Surface Tension of Organophosphorus Compounds: Sarin and its Surrogates.

While the production and stockpiling of organophosphorus chemical warfare agents (CWAs), such as sarin, was banned three decades ago, CWAs have remained a threat. New approaches for decontamination and destruction of CWAs require detailed knowledge of their various physicochemical properties. In particular, surface tension is needed to describe the formation and evolution of hazardous aerosols when CWA liquids are dispersed in the air. Due to the extreme toxicity of sarin, most experimental studies are carried out using its surrogates─organophosphorus compounds which, while having similar structures, are much less toxic, e.g., dimethyl methylphosphonate (DMMP) and diisopropyl methylphosphonate (DIMP). However, not only for sarin, but also for its surrogates, literature data on the surface tension are scarce. Here we present experimental measurements and computational predictions of the surface tension of DMMP and DIMP. Classical molecular dynamics simulations using the Transferable Potentials for Phase Equilibria (TraPPE) force field produced an excellent agreement with the experimental results in the temperature range from 3 to 60 °C, validating the predictive capability of TraPPE. Consequently, we applied the TraPPE force field to sarin. Our modeled values for the sarin surface tension cover the range of temperatures from 0 to 85 °C, and the four experimental data points from the literature measured between 20 and 35 °C agree perfectly with our predictions. The temperature-dependent surface tension values for sarin and its surrogates obtained in our study can be used in models predicting the formation and evolution of aerosols made of these chemicals. Furthermore, our results justify the use of the TraPPE force field to derive the thermodynamic properties of other organophosphorus compounds with structures similar to the ones studied here.

Removal of diisopropyl methyl phosphonate (DIMP) from heated metal oxide surfaces.

Diisopropyl methyl phosphonate (DIMP) is an organophosphorus compound used as a surrogate of sarin, a chemical weapon agent. Thermal decomposition of DIMP and similar liquids may be affected by added inorganic solids. Understanding such effects is needed to guide decontamination and environmental mitigation work. Here, liquid DIMP mixed with powders of γ-Al2O3 or SiO2, was heated to 350 °C in a thermogravimetric analyzer while observing effluent gas using a mass spectrometer. For both powders, evaporation of DIMP occurred between 50 and 200 °C, followed by a second mass loss step up to 350 °C. The amount of DIMP evaporated in the first step varied; however, the size of the second, mass loss step was consistent between experiments for each solid used. For γ-alumina, 2-propanol and propene were released below the DIMP boiling point and mostly propene at higher temperatures. Calcining alumina prior to exposure to DIMP reduced the release of 2-propanol. For silica, the second mass loss step was smaller and only propene was released. Powders exposed to DIMP and recovered at different temperatures showed FTIR peaks corresponding to the individual bond vibrations of DIMP. At higher temperatures, only the P-CH 3 stretching vibration was observed.