The compression of liquids

Abstract

The compression of liquids can be measured either directly by applying a pressure and noting the volume change, or indirectly, by measuring the magnitude of the fluctuations of the local volume. The methods used in Ottawa for the direct measurement of the compression are reviewed. The mean-square deviation of the volume from the mean at constant temperature can be measured by X-ray and neutron scattering at low angles, and the meansquare deviation at constant entropy can be measured by measuring the speed of sound. The speed of sound can be measured either acoustically, using an acoustic transducer, or by Brillouin spectroscopy. Brillouin spectroscopy can also be used to study the shear waves in liquids if the shear relaxation time is > ∼ 10 ps. The relaxation time of water is too short for the shear waves to be studied in this way, but they do occur in the low-frequency Raman and infrared spectra. The response of the structure of liquids to pressure can be studied by neutron scattering, and recently experiments have been done at Atomic Energy of Canada Ltd, Chalk River, on liquid D 2O up to 15.6 kbar. They show that the near-neighbor intermolecular O-D and D-D distances are less spread out and at shorter distances at high pressure. Raman spectroscopy can also provide information on the structural response. It seems that the O-O distance in water decreases much less with pressure than it does in ice. Presumably, the bending of O-O-O angles tends to increase the O-O distance, and so to largely compensate the compression due to the direct effect of pressure.