A High-Level Computational Study on the Thermochemistry and Thermal Decomposition of Sulfur Mustard (2,2‘-Dichloroethyl Sulfide):  A Chemical Warfare Agent

Abstract

The calculations of enthalpies and free energies for various monomolecular decompositions of sulfur mustard using G2(MP2) theory have shown that noncatalytic thermal destruction of this chemical warfare agent apparently is not feasible at temperatures up to 1800 K at least. Environmentally robust decomposition/destruction demands operating conditions in excess of 2000 K to insure intrinsic safety in the absence of a catalyst. The preferable decomposition pathways involve C−C and C−S bond cleavages. The G2(MP2)-calculated enthalpy of formation of sulfur mustard is −36.86 kcal/mol for the lowest energy C 2 conformation.

Shapes of Sulfur, Oxygen, and Nitrogen Mustards

“…Sulfur mustard (bis(2-chloroethyl)sulfide, also known as mustard gas) is a potent chemical warfare agent (CWA) first used on the battlefield during World War I (WWI) and since used sporadically in subsequent wars and terrorist attacks. 1 Research concerning sulfur mustard, SM, has focused on its mechanism of action, 2 diffusion and sorption properties, 3 ease of its incineration, 4 and on creating tools for its detection. 5,6 Oxygen mustard, OM, has been used as a surrogate for SM in diffusion and sorption studies.…”

A comparison of sulfur mustard and heptane penetrating a dipalmitoylphosphatidylcholine bilayer membrane

“…The deviation of these results of this force field from the experimental value is of the same size and in the same direction as the ones for the membrane and heptane. Comparing the force field parameters for bond lengths and bond angles to results of ab initio calculations by Glukhovtsev et al [41] we find the force field bond lengths up to 1.5% longer than the ab initio ones and the angle at the sulfur atom is bigger by 0.9% in the force field. But the thus expected lower density is overcompensated by the force field parameters for the charges and the Lennard-Jones parameters ε and .…”

Catalytic Processes for the Neutralization of Sulfur Mustard

“…[54] The associated product distribution includes al arge variety of organic compounds (sulfoxides, sulfones,d isulfides, ketones, aldehydes) but also complete mineralization products (CO 2 ,H 2 O, SO 2 ). In aliphatic thioethers, the SÀCb ond dissociation energy is higher than 70 kcal mol À1 , [55] and its cleavage is associated with highly energetic processess uch as pyrolysis, [56] or UV-C photolysis, [57,58] but also catalysis and photocatalysis. The mineralizationo fs ulfur mustard via these strategies has been proposed as apath of decontamination.T he process generally suffers from poor chemoselectivity with some partial oxidation products being potentially toxic.…”