Abstract
Measurements of ultra-sonic absorption at different temperatures in the mixtures of glycerol and dioxane below 1 MHz using the pulse-comparison method reveal the presence of hydrogen-bonded complexes. The observed excess absorption goes through peaks at 0.21 and 0.81 mole fractions of glycerol thereby indicating the compositions of the complexes to be AB4 and A4B, where A and B refer to glycerol and dioxane molecules respectively. The present results have been explained in terms of the formation and dissolution of the above complexes leading to relaxation mechanisms such thatωτ ≪ 1. The formation of hydrogen bonded complexes is further supported by the calculation of the free-energy difference ΔF between the two states. Measurements of ultra-sonic velocity in the mixtures using the total-reflection technique also show a slight hump near the concentration at which the first absorption peak is formed. The formation of bonds in the complexes is also discussed.
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