Isobaric thermal expansivities of mixtures ofm-cresol and quinoline from 0.1 to 400 MPa at 303 to 503 K

Isobaric thermal expansivities, α _p (p, T), of five binary mixtures ofm-cresol with quinoline (0.1499, 0.2998, 0.5005, 0.6325, and 0.8501 mol fraction ofm-cresol) were measured in a pressure-controlled scanning calorimeter over the pressure range from just above the saturation vapor pressures to 400 MPa, and at 303.15, 353.15, 403.15, 453.15, and 503.15 K. Molecular association ofm-cresol with itself and ofm-cresol with quinoline exerts large effects on the pressure and temperature behavior of α _p isotherms. The extent of association changes significantly with conditions in all except the 2∶1 mixture as demonstrated by the crossing of isotherms at lower pressures as the temperature increases. In the 2∶1m-cresol quinoline mixture the extent of association is not perturbed significantly by temperature change and the mixture behaves like a simple liquid, exhibiting a unique crossing point of α _p isotherms.     

Volume ratios for n-pentane in the temperature range 278–338 K and at pressures up to 280 MPa

Volume ratios (V _P/V _0.1), and isothermal compressibilities calculated from them, are reported for n-pentane for seven temperatures in the range 278 to 338 K for pressures up to 280 MPa. The isobaric measurements were made with a bellows volumometer for which a novel technique had to be devised to enable measurements to be made above the normal boiling point (309.3 K). The accuracy of the volume ratios is estimated to be ±0.05 to 0.1% up to 303.15 K and ±0.1 to 0.2% from 313.15 to 338.15 K. The volume ratios are in good agreement with those calculated from recent literature data up to the maximum pressure of the latter, viz., 60 MPa.     

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.     

A vibrating tube flow densitometer for measurements with corrosive solutions at temperatures up to 723 K and pressures up to 40 MPa

A new version of a vibrating tube flow densitometer has been designed permitting measurements of density differences between two fluids in the temperature range from 298 to 723 K and at pressures up to 40 MPa. The instrument is equipped with a Pt/Rh20 vibrating tube (1.6-mm o.d.) and a Pt/Rh10 transporting tube (1.2-mm o.d.) permitting measurements with highly corrosive liquids. The period of oscillation of the tube is about 7.5 ms, with a typical stability better than 10⁻⁴% over about a 1-h period over the entire temperature interval. The calibration constantK at room temperature is about 530 kg·m⁻³·ms⁻², with a temperature coefficient of approximately −0.13kg·m⁻³·ms⁻²·K⁻¹, and is practically pressure independent. It can be determined by calibration with a reproducibility generally better than 0.1%. The instrument was tested with NaCl(aq) solutions in the temperature range from 373 to 690 K for density differences between sample and reference liquid ranging from 200 to 2 kg·m⁻³; the corresponding errors are believed to be below 0.3 and 5%, respectively. A highly automated temperature control maintains the temperature of the tube stable to within ±0.02 K.     

Thermal properties of superheated potassium vapor at temperatures up to 2150 k and pressures up to 10 MPa

Based on experimental data on thermalproperties, we have constructed tables of thermodynamic fonctions for superheated potassium vapor, and these include the values of the specific volume v, enthalpy h, entropy s, isobaric C _p and isochronous C _v heat capacities, speed of sound A, coefficient of compressibility Z, and they encompass areas of parameters related to pressure P=0.1–10.0 MPa and temperature T=1075–2150 K.Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 60, No. 3, pp. 467–473, March, 1991.     

Thermodynamic functions of ScVO<Subscript>4</Subscript> at temperatures from 0 to 350 K

The heat capacity of ScVO₄ has been determined by adiabatic calorimetry at temperatures from 14.52 to 347.13 K, and smoothed heat capacity data have been used to evaluate its thermodynamic functions (entropy, enthalpy increment, and reduced Gibbs energy). At 298.15 K, the thermodynamic functions of scandium orthovanadate are C _p ⁰(298.15 K) = 110.5 ± 0.1 J/(mol K), S ⁰(298.15 K) = 110.9 ± 0.1 J/(mol K), H ⁰(298.15 K) − H ⁰(0) = 18.53 ± 0.01 kJ/mol, and Φ⁰(298.15 K) = −[G ⁰(298.15 K)/298.15] = 48.75 ± 0.12 J/(mol K). The calculated Gibbs energy of formation of scandium orthovanadate from its constituent elements is Δ_f G ⁰(ScVO₄, 298.15 K) = −1644.0 ± 2.2 kJ/mol.     

Speed-of-Sound Measurements in n-Nonane at Temperatures between 293.15 and 393.15 K and at Pressures up to 100 MPa

Speed-of-sound measurements in liquid phase n-nonane (C₉H₂₀) are reported along six isotherms between 293.15 and 393.15 K and at pressures up to 100 MPa. The experimental technique is based on a double reflector pulse-echo method. The acoustic path lengths were obtained by comparison with measurements carried out at atmospheric pressure and ambient temperature in pure water. The values of the speed of sound are characterized by an overall estimated uncertainty of less than 0.2 %. These results were compared with literature values and with predictions of a dedicated equation of state.Paper presented at the Seventeenth European Conference on Thermophysical Properties, September 5–8, 2005, Bratislava, Slovak Republic.     

Viscosity of twelve hydrocarbon liquids in the temperature range 298–348 K at pressures up to 110 MPa

New experimental data on the viscosity of 12 organic liquids are presented at temperatures of 25, 30, 50, and 75°C and at pressures up to 110 MPa. The liquids measured are five n-alkanes (C₆, C₇, C₈, C₁₀, C₁₂), cyclohexane, and six aromatic hydrocarbons (benzene, toluene, ethylbenzene, o-, m-, p-xylenes). The measurements were performed using a torsionally vibrating crystal method on a relative basis with an uncertainty less than 2%. A linear relationship between fluidity and molar volume, which is predicted from the hard-sphere theory, fails at pressures above 50 MPa. The rough hard-sphere model proposed by Chandler provides a reasonable representation of the data for aromatic hydrocarbons, while for n-alkanes the agreement is not satisfactory because of an aspherical shape of molecules. The viscosity data can be correlated well with the molar volume by a free-volume expression and also can be represented as a function of pressure by a similar expression to the Tait equation.     

A thermodynamic property formulation for nitrogen from the freezing line to 2000 K at pressures to 1000 MPa

A new fundamental equation explicit in Helmholtz energy for thermodynamic properties of nitrogen from the freezing line to 2000 K at pressures to 1000 MPa is presented. A new vapor pressure equation and equations for the saturated liquid and vapor densities as functions of temperature are also included. The techniques used for development of the fundamental equation are those reported in a companion paper for ethylene. The fundamental equation and the derivative functions for calculating internal energy, enthalpy, entropy, isochoric heat capacity (C _v), isobaric heat capacity (C _p), and velocity of sound are also included in that paper. The property formulation using the fundamental equation reported here may generally be used to calculate pressures and densities with an uncertainty of ±0.1%, heat capacities within ± 2%, and velocity of sound values within ±2%. The fundamental equation is not intended for use near the critical point.Paper presented at the Ninth Symposium on Thermophysical Properties, June 24–27, 1985, Boulder, Colorado, U.S.A.     

Second-Order Derivatives of the Gibbs Energy for Liquid Mixtures of Alcohol + Heptane at Pressures up to 100 MPa

Second-order thermodynamic derivative properties, such as isobaric thermal molar expansions, isothermal and adiabatic molar compressibilities, and isochoric molar heat capacities of (ethanol, decan-1-ol, 2-methyl-2-butanol) +  heptane mixtures at pressures up to 100 MPa and in the temperature range from 293.15 K to 318.15 K were derived from experimental speed-of-sound u(T, p), density ρ(T, p = 0.1 MPa), and isobaric heat-capacity C _p (T, p = 0.1 MPa) data using appropriate thermodynamic relations. Excess values for the given properties were calculated according to the criterion of thermodynamic ideality of a mixture (Douhéret et al., Chem. Phys. Chem. 2, 148 (2001)), i.e., assuming that the chemical potential of component i in the ideal liquid mixture is equal to the chemical potential of component i in the mixture of perfect gases. The deviations from ideality for the mixtures under test have been explained in terms of the self-association of alcohols in solution which produces a strong departure from random mixing, the change in the non-specific interactions during mixing, and the packing effects.     

<Emphasis Type="Italic">PVT</Emphasis> Relationships of Binary Mixtures of Indole with 2-Methylnaphthalene and Biphenyl at 333.15 K and Pressures up to 270 MPa

PVT relationships of two binary mixtures of indole with 2-methylnaphthalene and with biphenyl have been measured at 333.15 K and at pressures up to 270 MPa or up to near the freezing pressure of each mixture. The compositions in mole fraction of indole were set to be 0.2500, 0.5000, and 0.7500 for both systems. PVT relationships of indole (at 343.15 K and 353.15 K), 2-methylnaphthane (at 333.15 K and 343.15 K), and biphenyl (at 353.15 K and 363.15 K) under pressure and those for the binary mixtures at 0.1 MPa in the temperature range from 293.15 K to 363.15 K were also measured. PVT data were analyzed with the use of the Tait equation and Carnahan–Starling–van der Waals (CS–vdW) equation. It was found that both the equations can be used to represent the experimental PVT relationships for the pure compounds and the binary mixtures with an average absolute deviations of 0.04% for the Tait equation and 0.29% for the CS–vdW equation. As for mixture density calculations with the CS–vdW equation, the effect of mixing rules was investigated.     

Thermal conductivity and heat capacity of liquid toluene at temperatures between 255 and 400 K and at pressures up to 1000 MPa

The thermal conductivity and heat capacity c _p of liquid toluene have been measured by the ac-heated wire method up to 1000 MPa in the temperature range from 255 to 400 K. The total error of thermal conductivity measurements is estimated to be about 1 %, and the precision 0.3 %. The heat capacity per unit volume, pc _p, obtained directly from the experiment is uncertain within 2 or 3%. The vs p isotherms are found to cross one another at approximately 700 MPa. The minima in the pressure (or volume) dependence of c_p of toluene are evident at all temperatures investigated.     

PVT Measurements for Pure Ethanol in the Near-Critical and Supercritical Regions

The PVT properties of pure ethanol were measured in the near-critical and supercritical regions. Measurements were made using a constant-volume piezometer immersed in a precision thermostat. The uncertainty of the density measurements was estimated to be 0.15%. The uncertainties of the temperature and pressure measurements were, respectively, 15 mK and 0.05%. Measurements were made along various near-critical isotherms between 373 and 673 K and at densities from 91.81 to 497.67 kg · m⁻³. The pressure range was from 0.226 to 40.292 MPa. Using two-phase PVT results, the values of the saturated-liquid and -vapor densities and the vapor pressure for temperatures between 373.15 and 513.15 K were obtained by means of an analytical extrapolation technique. The measured PVT data and saturated properties for pure ethanol were compared with values calculated from a fundamental equation of state and correlations, and with experimental data reported by other authors. The values of the critical parameters (T _C,P _C,ρ _C) were derived from the measured values of saturated densities and vapor pressure near the critical point. The derived values of the saturated densities near the critical point for ethanol were interpreted in term of the “complete scaling” theory.     

A thermodynamic property formulation for ethylene from the freezing line to 450 K at pressures to 260 MPa

A new thermodynamic property formulation based upon a fundamental equation explicit in Helmholtz energy of the form A=A(, T) for ethylene from the freezing line to 450 K at pressures to 260 MPa is presented. A vapor pressure equation, equations for the saturated liquid and vapor densities as functions of temperature, and an equation for the ideal-gas heat capacity are also included. The fundamental equation was selected from a comprehensive function of 100 terms on the basis of a statistical analysis of the quality of the fit. The coefficients of the fundamental equation were determined by a weighted least-squares fit to selected P--T data, saturated liquid and saturated vapor density data to define the phase equilibrium criteria for coexistence, C _v data, velocity of sound data, and second virial coefficients. The fundamental equation and the derivative functions for calculating internal energy, enthalpy, entropy, isochoric heat capacity (C _v), isobaric heat capacity (C _p), and velocity of sound are included. The fundamental equation reported here may be used to calculate pressures and densities with an uncertainty of ±0.1%, heat capacities within ±3 %, and velocity of sound values within ±1 %, except in the region near the critical point. The fundamental equation is not intended for use near the critical point. This formulation is proposed as part of a new international standard for thermodynamic properties of ethylene.Paper presented at the Ninth Symposium on Thermophysical Properties, June 24–27, 1985, Boulder, Colorado, U.S.A.     

Molar heat capacity at constant volume for air from 67 to 300 K at pressures to 35 MPa

Measurements of the molar heat capacity at constant volumeC _v for air were conducted with an adiabatic calorimeter. Temperatures ranged from 67 to 300 K, and pressures ranged up to 35 MPa. Measurements were conducted at 17 densities which ranged from gas to highly compressed liquid states. In total, 227C _v values were obtained. The air sample was prepared gravimetrically from research purity gases resulting in a mole fraction composition of 0.78112 N₂ + 0.20966 O₂ + 0.00922 Ar. The primary sources of uncertainty are the estimated temperature rise and the estimated quantity of substance in the calorimeter. Overall, the uncertainty (± 2) of theC _v values is estimated to be less than ± 2% for the gas and ±0.5% for the liquid.Nomenclature C _v Molar heat capacity at constant volume, J · mol^–1 K^–1 - C _v ⁰ Molar heat capacity in the ideal-gas state, J · mol^–1 · K^–1 - V _bomb Volume of the calorimeter containing sample, cm³ - P Pressure, MPa - P Pressure rise during a heating interval, MPa - T Temperature, K - T ₁,T ₂ Temperature at start and end of heating interval, K - T Temperature rise during a heating interval, K - Q Calorimetric heat energy input to bomb and sample, J - Q ₀ Calorimetric heat energy input to empty bomb, J - N Moles of substance in the calorimeter, mol - Fluid density, mol · dm^–3     

Role of Ti<Subscript>3</Subscript>Al/silicides on tensile properties of Timetal 834 at various temperatures

Extremely fine coherent precipitates of ordered Ti₃Al and relatively coarse incoherent precipitates of S₂ silicide exist together in the near α-titanium alloy, Timetal 834, in the dual phase matrix of primary α and transformed β. In order to assess the role of these precipitates, three heat treatments viz. WQ, WQ-A and WQ-OA, were given to have no precipitates, Ti₃Al and silicide and only silicide precipitates in the respective conditions. Tensile properties in the above three heat treated conditions were determined at room temperature, 673 K and 873 K. It was observed that largely Ti₃Al precipitates were responsible for increase in the yield strength and decrease in ductility in this alloy.     

Thermal conductivity of air in the range 312 to 373 K and 0.1 to 24 MPa

We have used the transient hot-wire technique to make absolute measurements of the thermal conductivity of dry, CO₂-free air in the temperature range from 312 to 373 K and at pressures of up to 24 MPa. The precision of the data is typically ±0.1%, and the overall absolute uncertainty is thought to be less than 0.5%. The data may be expressed, within their uncertainty, by polynomials of second degree in the density. The values at zero-density agree with other reported data to within their combined uncertainties. The excess thermal conductivity as a function of density is found to be independent of the temperature in the experimental range. The excess values at the higher densities are lower than those reported in earlier work.Nomenclature Thermal conductivity, mW · m^–1 · K^–1 - Density, kg · m^–3 - C _p Specific heat capacity at constant pressure, J · kg^–1 · K^–1 - T Absolute temperature, K - q Heat input per unit wire length, W · m^–1 - t Time, s - K(=/C _p) Thermal diffusivity, m² · s^–1 - a Wire radius, m - Euler's constant (=0.5772 ) - p _c Critical pressure, MPa - T _c Critical temperature, K - _c Critical density, kg · m^–3 - R Gas constant (=8.314 J · mol^–1 · K^–1) - V _c Critical volume, m³ · mol^–1 - Z _c(=p _c V _c/RT _c) Critical compressibility factor     

Special Equations of State for Methane,Argon, and Nitrogen for the Temperature Range from 270 to 350 K at Pressures up to 30 MPa

In order to describe the thermodynamic behavior of methane, argon, and nitrogen in the so-called “natural-gas region,” namely, from 270 to 350 K at pressures up to 30 MPa as accurate as possible with equations of a very simple form, new equations of state for these three substances have been developed. These equations are in the form of a fundamental equation in the dimensionless Helmholtz energy; for calculating the pressure or the density, the corresponding equations explicit in pressure are also given. The residual parts of the Helmholtz function representing the behavior of the real gas contain 12 fitted coefficients for methane, 8 for argon, and 7 for nitrogen. The thermodynamic relations between the Helmholtz energy and the most important thermodynamic properties and the needed derivatives of the equations are explicitly given; to assist the user there is also a table with values for computer-program verification. The uncertainties when calculating the density ρ, the speed of sound w, the isobaric specific heat capacity c _p, and the isochoric specific heat capacity c _v are estimated as follows. For all three substances it is Δρ/ρ≤±0.02 % for p≤ 12 MPa and Δρ/ρ ≤ ±0.05% for higher pressures. For methane it is Δw/w≤±0.02% for p≤10 MPa and Δw/w≤+-0.1% for higher pressures; for argon it is Δw/w?-0.1 % for p≤ 7 MPa, Δw/w≤±0.3 % for 7 <p≤30 MPa; and for nitrogen it is Δw/w≤±0.1% for p≤1.5 MPa and Δw/w±0.5% for higher pressures. For all three substances it is Δc _p/c _p≤±1 % and ΔC _v/C _v≤±1 % in the entire range.     

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.     

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.