Surface Tensions in NaCl−Water−Air Systems from MD Simulations

Abstract

Surface tensions for liquid-vapor (lv), solid-liquid (sl), and solid-vapor (sv) interfaces are calculated from molecular dynamics simulations of the NaCl-water-air system. Three distinct calculation techniques based on thermodynamic properties are used to describe the multicomponent mixtures. Simulations of each bulk phase (including a liquid saturated solution) and various interfaces are carried out at both NPT and NVT conditions. The thermodynamic relation for energy difference between interface and bulk phases provides an upper bound to the surface tension, while the energy-integral and test area methods provide direct estimates. At 1 atm and 300 K, the best predictions for surface tensions are sigmasv (NaCl-air) of 114 mN m(-1), sigmasl (NaCl- soln) of 63 mN m(-1), sigmalv (soln-air) of 82 mN m(-1), and sigmalv (water-air) of 66 mN m(-1). The calculated surface tensions from simulations have uncertainties between 5 and 10%, which are higher than measurements for the liquid interfaces and lower than the measurement uncertainty for the solid interfaces. The calculated upper bounds for surface tensions of liquid interfaces compare well with experimental results but provide no improvement over existing measurements. However, the bounding values for solid interfaces lower uncertainty by as much as a factor of 10 as compared to the indirect experimental measurements currently available. The energy-integral and test area methods appear to underestimate the surface tension of water by 10%, which is consistent with previous studies using similar model potentials. The calculated upper bounds of surface tension show a weakly positive correlation with pressure in the 0.1-100 atm range for liquid-solid, liquid-vapor, and solid-vapor interfaces.