Effect of the nitrate group on yields and composition of secondary organic aerosol formed from reactions of alkyl nitrates with OH radicals in the presence of NO x
Effect of the nitrate group on yields and composition of secondary organic aerosol formed from reactions of alkyl nitrates with OH radicals in the presence of NO x
复制标题
硝酸盐基团对硝酸烷基酯与 OH 自由基在 NO x 存在下反应形成的二次有机气溶胶的产率和组成的影响
DOI：
10.1080/02786826.2020.1757033
复制
发表时间：
2020
影响因子：
5.2
通讯作者：
Ziemann, Paul J.
中科院分区：
文献类型：
--
作者：
Algrim, Lucas B.;Ziemann, Paul J.
系统研究了在NOx存在下，硝酸酯官能团对C10烷基硝酸酯异构体与OH自由基反应的二次有机气溶胶（SOA）产物和产率的影响. 1-至5-癸基硝酸酯异构体从其相应的醇合成，在环境室中反应，并使用在线和离线技术分析前体和SOA。SOA产物类似于C10正烷烃（癸烷）的类似反应所形成的产物，但具有额外的硝酸根基团。当硝酸根基团位于末端碳上时，SOA产率最高，并且随着其向分子中心移动而从0.51单调下降至0.50、0.44、0.28和0.15，在该点处，其与癸烷的产率相似。这种趋势的解释，这是支持使用动力学模型进行的计算结果，涉及的硝酸根基团对产品的蒸汽压和反应的分支比的影响的组合。一般来说，虽然硝酸根基团相对于癸烷反应的相应产物降低了产物的蒸气压，从而增强了气体-颗粒分配和SOA形成，但当它向分子中心移动时，它也改变了反应途径的分支比，从而增强了更易挥发的产物的形成。将结果与酮和醇异构体的类似研究进行比较，以更全面地了解官能团对SOA组成和产率的影响。版权所有© 2020美国气溶胶研究协会
A systematic study was conducted on the effect of a nitrate functional group on secondary organic aerosol (SOA) products and yields from reactions of C10alkyl nitrate isomers with OH radicals in the presence of NOx. The 1- through 5-decyl nitrate isomers were synthesized from their corresponding alcohols, reacted in an environmental chamber, and the precursors and SOA were analyzed using online and offline techniques. SOA products were analogous to those formed from similar reactions of the C10n-alkane (decane), but with an additional nitrate group. The SOA yield was highest when the nitrate group was on the terminal carbon and decreased monotonically from 0.51 to 0.50, 0.44, 0.28, and 0.15 as it moved toward the center of the molecule, at which point it was similar to that from decane. The explanation for this trend, which is supported by results of calculations performed using a kinetics model, involves a combination of the effects of the nitrate group on product vapor pressures and reaction branching ratios. In general, although the nitrate group lowers the vapor pressures of products relative to the corresponding products of the decane reaction, thus enhancing gas-to-particle partitioning and SOA formation, as it moves toward the center of the molecule it also alters the branching ratios for reaction pathways so as to enhance the formation of more volatile products. The results are compared with those from similar studies on ketone and alcohol isomers to gain a more comprehensive understanding of the effects of functional groups on SOA composition and yields.Copyright © 2020 American Association for Aerosol Research