The structure of water and methanol in p-dioxane as determined by microwave dielectric spectroscopy

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Abstract
Dielectric measurements were performed on water–p‐dioxane and methanol–p‐dioxane mixtures using time domain reflectometry over the frequency range 0.1–10 GHz. In the case of water–p‐dioxane mixtures, the relaxation strength normalized by the number of water molecules per unit volume is independent of the molar fraction of water xW if xWxW is larger than 0.83, the normalized strength increases linearly with xW. The clusters of pure water which appear in this region are cyclic and consist of six molecules. In the case of methanol–p‐dioxane, the normalized strength is independent of xM for xM0.66. However, the relaxation time of pure methanol is too large for clusters consisting of three molecules. It is suggested that the chainlike clusters form network structures.