Raman spectroscopy is used to study the thermal dissociation of molten KHSO4 at temperatures of 240-450 degrees C under static equilibrium conditions. Raman spectra obtained at 10 different temperatures for the molten phase and for the vapors thereof exhibit vibrational wavenumbers and relative band intensities inferring the occurrence of the temperature-dependent dissociation equilibrium 2HSO(4)(-) (1) <-> S2O72-(1) + H2O(g). The Raman data are adequate for determining the partial pressures of H2O in the gas phase above the molten mixtures. A formalism for correlating relative Raman band intensities with the stoichiometric coefficients, the equilibrium constant, and the thermodynamics of the reaction equilibrium is derived. The method is used-along with the temperature-dependent features of the Raman spectra-to show that the studied equilibrium 2HSO(4)(-) (1) <-> S2O72-(1) + H2O(g) is the only process taking place to a significant extent in the temperature range of the investigation and for determining its enthalpy to be Delta H degrees = 64.9 +/- 2.9 kJ mol(-1). The importance of these findings for the understanding of the performance of the industrially important sulfuric acid catalyst. under "wet" conditions is briefly addressed.