Mechanism of the diffusion of sulfur mustard, a chemical warfare agent, in butyl and nitrile rubbers

The diffusion of sulfur mustard (SM), a chemical warfare agent, through butyl (IIR) and nitrile (NBR) rubber membranes was studied with a standard spot disc breakthrough time test at temperatures ranging from 298 to 333 K. The mechanism of diffusion was interpreted on the basis of an Arrhenius relation and dynamic adsorption theory. The permeant SM was pictured to reversibly dwell at each adsorption site for about 1.5 × 10 −13 s and hop randomly through the polymer matrices in small steps, with jump lengths of the order of a picometer. A comparatively lower activation energy, a solubility parameter closer to that of SM, and a lower thermodynamic interaction parameter also contributed toward faster uptake of SM by NBR in comparison with IIR. The diffusion data were also used to derive the collision diameter of SM in these polymer matrices.