Elastic properties of liquid and glassy propane-based alcohols under high pressure: the increasing role of hydrogen bonds in a homologous family

We have measured the elastic moduli of liquid and glassy n-propanol and propylene glycol (PG) under pressure by ultrasonic techniques and have recalculated similar characteristics for glycerol from the previous experiment. All three substances form a ternary homologous family with the common formula C3H8−n(OH)n (n = 1, 2, 3), where the number of hydrogen bonds per molecule increases with the number of oxygen atoms approximately as ≈2n. In turn, the enhancement of hydrogen bonding results in an increase in elastic moduli (bulk modulus for liquids or bulk and shear moduli for glasses) from n-propanol to glycerol at all pressures, while the volume per molecule Vm shows the opposite trend at atmospheric pressure in spite of an increase in the molecular size. Nevertheless, the ratios between the Vm values at pressure P > 0.05 GPa are inverted in liquids and tend to the ratios of molecule volumes which indicates a decrease of the relative contribution of hydrogen bonds to the repulsive intermolecular forces with increasing pressure regardless of increase or decrease in the number of hydrogen bonds and their strength. A similar volume behavior is observed for glasses at T = 77 K. We have also established that the relative difference between corresponding moduli of liquid or glassy n-propanol and PG is remarkably less than that between corresponding values for PG and glycerol. We explain this property by the formation of a three-dimensional network of hydrogen bonds in glycerol, where the number of hydrogen bonds per molecule is close to six.