Measurements of Vapor Pressures from 280 to 369 K and (p, ρ, T) Properties from 340 to 400 K at Pressures to 200 MPa for Propane

Measurements of (p, ρ, T) properties for compressed liquid propane have been obtained by means of a metal-bellows variable volumometer at temperatures from 340 to 400 K at pressures up to 200 MPa. The volume- fraction purity of the propane sample was 0.9999. The expanded uncertainties (k = 2) of temperature, pressure, and density measurements have been estimated to be less than 3 mK; 1.5 kPa ( MPa), 0.06% (7 MPa MPa), 0.1% (50 MPa MPa) , and 0.2% (p>150 MPa); and 0.11%, respectively. Four (p, ρ, T) measurements at the same temperatures and pressures as literature values have been conducted for comparisons. In addition, vapor pressures were measured at temperatures from 280 to 369 K. Furthermore, comparisons of available equations of state with the present measurements are reported.Paper presented at the 17th European Conference on Thermophysical Properties, September 5–8, 2005, Bratislava, Slovak Republic.     

Speed of Sound in Pure Water at Temperatures between 274 and 394 K and at Pressures up to 90 MPa

A newly designed experimental apparatus has been used to measure the speed of sound u in high-purity water on nine isotherms between 274 and 394 K and at pressures up to 90 MPa. The measurement technique is based on a traditional double-reflector pulse-echo method with a single piezoceramic transducer placed at unequal distances from two stainless steel reflectors. The transit times of an acoustic pulse are measured at a high sampling rate by a digital oscilloscope. The distances between the transducer and the reflectors were obtained at ambient temperature and pressure by direct measurements with a coordinate measuring machine. The speeds of sound are subject to an overall estimated uncertainty of 0.05 %. The acoustic data were combined with available values of density ρ and isobaric heat capacity c_p along one isobar at atmospheric pressure to calculate the same quantities over the whole temperature and pressure range by means of a numerical integration technique. These results were compared with those calculated from the IAPWS-95 formulation with corresponding relative deviations which are within 0.1%. Paper presented at the Fifteenth Symposium on Thermophysical Properties, June 22–27, 2003, Boulder, Colorado, U.S.A.     

Burnett PVT Measurements of Hydrogen and the Development of a Virial Equation of State at Pressures up to 100 MPa

PVT properties were measured for hydrogen by the Burnett method in the temperature range from 353 K to 473 K and at pressures up to 100 MPa. In the present Burnett method, the pressure measurement was simplified by using an absolute pressure transducer instead of a differential pressure transducer, which is traditionally used. The experimental procedures become easier, but the absolute pressure transducer is set outside the constant temperature bath because of the difficulty of its use in the bath, and the data acquisition procedure is revised by taking into account the effects of the dead space in the absolute pressure transducer. The measurement uncertainties in temperature, pressure, and density are 20 mK, 28 kPa, and 0.07 % to 0.24 % (k = 2), respectively. Based on the present data and other experimental data at low temperatures, a virial equation of state (EOS) from 220 K to 473 K and up to 100 MPa was developed for hydrogen with uncertainties in density of 0.15 % (k = 2) at P ≤ 15 MPa, 0.20 % at 15 MPa < P ≤ 40 MPa, and 0.24 % at P > 40 MPa, and this EOS shows physically reasonable behavior of the second and third virial coefficients. Isochoric heat capacities were also calculated from the virial EOS and were compared with the latest EOS of hydrogen. The calculated isochoric heat capacities agree well with the latest EOS within 0.5 % above 300 K and up to 100 MPa, while at lower temperatures, as the pressure increases, the deviations become larger (up to 1.5 %).     

Density and Viscosity Measurements of Dimethoxymethane and 1,2-Dimethoxyethane from 243 K to 373 K up to 20 MPa

Measurements of the density and viscosity of dimethoxymethane and 1,2-dimethoxyethane are reported over the temperature range from 243 K to 373 K and at pressures up to 20 MPa. The measurements were performed simultaneously using a vibrating-wire instrument operated in the forced mode of oscillation. The overall uncertainties of these results are 2.0% in viscosity and 0.2% in density. The measurements were correlated with a Tait-type equation for density and a hard-sphere model for viscosity. The maximum absolute deviation and the average absolute deviation (AAD) of the density measurements from the correlation for dimethoxymethane are 0.065% and 0.012%, respectively, and for 1,2-dimethoxyethane, are 0.16% and 0.044%. With regard to viscosity, the maximum absolute deviation and the AAD of the present results from the correlation for dimethoxymethane are 1.55% and 0.40%, respectively, and for 1,2-dimethoxyethane, are 1.05% and 0.26%. Comparisons of the experimental data and measurements from the literature with values calculated by the correlations at different temperatures and pressures are presented.     

Measurement of the (p, \rho,T) Properties for Pure Hydrocarbons at Temperatures up to 600 K and Pressures up to 200 MPa

The data available for the thermodynamic properties of propane, \(n\) -butane, and isobutane at temperatures above 440 K are outdated and show significant discrepancies with each other. The ambiguity associated with these data could be limiting to the development of any understanding related to the effects of mixing of these substances with other materials such as \(\text{ CO}_{2}\) , ammonia, and non-flammable or lower-flammable HFC refrigerants. In this study, the (p, \(\rho \) , T) properties of propane, \(n\) -butane, and isobutane were measured at temperatures ranging from (360 to 600) K and pressures ranging from (50 to 200) MPa. Precise measurements were carried out using a metal-bellows variable volumometer with a thermostatted air bath. The expanded uncertainties \((k = 2)\) in the temperature, pressure, and density measurements were estimated to be \(<\) 5 mK, 0.02 MPa, and 0.88 kg  \(\cdot \)  m \(^{-3}\) ( \(T\le 423\)  K, \(p<100\)  MPa), 0.76 kg  \(\cdot \)   \(\text{ m}^{-3}\) ( \(T\le 423\)  K, \(p\ge 100\)  MPa), 0.76 kg  \(\cdot \)   \(\text{ m}^{-3}\) ( \(T>423\)  K, \(p < 100\)  MPa), and 2.94 kg  \(\cdot \)   \(\text{ m}^{-3}\) ( \(T>423\)  K, \(p \ge 100\)  MPa), respectively. The data obtained throughout this study were systematically compared with the calculated values derived from the available equations of state. These models agree well with the measured data at higher temperatures up to 600 K, demonstrating their suitability for an effective and precise examination of the mixing effects of potential alternative mixtures.     

Density and Viscosity of the 1-Methylnaphthalene+2,2,4,4,6,8,8-Heptamethylnonane System from 293.15 to 353.15 K at Pressures up to 100 MPa

The dynamic viscosity of the binary mixture 1-methylnaphthalene+2,2,4,4,6,8,8-heptamethylnonane was measured in the temperature range 293.15 to 353.15K (in progressive 10K steps) at pressures of 0.1, 20, 40, 60, 80, and 100MPa. The composition of the system is described by nine molar fractions (0 to 1 in 0.125 progressive steps). The density was measured at pressures from 0.1 to 60MPa in progressive 5 MPa steps. The measurements of are used to determine the excess viscosity ^E and the excess activation energy of flow G ^E as a function of pressure, temperature, and composition. Some models have been used to represent the viscosity of this binary mixture.     

Isochoric Heat Capacities of Propane + Isobutane Mixtures at Temperatures from 280 to 420 K and at Pressures to 30 MPa

The isochoric heat capacity (c_v) and pressure–volume–temperature-composition (pvTx) properties were measured for propane + isobutane mixtures in the liquid phase and in the supercritical region. The expanded uncertainty (k = 2) of temperature measurements is estimated to be ±13 mK, and that of pressure measurements is ±8 kPa. The expanded relative uncertainty for c_v is ±3.2% for the liquid phase, increasing to ±4.8% for near-critical densities. The expanded uncertainty for density is estimated to be ±0.16%. The present measurements for {xC₃H₈ +(1−x)i-C₄H₁₀} with x = 0.0, 0.498, 0.756, and 1.0, were obtained at 659 state points at temperatures from 270 to 420 K and at pressures up to 30 MPa. The experimental data were compared with a published equation of state. Paper presented at the Fifteenth Symposium on Thermophysical Properties, June 22–27, 2003, 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.     

Primary Dielectric-Constant Gas Thermometry in the Range from 2.4 K to 26 K at PTB

New dielectric-constant gas-thermometry (DCGT) measurements were performed at PTB from 2.4 K to 26 K in order to establish a temperature scale with reduced uncertainty. The progress concerning the measurement of capacitance changes, temperature, and pressure compared with the results published in 1996 is described. This is the first step on the way to determine the Boltzmann constant at the triple point of water. At more than 20 temperatures, isotherms were measured and evaluated performing both single- and multi-isotherm fits. Based on this evaluation, a more accurate DCGT scale has been established that is compared with the constant-volume gas-thermometry scale NPL-75, being one basis of the International Temperature Scale of 1990. Coincidence has been found within only a few tenths of a millikelvin above 3.3 K. This gives, together with literature data, confidence with respect to thermodynamic temperature at this level. Emphasis is also given to the results obtained for the virial coefficients, especially below 3.3 K, where the 1996 DCGT results show strong deviations from the expected behavior. The new experimental data for the second virial coefficient are compared with ab initio calculations.     

Isochoric p-ρ-T Measurements on 1,1-Difluoroethane (R152a) from 158 to 400 K and 1,1,1-Trifluoroethane (R143a) from 166 to 400 K at Pressures to 35 MPa

The p--T relationships have been measured for 1,1-difluoroethane (R152a) and 1,1,1-trifluoroethane (R143a) by an isochoric method with gravimetric determinations of the amount of substance. Temperatures ranged from 158 to 400 K for R152a and from 166 to 400 K for R143a, while pressures were up to 35 MPa. Measurements were conducted on compressed liquid samples. Determinations of saturated liquid densities were made by extrapolating each isochore to the vapor pressure, and determining the temperature and density at the intersection. Published p--T data are in good agreement with this study. For the p--T apparatus, the uncertainty of the temperature is ±0.03 K, and for pressure it is ±0.01% at p>3 MPa and ±0.05% at p&#60;3 MPa. The principal source of uncertainty is the cell volume (28.5 cm³), which has a standard uncertainty of ±0.003 cm³. When all components of experimental uncertainty are considered, the expanded relative uncertainty (with a coverage factor k=2 and thus a two-standard deviation estimate) of the density measurements is estimated to be ±0.05%.     

Validation of Primary Water Dew-Point Generator for Methane at Pressures up to 6 MPa

In this paper, the validation of the water dew-point generator with methane as a carrier gas in the temperature range from \(-41\,^{\circ }\hbox {C}\) to \(+15\,^{\circ }\hbox {C}\) and at pressures up to 6 MPa is reported. During the validation, the generator was used with both nitrogen and methane to investigate the effect of methane on the generator and the chilled mirror dew-point meters. The effect of changing the flow rate and the dew-point temperature of the gas entering the generator, on the gas exiting the generator was investigated. As expected, methane at high pressures created hydrates in combination with water and low temperatures, thus limiting the temperature range of the generator to \(+8\,^{\circ }\hbox {C}\) to \(+15\,^{\circ }\hbox {C}\) at its maximum operating pressure of 6 MPa. A lower operating pressure extended the temperature range; for example, at 3 MPa, the temperature range was already extended down to \(-15\,^{\circ }\hbox {C}\) , and at 1 MPa, the range was extended down to \(-41\,^{\circ }\hbox {C}\) . The validation showed that, in its operating range, the generator can achieve with methane the same standard uncertainty of \(0.02\,^{\circ }\hbox {C}\) frost/dew point already demonstrated for nitrogen and air carrier gases.     

pρT Measurements of Polyethylene Glycol Dimethylethers Between 278.15 and 328.15 K at Pressures to 12 MPa

In this paper we present a new experimental apparatus designed to measure pressure–density–temperature (pT ) properties with a high-pressure vibrating tube densimeter. Data reliability has been verified by comparing our experimental results for methanol, n-heptane, toluene, and HFC-134a with literature data. In this work we also report new experimental densities from 278.15 to 328.15 K, and up to 12 MPa, of triethylene glycol dimethylether (TrEGDME) and tetraethylene glycol dimethylether (TEGDME). The isobaric thermal expansion coefficients, isothermal compressibility, and internal pressure have been calculated. The dependence of these properties on the length of polyethylene glycol dimethylether, CH₃O–((CH₂)₂O) _n –CH₃, is analyzed.     

Experimental Study of the Velocity of Sound in Liquid n‐Tetradecane at Temperatures from 303.15 to 433.15 K and Pressures to 100 MPa

The velocity of sound in liquid ntetradecane has been studied experimentally in the interval of temperatures from 303 to 433 K and pressures to 100 MPa. The maximum measurement error amounts to 0.1%. Experimental data on the velocity of sound in liquid ntetradecane in the region of the state variables p = 50–100 MPa and T > 373 K have been obtained for the first time. It has been shown that the new data demonstrate the reliability of the structure–property quantitative correlation proposed earlier for the acoustic quantity in the series of nalkanes.     

Measurement and Estimation of High-Vacuum Effective Thermal Conductivity of Polyimide Foam in the Temperature Range from 160 K to 370 K for Outer Space Applications

Polyimide foam (PF) is a low-thermal conductivity and lightweight material with high resistances against heat, protons, and UV irradiation. A new thermal insulation composed of PFs and multiple aluminized films (PF–MLI) has potential to be used in outer space as an alternative to conventional multilayer insulation (MLI). As fundamental numerical data, the effective thermal conductivity of PF in wide ranges of density and temperature need to be determined. In the present study, thermal-conductivity measurements were performed by both the periodic heating method and the guarded hot-plate method in the temperature range from 160 K to 370 K and the density range from 6.67  \(\mathrm{kg} \cdot \mathrm{m}^{-3}\) to 242.63  \(\mathrm{kg}\cdot \mathrm{m}^{-3}\) . The experiments were carried out in a vacuum and under atmospheric pressure. For confirmation of the validity of the present guarded hot-plate apparatus under atmospheric pressure, the effective thermal conductivity of the lowest-density PF was measured with the aid of the heat flow meter apparatus calibrated by the standard reference material (NIST SRM 1450c) in the temperature range from 303 K to 323 K. In order to cross-check the present experimental results, the temperature and density dependences of the effective thermal conductivity of PF were estimated by means of the lattice Boltzmann method based on a dodecahedron inner microscopic complex structure model which reflects a real 3D X-ray CT image of PF.     

The Viscosity of Aqueous Alkali-Chloride Solutions up to 623 K, 1,000 bar,and High Ionic Strength

An accurate viscosity (dynamic viscosity) model is developed for aqueous alkali-chloride solutions of the binary systems, LiCl–H₂O, NaCl–H₂O, and KCl–H₂O, from 273 K to 623 K, and from 1 bar to 1,000 bar and up to high ionic strength. The valid ionic strengths for the LiCl–H₂O, NaCl–H₂O, and KCl–H₂O systems are 0 to 16.7 mol · kg⁻¹, 0 to 6 mol · kg⁻¹, and 0 to 4.5 mol · kg⁻¹, respectively. Comparison of the model with about 4,150 experimental data points concludes that the average absolute viscosity deviation from experimental data in the above range is within or about 1 % for the LiCl–H₂O, NaCl–H₂O, and KCl–H₂O mixtures, indicating the model is of experimental accuracy. With a simple mixing rule, this model can be extrapolated to predict the viscosity of ternary aqueous alkali-chloride solutions, making it useful in reservoir fluid flow simulation. A computer code is developed for this model and can be obtained from the author: (maoshide@cugb.edu.cn).     

Isochoric p–ρ–T Measurements for 2,2-Dichloro-1,1,1-Trifluoroethane (R123) at Temperatures from 176 to 380 K and 1-Chloro-1,2,2,2-Tetrafluoroethane (R124) from 104 to 400 K at Pressures to 35 MPa

The p––T relationships were measured for 2,2-dichloro-1,1,1-trifluoroethane (R123) and 1-chloro-1,2,2,2-tetrafluoroethane (R124) by an isochoric method with gravimetric determinations of the amount of substance. Temperatures ranged from 176 to 380 K for R123 and from 104 to 400 K for R124, while pressures extended up to 35 MPa. Measurements were conducted on compressed liquid samples. Most published p––T data are in good agreement with this study. The uncertainty is 0.03 K for temperature and 0.01% for pressure at p>3 MPa and 0.05% at p<3 MPa. The principal source of uncertainty is the cell volume (28.5 cm³), with a standard uncertainty of 0.003 cm³. When all components of experimental uncertainty are considered, the expanded relative uncertainty (with a coverage factor k=2 and, thus, a 2-SD estimate) of the density measurements is estimated to be 0.05%.