J. M. N. A. Fareleira

Validation of an accurate vibrating-wire densimeter: Density and viscosity of liquids over wide ranges of temperature and pressure

A new vibrating-wire instrument for the meaasurement of the density of fluids at high pressures was described in a previous paper. The technique makes use of the buoyancy force on a solid sinker and detect, this force with a vibrating wire placed inside the measuring cell. Owing to the simple geometry of the oscillating element there exists a complete theoretical description of its resonance characteristics. enabling the calculation of the density of the fluid from their measurement. In the present paper a new method for the determination of the cell constants is outlined which permits the operation of the densimeter essentially as an absolute instrument. Furthermore. it is shown that the viscosity ol the fluid can be measured Simultaneously with the density. New results for three fluids are presented: for cyclohexane at temperatures from 298 to 348 K and pressures up to 40 MPa. for 2,2,4-trimethylpentane between 197 and 348 K at 0.1 MPa, and for 1,1,1,2-tetrafluoroethane from 197 to 298 K close to saturation. The sets of measurements where chosen with the intention of testing the performance of the apparatus. complementing previous work at higher pressures. The densities and viscosities measured exhibit the same accuracy for all of the three fluids over the entire temperature and pressure ranges and were obtained using the same set of cell parameters The precision of the densities is ±0.03% and their estimated accuracy is ±0.05%. File viscosities have a precision of ±0.6%, and an estimated accuracy of ±2%.

Reference Correlation for the Viscosity of Liquid Toluene from 213 to 373 K at Pressures to 250 MPa

A correlation in terms of temperature and molar volume is recommended for the viscosity of liquid toluene as a reference for high-pressure viscosity measurements. The temperature range covered is from 213 to 373 K, and the pressure range from atmospheric up to 250 MPa. The standard deviation of the proposed correlation is 1.36%, and, within a 95% confidence limit, the error is 2.7%. It is estimated that for densities up to 920 kg·m−3the uncertainty of the viscosity values generated by this correlation is about ±2%.

Viscosity Measurements of Liquid Toluene at Low Temperatures Using a Dual Vibrating-Wire Technique

A recently developed dual vibrating-wire technique has been used to perform viscosity measurements of liquid toluene in the temperature range 213 K≤T≤298 K, and at pressures up to approximately 20 MPa. The results were obtained by operating the vibrating-wire sensor in both forced and free decay modes. The estimated precision of the viscosity measurements, in either mode of operation, is ±0.5%, for temperatures above or equal to 273 K, increasing with decreasing temperature up to ±1% at 213 K. The corresponding overall uncertainty is estimated to be within ±1% and ±1.5%, respectively.

Thermal conductivity of five hydrocarbons along the saturation line

The paper presents the results of new, absolute measurements of the thermal conductivity of five alkanes as a function of temperature at their saturation vapor pressure. The alkanes studied include the four normal alkanes n-octane, n-nonane, n-undecane, and n-tetradecane as well as the branched alkane, iso-octane. The results, which extend over the temperature range 282–373 K, have an estimated uncertainty limit of 1.5% deriving mainly from a correction for the effects of radiation absorption in the measurement process. The results are employed to generate effective core volumes for the fluids studied which may be employed to predict the density dependence of the thermal conductivity by means of an existing correlation.

Volumetric Properties and Spectroscopic Studies of Pyridine or Nicotine Solutions in Liquid Polyethylene Glycols

Densities and molar excess volumes of the solutions of pyridine or nicotine in liquid polyethylene glycol, PEG200 and PEG400, have been determined at several temperatures. The experimental molar excess volumes are negative, thus indicating strong attractive interactions between the components, as could be expected considering their highly polar nature and good hydrogen bond abilities. For the pyridine systems, this negativity is slightly increased as the temperature rises, while the opposite tendency is observed for the nicotine mixtures. When pyridine and nicotine solutions are compared, the former-particularly those with PEG400-exhibit substantially more negative molar excess volumes than the latter. The effect of the polymer chain length on the results for the nicotine solutions is almost negligible. However, this is not the case when pyridine is one of the components: a longer chain induced considerably higher compression on mixing. The Fourier-transform infrared analysis allowed interpretation of the negative experimental molar excess volumes in terms of specific inter- and intramolecular interactions.

A vibrating-wire densimeter for liquids at high pressures: The density of 2,2,4-trimethylpentane from 298.15 to 348.15 K and up to 100 MPa

A new apparatus for the measurement of liquid densities at high pressures is presented. The instrument is a development of a vibrating-wire densimeter described earlier and uses the buoyancy force exerted by the sample fluid on an immersed buoy to alter the tension of a wire from which it is suspended. The tension of the wire is related to its resonant frequency under steady-state transverse vibrations through a rigorous theoretical model which includes a complete analysis of the hydrodynamic effect of the fluid surrounding the wire. The present instrument uses a new design for the measuring cell with the purpose of relieving the degeneracy of perpendicular oscillation modes of the vibrating wire. The modifications lead to a significant increase in the precision of the results. Tests performed on the new apparatus and the operating procedure used, which requires the determination of one cell parameter from one density datum at atmospheric pressure, are described. New results for the density of liquid 2,2,4-trimethylpentane at temperatures from 298.15 to 348.15 K and pressures up to 100 MPa are presented. The data obtained have a precision of ±0.05% at a 2a level and an estimated accuracy of approximately ±0.1%.

A vibrating-wire densimeter for measurements in fluids at high pressures

The paper describes a new type of densimeter especially designed for the accurate measurement of fluid densities at pressures up to 400 MPa. The densimeter makes use of the buoyancy force exerted on a mass immersed in the test fluid to alter the resonant frequency of a thin wire from which the mass is suspended. The resonant frequency of the wire carrying the mass is related to the fluid density by means of working equations which are based on a complete analysis of the fluid motion around the wire. Preliminary results are presented for n-octane at pressures up to about 100 MPa near ambient temperature. The results show that the instrument has a precision of ±0.1 % in density at elevated pressures when evaluated on a relative basis, while the accuracy is estimated to be one of ±0.2%.

The Thermal Conductivity of Toluene and Water

A new instrument is presented to measure the thermal conductivity of polar and electrically conducting liquids based on the transient coated hot-wire method. The performance of the apparatus has been assessed with toluene and water, which are recognized as standard reference materials for nonpolar and polar fluids, respectively. New results are reported fort the thermal conductivity of these liquids between 298 and 370 K and at pressures slightly above the saturation. The results show that the instrument is capable of an accuracy better than ±0.5%, while the precision and reproducibility are better than ±0.3%.

The thermal conductivity of liquid mixtures at elevated pressures

This paper reports new, absolute measurements of the thermal conductivity of liquid mixtures of n-heptane and isooctane in the pressure range 0.1 to 430 MPa for temperatures of 307.85 and 337.15 K. The results represent a preliminary investigation of the advantages of attempting to describe the isothermal composition dependence of the thermal conductivity of liquid mixtures along isochores, rather than isobars as has been traditional. However, no significant differences were found between the composition dependences in the two circumstances, possibly due to the lack of experimental data on the density of these mixtures. The availability of a theoretical description of the isochoric composition dependence suggests that this is the most appropriate description which reinforces the need for further high-pressure measurements of the thermal conductivity and density.

Thermal conductivity of liquid n-alkanes

The thermal conductivity of liquids has been shown in the past to be difficult to predict with a reasonable accuracy, due to the lack of accurate experimental data and reliable prediction schemes. However, data of a high accuracy, and covering wide density ranges, obtained recently in laboratories in Boulder, Lisbon, and London with the transient hot-wire technique, can be used to revise an existing correlation scheme and to develop a new universal predictive technique for the thermal conductivity of liquid normal alkanes. The proposed correlation scheme is constructed on a theoretically based treatment of the van der Waals model of a liquid, which permits the prediction of the density dependence and the thermal conductivity of liquid n-alkanes, methane to tridecane, for temperatures between 110 and 370 K and pressures up to 0.6 MPa, i.e., for 0.3⩽T/Tc⩽0.7 and 2.4⩽P/Pc⩽3.7, with an accuracy of ±1%, given a known value of the thermal conductivity of the fluid at the desired temperature. A generalization of the hard-core volumes obtained, as a function of the number of carbon atoms, showed that it was possible to predict the thermal conductivity of pentane to tetradecane±2%, without the necessity of available experimental measurements.