Pressure dependence of the density of n-alkanes

Accurate density data for n-alkanes are essential for the measurement of interfacial tension of liquid-liquid systems as a function of pressure. The variation of density with pressure for three n-alkanes, n-hexane, n-heptane, and n-decane, was measured at 21.2°C and pressures ranging from 0.1 to 35 MPa with a digital density meter. The Tait equation of the form (– ₀)/=C log[(B+P)/ (B+P₀)] was used to represent the experimental data.     

Densities of tetramethylsilane,tetraethylsilane, and tetraethoxysilane under high pressures

Accurate density data for tetramethylsilane, tetraethylsilane, and tetraethoxysilane in the temperature range from 283.15 to 333.15 K under pressure up to 100 MPa have been measured in order to test existing correlation methods. We have also measured the saturated liquid densities of tetramethylsilane, tetraethylsilane, and tetraethoxysilane in the temperature range from 283 to 343 K. The modified Rackett equation and the COSTAD correlation were used to correlate the saturated liquid density data. The Tait equation and a modified van der Waals equation of state were used to correlate the liquid density data under pressure. It was found that the average absolute deviations of the experimental values from those calculated with the Tait equation and the modified van der Waals equation of state were less than 0.01 and 0.21%, respectively. The effective hard sphere diameters for these three silane compounds were determined from the modified van der Waals equation of state parameter. It was found that the effective hard-sphere diameter decreases with temperature.     

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.     

Auto-ignition and upper explosion limit of rich propane-air mixtures at elevated pressures

The auto-ignition limits of propane-air mixtures at elevated pressures up to 15 bar and for concentrations from 10 mol% up to 70 mol% are investigated. The experiments are performed in a closed spherical vessel with a volume of 8 dm3. The auto-ignition temperatures decrease from 300 degrees C to 250 degrees C when increasing the pressure from 1 bar to 14.5 bar. It is shown that the fuel concentration most sensitive to auto-ignition depends on initial pressure. A second series of experiments investigates the upper flammability limit of propane-air mixtures at initial temperatures up to 250 degrees C and pressures up to 30 bar near the auto-ignition area. Finally the propane auto-oxidation is modelled using several detailed kinetic reaction mechanisms and these numerical calculations are compared with the experimental results.     

Inter- and intradiffusion in liquid mixtures of methane andn-decane

The interdiffusion coefficient,D ₁₂, has been measured by Mach-Zehnder interferometry for liquid mixtures of methane andn-decane at 303 K. The mole fraction of methane was from 0.11 to 0.96 and the pressure was from 30 to 60 MPa. This includes measurements in the critical region, the critical locus being approached from supercritical pressures to within 0.4 MPa. The accuracy inD ₁₂ is estimated to be from 3 to 10%, depending on the composition. Our data are compared with the Sigmund correlation, which is widely used to estimate diffusion coefficients in hydrocarbons at high pressures. The deviation between estimate and measurement is one order of magnitude for some of the states. We have also compared with a more recent correlation used by Erkey, but this one is not found to be applicable to the compositions studied in the present work. Our data were related to recently measured intradiffusion coefficients,D ₁ andD ₂, at the same state points. On this basis, we have evaluated different mixing rules for obtaining the interdiffusion coefficient from intradiffusion coefficients, both close to and away from the critical region. It is found that the so-called Darken and Adamson relations have the right qualitative behavior.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

Phase behavior of mixtures at very high pressures

The invention of the diamond anvil cell (DAC) has been an enormous stimulus to high-pressure research. This technique has only recently been used to investigate the behavior of binary systems, probably because of the extra experimental problems which arise in the study of mixtures. It will be shown that a variety of aspects of the behavior of the mixture can, nevertheless, be studied under extreme conditions. Although the first investigations were carried out only recently, some very interesting results have already been obtained. A variety of two-components systems has been studied, e.g., He-Kr, Ne-Xe, He-H₂, NH₃-H₂O, and N₂-He₂. Some of these results are discussed. Finally, a comparison is made between experimental results and theoretical calculations.Invited paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

The Tait equation: 100 years on

The Tait equation, which is now widely used to fit liquid density data over wide pressure ranges, is a modification of the original equation of Tait, published 100 years ago, to fit his results on the compressibility of fresh water and seawater at different pressures. The range of applicability of these different equations is discussed and it is concluded that their simplicity and accuracy in reproducing high pressure density data for dense gases, liquids, solids, and liquid mixtures will ensure their continued use.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

Viscosities of nonelectrolyte liquid mixtures. II. Binary and quaternary systems of some n-alkanes

This paper is the second in a series of viscosity and density studies on multicomponent mixtures of n-alkanes from 303 to 338 K. Reported here are the results of binary mixtures of n-tetracosane + n-octane as well as quaternary mixtures of n-tetracosane + n-octane + n-decane + n-hexane at 318.16, 328.16, and 338.16 K. Viscosities were determined using a standard U-tube Ostwald viscometer, and densities were determined using a flask-type pycnometer. Empirical relations tested include the Grunberg and Nissan equation and the method of corresponding states. In addition, comparisons were made regarding the behavior of this quaternary system and homologous binary mixtures of n-hexadecane + n-octane and n-tetracosane + n-octane at the same temperatures.     

Density and viscosity of linear perfluoropolyethers under high pressures

New experimental data on the density and viscosity of linear, unbranched perfluoropolyethers are presented at temperatures from 273 to 333 K and pressures up to 180 MPa. The measurements were carried out by a high-pressure burrette apparatus and a falling-cylinder viscometer. The uncertainties of the measurements are estimated to be less than 0.09% for the specific volume and 2.5% for the viscosity. The P-V data at each temperature are correlated satisfactorily by the Tait equation. The viscosity data are also analyzed and correlated with pressure or molar volume by several empirical and theoretical equations.     

Volumetric behavior of pure alcohols and their water mixtures under high pressure

The specific volumes of C₁-C₄ alcohols and binary mixtures of water with methanol, ethanol, 1-propanol, 2-propanol, and 2-methyl-2-propanol are presented as functions of temperature, pressure, and composition. The measurements were carried out using a modified Adams piezometer and a high-pressure burette method in a temperature range from 283.15 to 348.15 K at pressures up to 350 MPa. The uncertainties in the specific volume obtained are estimated to be less than 0.09%. The specific volumes of the pure alcohols and their mixtures with water are found to decrease monotonously with increasing pressure. The numerical P-V relations at each temperature and composition are correlated satisfactorily as a function of pressure by the Tait equation. Definite inflections appear on the isobars of isothermal compressibility or partial molar volume versus composition of alcohol + water mixtures.     

Measurements of the viscosity of toluene + mesitylene mixtures at pressures up to 55 MPa

New absolute measurements of the viscosity of mesitylene and binary mixtures of toluene + mesitylene are presented. The measurements were performed in a vibrating-wire instrument and cover a temperature range of 295–330 K and pressures up to 55 MPa. The concentrations studied were 40 and 70%, by weight, of toluene. The overall uncertainty in the reported data is estimated to be ±0.5%. A recently extended semiempirical scheme for the prediction of the viscosity of mixtures from the pure components is used to predict successfully the viscosity of these mixtures, as a function of composition, temperature, and pressure.     

The thermal conductivity of pure nitrogen and of mixtures of nitrogen and carbon dioxide at elevated temperatures and pressures

The thermal conductivities of nitrogen at 470 K and six mixtures of nitrogen and carbon dioxide at various temperatures have been measured as a function of pressure up to 25 MPa. The mixtures were measured at the following temperatures: one at 302 K, three at 380 K, one at 430 K, and one at 470 K. The data were used to test three prediction methods for the thermal conductivity of gas mixtures under pressure. Surprisingly good agreement was found with predictions using the corresponding-states method of Ely and Hanley. The predictions of the more theoretically based method of Mason et al. were low throughout, due partly to its use of the Hirschfelder-Eucken equation as the low-density limit, but also because the predicted density dependence rises too slowly. The simplified version of this method proposed by Svojskij gave slightly worse predictions, particularly at higher densities. The zero- density results for nitrogen are examined by comparing the zero-and first-density coefficients with the trends shown at lower temperatures.     

Thermal conductivity of liquid mixtures of benzene and 2,2,4-trimethylpentane at pressures up to 350 MPa

This paper contains the results of new measurements of the thermal conductivity of mixtures of benzene and 2,2,4-trimethylpentane in the liquid phase within the temperature range 313 to 344 K at pressures up to 350 MPa. The measurements were carried out with a transient hot-wire instrument and have an estimated accuracy of ±0.3%. The study is the first conducted at high pressures on mixtures of components of greatly differing volatilities and therefore provides a further test of methods of representing the thermal conductivity of liquid mixtures based upon the hard-sphere theory of transport in liquids. It is shown that the procedure is capable of representing all of the present experimental data within ±5%. A more detailed examination of the results reveals small, but systematic, deviations from universality of the behavior of the thermal conductivity as a function of density implied by the hard-sphere theory, which merit further investigation.     

Temperature dependence of the surface tension for binary mixtures ofn-butanenitrile +n-alkanes

The differential capillary-rise method was used to determine the orthobaric surface tension of binary liquid mixtures ofn-butanenitrile mixed withn-pentane,n-hexane, andn-heptane, throughout the composition range. at 293.15, 303.15, 313.15, 323.15, 333.15. and 343.15 K. Furthermore, the system withn-hexane was also studied al 263.15 K. i.e., 19 K above its upper critical solution temperature, over the whole composition range. For each binary system the surface tension changes regularly with both temperature and composition between the values of the pure components. The results are discussed in terms of deviations from surface ideality and related to the large positive deviations observed for bulk properties of the same systems.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

Thermophysical properties of liquids at high pressures

Most of the thermophysical properties of fluids are greatly altered at high pressures, and the studies of these changes are of much scientific and technological importance. In this paper, the effects of temperature and pressure on the density, viscosity, and thermal conductivity of various liquids are described briefly, based on recent experimental results from the author's laboratory. The objectives of this investigation, methods of measurements, and some of the experimental results are reviewed, as well as the present aspects in this field. Several important problems to be interpreted are also pointed out from the present measurements.Presented at the Japan-United States Joint Seminar on Thermophysical Properties, October 24–26, 1983, Tokyo, Japan.     

The viscosity of liquid toluene at elevated pressures

This paper reports new measurements on the viscosity of toluene at pressures up to 500 MPa at 299 K and pressures up to 435 MPa at 323 K. The results are in close agreement with recent viscosity measurements from a vibrating-wire viscometer at pressures up to 250 MPa but confirm earlier measurements from a falling-body viscometer which show that the recently recommended polynomial expression for the representation of the pressure dependence of the viscosity of toluene up to 250 MPa underestimates the viscosity if applied at 500 MPa by about 30%. Modification of this polynomial expression by inclusion of one additional term is found to represent the data satisfactorily over the whole pressure range.     

Volumetric properties of mixtures of fluoroalcohols and water at high pressures

Densities of aqueous solutions of 2,2,2-trifluoroethanol, 2,2,3,3-tetranuoropropanol, and 2,2,3,3,3-pentanuoropropanol have been measured with a vibrating-tube densitometer. Measurements were performed at temperatures of 298 and 323 K and at pressures up to 80 MPa with an estimated uncertainty of ±0.2 %. Molar volumes obtained for these mixtures are correlated with pressure by the Tait equation within the experimental uncertainty. Excess molar volume, isothermal compressibility, and partial molar volume of these mixtures are determined in terms of this correlation equation and compared with those of the aqueous solutions of hydrocarbon alcohols. Composition dependence of partial molar volume is discussed in comparison with that of Raman spectroscopic data.     

Volumetric properties of mixtures of 1,4-dioxane and water at high pressures

Densities of aqueous of 1,4-dioxane have been measured at temperatures from 298 to 348 K and at pressures up to 40 MPa by a vibrating-tube method. Molar volumes obtained with an estimated uncertainty of ±0.2°,% are correlated with pressure by the Tait equation within the experimental uncertainty. Pressure and composition dependences of the excess molar volume, partial molar volume, and isothermal compressibility are determined and they are compared with those of other aqueous solutions.     

Thermal conductivity of methane-ethane mixtures at temperatures between 140 and 330 K and at pressures up to 70 MPa

The paper presents new measurements on the thermal conductivity of three methane-ethane mixtures with methane mole fractions of 0.69, 0.50, and 0.35. The thermal conductivity surface for each mixture is defined by up to 13 isotherms at temperatures between 140 and 330 K with pressures up to 70 MPa and densities up to 25 mol · L^–1. The measurements were made with a transient hot-wire apparatus. They cover a wide range of physical states including the dilute gas, the single-phase fluid at temperatures above the maxcondentherm, the compressed liquid states, and the vapor at temperatures below the maxcondentherm. The results show an enhancement in the thermal conductivity in the single-phase fluid down to the maxcondentherm temperature, as well as in the vapor and in the compressed liquid. A curve fit of the thermal conductivity surface is developed separately for each mixture.Paper presented at the Ninth Symposium on Thermophysical Properties, June 24–27, 1985, Boulder, Colorado, U.S.A.