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Temperature and pressure dependence of the volumetric properties of binary mixtures containing polyhaloalkanes
Abstract
Densities of binary mixtures of 1,1,2-trichlorotrifluoroethane + dibromomethane, + bromochloromethane, or + bromotrichloromethane were measured over their entire composition ranges at 288.15 and 308.15 K. Thermal expansion coefficients (α) and excess molar volumes (V m E) were calculated. Moreover, densities at 298.15 K and pressures up to 80 bar (1 bar = 100 kPa) were determined for these same mixtures. Isothermal compressibilities (κ T) of the pure liquids and their mixtures were obtained.
... Apart from vapor pressure data, there exists a literature gap and anomalies in the volumetric properties (density) and transport properties (viscosity). To best our knowledge, there exist 27 research articles that report the density in the range 288-359 K with large deviations among them [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38]. Therefore density measurements were carried out in temperature range of 288.15 to 338.15 K and correlated with the linear equation which includes the previous literature findings. ...
... The density of Dibromomethane measured at different temperatures 288.15-338.15 K using Anton Paar densitometer (Model: DMA 4500), were reported in Table 6 [7,[21][22][23][24][25][26][27][28][29][30][31][32][33][34][35]37,38,61]. The data tabulated in the table revealed that density decreases with increasing temperature, resulting in a decrease in interactions of molecules due to the translational motion [46,47]. ...
Densities of ethyl acetate + dibromomethane, + bromochloromethane, + 1,2-dichloroethane, or + 1-bromo-2-chloroethane binary mixtures were measured at 288.15, 298.15, and 308.15 K over the entire composition range. Thermal expansion coefficients and excess molar volumes were calculated. Moreover, densities at 298.15 K at pressures up to 200bar were determined for the same mixtures. Isothermal compressibilities of the pure liquids and their mixtures were obtained. The excess molar volumes are positive, and the excess isothermal compressibilities are negative for all the studied mixtures.
Isothermal compressibilities have been determined from density measurements of the liquid mixtures of 1,2-dichloroethane, of trans-1,2-dichloroethene, and of cis-1,2-dichloroethene + heptane, + decane, + dodecane, + tetradecane, + hexadecane, and + 2,2,4-trimethylpentane at pressures from (0.1 to 10) MPa and 293.15 K. The compressibilities were calculated from a fit of the molar volumes to a modified Tait equation. The data could also be correlated surprisingly well by a new linear p-V-T relationship suggested in the literature recently. This correlation makes it possible to judge the quality of the measurements.
The change of density of liquid water under pressure has been calculated from the speed of sound u by fitting u−2 as a polynomial in temperature and pressure, integrating with respect to pressure, and allowing for the difference between isothermal and adiabatic compressions. By comparing calculations done by different methods on the same data and on different data it appears that the densities so obtained are accurate to about 20 ppm at 1 kbar. These densities are about 100 ppm greater than the densities obtained by us some years ago by direct measurement of the compressions in the range 0–150 °C and 0–1 kbar relative to a stainless steel vessel. It seems likely that the compressibility of the vessel used in this work is too high by about 0.1 Mbar−1. A correction to the compressibility of the vessel is proposed to bring the densities in the range 0–100 °C and 0–1 kbar into agreement with the values from the speed of sound. The same correction should apply in the range 100–150 °C, and the corrected values appear to be the best available. A hysteresis between the runs at increasing and decreasing pressures is now ascribed to a hysteresis in the position of some nylon washers. The two types of runs have therefore now been analyzed independently, and revised densities are tabulated.
Isothermal vapor-liquid equilibria (VLE) have been measured for liquid bromochloromethane + heptane or cyclohexane at 25‡C
and 40‡C, and for 1-bromo-chloroethane + heptane or cyclohexane at 40‡C. These experimental results, along with our previous
ones on excess enthalpies, as well as literature data on activity coefficients at infinite dilution, are interpreted in terms
of the DISQUAC group contribution model, and are compared with UNIFAC predictions.
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