Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 112, Issue 48, Pages 15382-15390Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp8055366
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Funding
- NASA [NNG05GN60G, NNG05GL88G]
- SwRI Internal Research
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We measured the 1 mHz-1 MHz electrical properties of ice-hydrate binary systems formed from solutions of NaCl, CaCl2, and MgSO4, with supplementary measurements of HCl. Below the eutectic temperature, electrical parameters are well described by mixing models in which hydrate is always the connected phase. Above the eutectic temperature, a salt concentration threshold of similar to 3 mM in the initial solution is required for the unfrozen brine fraction to form interconnected, electrically conductive networks. The dielectric relaxation frequency for saline ice increases with increasing impurity content until Cl- reaches saturation. Because there is insufficient H3O+ for charge balance, salt cations must be accommodated interstitially in the ice. Dielectric relaxations near the ice signature were identified for CaCl2 center dot 6H(2)O and MgSO4 center dot 11H(2)O but not for NaCl center dot 2H(2)O. Ionic and L-defect concentrations in salt hydrates up to similar to 10(-4) and 10(-3) per H2O molecule, respectively, follow from the electrical properties, Jaccard theory, and the assumption that protonic-defect mobilities are similar to ice. These high defect concentrations-up to a few orders of magnitude greater than saturation values in ice-indicate that intrinsic disruption of hydrogen bonding in salt hydrates is common.
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