Rate coefficients of C(1) and C(2) Criegee intermediate reactions with formic and acetic Acid near the collision limit: direct kinetics measurements and atmospheric implications.
Rate coefficients of C(1) and C(2) Criegee intermediate reactions with formic and acetic Acid near the collision limit: direct kinetics measurements and atmospheric implications.
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DOI：
10.1002/anie.201400964
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发表时间：
2014-04-25
影响因子：
16.6
通讯作者：
Taatjes, Craig A.
中科院分区：
文献类型：
--
作者：
Welz, Oliver;Eskola, Arkke J.;Sheps, Leonid;Rotavera, Brandon;Savee, John D.;Scheer, Adam M.;Osborn, David L.;Lowe, Douglas;Booth, A. Murray;Xiao, Ping;Khan, M. Anwar H.;Percival, Carl J.;Shallcross, Dudley E.;Taatjes, Craig A.
利用两种互补的技术：多路光电离质谱和腔增强宽带紫外吸收光谱，直接测定了Criegee中间体(CI)CH2OO和CH3CHOO与两种最简单的羧酸甲酸(HCOOH)和醋酸(CH3COOH)的反应速率系数。测得的速率系数超过1×10−10 cm~3 S−1，比以往许多烯烃臭氧氧化实验和大气模拟研究中假定的速率系数大几个数量级。这些结果表明，与羧酸的反应对于顺式来说是一个比目前假设的更重要的损失过程。在全球大气模式中实施这些速率系数表明，CI和有机酸之间的反应对陆地赤道地区和发生CI高浓度的其他地区(如北纬高纬度)这些酸的去除做出了重大贡献，并意味着这些地区的酸源比以前认识到的更大。
Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH2OO and CH3CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH3COOH), employing two complementary techniques: multiplexed photoionization mass spectrometry and cavity-enhanced broadband ultraviolet absorption spectroscopy. The measured rate coefficients are in excess of 1×10−10 cm3 s−1, several orders of magnitude larger than those suggested from many previous alkene ozonolysis experiments and assumed in atmospheric modeling studies. These results suggest that the reaction with carboxylic acids is a substantially more important loss process for CIs than is presently assumed. Implementing these rate coefficients in global atmospheric models shows that reactions between CI and organic acids make a substantial contribution to removal of these acids in terrestrial equatorial areas and in other regions where high CI concentrations occur such as high northern latitudes, and implies that sources of acids in these areas are larger than previously recognized.
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