Premium
Formation pathways of DMSO from DMS‐OH in the presence of O 2 and NO x : A theoretical study
Author(s) -
RamírezAnguita Juan M.,
GonzálezLafont Àngels,
Lluch José M.
Publication year - 2008
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21049
Subject(s) - chemistry , dimethyl sulfide , ab initio , dimethyl sulfoxide , density functional theory , kinetic energy , nitrogen , computational chemistry , oxidation process , reaction mechanism , organic chemistry , chemical engineering , catalysis , sulfur , physics , quantum mechanics , engineering
The relative importance of the reaction pathways and thus the product yields in the dimethyl sulfide (DMS) degradation scheme initiated by the hydroxyl (OH) radical has been said to be influenced by the content of nitrogen oxides (NO x ) in chamber experiments. In this study, ab initio and density functional electronic structure calculations of all the possible reaction pathways corresponding to the reaction process initiated by DMS‐OH + oxygen (O 2 ), leading to the formation of the dimethyl sulfoxide (DMSO) product in the presence of NO x (NO and NO 2 ), are carried out for the first time. The results for the different pathways are compared with the objective of inferring their kinetic relevance in the laboratory experiments that measure DMSO formation yields. Our theoretical results clearly show the existence of NO x ‐dependent pathways leading to the formation of DMSO in addition to O 2 ‐dependent channels. So then, NO x ‐containing conditions would have to modify the relative importance of the addition channel in the DMS oxidation process. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009