Kinetic and mechanistic study of the gas-phase reactions of a series of vinyl ethers with the nitrate radical.
Kinetic and mechanistic study of the gas-phase reactions of a series of vinyl ethers with the nitrate radical.
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DOI：
10.1021/jp063357j
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发表时间：
2006-09
期刊：
影响因子：
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通讯作者：
M. Scarfogliero;B. Picquet-Varrault;J. Salce;R. Durand-Jolibois;J. Doussin
中科院分区：
文献类型：
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作者：
M. Scarfogliero;B. Picquet-Varrault;J. Salce;R. Durand-Jolibois;J. Doussin
在LISA室内模拟室中，在对流层条件下（大气压和T = 293 +/- 3k），研究了甲基、乙基、丙基和丁基乙烯基醚的NO(3)氧化。NO(3)是在反应器内通过之前添加到空气- voc混合物中的N(2)O(5)的热分解产生的，并使用FTIR光谱法监测其浓度。以异戊二烯为参比化合物，采用相对速率法进行动力学实验，得到甲基、乙基、丙基和丁基乙烯醚的速率常数分别为k(1) = (7.2 +/- 1.5) × 10（-13）、k(2) = (13.1 +/- 2.7) × 10（-13）、k(3) = (13.3 +/- 3.0) × 10(-13) cm(3)分子（-1）s（-1）。主要氧化产物为甲醛，甲酸甲酯、甲酸乙酯、甲酸丙酯和甲酸丁酯。氧化产物的产率接近50%。氧合硝酸盐和过氧硝酸盐也被检测到。
NO(3) oxidation of methyl, ethyl, propyl, and butyl vinyl ethers has been studied under tropospheric conditions (atmospheric pressure and T = 293 +/- 3 K) in the LISA indoor simulation chamber. NO(3) was produced inside the reactor by thermal decomposition of N(2)O(5) previously added to the air-VOC mixture, and concentrations were monitored using FTIR spectrometry. All the kinetic experiments were carried out by relative rate technique using isoprene as reference compound, leading to the rate constants k(1) = (7.2 +/- 1.5) x 10(-13), k(2) = (13.1 +/- 2.7) x 10(-13), k(3) = (13.3 +/- 3.0) x 10(-13), and k(4) = (17.0 +/- 3.7) x 10(-13) cm(3) molecule(-1) s(-1) for methyl, ethyl, propyl, and butyl vinyl ethers, respectively. Main oxidation products have been identified like being formaldehyde and respectively methyl, ethyl, propyl, and butyl formates. Production yields of oxidation products were close to 50%. Oxygenated nitrates and peroxynitrates were also detected.