Experimental densities, vapor pressures, and critical point, and a fundamental equation of state for dimethyl ether

Densities, vapor pressures, and the critical point were measured for dimethyl ether, thus, filling several gaps in the thermodynamic data for this compound. Densities were measured with a computer-controlled high temperature, high-pressure vibrating-tube densimeter system in the sub- and supercritical states. The densities were measured at temperatures from 273 to 523 K and pressures up to 40 MPa (417 data points), for which densities between 62 and 745 kg/m(3) were covered. The uncertainty (where the uncertainties can be considered as estimates of a combined expanded uncertainty with a coverage factor of 2) in density measurement was estimated to be no greater than 0.1% in the liquid and compressed supercritical states. Near the critical temperature and pressure, the uncertainty increases to 1%. Using a variable volume apparatus with a sapphire tube, vapor pressures and critical data were determined. Vapor pressures were measured between 264 and 194 kPa up to near the critical point with an uncertainty of 0.1 kPa. The critical point was determined visually with an uncertainty of 1% for the critical volume, 0.1 K for the critical temperature, and 5 kPa for the critical pressure. The new vapor pressures and compressed liquid densities were correlated with the simple TRIDEN model. The new data along with the available literature data were used to develop a first fundamental Helmholtz energy equation of state for dimethyl ether, valid from 131.65 to 525 K and for pressures up to 40 MPa. The uncertainty in the equation of state for density ranges from 0.1% in the liquid to 1% near the critical point. The uncertainty in calculated heat capacities is 2%, and the uncertainty in vapor pressure is 0.25% at temperatures above 200 K. Although the equation presented here is an interim equation, it represents the best currently available. (c) 2006 Elsevier B.V. All rights reserved.