Biomaterial Database

Nitrate radical addition-elimination reactions of atmospherically relevant sulfur-containing molecules. 2010

Theo Kurtén, and Joseph R Lane, and Solvejg Jørgensen, and Henrik G Kjaergaard

Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 København, ∅, Denmark. theo.kurten@helsinki.fi

We have used different computational methods, including B3LYP, CCSD(T)-F12 and CBS-QB3, to study and compare the addition-elimination reaction of the nitrate radical NO(3) with four sulfur-containing species relevant to atmospheric chemistry: hydrogen sulfide (H(2)S), dimethyl sulfide [(CH(3))(2)S], dimethyl sulfoxide [(CH(3))(2)SO] and sulfur dioxide (SO(2)). We find that the reaction with (CH(3))(2)SO to give NO(2) + (CH(3))(2)SO(2) has a very low barrier, and is likely to be the dominant oxidation mechanism for (CH(3))(2)SO in the atmosphere. In agreement with previous experimental data and computational results, we find that the reaction with H(2)S and SO(2) is very slow, and the reaction with (CH(3))(2)S is not competitive with the hydrogen abstraction route. The differences in reaction energetics and rates between the four species are explained in terms of stabilizing interactions in the transition states and differences in sulfur-oxygen bond strengths.

UI	MeSH Term	Description	Entries
D008956	Models, Chemical	Theoretical representations that simulate the behavior or activity of chemical processes or phenomena; includes the use of mathematical equations, computers, and other electronic equipment.	Chemical Models,Chemical Model,Model, Chemical
D009566	Nitrates	Inorganic or organic salts and esters of nitric acid. These compounds contain the NO3- radical.	Nitrate
D003198	Computer Simulation	Computer-based representation of physical systems and phenomena such as chemical processes.	Computational Modeling,Computational Modelling,Computer Models,In silico Modeling,In silico Models,In silico Simulation,Models, Computer,Computerized Models,Computer Model,Computer Simulations,Computerized Model,In silico Model,Model, Computer,Model, Computerized,Model, In silico,Modeling, Computational,Modeling, In silico,Modelling, Computational,Simulation, Computer,Simulation, In silico,Simulations, Computer
D004121	Dimethyl Sulfoxide	A highly polar organic liquid, that is used widely as a chemical solvent. Because of its ability to penetrate biological membranes, it is used as a vehicle for topical application of pharmaceuticals. It is also used to protect tissue during CRYOPRESERVATION. Dimethyl sulfoxide shows a range of pharmacological activity including analgesia and anti-inflammation.	DMSO,Dimethyl Sulphoxide,Dimethylsulfoxide,Dimethylsulphinyl,Dimethylsulphoxide,Dimexide,Rheumabene,Rimso,Rimso 100,Rimso-50,Sclerosol,Sulfinylbis(methane),Rimso 50,Rimso50,Sulfoxide, Dimethyl,Sulphoxide, Dimethyl
D006862	Hydrogen Sulfide	A flammable, poisonous gas with a characteristic odor of rotten eggs. It is used in the manufacture of chemicals, in metallurgy, and as an analytical reagent. (From Merck Index, 11th ed)	Hydrogen Sulfide (H2(Sx)),Hydrogen Sulfide (H2S2),Hydrogen Sulfide (H2S3),Sulfide, Hydrogen
D000393	Air Pollutants	Any substance in the air which could, if present in high enough concentration, harm humans, animals, vegetation or materials. Substances include GASES; PARTICULATE MATTER; and volatile ORGANIC CHEMICALS.	Air Pollutant,Air Pollutants, Environmental,Environmental Air Pollutants,Environmental Pollutants, Air,Air Environmental Pollutants,Pollutant, Air,Pollutants, Air,Pollutants, Air Environmental,Pollutants, Environmental Air
D001272	Atmosphere	The gaseous envelope surrounding a planet or similar body. (From Random House Unabridged Dictionary, 2d ed)	Atmospheres
D013440	Sulfides	Chemical groups containing the covalent sulfur bonds -S-. The sulfur atom can be bound to inorganic or organic moieties.	Sulfide,Thioether,Thioethers,Sulfur Ethers,Ethers, Sulfur
D013457	Sulfur Compounds	Inorganic or organic compounds that contain sulfur as an integral part of the molecule.	Sulfur Compound,Compound, Sulfur,Compounds, Sulfur
D013458	Sulfur Dioxide	A highly toxic, colorless, nonflammable gas. It is used as a pharmaceutical aid and antioxidant. It is also an environmental air pollutant.	Sulfurous Anhydride