The following is an abstract for the selected article. A PDF download of the full text of this article is available here. Members may download full texts at no charge. Non-members may be charged a small fee for certain articles.

Thermodynamic Analysis of Reaction Equilibria in Ionic and Molecular Liquid Systems by High-Temperature Raman Spectroscopy

Volume 63, Number 9 (Sept. 2009) Page 1050-1056

Kalampounias, Angelos G.; Boghosian, Soghomon

A formalism for correlating relative Raman band intensities with the stoichiometric coefficients, the equilibrium constant, and the thermodynamics of reaction equilibria in solution is derived. The proposed method is used for studying: (1) the thermal dissociation of molten KHSO4 in the temperature range 240-450 °C; (2) the dinuclear complex formation in molten TaCl5-AlCl3 mixtures at temperatures between 125 and 235 °C. The experimental and calculational procedures for exploiting the temperature-dependent Raman band intensities in the molten phase as well as (if applicable) in the vapors thereof are described and used for determining the enthalpy of the equilibria: (1) 2HSO4(l) ↔ S2O72−(l) + H2O(g), ΔH0=64.9 ± 2.9 kJ mol−1; and (2) 1/2Ta2Cl10(l) + 1/2Al2Cl6(l) ↔ TaAlCl8(l), ΔH0=−12.1 ± 1.5 kJ mol−1.