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.     

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.     

The viscosity of five liquid hydrocarbons at pressures up to 250 MPa

This paper reports new measurements of the viscosity of toluene, n-pentane, n-hexane, n-octane, and n-decane at pressures up to 250 MPa in the temperature range 303 to 348 K. The measurements were performed with a vibrating-wire viscometer and with a relative method of evaluation. Calibration of the instrument was carried out with respect to reference values of the viscosity of the same liquids at their saturation vapour pressure. The viscosity measurements have a precision of ±0.1% but the accuracy is limited by that of the calibration data to be ±0.5%. The experimental data have been represented by polynomial functions of pressure for the purposes of interpolation. The data are also used as the most precise test yet applied to a representation of the viscosity of liquids based upon hard-sphere theory.     

Viscosity and density of binary mixtures of cyclohexane with n-octane,n-dodecane,and n-hexadecane under high pressures

The viscosity and density of three binary mixtures of cyclohexane with n-octane, n-dodecane, and n-hexadecane have been measured at 298, 323, and 348 K at pressures up to 150 MPa or freezing pressures. The measurements of the viscosity were performed by a torsionally vibrating crystal viscometer on a relative basis using benzene and cyclohexane as reference materials. The density was measured using a high-pressure burette apparatus. The uncertainties of the measurements are estimated to be less than 2% for viscosity and 0.1% for density, respectively. The effects of temperature, pressure, density, and composition on the viscosity are discussed. Applicabilities of several empirical correlating equations to the viscosity data were examined.     

Application of rough hard-sphere theory to diffusion in n-alkanes

Tracer diffusion coefficients are reported for n-alkane solutes in n-dodecane, n-eicosane, n-eicosane, and n-octacosane in the temperature range 304–533 K at 1.38 MPa. Rough hard-sphere theory is used to interpret the data. The translational-rotational coupling parameters are determined for each solute-solvent pair at each temperature. The nature of the coupling parameter and the possibility of relating it to molecular properties and temperature in a homologous series are discussed.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

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.     

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.     

Thermodynamic and transport properties of 1, 2-dichloroethane

(p, V, T) data for dichloroethane (DCE) have been obtained at 278.15, 288.15, 298.15, 313.15, 323.15, and 338.15 K for pressures either slightly below the freezing pressure or up to a maximum of 280 M Pa, together with densities at 0.1 MPa. A high-pressure self-centering falling-body viscometer method has been used to measure shear viscosities at 278.15, 288.15, 298.15, 313.15, and 323.15 K for pressures either slightly below the freezing pressure or up to a maximum of 330 MPa. Self-diffusion coefficients for DCE are reported at 278.15, 288.15, 298.15, and 313.15 K for maximum pressures up to 300 MPa. Isothermal compressibilities, isobaric expansivities, and internal pressures have been evaluated from the volumetric data. The shear viscosities and self-diffusion coefficients have been interpreted in terms of a modified rough hard-spheres theory. The anomalous behavior observed for p-V-T, shear viscosities, and self diffusion at higher temperatures and pressures is suspected to be the result of temperature and pressure altering the population ratio of the two molecular conformers, trans and gauche.     

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.     

Thermodynamic Properties of Heavy n-Alkanes in the Liquid State: n-Dodecane

A grid algorithm based on sound speed data, was used to calculate the thermodynamic properties of liquid n-dodecane. The density, isobaric expansion coefficient, isothermal compressibility, isobaric and isochoric heat capacities, enthalpy, and entropy of liquid n-dodecane were calculated in the range of temperatures from 293 to 433 K and pressures from 0.1 to 140 MPa. Coefficients of the Tait equation were determined in the above-identified range of parameters. A table of the thermodynamic properties of n-dodecane is presented.     

Isobaric thermal expansivities of binary mixtures ofn-Hexane with 1-hexanol at pressures from 0.1 to 350 MPa and at temperatures from 303 to 503 K

Isobaric thermal expansivities, α_p(p, T), of seven binary mixtures ofn-hexane with l-hexanol (0.0553, 0.1088, 0.2737, 0.2983, 0.4962, 0.6036, and 0.7455 mol fraction of l-hexanol) have been measured with a pressure-controlled scanning calorimeter over the pressure range from just above the saturation pressures to 350 MPa and at temperatures from 302.6 to 503.1 K. The low-temperature isotherms of α_p for particular mixtures observed with respect to the unique crossing point ofn-hexane isotherms reveal an association effect which is reduced when the temperature increases. The high-temperature isotherms of α_p are very similar to the isotherms of puren-hexane, especially for lower mole fractions ofn-hexanol. No known equation of state can reproduce these properties.     

Acoustic and thermodynamic properties of the binary liquid system <Emphasis Type="Italic">n</Emphasis>-dodecane+<Emphasis Type="Italic">n</Emphasis>-hexadecane

By the method of direct measurement of the pulse-passage time, the velocity of sound in a binary liquid mixture n-dodecane+n-hexadecane has been investigated in the temperature range 298–433 K and in the pressure range 0.1–100.1 MPa. The maximum measurement error is 0.1%. Experimental data on the velocity of sound for the investigated mixture have been obtained for the first time. On the basis of the data on the velocity of sound, we have determined the density, the isobaric expansion coefficient, the isobaric and isochoric heat capacities, and the isothermal compressibility coefficient of a mixture of three compositions in the 298–433 K temperature range and in the 0.1–100.1 MPa range of pressures. The coefficients of the Tate equations in the above range of parameters have been calculated. A table of thermodynamic properties of the mixture is presented.     

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.     

Transport properties of nonelectrolyte liquid mixtures—VII. Viscosity coefficients for isooctane and for equimolar mixtures of isooctane + n-octane and isooctane + n-dodecane from 25 to 100°C at pressures up to 500 MPa or to the freezing pressure

Changes in the high-pressure self-centering falling-body viscometer system, and the new automated data logging system, are described. Viscosity coefficient measurements made with an estimated accuracy of ± 2 % are reported for isooctane and for equimolar mixtures of isooctane + n-octane and isooctane + n-dodecane at 25, 50, 75, and 100°C at pressures up to 500 MPa or to the freezing pressure. The pressure dependence of the results is found to be represented equally well by the recent equation of Makita and by a free-volume form of equation. The Grunberg and Nissan equation gives a good fit to the mixture viscosity coefficient data.     

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.     

Thermodynamics of hydrogen-bonding mixtures 2.G E,H E,andS E of 1-propanol +n-heptane

A metal ebulliometcr was used to measure total vapor-pressure (PTx) data on 18 mixtures of 1-propanol +n-heptane (and the pure components) between 380 and 445 K. Bubble-point data were measured at seven pressures between 200 kPa and I MPa. These data cover an intermediate region between previous data reported near atmospheric pressure and below and high-temperature data extending to the critical region. A Redlich--Kister G' model fit isotherms between 373.15 and 463.15 K via Barker's method with an average standard error of 0.2 to 0.5% in pressure. The system exhibits large positive deviations from ideality (derived =2.7–10.5) which decrease with temperature. EquimolarG ^E/T values thus derived also decrease with increasing temperature, which predicts a positiveH ^E An azeotrope exists under all conditions studied: the azeotropic composition increases in alcohol content with increasing temperature. These mixture thermodynamic data show that, above 345 K, the system 1-propanol +n-heptane belongs to the class of mixtures whereG ^E > 0,H ^E >0. andTS ^E > 0. This probably occurs because the 1-I orientational effect (in this case, hydrogen-bonding of the alcohol molecules) is more readily disrupted in the inert solvent than it would be a( lower temperatures, where the effect of hydrogen-bonding is stronger.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

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.     

The thermal conductivity of n-hexane,n-heptane,and n-decane by the transient hot-wire method

New absolute measurements of the thermal conductivity of liquid n-hexane, n-heptane, and n-decane are reported. The measurements have been carried out in the temperature range 300–370 K at atmospheric pressure in a transient hotwire instrument. The accuracy of the measurements is estimated to be ±0.5%. The density dependence of the thermal conductivity of n-hexane and n-heptane is found to be well described by a universal equation for the hydrocarbons based on a rough hard-sphere model. The measurements of the three hydrocarbons studied are also employed to generate more accurate effective core volumes, which are the only parameters characteristic of the fluid required for the application of the proposed universal scheme.     

Interplay of low and highT c phases in Bi-Sr-Ca-Cu-O superconductor

In the Bi-Sr-Ca-Cu-O system stringent conditions of heat-treatment lead to the formation of a mixture of both the low and highT _c phases and obtaining a single-phase material becomes extremely difficult. This study reports preparation of samples with single superconducting transitions at ∼ 75 K and ∼ 108 K; the compositions of which correspond ton=2,3 in the series Bi₂Sr₂Ca _n−1Cu _n O_{4 + 2n} . X-ray diffraction studies show that the lowerT _c material is a relatively pure phase while the higherT _c phase only co-exists with the lowerT _c phase. The most obvious effect of doping the system with lead is to make the reaction take place faster and thereby increase the volume fraction of the 110K phase.     

Anomalous Excess Heat Capacities of Ethanol + Alkane Mixtures

A thermodynamic study at atmospheric pressure on the ethanol + n-dodecane and ethanol + n-tridecane binary systems near their liquid-liquid critical points has been carried out. To this end, densities and speeds of sound were determined in the temperature range from 288.15 to 308.15 K, whereas differential scanning calorimetry was used to obtain isobaric heat capacities per unit volume from 288.15 to 303.15 K as well as liquid-liquid equilibrium curves. All these results for the mentioned properties were obtained over the complete composition range. They were used to obtain molar volumes, isentropic compressibilities, isobaric thermal expansivities, isothermal compressibilities, isochoric heat capacities, and the excess quantities of all these properties. An untypical behavior of the excess heat capacities at the lowest measuring temperatures resulting from the critical behavior of the isobaric heat capacity is observed. No clear anomalies for the excess volumetric properties are detected.