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.
All Science Journal Classification (ASJC) codes
- General Materials Science
- Condensed Matter Physics
- Surfaces and Interfaces