Research ArticleATMOSPHERIC SCIENCE

Mechanisms and competition of halide substitution and hydrolysis in reactions of N2O5 with seawater

See allHide authors and affiliations

Science Advances  05 Jun 2019:
Vol. 5, no. 6, eaav6503
DOI: 10.1126/sciadv.aav6503

Abstract

SN2-type halide substitution and hydrolysis are two of the most ubiquitous reactions in chemistry. The interplay between these processes is fundamental in atmospheric chemistry through reactions of N2O5 and seawater. N2O5 plays a major role in regulating levels of O3, OH, NOx, and CH4. While the reactions of N2O5 and seawater are of central importance, little is known about their mechanisms. Of interest is the activation of Cl in seawater by the formation of gaseous ClNO2, which occurs despite the fact that hydrolysis (to HNO3) is energetically more favorable. We determine key features of the reaction landscape that account for this behavior in a theoretical study of the cluster N2O5/Cl/H2O. This was carried out using ab initio molecular dynamics to determine reaction pathways, structures, and time scales. While hydrolysis of N2O5 occurs in the absence of Cl, results here reveal that a low-lying pathway featuring halide substitution intermediates enhances hydrolysis.

This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license, which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.

View Full Text