296±2K下NO₃自由基和O₃与C₆ - C₁₄ 1 - 烯烃及2 - 甲基 - 1 - 烯烃的气相反应速率常数。
Rate constants for the gas-phase reactions of NO3 radicals and O3 with C6-C14 1-alkenes and 2-methyl-1-alkenes at 296 +/- 2 K.
作者信息
Mason Sherri A, Arey Janet, Atkinson Roger
机构信息
Air Pollution Research Center, University of California, Riverside, California 92521, USA.
出版信息
J Phys Chem A. 2009 May 14;113(19):5649-56. doi: 10.1021/jp9014614.
Rate constants for the gas-phase reactions of NO(3) radicals and O(3) with a series of C(6)-C(14) 1-alkenes and 2-methyl-1-alkenes have been measured at 296 +/- 2 K and atmospheric pressure of air using relative rate methods. For the NO(3) radical reactions, the rate constants obtained (in units of 10(-14) cm(3) molecule(-1) s(-1)) were: 1-hexene, 2.00 +/- 0.16; 1-octene, 2.35 +/- 0.15; 1-decene, 2.55 +/- 0.16; 1-dodecene, 2.79 +/- 0.36; 1-tetradecene, 2.87 +/- 0.21; 2-methyl-1-pentene, 43.8 +/- 2.3; 2-methyl-1-hexene, 52.4 +/- 2.5; 2-methyl-1-octene, 57.8 +/- 2.6; 2-methyl-1-nonene, 60.8 +/- 2.9; 2-methyl-1-undecene, 60.8 +/- 3.3; 2-methyl-1-tridecene, 60.3 +/- 3.4; and cycloheptene, 49.4 +/- 2.0. For the O(3) reactions, the rate constants obtained (in units of 10(-17) cm(3) molecule(-1) s(-1)) were: 1-hexene, 0.898 +/- 0.054; 1-heptene, 1.05 +/- 0.07; 1-octene, 1.01 +/- 0.04; 1-decene, 1.11 +/- 0.05; 1-dodecene, 1.38 +/- 0.14; 1-tridecene, 1.92 +/- 0.12; 1-tetradecene, 2.44 +/- 0.24; 2-methyl-1-pentene, 1.26 +/- 0.13; 2-methyl-1-heptene, 1.35 +/- 0.05; 2-methyl-1-octene, 1.38 +/- 0.06; 2-methyl-1-decene, 1.48 +/- 0.07; 2-methyl-1-undecene, 1.46 +/- 0.11; and 2-methyl-1-tridecene, 2.85 +/- 0.42. The rate constants for the NO(3) radical reactions significantly increase with increasing carbon number, attaining a plateau at > or = C(14) for the 1-alkenes and at C(10)-C(14) for the 2-methyl-1-alkenes. In contrast, the rate constants for O(3) reactions increase only slightly with increasing carbon number up to approximately C(10) for the 1-alkenes and approximately C(12) for the 2-methyl-1-alkenes, with the significant increase in the measured rate constants for the > C(10) 1-alkenes and > C(12) 2-methyl-1-alkenes possibly being due to heterogeneous reactions. Reasons for the observed trends in NO(3) radical and O(3) reaction rate constants with alkene carbon number are discussed.
采用相对速率法，在296±2 K和大气压力的空气中，测量了一系列C(6)-C(14) 1-烯烃和2-甲基-1-烯烃与NO(3)自由基及O(3)的气相反应速率常数。对于NO(3)自由基反应，得到的速率常数（单位为10^(-14) cm³·分子⁻¹·s⁻¹）为：1-己烯，2.00±0.16；1-辛烯，2.35±0.15；1-癸烯，2.55±0.16；1-十二碳烯，2.79±0.36；1-十四碳烯，2.87±0.21；2-甲基-1-戊烯，43.8±2.3；2-甲基-1-己烯，52.4±2.5；2-甲基-1-辛烯，57.8±2.6；2-甲基-1-壬烯，60.8±2.9；2-甲基-1-十一碳烯，60.8±3.3；2-甲基-1-十三碳烯，60.3±3.4；环庚烯，49.4±2.0。对于O(3)反应，得到的速率常数（单位为10^(-17) cm³·分子⁻¹·s⁻¹）为：1-己烯，0.898±0.054；1-庚烯，1.05±0.07；1-辛烯，1.01±0.04；1-癸烯，1.11±0.05；1-十二碳烯，1.38±0.14；1-十三碳烯，1.92±0.12；1-十四碳烯，2.44±0.24；2-甲基-1-戊烯，1.26±0.13；2-甲基-1-庚烯，1.35±0.05；2-甲基-1-辛烯，1.38±0.06；2-甲基-1-癸烯，1.48±0.07；2-甲基-1-十一碳烯，1.46±0.11；2-甲基-1-十三碳烯，2.85±0.42。NO(3)自由基反应的速率常数随碳原子数增加而显著增大，对于1-烯烃在≥C(14)时达到平稳，对于2-甲基-1-烯烃在C(10)-C(14)时达到平稳。相比之下，O(3)反应的速率常数随碳原子数增加仅略有增大，对于1-烯烃直至约C(10)，对于2-甲基-1-烯烃直至约C(12)，而对于>C(10)的1-烯烃和>C(12)的2-甲基-1-烯烃，测量得到的速率常数显著增大可能是由于非均相反应。讨论了观察到的NO(3)自由基和O(3)反应速率常数随烯烃碳原子数变化趋势的原因。
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