Abstract
In basic mixtures of the molten salt composed of aluminum chloride and 1 -ethyl-3-methylimidazolium chloride, proton, in the absence of oxides, is partitioned between hydrogen chloride and hydrogen dichloride ion. The equilibrium between these two species has been examined by 2H and 'H NMR spectroscopies. The magnitude of the hydrogen chloride/dichloride equilibrium constant demonstrates that the equilibrium strongly favors the formation of the hydrogen dichloride ion. The ratio of 2H and IH equilibrium constants at 90 OC gave an equilibrium isotope effect of 0.67 f 0.26, which indicates that deuterium accumulates in the hydrogen chloride molecule. An equilibrium isotope effect of 0.7 12 was calculated from hydrogen chloride and hydrogen dichloride vibrational frequencies. Analysis of the temperature dependence of the hydrogen chloride/dichloride equilibrium constant gave values for the enthalpy of reaction, MMN, and the entropy of reaction, LS, of -9.8 f 0.8 kJ mol-' and 4.8 f 2.5 J mol-' K-1, respectively. Comparison of the AH for the hydrogen chloride/dichloride equilibrium in the melts with values obtained for other solvents suggests that the melt interacts more strongly with chloride ion than with hydrogen dichloride ion.
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