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Infrared spectra of binary mixtures of water with hexane and decane were measured at temperatures and pressures in the 473–648  K and 70–350  bar ranges, respectively. Volumetric concentrations of water and the hydrocarbons in the mixtures were obtained from absorption intensities of the fundamental OH stretching band of HDO and combination transitions of the hydrocarbons. Using both the concentrations, densities of the aqueous mixtures were estimated and compared with densities before mixing, which were calculated using literature densities of the neat liquids. It is found that anomalously large volume expansion on mixing occurs in the vicinity of the critical region of the mixtures

Anomalous volumetric behavior of water-hexane and water-decane mixtures in the vicinity of the critical region as studied by infrared spectroscopy