Impact of the sodium and calcium chlorides uptake on the interfacial behavior of ice: premelting, structure, and dynamics

Abstract

Hypothesis: Seawater ice and frozen aqueous solutions in contact with air can exhibit a thin quasi-brine surface layer intruding between ice and vapor, but a detailed characterization of surface properties and its relation to three phase coexistence has been lacking. Using thermodynamic arguments we show how it is possible to characterize the surface layers by comparison to the three phase ice-brine-air bulk phase diagram, despite the difficulty to control or monitor all of the relevant thermodynamic fields of the two component system. Simulations: We performed computer simulations of surface briny layers of sodium and calcium chloride adsorbed on ice. Using suitable order parameters and a rigorous geometrical dividing surface, we are able to characterize the layer's thermodynamic state, measure its properties and relate them to the corresponding properties of the bulk solution. Results: Our results confirm that undersaturated briny surface layers can form down to the eutectic point, with a maximum concentration that is bound by the liquidus line of the ice-brine phase diagram. Such layers are distinct from finite size realizations of three phase coexistence, and can be regarded as genuine surface states, but their salt content can increase the premelting layer thickness by a factor of two or more. Owing to this significant thickness, these layers can be related to bulk electrolyte solutions of similar concentration, both as regards the structural organization of ions and the dynamical properties of the quasi-liquid film.

References in corpus (12)

• Ice structures, patterns, and processes: A view across the ice-fields
• The thickness of a liquid layer on the free surface of ice as obtained from computer simulation
• Scaled charges for ions: an improvement but not the final word for modeling electrolytes in water
• Intermolecular forces at ice and water interfaces: premelting, surface freezing and regelation
• Ice friction at the nanoscale
• In Silico Seawater
• Effect of Sodium Chloride Adsorption on the Surface Premelting of Ice
• How important is the dielectric constant in water modeling? Evaluation of the performance of the TIP4P/$\epsilon$ force field and its compatibility with the Joung-Cheatham NaCl model
• Is it possible to overheat ice? The activated melting of TIP4P/Ice at solid-vapor coexistence
• The macroscopic contact angle of water on ice
• Kinetic roughening transition of ice crystals and its implications during recrystallization
• The Key Physics of Ice Premelting