Thermodynamic properties of liquid 2,2-difluoroethanol

p-V-T data for liquid 2,2-difluoroethanol (DFE) have been obtained in the form of volume ratios at six temperatures, 278.15, 288.15, 298.15, 313.15, 323.15, and 338.15 K, at pressures from atmospheric to 151 MPa or higher. Densities at atomospheric pressure in the same temperature range are also reported. Isothermal compressibilities, isobaric expansivities, and internal pressures have been calculated from the volumetric data. They show that DFE is much less compressible than 2,2,2-trifluoroethanol and indicate that 2-fluoroethanol may be even less compressible.     

Volumetric measurements under pressure for 2,2,4-trimethylpentane at temperatures up to 353.15 K and for benzene and three of their mixtures at temperatures up to 348.15 K

(p, V, T) data have been obtained in the form of volume ratios relative to 0.1 MPa for benzene (298.15 to 348.15 K), 2,2,4-trimethylpentane (TMP) (313.15 to 353.15 K), and their mixtures near 0.25, 0.5, and 0.75 mole fraction of benzene (313.15 to 348.15 K) for pressures up to near the freezing pressures for benzene and the mixtures, and up to 400 MPa for TMP. Isothermal compressibilitiesκ _T, isobaric expansivitie α, changes in heat capacity at constant pressureΔC _p, and excess molar volumesV ^E have been determined from the data. Literature data at atmospheric pressure have been used to convert theΔC _p toC _p at several temperatures. The isobars for α over the temperature range 278.15 to 353.15 K for TMP intersect near 47 MPa and reverse their order in temperature when plotted against pressure; normalization of the α's by dividing the values at each temperature by the α at 0.1 MPa prevents both the intersection and the reversal of the order. TheV ^E are positive and have an unusual dependence on pressure: they increase with temperature and pressure so that the order of the curves for 0.1, 50, and 100 MPa changes in going from 313.15 to 348.15 K.     

Volumetric and thermodynamic properties of liquid 2-fluoroethanol

p-V T data for liquid 2-fluoroethanol (FE) have been obtained in the form of volume ratios at six temperatures (278.15, 288.15, 298.14, 313.14, 323.14, and 338.130 K) at pressures from atmospheric to 314 MPa or higher. Freezing pressures have also been measured in the temperature range from the normal freezing point to 288 K. Densities at atmospheric pressure in the same temperature range as that for thep V T data are also reported. Isothermal compressibilities, isobaric expansivities, changes in the isobaric heat capacity, and internal pressures have been calculated from the volumetric data. Representation of the volume ratios for FE, 2,2-difluoroethanol, 2,2,2-trifluoroethanol, and ethanol by a form of the modified Tait equation shows that the effect of the progressive substitution of fluorine into ethanol cannot be represented by a simple correlation.     

The Viscosity and Density of <Emphasis Type="Italic">n</Emphasis>-Dodecane and <Emphasis Type="Italic">n</Emphasis>-Octadecane at Pressures up to 200 MPa and Temperatures up to 473 K

A vibrating-wire instrument for simultaneous measurement of the density and viscosity of liquids under conditions of high pressure is described. The instrument is capable of operation at temperatures between 298.15 and 473.15 K at pressures up to 200 MPa. Calibration was performed by means of measurements in vacuum, air, and toluene at 298.15 K. For n-dodecane measurements were made along eight isotherms between 298.15 and 473.15 K at pressures up to 200 MPa while for n-octadecane measurements were measured along seven isotherms between 323.15 and 473.15 K at pressures up to 90 MPa. The estimated uncertainty of the results is 2% in viscosity and 0.2% in density. Comparisons with literature data are presented.     

Thermodynamic properties of 2,2,4-trimethylpentane

p, V, T data for 2,2,4-trimethylpentane (TMP) have been obtained in the form of volume ratios for six temperatures in the range 278.15 to 338.15 K for pressures up to 280 MPa. Isothermal compressibilities, isobaric expansivities, and internal pressures have been evaluated from the volumetric data. There are strong indications that the combination of the present results with literature data at 348 and 373 K enable accurate extrapolations in the liquid range up to 473 K, and possibly to as low as 170 K, for pressures up to 980 MPa; use of only the present results with the requirement that the B coefficient of the Tait equation should become equal to the negative of the critical pressure at the critical temperature provides interpolations and extrapolations of comparable accuracy. It is suggested that 2,2,4-trimethylpentane is a suitable secondary reference material (because of its large liquid range at atmospheric pressure and the similarity of its volumetric properties to a wide range of fluids) for calibration of measuring cells used for determining volumes of fluids under pressure.     

An automated volumometer: Thermodynamic properties of 1,1-dichloro-2,2,2-trifluoroethane (R123) for temperatures of 278.15 to 338.15 K and pressures of 0.1 to 380 MPa

An automated bellows volumometer is described which is capable of obtaining p-V-T data in the form of volume ratios for pressures up to 380 MPa. Volume ratios for 1,1-dichloro-2,2,2-trifluoroethane (R123) have been measured for six temperatures in the range of 278.15 to 338.15 K in the liquid phase. The accuracy of the volume ratios is estimated to be ±0.05 to 0.1% for the experimental temperatures up to 298.15 K and better than ±0.15% for temperatures above the normal boiling point of R123 (300.15 K). They agree with the literature data (which do not extend beyond 4 MPa) within the experimental uncertainty of those results. Isothermal compressibilities, isobaric expansivities, internal pressures, and isobaric molar heat capacities have been evaluated from the volumetric data. The pressure dependence of isobaric molar heat capacities obtained from the data generally agree with the pressure dependence of experimentally measured literature values within the latter's accuracy of ±0.4%.     

Freezing pressures,p, V,T, and self-diffusion data at 298 and 313 K and pressures up to 300 MPa for 1,3,5-trimethylbenzene

Mesurements are reported for the melting point of 1,3,5-trimethylbenzene at pressures up to 345 MPa. Self-diffusion coefficients and p, V, T data have been obtained at 298 and 313 K for pressures up to 280 MPa. Isothermal compressibilities have been calculated from the p, V, T results. The freezing pressures at 0.1 MPa correspond to previously reported values for modification III of trimethylbenzene. Equivalent hard-sphere diameters estimated from the melting point and p, V, T data are used to apply the rough hard-spheres theory to the self-diffusion data; the calculations indicate that there is random packing of the particles.On leave from Department of Chemistry, University of Auckland, Auckland, New Zealand.     

Thermodynamic properties of 2,2,2-trifluoroethanol

(p, V, T) data for 2,2,2-trifiuoroethanol (TFE) have been obtained in the form of volume ratios for six temperatures in the range 278.15 to 338.15 K for pressures up to 280 MPa. Isothermal compressibilities, isobaric expansivities, and internal pressures have been evaluated from the volumetric data. The compressibilities and internal pressures indicate that the behavior of TFE is closer to that of methanol than of ethanol for most of the pressure range. The use of only the present volumetric results together with the requirement that the B coefficient of the Tait equation should become equal to the negative of the critical pressure at the critical temperature provides interpolations and extrapolations up to 413 K of comparable accuracy.     

Compressibility and sound velocity measurements on N2 up to 1 GPa

A gas expansion technique has been used to determine the pVT properties of N₂ up to 1 GPa at 298.15 K, with an accuracy of 0.08% in density, 1 mK in temperature, and 0.05%+0.2 MPa in pressure. The sound velocity has been measured by a phase-comparison pulse-echo technique between 123 and 298 K at intervals of 25 K and at pressures up to 1 GPa, with an accuracy of better than 0.02% in sound velocity, 10 mK in temperature, and 0.05%+0.2 MPa in pressure. An equation of state is presented that correlates the density data over the wide pressure range of 36–1000 MPa with maximum deviations between the calculated and the experimental densities of less than 0.05%.     

The PVT behavior of liquid 1,1,1- and 1,1,2-trichloroethane

The PVT behavior of liquid 1,1,1- and 1,1,2-C₂H₃Cl₃ has been determined at 298.15, 323.15, 348.15, 373.15, and 398.15 K and at different pressures to about 100 MPa. The experimental results are shown in tabulated form. Specific volumes at high pressures are represented by the Tait equation. These results are also compared with the results obtained by a generalized Tait equation and other correlation methods. The generalized Tait equation is found to be more suitable to explain this study than the other correlations tested.     

Volume ratios for n-pentane in the temperature range 278–338 K and at pressures up to 280 MPa

Volume ratios (V _P/V _0.1), and isothermal compressibilities calculated from them, are reported for n-pentane for seven temperatures in the range 278 to 338 K for pressures up to 280 MPa. The isobaric measurements were made with a bellows volumometer for which a novel technique had to be devised to enable measurements to be made above the normal boiling point (309.3 K). The accuracy of the volume ratios is estimated to be ±0.05 to 0.1% up to 303.15 K and ±0.1 to 0.2% from 313.15 to 338.15 K. The volume ratios are in good agreement with those calculated from recent literature data up to the maximum pressure of the latter, viz., 60 MPa.     

Volumetric and Thermodynamic Properties of Liquid Mixtures of 2-n-Butoxyethanol with Water

p–V–T data for six compositions of 2-n-butoxyethanol (BE) and water have been obtained in the form of volume ratios at several temperatures in the range 278.15 to 353.13 K at pressures from atmospheric to 347 MPa or higher. One of the compositions is in the region where two phases exist at certain temperatures, while two compositions are near the boundary of that region. Densities at atmospheric pressure in a temperature range similar to that for the p–V–T data are also reported. Isothermal compressibilities, isobaric expansivities, and changes in the isobaric heat capacity have been calculated from the volumetric data for pressures up to 300 MPa. The values of normalized volume fluctuations obtained from the data at 0.1 MPa approach those of water for conditions which are close to those for phase separation in this system. Such behavior is not observed at 100 MPa, where such separation is suppressed.     

Volumetric Properties, Viscosities, and Refractive Indices of the Binary Systems 1-Butanol + PEG 200, + PEG 400, and + TEGDME

Densities, viscosities, and refractive indices of three binary systems consisting of 1-butanol with polyethylene glycols of different molecular weights (PEG 200 and PEG 400) or tetraethylene glycol dimethyl ether (TEGDME) were measured at ten temperatures (288.15, 293.15, 298.15, 303.15, 308.15, 313.15, 318.15, 323.15, 328.15, and 333.15) K and atmospheric pressure. Densities of the selected binary mixtures were measured with an Anton Paar DMA 5000 digital vibrating U-tube densimeter, refractive indices were measured with an automatic Anton Paar RXA-156 refractometer, while for viscosity measurements, a digital Stabinger SVM 3000/G2 viscometer was used. From these data, excess molar volumes were calculated and fitted to the Redlich–Kister equation. The obtained results have been analyzed in terms of specific molecular interactions and mixing behavior between mixture components, as well as the influence of temperature on them. Viscosity data were also correlated by Grunberg–Nissan, Eyring–UNIQUAC, three-body McAlister, and Eyring–NRTL models.     

p,V, T and derived thermodynamic data for toluene,trichloromethane, dichloromethane,acetonitrile, aniline,and n-dodecane

Experimentally determined p,V,T data are reported for toluene, trichloromethane, dichloromethane, acetonitrile, aniline, and n-dodecane at 278, 288, 298, 313, and 323 K, except for dichloromethane, for which the highest temperature was 298 K. At each temperature, measurements were done at pressures up to about 280 MPa or (for aniline and n-dodecane) at a lower pressure slightly below the freezing pressure at the temperature of measurement. Values of the isobaric expansivity isothermal compressibility and (for toluene, trichloromethane, dichloromethane, and acetonitrile) internal pressure, derived from the p,V,T data, are presented.     

p,V, T and derived thermodynamic data for bromobenzene at temperatures from 278 to 323 K and pressures up to 280 MPa

Experimentally determined p, V, T data are reported for bromobenzene at 278, 288, 298, 313, and 323 K, at pressures up to about 280 MPa or (at 278 and 288 K) a lower pressure slightly below the freezing pressure at the temperature of measurement. Values of the isobaric expansivity, isothermal compressibility, internal pressure, and equivalent hard-sphere diameter, derived from the p, V, T data, are presented.On leave from the Department of Chemistry, The University of Auckland, Auckland, New Zealand.     

Thermodynamic properties and excess volumes of 2,2,4-trimethylpentane + n-heptane mixtures from 298 to 338 K for pressures up to 400 MPa

(p, V, T) data for mixtures of 2,2,4-trimethylpentane (TMP) and heptane have been obtained in the form of volume ratios for four temperatures in the range 298.15 to 338.15 K for pressures up to 390 MPa. The data have been represented by the Tait equation of state for the purposes of interpolation and extrapolation. The atmospheric pressure densities of both pure components and their mixtures for three temperatures have been measured and used to determine the excess molar volumes. Isothermal compressibilities have been evaluated from the volumetric data.     

Viscosity Measurements on Gaseous Argon, Krypton, and Propane1

A new vibrating-wire viscometer was designed to perform quasi-absolute measurements of very high precision on gases. It was applied to determine the viscosity of argon at temperatures of 298.15, 348.15, and 423.15 K and pressures up to 20 MPa, and the viscosity of krypton at 298.15 and 348.15 ,K and pressures up to 16 MPa. Furthermore, several isothermal series of viscosity measurements on gaseous propane were carried out. The subcritical isotherms at 298.15, 323.15, 348.15, and 366.15 K were restricted to 95% of the saturated vapor pressure, the supercritical isotherms at 373.15, 398.15, and 423.15 K to 20 MPa. In general, the measurements are characterized by a reproducibility of ±0.05% and an accuracy of ±0.2%. However, close to the critical point an accuracy of ±3% has to be accepted, mainly due to the uncertainty of the density. In this context the influence of the equation of state used for propane is discussed.     

Thermophysical properties ofm-cresol as a function of temperture (303 to 503 K) and pressure (0.1 to 400 MPa)

Measured and derived thermophysical properties ofm-cresol are reported for pressures up to 400 MPa at temperatures from 303 to 503 K. Isobaric thermal expansivities were measured by pressure-scanning calorimetry from 303 to 503 K and 0.1 to 400 MPa. The specific volume at 353 K was determined by pycnometry at atmospheric pressure and calculated from isothermal compressibilities measured as a funtion of pressure up to 400 MPa. Specific volumes at other temperatures and pressures are calculated from isothermal compressibilities measured as a function of pressure up to 400 MPa. Specific volumes, isothermal compressibilities, thermal coefficients of pressure, and isobaric and isochoric heat capacities at pressures up to 400 MPa are derived at several temperatures. The effects of pressure on the isobaric heat capacities ofm-cresol,n-hexane, and water are compared. The effects of self-association ofm-cresol are apparent in both the thermal expansivity and the heat capacity data.     

Measurement of the compressibility and sound velocity of neon up to 1 GPa

The density of neon has been determined at 298.15 K as a function of pressure from 80 MPa to 1 GPa. The precision of the measurements is 0.03%, while the estimated absolute accuracy is between 0.05 and 0.09%. The sound velocity has been measured between 98 and 298 K with intervals of 25 K and at pressures up to 1 GPa, with an accuracy generally better than 0.06%. The adiabatic compressibility and the ratio of the specific heats are calculated by combining pVT with velocity-of-sound data at 298 K. Several equations of state are fitted to the density data at 298.15 K.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

Measurements of the viscosity of n-heptane,n-nonane,and n-undecane at pressures up to 70 MPa

New absolute measurements of the viscosity of n-heptane, n-nonane, and n-undecane are presented. The measurements were performed with a vibrating-wire instrument at temperatures of 303.15 and 323.15 K and pressures up to 70 MPa. The overall uncertainty in the reported viscosity data is estimated to be ±0.5%. A recently developed semiempirical scheme for the correlation and prediction of the thermal conductivity, viscosity, and self-diffusion coefficients of n-alkanes is applied to the prediction of the viscosity of n-heptane, n-nonane, and n-undecane. The comparison of these predicted values with the present high-pressure measurements demonstrates the predictive power of this scheme.