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.     

Gaseous thermal conductivity of difluoromethane (HFC-32), pentafluoroethane (HFC-125), and their mixtures

The gaseous thermal conductivity of dilluoromethane (HFC-32). pentalluoroethane (HFC-125). and their binary mixtures was measured with a transient hot-wire apparatus in the temperature ranges 283–333 K at pressures up to saturation. The uncertainty of the data is estimated to be within I %. The thermal conductivity as a function of composition of the mixtures at constant pressure and temperature is found to have a small maximum near 0.3–0.4 mole fraction of HFC-32. The gaseous thermal-conductivity data obtained for pure HFC-32 and HFC-125 were correlated with temperature and density together with the liquid thermal-conductivity data from the literature, based on the excess thermal-conductivity concept. The composition dependence of the thermal conductivity at a constant temperature is represented with the aid of the Wassiljewa equation.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado. U.S.A.     

A New Instrument for the Measurement of the Thermal Conductivity of Fluids

The transient hot-wire technique is at present the best technique for obtaining standard reference data for the thermal conductivity of fluids. It is an absolute technique, with a working equation and a complete set of corrections reflecting departures from the ideal model, where the principal variables are measured with a high degree of accuracy. It is possible to evaluate the uncertainty of the experimental thermal conductivity data obtained using the best metrological recommendations. The liquids proposed by IUPAC (toluene, benzene, and water) as primary standards were measured with this technique with an uncertainty of 1% or better (95% confidence level). Pure gases and gaseous mixtures were also extensively studied. It is the purpose of this paper to report on a new instrument, developed in Lisbon, for the measurement of the thermal conductivity of gases and liquids, covering temperature and pressure ranges that contain the near-critical region. The performance of the instrument for pressures up to 15 MPa was tested with gaseous argon, and measurements on dry air (Synthetic gas mixture, with molar composition certified by Linde AG, Wiesbaden, Germany, Ar – 0.00920; O₂ – 0.20966; N₂ – 0.78114), from room temperature to 473 K and pressures up to 10 MPa are also reported. The estimated uncertainty is 1%.M. L. V. Ramires: DeceasedPaper presented at the Seventeenth European Conference on Thermophysical Properties, September 5–8, 2005, Bratislava, Slovak Republic.     

Thermal conductivity andPVT measurements of pentafluoroethane (refrigerant HFC-125)

By means of the transient and steady-state coaxial cylinder methods, the thermal conductivity of pentafluoroethane was investigated at temperatures from 187 to 419 K and pressures from atmospheric to 6.0 MPa. The estimated uncertainty of the measured results is ±(2–3)%. The operation of the experimental apparatus was validated by measuring the thermal conductivity of R22 and R12. Determinations of the vapor pressure andPVT properties were carried out by a constant-volume apparatus for the temperature range 263 to 443 K, pressures up to 6 MPa, and densities from 36 to 516 kg m^–3. The uncertainties in temperature, pressure, and density are less than ±10 mK, ±0.08%, and ±0.1%, respectively.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

Thermal conductivity of water and 2-n-butoxyethanol and their mixtures in the temperature range 305–350 K at pressures up to 150 MPa

The thermal conductivity of binary liquid mixtures of water and 2-n-butoxyethanol has been measured within the temperature range 305–350 K at pressures up to 150 MPa. The measurements have been carried out with a transient hotwire instrument suitable for electrically conducting liquids and have an estimated accuracy of ±0.3%. The liquid mixture has a closed-loop solubility and reveals a lower critical solution temperature for a mole fraction of 2-n-butoxyethanol of 0.0478 at a temperature of 322.25 K. The results of the measurements reveal a small, but discernible, enhancement of the thermal conductivity of the solution at the critical composition.Paper presented at the Twelfth Symposium on Thermophysical Properties. June 19–24, 1994, Boulder, Colorado, U.S.A.     

Thermal Conductivity of Carbon Dioxide–Methane Mixtures at Temperatures Between 300 and 425 K and at Pressures up to 12 MPa

The thermal conductivities of carbon dioxide and three mixtures of carbon dioxide and methane at six nominal temperatures between 300 and 425 K have been measured as a function of pressure up to 12 MPa. The measurements were made with a transient hot-wire apparatus. The relative uncertainty of the reported thermal conductivities at a 95% confidence level is estimated to be ±1.2%. Results of the low-density analysis of the obtained data were used to test expressions for predicting the thermal conductivity of nonpolar mixtures in a dilute-gas limit developed by Schreiber, Vesovic, and Wakeham. The scheme was found to underestimate the experimental thermal conductivity with deviations not exceeding 5%. The dependence of the thermal conductivity on density was used to test the predictive scheme for the thermal conductivity of gas mixtures under pressure suggested by Mason et al. and improved by Vesovic and Wakeham. Comparisons reveal a pronounced critical enhancement on isotherms at 300 and 325 K for mixtures with methane mole fractions of 0.25 and 0.50. For other states, comparisons of the experimental and predicted excess thermal conductivity contributions showed a smaller increase of the experimental data with deviations approaching 3% within the examined range of densities.     

Thermal Conductivity Measurements of Aqueous SrCl2 and Sr(NO3)2 Solutions in the Temperature Range Between 293 and 473 K at Pressures up to 100 MPa

Accurate high-pressure thermal conductivity measurements have been performed on H₂O+SrCl₂ and H₂O+Sr(NO₃)₂ mixtures at pressures up to 100 MPa over a temperature range between 293 and 473 K using a parallel-plate apparatus. The concentrations studied were 0.025, 0.05, 0.10, 0.15, and 0.20 mass fraction of the salts. The estimated accuracy of the method is about ±1.6%. The pressure, temperature, and concentration dependences of the thermal conductivity have been studied. Measurements were made on six isobars, namely, 0.1, 20, 40, 60, 80, and 100 MPa. The thermal conductivity shows a linear dependence on pressure and concentration for all isotherms. Along each isobar, a given concentration shows the thermal-conductivity maximum at a temperature of about 413 K. The measured values of thermal conductivity at atmospheric pressure are compared with the results of other investigators. Literature data at atmospheric pressure reported by Ridel and by Zaitzev and Aseev agree with our thermal conductivity values within the estimated uncertainty.     

Thermal Conductivities of Imidazolium-Based Ionic Liquid + CO<Subscript>2</Subscript> Mixtures

Experimental results for the thermal conductivities of imidazolium-based ionic liquid + CO₂ mixtures are reported. The thermal conductivities were measured with a transient short-hot-wire method. The experimental temperatures were from 294 K to 334 K, and pressures were 10.0 MPa and 20.0 MPa. The CO₂ mole fractions of the mixtures covered a range up to 0.42. It was found that the thermal conductivities of ionic liquids have a very small CO₂ mole fraction dependence.     

Thermal Conductivity of Binary Refrigerant Mixtures of HFC-32/125 and HFC-32/134a in the Liquid Phase

The liquid thermal conductivity of mixtures of HFC-32/125 and HFC-32/134a was measured using the transient hot-wire apparatus in the temperature ranges from 213 to 293 K and from 193 to 313 K, respectively, in the pressure range from 2 to 30 MPa and with HFC-32 mass fractions of 0.249, 0.500, and 0.750 for each system. The uncertainty of the thermal conductivity was estimated to be ±0.7%. For practical applications, the thermal conductivity data for the two mixtures were represented by a polynomial in temperature, pressure, and mass fraction of HFC-32 with a standard deviation of 1.0%.     

Measuring Humidity in Methane and Natural Gas with a Microwave Technique

The results of microwave measurements with a quasi-spherical resonator in humid methane samples realized under laboratory conditions at the Istituto Nazionale di Ricerca Metrologica (INRiM) and under industrial conditions in a natural gas sample made available at the facilities of the Technical Manager of the Spanish Gas System and main supplier of natural gas in Spain (ENAGAS) are reported. Measurements at INRiM included vapor phase and condensation tests on methane samples prepared with amount fractions of water between 600 ppm and 5000 ppm at temperatures between 273 K and 295 K and pressures between 150 kPa and 1 MPa. ENAGAS measurements were performed at ambient temperature, 750 kPa on natural gas sampled from the pipeline and successively humidified at amount fractions of water between 140 ppm and 250 ppm for completeness of the comparison with several humidity sensors and instrumentation based on different technologies. To enhance the sensitivity of the microwave method at low humidity, an experimental procedure based on the relative comparison of the dielectric permittivity of the humid gas sample before and after being subject to a chemical drying process was conceived and implemented. The uncertainty budget and the final sensitivity of this procedure are discussed.     

Thermal conductivity of aqueous solutions of NaCl and KCI at high pressures

This paper presents new experimental measurements of the thermal conductivity of aqueous solutions of NaCl and KCl at high pressures. The measurements were made with a parallel-plate apparatus. The temperatures covered the range from 293 to 473 K at pressures up to 100 MPa and concentrations from 0.025 to 0.25 mass fraction of NaCl and KCl. The measurements included 6 isobars at pressures from 0.1 to 100 MPa at intervals of 20 MPa, 10 isotherms at temperatures from 293 to 473 K at intervals of 20 K, and 6 isopleths at concentrations from 0.025 to 0.25 mass fraction of NaCl and KCl at intervals of 0.05. The precision of the measurements was ±1.6%. The thermal conductivity obtained for NaCl + H₂O and KCl + H₂O was compared with data of other authors, with satisfactory agreement. The viability of the technique was confirmed and the essential features of a high-precision instrument were established.     

Thermal-Conductivity Measurements of Aqueous Orthophosphoric Acid Solutions in the Temperature Range from (293 to 400) K and at Pressures up to 15 MPa

A new improved guarded parallel-plate thermal-conductivity cell for absolute measurements of corrosive (chemically aggressive) fluids under pressure has been developed. Using the new modified guarded parallel-plate apparatus the thermal conductivity of aqueous orthophosphoric acid solutions was measured over the temperature range from (293 to 400) K and pressures up to 15 MPa. Measurements were made for three compositions of \(\text {H}_{3}\text {PO}_{4}\) (8 mass%, 15 mass%, and 50 mass%) along three isobars of (0.101, 5, and 15) MPa. The combined expanded uncertainty of the thermal-conductivity \((\lambda )\) measurements at the 95 % confidence level with a coverage factor of \(k=2\) is estimated to be 2 %. The uncertainties of the temperature, pressure, and concentration measurements were 15 mK, 0.05 %, and 0.01 %, respectively. The temperature, concentration, and pressure dependences of the thermal conductivity of the solution were studied. The measured values of thermal conductivity were compared with the available reported data and the values calculated from various correlation and prediction models. A new wide-range correlation model (extended Jones–Dole type equation with pressure-dependent coefficients) for the \(\text {H}_{3}\text {PO}_{4}\) (aq) solution was developed using the present experimental data.     

Equation of State for the Thermodynamic Properties of 1,1,2,2,3-Pentafluoropropane (R-245ca)

An equation of state for the calculation of the thermodynamic properties of 1,1,2,2,3-pentafluoropropane (R-245ca), which is a hydrofluorocarbon refrigerant, is presented. The equation of state (EOS) is expressed in terms of the Helmholtz energy as a function of temperature and density, and can calculate all thermodynamic properties through the use of derivatives of the Helmholtz energy. The equation is valid for all liquid, vapor, and supercritical states of the fluid, and is valid from the triple point to 450 K, with pressures up to 10 MPa. Comparisons to experimental data are given to verify the stated uncertainties in the EOS. The estimated uncertainty for density is 0.1 % in the liquid phase between 243 K and 373 K with pressures up to 6.5 MPa; the uncertainties increase outside this range, and are unknown. The uncertainty in vapor-phase speed of sound is 0.1 %. The uncertainty in vapor pressure is 0.2 % between 270 K and 393 K. The uncertainties in other regions and properties are unknown due to a lack of experimental data.     

The Precise Measurement of Vapor–Liquid Equilibrium Properties of the CO$$_{}$$/Isopentane Binary Mixture,and Fitted Parameters for a Helmholtz Energy Mixture Model

Natural working fluid mixtures, including combinations of CO\(_{2}\), hydrocarbons, water, and ammonia, are expected to have applications in energy conversion processes such as heat pumps and organic Rankine cycles. However, the available literature data, much of which were published between 1975 and 1992, do not incorporate the recommendations of the Guide to the Expression of Uncertainty in Measurement. Therefore, new and more reliable thermodynamic property measurements obtained with state-of-the-art technology are required. The goal of the present study was to obtain accurate vapor–liquid equilibrium (VLE) properties for complex mixtures based on two different gases with significant variations in their boiling points. Precise VLE data were measured with a recirculation-type apparatus with a 380 cm\(^{3}\) equilibration cell and two windows allowing observation of the phase behavior. This cell was equipped with recirculating and expansion loops that were immersed in temperature-controlled liquid and air baths, respectively. Following equilibration, the composition of the sample in each loop was ascertained by gas chromatography. VLE data were acquired for CO\(_{2}\)/ethanol and CO\(_{2}\)/isopentane binary mixtures within the temperature range from 300 K to 330 K and at pressures up to 7 MPa. These data were used to fit interaction parameters in a Helmholtz energy mixture model. Comparisons were made with the available literature data and values calculated by thermodynamic property models.     

Measurements of the viscosity of n-heptane + n-undecane mixtures at pressures up to 75 MPa

New absolute measurements of the viscosity of binary mixtures of n-heptane and n-undecane are presented. The measurements, performed in a vibrating-wire instrument, cover the temperature range 295–335 K and pressures up to 75 MPa. The concentrations studied were 40 and 70%, by weight, of n-heptane. The overall uncertainty in the reported viscosity data is estimated to be ±0.5%. A recently extended semiempirical scheme for the prediction of the thermal conductivity of mixtures from the pure components is used to predict successfully both the thermal conductivity and the viscosity of these mixtures, as a function of composition, temperature, and pressure.     

Thermal conductivity and density of toluene in the temperature range 273–373 K at pressures up to 250 MPa

New experimental data on the thermal conductivity and the density of liquid toluene are presented in the temperature range 0–100°C at pressures up to 250 MPa. The measurements of thermal conductivity were performed with a transient hot-wire apparatus on an absolute basis with an inaccuracy less than 1.0%. The density was measured with a high-pressure burette method with an uncertainty within 0.1%. The experimental results for both properties are represented satisfactorily by the Tait-type equations, as well as empirical polynomials, covering the entire ranges of temperature and pressure. Furthermore, it is found that simple relations exist between the temperature dependence of thermal conductivity and the thermal expansion coefficient, and also between the pressure dependence of thermal conductivity and the isothermal compressibility, as are suggested theoretically.     

The transport properties of ethane. II. Thermal conductivity

A new representation of the thermal conductivity of ethane is presented. The representative equations are based upon a body of experimental data that have been critically assessed for internal consistency and for agreement with theory in the zero-density limit and in the critical region. The representation extends over the temperature range from 100 K to the critical temperature in the liquid phase and from 225 K to the critical temperature in the vapor phase. In the supercritical region the temperature range extends to 1000 K for pressures up to 1 MPa and to 625 K for pressures up to 70 MPa. The ascribed accuracy of the representation varies according to the thermodynamic state from ±2% for the thermal conductivity of the dilute gas near room temperature to ±5% for the thermal conductivity at high pressures and temperatures. Tables of the thermal conductivity, generated by the relevant equations, at selected temperatures and pressures and along the saturation line are also provided.     

Equation of State for the Thermodynamic Properties of <Emphasis Type="Italic">trans</Emphasis>-1,3,3,3-Tetrafluoropropene [R-1234ze(E)]

An equation of state for the calculation of the thermodynamic properties of the hydrofluoroolefin refrigerant R-1234ze(E) is presented. The equation of state (EOS) is expressed in terms of the Helmholtz energy as a function of temperature and density. The formulation can be used for the calculation of all thermodynamic properties through the use of derivatives of the Helmholtz energy. Comparisons to experimental data are given to establish the uncertainty of the EOS. The equation of state is valid from the triple point (169 K) to 420 K, with pressures to 100 MPa. The uncertainty in density in the liquid and vapor phases is 0.1 % from 200 K to 420 K at all pressures. The uncertainty increases outside of this temperature region and in the critical region. In the gaseous phase, speeds of sound can be calculated with an uncertainty of 0.05 %. In the liquid phase, the uncertainty in speed of sound increases to 0.1 %. The estimated uncertainty for liquid heat capacities is 5 %. The uncertainty in vapor pressure is 0.1 %.