Tetra-n-butyl ammonium chloride (TBAC) is an organic salt known to form semiclathrate complexes in the presence of water at atmospheric pressure and temperatures above the melting temperature of water. In these structures, the TBA+ion sits within a water cage (i.e., 24 to 38 water molecules per TBA+ion) while the anion, in this case the chloride, replaces one or more of these water molecules. Previous studies, using Differential Scanning Calorimetry (DSC), have shown that the addition of either NaCl or KCl can affect these TBAC-H2O structures, causing them to melt at lower temperatures in the case where there is sufficient free, bulk water present to solvate the electrolyte or, if there is insufficient water, then the electrolyte forms new semiclathrate complexes with the TBAC. In this work, the effect of adding LiCl to aqueous TBAC solutions were determined and compared to the results of adding either NaCl or KCl. Ternary TBAC-LiCl-H2O systems were created by adding LiCl to approximately1, 1.5, 2, 3 and 4 molal TBAC-H2O solutions to give ionic strength fractions of TBAC (YTBAC) from 0.25 to 1. It is hypothesized that lithium, being a relatively small cation, in comparison to sodium and potassium, with a high charge-to-surface density, is more likely to disrupt the TBAC-H2O semiclathrate structures when there is insufficient free bulk water present.

Effect of adding lithium chloride on tetra-n-butyl ammonium chloride semiclathrate thermal stability at atmospheric pressure

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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