Measurement of the PVTx properties of n-heptane in supercritical water

By means of a constant-volume piezometer, measurements have been made of the PVTx properties of water-n-heptane mixtures at supercritical conditions. The measurements cover the temperature range from 573 to 673 K and pressures from 2 to 30 MPa. Values of excess, partial, and apparent molar volumes were obtained from these measurements. Tests on the piezometer and consistency tests on the measurements suggest that the results are free from significant 'dead volume' error. The PVT data for the pure components (water and n-heptane) obtained using the piezometer are in excellent agreement with results obtained by other investigators. The overall accuracy of the pressure, density, temperature, and mole fraction are +/-0.15%, +/-0.5%, +/-10 mK and +/-0.002, respectively. Analysis of the results for dilute water-n-heptane mixtures show that the partial molar volume of n-heptane (solute) and the excess molar volume of the mixture near the critical point of pure water (solvent) exhibit remarkable anomalies. Our results contribute to the formulation of supercritical solubility in near-critical fluids. (C) 1997 Elsevier Science B.V.