Department of Chemistry, University of Georgia, Athens, Georgia 30602, United States.
J Phys Chem A. 2011 Nov 10;115(44):12161-72. doi: 10.1021/jp206899w. Epub 2011 Oct 13.
The gas-phase reactions of NO(3) radicals with series of 1-alkenes, dienes, cycloalkenes, alkenols, and alkenals were studied in pure N(2) or 20% O(2)/80% N(2) bath gas at room temperature and atmospheric pressure using a relative rates technique. Rate coefficients were derived from rates of loss of the organic compounds observed using a chemical ionization mass spectrometer. No difference in the measured kinetic data was observed in the presence or absence of O(2). The rate coefficients obtained (k (10(-13) cm(3) molecule(-1) s(-1)), with uncertainties representing 95% confidence intervals) are as follows: 1-hexene, 0.233 ± 0.021; 1-heptene, 0.245 ± 0.029; 1-octene, 0.292 ± 0.044; 1,3-butadiene, 1.24 ± 0.09; isoprene, 6.24 ± 0.11; 2,3-dimethyl-1,3-butadiene, 14.1 ± 0.5; 1,3-cyclohexadiene, 112 ± 8; cyclopentene, 4.82 ± 0.13; cyclohexene, 5.38 ± 0.20; cycloheptene, 5.28 ± 0.23; 2-buten-1-ol (crotyl alcohol), 3.23 ± 0.12; cis-2-penten-1-ol, 3.11 ± 0.11; cis-2-hexen-1-ol, 3.81 ± 0.38; trans-2-pentenal, 0.193 ± 0.040; trans-2-hexenal, 0.136 ± 0.029; trans-2-heptenal, 0.231 ± 0.036; cis-4-heptenal, 4.03 ± 0.24. The measured rate coefficients are compared to values from previous studies and three structure-activity relationships (SARs), and good agreement is found, in general. In particular, the recently developed SAR of Kerdouci et al. (Kerdouci, J.; Picquet-Varrault, B.; Doussin, J. ChemPhysChem2010, 11, 3909-3920.) is found to estimate the rate coefficients within 35% for all of the measured reactions except for NO(3) + 1,3-butadiene. The SAR prediction for that reaction is nearly 50% lower than the measured value, suggesting that it underestimates the effect of conjugation on the reaction of NO(3) with this small diene. The measured rate coefficients for reactions with a series of alkenols are used to modify the SAR substituent factor for the -CH(2)OH group, and those for reactions with a series of trans-2-alkenals are used to derive a substituent factor for the -C(O)H group, which was not included in the original SAR because of insufficient experimental data.
在室温及常压下，使用相对速率技术，在纯 N(2)或 20% O(2)/80% N(2)浴气中，研究了 NO(3)自由基与一系列 1-烯烃、二烯烃、环烯烃、烯醇和烯醛的气相反应。通过使用化学电离质谱仪观察到的有机化合物的损失速率推导出速率系数。在存在或不存在 O(2)的情况下，测量的动力学数据没有差异。得到的速率系数 (k (10(-13) cm(3) molecule(-1) s(-1))，不确定度表示为 95%置信区间)如下：1-己烯，0.233 ± 0.021；1-庚烯，0.245 ± 0.029；1-辛烯，0.292 ± 0.044；1,3-丁二烯，1.24 ± 0.09；异戊二烯，6.24 ± 0.11；2,3-二甲基-1,3-丁二烯，14.1 ± 0.5；1,3-环己二烯，112 ± 8；环戊烯，4.82 ± 0.13；环己烯，5.38 ± 0.20；环庚烯，5.28 ± 0.23；2-丁烯-1-醇（巴豆醇），3.23 ± 0.12；顺-2-戊烯-1-醇，3.11 ± 0.11；顺-2-己烯-1-醇，3.81 ± 0.38；反-2-戊烯醛，0.193 ± 0.040；反-2-己烯醛，0.136 ± 0.029；反-2-庚烯醛，0.231 ± 0.036；顺-4-庚烯醛，4.03 ± 0.24。测量的速率系数与先前研究中的值和三个结构-活性关系 (SAR) 进行了比较，总体上发现存在良好的一致性。特别是，最近由 Kerdouci 等人开发的 SAR（Kerdouci，J.；Picquet-Varrault，B.；Doussin，J. ChemPhysChem2010，11，3909-3920.）被发现可以在 35%以内估计所有测量反应的速率系数，除了 NO(3) + 1,3-丁二烯。该反应的 SAR 预测值比实测值低近 50%，表明它低估了共轭效应对 NO(3)与这种小二烯反应的影响。用一系列烯醇的反应速率系数来修正 -CH(2)OH 基团的 SAR 取代基因子，用一系列反-2-烯醛的反应速率系数来推导出 -C(O)H 基团的取代基因子，由于实验数据不足，该因子未包含在原始 SAR 中。
