LIGHT-SCATTERING STUDY OF CLATHRATE HYDRATE FORMATION IN BINARY-MIXTURES OF TERT-BUTYL ALCOHOL AND WATER .2. TEMPERATURE EFFECT

Temperature dependence of the concentration fluctuations, N 〈(Δx)2〉, was observed for binary mixtures of tert-butyl alcohol (TBA)-water and dioxane-water at various concentrations by the use of light-scattering spectra. In TBA-water mixtures the rapid increase of N〈(Δx)2〉 values due to the temperature increase in the range of 17.5-63 °C was observed for xTBA > 0.05, where xTBA is the mole fraction of TBA. This result is reasonably interpreted by considering the breakdown of the clathrate hydrate-like structure and the growth of the water part of the local structure which is composed of water and TBA molecules. In contrast to the result observed for TBA-water mixtures, the N 〈(Δx)2〉 values observed for dioxane-water mixtures are small and hardly change magnitude in the temperature range 18-49.5 °C. The analysis of this result suggests that the clathrate hydrate-like structure does not exist in dioxane-water mixtures. © 1979 American Chemical Society.