Mechanism, Kinetics, and Potential of Mean Force of Evaporation of Water from Aqueous Sodium Chloride Solutions of Varying Concentrations.

The mechanism, kinetics, and potential of mean force of evaporation of water from aqueous NaCl solutions are investigated through both unbiased molecular dynamics simulations and also biased simulations using the umbrella sampling method. The results are obtained for aqueous solutions of three different NaCl concentrations ranging from 0.6 to 6.0 m and also for pure water. The rate of evaporation is found to decrease in the presence of ions. It is found that the process of evaporation of a surface water molecule from ionic solutions can be triggered through its collision with another water or chloride ion. Such collisions provide the additional kinetic energy that is required for evaporation. However, when the collision takes place with a Cl - ion, the evaporation of the escaping water also involves a collision with water in the vicinity of the ion at the same time along with the ion-water collision. These two collisions together provide the required kinetic energy for escape of the evaporating water molecule. Thus, the mechanism of evaporation process of ionic solutions can be more complex than that of pure water. The potential of mean force (PMF) of evaporation is found to be positive and it increases with increasing ion concentration. Also, no barrier in the PMF is found to be present for the condensation of water from vapor phase to the surfaces of the solutions. A detailed analysis of the unsuccessful evaporation attempts by surface water molecules is also made in the current study.