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OH 自由基与 3-甲氧基-3-甲基-1-丁醇反应的动力学和产物。

Kinetics and products of the reaction of OH radicals with 3-methoxy-3-methyl-1-butanol.

机构信息

Air Pollution Research Center, University of California Riverside, Riverside, California 92521, USA.

出版信息

Environ Sci Technol. 2011 Aug 15;45(16):6896-901. doi: 10.1021/es201475g. Epub 2011 Jul 20.

Abstract

3-Methoxy-3-methyl-1-butanol [CH(3)OC(CH(3))(2)CH(2)CH(2)OH] is used as a solvent for paints, inks, and fragrances and as a raw material for the production of industrial detergents. A rate constant of (1.64 ± 0.18) × 10(-11) cm(3) molecule(-1) s(-1) for the reaction of 3-methoxy-3-methyl-1-butanol with OH radicals has been measured at 296 ± 2 K using a relative rate method, where the indicated error is the estimated overall uncertainty. Acetone, methyl acetate, glycolaldehyde, and 3-methoxy-3-methylbutanal were identified as products of the OH radical-initiated reaction, with molar formation yields of 3 ± 1%, 35 ± 9%, 13 ± 3%, and 33 ± 7%, respectively, at an average NO concentration of 1.3 × 10(14) molecules cm(-3). Using a 12-h average daytime OH radical concentration of 2 × 10(6) molecules cm(-3), the calculated lifetime of 3-methoxy-3-methyl-1-butanol with respect to reaction with OH radicals is 8.5 h. Potential reaction mechanisms are discussed.

摘要

3-甲氧基-3-甲基-1-丁醇[CH(3)OC(CH(3))(2)CH(2)CH(2)OH] 用作油漆、油墨和香料的溶剂,以及工业清洁剂生产的原料。在 296 ± 2 K 下,使用相对速率法测量了 3-甲氧基-3-甲基-1-丁醇与 OH 自由基反应的速率常数为 (1.64 ± 0.18) × 10(-11) cm(3) molecule(-1) s(-1),其中指出的误差是估计的总不确定度。鉴定出丙酮、乙酸甲酯、乙二醛和 3-甲氧基-3-甲基丁醛为 OH 自由基引发反应的产物,在平均 NO 浓度为 1.3 × 10(14) 个分子 cm(-3)时,摩尔生成产率分别为 3 ± 1%、35 ± 9%、13 ± 3%和 33 ± 7%。根据 12 小时平均白天 OH 自由基浓度为 2 × 10(6) 个分子 cm(-3),计算出 3-甲氧基-3-甲基-1-丁醇与 OH 自由基反应的半衰期为 8.5 小时。讨论了潜在的反应机制。

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