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A vibrating wire instrument, in which the wire was clamped at both ends, was used to measure the viscosity of {xCO2 + (1  x)CH4} with x = 0.5174 with a combined uncertainty of 0.24 μPa · s (a relative uncertainty of about 0.8 %) at temperatures T between (229 and 348) K and pressures p from (1 to 32) MPa. The corresponding mass density ρ, estimated with the GERG-2008 equation of state, varied from (20 to 600) kg · m−3. The measured viscosities were consistent within combined uncertainties with data obtained previously for this system using entirely different experimental techniques. The new data were compared with three corresponding states-type models frequently used for predicting mixture viscosities: the Extended Corresponding States (ECS) model implemented in REFPROP 9.1; the SUPERTRAPP model implemented in MultiFlash 4.4; and a corresponding states model derived from molecular dynamics simulations of Lennard Jones fluids. The measured viscosities deviated systematically from the predictions of both the ECS and SUPERTRAPP models with a maximum relative deviations of 11 % at (229 K, 600 kg · m−3) and −16 % at (258 K, 470 kg · m−3), respectively. In contrast, the molecular dynamics based corresponding states model, which is predictive for mixtures in that it does not contain any binary interaction parameters, reproduced the density and temperature dependence of the measured viscosities well, with relative deviations of less than 4.2 %.  相似文献   

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Measurements of the critical parameters for {xNH3 + (1 ? x)H2O} with x = (0.9098, 0.7757, 0.6808) were carried out by using a metal-bellows variable volumometer with an optical cell. The expanded uncertainties (k = 2) in temperature, pressure, density, and composition measurements have been estimated to be less than 3.2 mK, 3.2 kPa, 0.3 kg · m?3, and 8.8 · 10?4, respectively. In each mole fraction, the critical temperature Tc was first determined on the basis of the intensity of the critical opalescence. The critical pressure pc and critical density ρc were then determined as the point at which the meniscus disappears on the isotherm at T = Tc. The expanded uncertainties (k = 2) in the present critical parameters have also been estimated. Comparisons of the present values with the literature data as well as the calculated values afforded using the equation of state are also presented.  相似文献   

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Measurements of the isobaric specific heat capacity of {xH2O + (1 ? x)NH3} with x = (0.0000, 0.1566, 0.1597, 0.3030, 0.3048, 0.4956, 0.7061, and 0.8489) were carried out by the calorimeter with the thermal relaxation method, which we have developed, at T = (280, 300, 320, and 360) K over the pressure range from (0.1 to 15) MPa. The comparison of the present cp values with the literature data as well as the calculated cp values by the equations of state (EoS) is presented. The behaviour of the present cp values are correlated as a function of temperature, and mole fraction, at p = 5 MPa.  相似文献   

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A flow mixing calorimeter, followed by a vibrating tube densimeter, has been used to measure excess molar enthalpies HmEand excess molar volumesVmE of {xCO2 +  (1   x)SF6}. Measurements over a range of mole fraction x have been made at the temperatures T =  302.15 K and T =  305.65 K at the pressures (3.76, 5.20, 6.20, and 7.38) MPa. The lowest pressure 3.76 MPa is close to thecritical pressure of SF6 and the highest pressure 7.38 MPa is close to the critical pressure of CO 2. Measurements atx =  0.5 have been made over the pressure range (2.5 to 10.0) MPa at the temperature 301.95 K. Some of the measurements are very close to the critical locus of the mixture. The measurements are compared with the Patel–Teja equation of state which reproduces the main features of the excess function curves as well as it does for similar measurements on {xCO2 +  (1   x)C2H6} and{xCO2 +  (1   x)C2H4} . The equation was used to calculate residual enthalpies and residual volumes for the pure components and for the mixture, and inspection of the way these combine to give excess enthalpies and volumes assisted the interpretation of the pressure scan measurements.  相似文献   

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Measurements of (p, ρ, T) for{xNH3 +  (1   x)H2O} at x =  (1.0000, 0.8374, 0.6005, and 0.2973) and at specified temperatures and pressures in the compressed liquid phase were carried out with a metal-bellows variable volumometer between T =  310 K and T =  400 K at pressures up to 17 MPa. The results cover the high-density region from ρ =  345 kg · m  3 for x =  1.0000 to ρ =  878 kg · m   3for x =  0.2973. The experimental uncertainties at a 95 per cent confidence interval in temperature T, pressure p, density ρ, and mole fraction x were estimated to be less than  ± 11 mK,  ± 2.6 kPa,  ± 2.1 · 10   3. ρ, and  ± 1.8 · 10  3· x, respectively. A detailed comparison of the density values with literature data as well as with an equation of state proposed by Tillner-Roth and Friend is also reported.  相似文献   

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In this article, the experimental data of excess molar enthalpies HmE and excess molar volumes VmE are presented for a set of 20 binary mixtures comprised of the first four butyl alkanoates (methanoate to butanoate) and five α,ω-dichloroalkanes (1,2-dichloroethane to 1,6-dichlorohexane), obtained at atmospheric pressure and at a temperature of 298.15 K. The results indicate the existence of specific interactions between both kinds of compounds resulting in exothermic processes for most mixtures, except for those containing butyl methanoate which give rise to net endo/exothermic effects. The VmE are positive for mixtures of (butyl esters + 1,2-dichloroethane or 1,3-dichloropropane) and negative for the remaining ones. The change in HmE with the dichloroethane chain length for a same ester is regular although the VmE presents an irregular variation. It can, therefore, be deuced from this that the mixing process involves both effects, exothermic/endothermic and expansion/contraction, simultaneously. The behaviour of the mixtures is interpreted on the basis of the results observed and attributed to different effects taking place among the molecules studied.To improve application of the UNIFAC model using the version of Dang and Tassios, average values were recalculated again for parameters of the ester/chloride interaction, distinguishing, during its application, the functional group of the acid part of the ester. In spite of this, the model does not adequately reproduce the systems’ behaviour.  相似文献   

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Relative permittivities of { CH3OH  +  CH3OCH2(CH2OCH2)3CH2OCH3(2,5,8,11,14-pentaoxapentadecane, tegdme)} at temperatures from 283.15 K to 323.15 K and atmospheric pressure, were measured over the whole composition range. Experimental relative permittivities were fitted by a polynomial function in mole fraction. Values of relative permittivity were measured using a HP4284A precision LCR Meter together with the measuring cell HP16452A at 1 MHz. Relative permittivity increments were determined from experimental data and fitted to a variable-degree polynomial function. Different theoretical models were used to predict the permittivity of this mixture. The predictions are better when the volume change on mixing is considered.  相似文献   

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Comprehensive (p, ρ, T) measurements on two binary mixtures (0.10 CO2 + 0.90 N2 and 0.15 CO2 + 0.85 N2) were carried out in the gas phase at seven isotherms between (250 and 400) K and pressures up to 20 MPa using a single sinker densimeter with magnetic suspension coupling. A total of 69 (p, ρ, T) data for the first mixture and 69 (p, ρ, T) data for the second are presented in this article. The uncertainty in density was estimated to be (0.02 to 0.15)%, while the uncertainty in temperature was 3.9 mK and the uncertainty in pressure was less than 0.015% (coverage factor k = 2). Experimental results were compared with densities calculated from the GERG equation of state and with data reported by other authors for similar mixtures. Results yielded that, while deviations between experimental data and values calculated from the GERG equation were lower than 0.05% in density for low pressures, the relative error at high pressures and low temperatures increased to about (0.2 to 0.3)%. The main aim of this work was to contribute to an accurate density data base for CO2/N2 mixtures and to check or improve equations of state existing for these binary mixtures.  相似文献   

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Comprehensive (p, ρ, T) measurements on cyclohexane, toluene, and ethanol were carried out in the homogeneous liquid phase for temperatures from 233.15 K to 473.15 K at pressures up to 30 MPa. The measurements were performed by using an accurate single-sinker densimeter based on the Archimedes’ buoyancy principle. The total uncertainty of the measurements in density was estimated to be 0.015% (level of confidence 95%). Based on the experimental results, accurate correlation equations for the density of the three liquids have been established; their uncertainty is 0.020%. Comparisons with previous results of other experimentalists and with values calculated from current equations of state are presented. In this context it is also shown that the density of a liquid can vary slightly depending on the batch of the liquid used for the measurements. The purpose of this work was to provide accurate correlation equations for the densities of the three selected liquids so that these liquids can be used as density reference liquids for the calibration of densimeters and, in particular, for the calibration of vibrating-tube densimeters.  相似文献   

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