH 2）3CHO、CH 3（CH 2）2CHO和HOCH 2CH 2CHO。同时测定了SOA的产率，（Z）-3-己烯醇、（Z）-3-庚烯醇和（Z）-3-辛烯醇的SOA产率分别为0.184 ± 0.013、0.213 ± 0.017和0.232 ± 0.021。提出并讨论了可能的反应机理。这里提出的动力学数据已被用来估计它们的大气寿命和反应活性。并讨论了这些反应的大气意义。
The gas-phase reactions of unsaturated alcohols with O3were investigated in FEP Teflon film chamber at 298 K and 760 torr of atmosphere pressure. The rate constants of the reactions of C6-C8 alkenols with O3were determined using both the absolute and the relative rate method, and the measured values were (5.96 ± 0.35) × 10−17cm3molecule−1s−1for (Z)-3-hexen-1-ol, (5.12 ± 0.30) × 10−17cm3molecule−1s−1for (Z)-3-hepten-1-ol, and (5.66 ± 0.52) × 10−17cm3molecule−1s−1for (Z)-3-octen-1-ol, respectively. The gas-phase products of these reactions mentioned above were detected using proton-transfer-reaction mass spectrum (PTR-MS). HOCH2CH2CHO, CH2CH2CHO, HCHO and CH3CHO were identified as the main gas products for (Z)-3-hexen-1-ol. HOCH2CH2CHO and CH3(CH2)2CHO dominated the gaseous products for (Z)-3-hepten-1-ol. And for (Z)-3-octen-1-ol, CH3(CH2)3CHO, CH3(CH2)2CHO and HOCH2CH2CHO were the main gaseous products. The SOA yields were monitored at the same time, which were 0.184 ± 0.013, 0.213 ± 0.017, 0.232 ± 0.021 for (Z)-3-hexen-1-ol, (Z)-3-hepten-1-ol and (Z)-3-octen-1-ol, respectively. The possible reaction mechanisms were proposed and discussed. The kinetic data presented here has been used to estimate their atmosphere lifetimes and the reaction reactivity. The atmosphere implication of these reactions has also been discussed.