Abstract
This work reports that the octahedral hydrated Al(3+) and Mg(2+) ions operate within electrolytic cells as kosmotropic (long-range order-making) "ice makers" of supercooled water (SCW). 10(-5) M solutions of hydrated Al(3+) and Mg(2+) ions each trigger, near the cathode (-20 ± 5 V), electro-freezing of SCW at -4 °C. The hydrated Al(3+) ions do so with 100% efficiency, whereas the Mg(2+) ions induce icing with 40% efficiency. In contrast, hydrated Na(+) ions, under the same experimental conditions, do not induce icing differently than pure water. As such, our study shows that the role played by Al(3+) and Mg(2+) ions in water electro-freezing is impacted by two synchronous effects: (1) a geometric effect due to the octahedral packing of the coordinated water molecules around the metallic ions, and (2) the degree of polarization which these two ions induce and thereby acidify the coordinated water molecules, which in turn imparts them with an ice-like structure. Long-duration molecular dynamics (MD) simulations of the Al(3+) and Mg(2+) indeed reveal the formation of "ice-like" hexagons in the vicinity of these ions. Furthermore, the MD shows that these hexagons and the electric fields of the coordinate water molecules give rise to ultimate icing. As such, the MD simulations provide a rational explanation for the order-making properties of these ions during electro-freezing.