Viscosities of nonelectrolyte liquid mixtures. I. binary mixtures containing p-dioxane

Viscosity measurements are reported for p-dioxans with cyclohexane, n-hexane, benzene, toluene, carbon tetrachloride, tetrachloroethane, chloroform, pentachloroethane, and ethyl acetate at 303.15 K. Excess Gibbs energies of activation G ^*E of viscous flow have been calculated with Eyring's theory of absolute reaction rates. The deviations of the viscosities from a linear dependence on the mole fraction and values of G ^*E for binary mixtures have been explained in terms of molecular interactions between unlike pairs. The Prigogine-Flory-Patterson theory has been used to estimate the excess viscosity, ln , and corresponding enthalpy ln _H, entropy ln _S, and free volume ln _v terms for binary mixtures of p-dioxane with cyclohexane, n-hexane, benzene, toluene, carbon tetrachloride, and chloroform. Estimates of excess viscosities from this theory for p-dioxane with benzene, toluene, and carbon tetrachloride are good, while for the other three mixtures they are poor. The local-composition thermodynamic model of Wei and Rowley estimates the excess viscosity quite well even for p-dioxane mixtures with cyclohexane and n-hexane.     

Viscosity of nonelectrolyte liquid mixtures. III Binary mixtures of methyl methacrylate with hydrocarbons,haloalkanes, and alkylamines

Measurements of the viscosity and the density are reported for 14 binary mixtures of methyl methacrylate (MMA) with hydrocarbons, haloalkanes, and alkylamines at 303.15 K. The viscosity data have been correlated with equations of Grunberg and Nissan, of McAllister, and of Auslaender. Furthermore, excess viscosity In and excess Gibbs energy of activationG* ^E of viscous flow have been calculated and have been used to predict molecular interactions occurring in present binary mixtures. The results show the existence of specific interactions in MMA + aromatic hydrocarbons, MMA + haloalkanes, and MMA + primary amines.     

Viscosities of nonelectrolyte liquid mixtures. II. Binary mixtures ofn-hexane with alkanoates and bromoalkanoates

Viscosity measurements are reported for mixtures of ethyl ethanoate, ethyl propionate, ethyl butyrate, ethyl-2-bromopropionate, ethyl-3-bromopropionate, ethyl-2-bromobutyrate, and ethyl-4-bromobutyrate withn-hexane at 303.15 K. The viscosity data have been correlated with equations of Grunberg and Nissan, of McAllister, and of Auslaender. Furthermore, excess Gibbs energies of activationG ^*E of viscous flow have been calculated with Eyring's theory of absolute reaction rates and values ofG ^*E for the present binary mixtures have been explained in terms of the dipole-dipole interaction in alkanoates and the intramolecular Br...O interaction in bromoalkanoates.     

Viscosities of nonelectrolyte liquid mixtures. II. Binary and quaternary systems of some n-alkanes

This paper is the second in a series of viscosity and density studies on multicomponent mixtures of n-alkanes from 303 to 338 K. Reported here are the results of binary mixtures of n-tetracosane + n-octane as well as quaternary mixtures of n-tetracosane + n-octane + n-decane + n-hexane at 318.16, 328.16, and 338.16 K. Viscosities were determined using a standard U-tube Ostwald viscometer, and densities were determined using a flask-type pycnometer. Empirical relations tested include the Grunberg and Nissan equation and the method of corresponding states. In addition, comparisons were made regarding the behavior of this quaternary system and homologous binary mixtures of n-hexadecane + n-octane and n-tetracosane + n-octane at the same temperatures.     

Viscosities and Excess Molar Volumes of Binary Mixtures of Alkyl Acetates with Di-, Tri-, and Tetrachloroethane

The excess molar volume V ^E, viscosity deviation , excess viscosity ^E, and excess Gibbs energy of activation G*^E of viscous flow have been investigated from density and viscosity measurements of nine binary mixtures of methyl acetate, ethyl acetate, and amyl acetate with dichloroethane, trichloroethane, and tetrachloroethane at 303.15 K. The results were fitted to polynomials of variable degree. The viscosity data have been correlated with the equations of Grunberg and Nissan, Hind, McLaughlin, and Ubbelohde, Tamura and Kurata, Katti and Chaudhri, McAllister, Heric, and Auslaender. The results have been analyzed in terms of molecular interactions between alkyl acetates and chloroethanes.     

Viscosities of nonelectrolyte liquid mixtures. III. Selected binary and quaternary mixtures

This paper is the final in a series of three viscosity and density studies of pure n-alkanes and selected binary and quaternary mixtures. A standard U-tube viscometer was used for viscosity measurements, and a Pyrex flask-type pycnometer was used for density determinations. Results are given here for pure alkane and selected binary mixtures of n-tetradecane + n-octane, for selected quaternary mixtures of n-hexadecane + n-dodecane + n-decane + n-hexane, and for pure and selected quaternary mixtures of n-hexadecane + n-dodecane + n-nonane + n-heptane at 303.16 and 308.16 K. The principle of congruence was tested, as was the Grunberg and Nissan equation, as they have been shown to be useful as prediction techniques for other n-alkane binary mixtures. Comparisons were made between the two groups of quaternary alkane mixtures and the binary n-tetradecane + n-octane mixtures of the same pseudo composition to understand better the dependence of mixture viscosities on the composition parameter.     

Viscosity of binary mixtures. IV. Triethylamine with alkanes and monoalkylamines at 303.15 and 313.15 K

Viscosities and densities of seven binary mixtures of n-hexane, n-octane, isooctane, n-propylamine, n-butylamine, n-hexylamine, and n-octylamine with triethylamine have been measured at 303.15 and 313.15 K. Deviations of viscosities from a linear dependence on the mole fraction and values of excess Gibbs energy of activation G ^*E of viscous flow are attributable to the H-bonding and to the size of the alkylamine and alkane molecules.     

Viscosities of nonelectrolyte liquid mixtures. I. n-hexadecane + n-octane

Viscosities and densities of the n-alkanes, hexane, heptane, octane, nonane, decane, dodecane, tetradecane, hexadecane, and tetracosane, were measured for temperatures from 303 to 338 K. Viscosities were measured using a standard Utube Ostwald viscometer; a pycnometer was used to measure both pure alkane and mixture densities. Results for the binary system n-hexadecane + n-octane at 318.16, 328.16, and 338.16 K are presented here, and comparisons with selected correlating equations are made.     

Viscosity and density of liquid mixtures ofn-alkanes with squalane

Viscosity and density measurements are reported for binary liquid mixtures ofn-butane andn-hexane with squalane in the temperature range from 273 to 333 K. The viscosity measurements have been carried out by using a capillary viscometer calibrated with standard liquids. that is. JS5, JSIO, JS20, and water. The uncertainty in the viscosity data was estimated to be ± 1.7%. The density needed for the calculation of the viscosity has been measured by using a glass pycnometer within an accuracy of ±0.04%. In the prediction of the viscosity, the scheme of Assael et al. fails for mixtures of this type differing greatly in size.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994. Boulder, Colorado, U.S.A.     

Transport properties of nonelectrolyte liquid mixtures—VI. Viscosimetric study of binary mixtures of hexafluorobenzene with aromatic hydrocarbons

Viscosity coefficients for binary mixtures of hexafluorobenzene with benzene, toluene, para-xylene, and mesitylene have been measured along the saturation line at temperatures from 15 to 120°C using specially designed capillary viscometers. Densities were measured using a pyknometer and volume-change apparatus. Deviations of the viscosities from a rectilinear dependence on mole fraction are consistent with enhanced interactions between unlike species, which increase with increasing number of methyl groups on the aromatic hydrocarbon and decrease with increasing temperature. The application of the Grunberg and Nissan equation, the Hildebrand equation, and energy of activation theories to these results is examined.     

Transport properties of nonelectrolyte liquid mixtures. X. Limiting mutual diffusion coefficients of fluorinated benzenes inn-hexane

Mutual diffusion coefficients.D ₁₂. have been measured for benzene, seven fluorinated benzenes. and octafluorotoluene diffusing inn-hexane at trace concentration in the temperature range 213.2–333.2 K by the chromatographic peak-broadening, technique with an estimated accuracy of ±2.5% These results are compared with the predictions of rough hard-sphere theory (RHS). The results are reproducible to within ±10% with the translational rotational coupling factor equal to the value for the solvent. The activation energy of diffusionE _D, computed from Arrhenius plots. is almost constant for these solutes.     

Transport properties of nonelectrolyte liquid mixtures—VII. Viscosity coefficients for isooctane and for equimolar mixtures of isooctane + n-octane and isooctane + n-dodecane from 25 to 100°C at pressures up to 500 MPa or to the freezing pressure

Changes in the high-pressure self-centering falling-body viscometer system, and the new automated data logging system, are described. Viscosity coefficient measurements made with an estimated accuracy of ± 2 % are reported for isooctane and for equimolar mixtures of isooctane + n-octane and isooctane + n-dodecane at 25, 50, 75, and 100°C at pressures up to 500 MPa or to the freezing pressure. The pressure dependence of the results is found to be represented equally well by the recent equation of Makita and by a free-volume form of equation. The Grunberg and Nissan equation gives a good fit to the mixture viscosity coefficient data.     

Empirical and Semi-theoretical Methods for Predicting the Viscosity of Binary <Emphasis Type="Italic">n</Emphasis>-Alkane Mixtures

In this study, empirical and semi-theoretical methods for predicting the viscosity of binary mixtures of n-alkanes are presented at atmospheric pressure and in the temperature range from 288 to 333 K. In the empirical viscosity calculation method, a modified version of the Andrade equation and a simple mixture rule are used. The proposed semi-theoretical method employs both the Enskog’s hard-sphere theory for dense fluids and the principle of corresponding states. The viscosities of binary mixtures of n-heptane with n-hexane and n-nonane covering different compositions were calculated using these methods which require only critical properties and the normal boiling point as input data. The predictions were compared with accurate experimental data in the literature. Highly satisfactory results were obtained. The percent average absolute deviations amount to 1.2 and 0.9% utilizing the empirical and semi-theoretical viscosity methods, respectively, for 27 data points. Paper presented at the Fifteenth Symposium on Thermophysical Properties, June 22–27, 2003, Boulder, Colorado, U.S.A.     

Viscosity of Binary Mixtures of Alkyl Acetates with Hexane, Tetrachloromethane, and Trichloromethane

The viscosity for binary mixtures of methyl acetate (MA), ethyl acetate (EA), n-amyl acetate (nAA), isoamyl acetate (iAA), decyl acetate (DeA), and dodecyl acetate (DoA) with hexane and of MA, EA, nAA, and iAA with tetrachloromethane and trichloromethane has been measured at 303.15 K over the entire range of composition. The viscosity data have been correlated with the equations of Grunberg and Nissan; Hind, McLaughlin, and Ubbelohde; Tamura and Kurata; Katti and Chaudhri; McAllister; Heric and Brewer; and Auslaender. The viscosity deviations and excess Gibbs energy of activation G*^E of viscous flow based on Eyring's theory have been calculated. The results have been analyzed in terms of disruption of dipolar association of alkyl acetate and molecular interaction between alkyl acetate and chloromethane.     

Viscosity and thermal conductivity of binary n-heptane + n-alkane mixtures

New absolute measurements of the viscosity of binary mixtures of n-heptane with n-hexane and n-nonane are presented. The measurements, performed in a vibrating-wire instrument, cover a temperature range 290–335 K and pressures up to 75 MPa. The concentrations studied are 40 and 70% by weight of n-heptane. The accuracy of the reported viscosity data is estimated to be ±0.5%. The present measurements, together with other n-heptane + n-alkane viscosity and thermal-conductivity measurements, are used to develop a consistent semiempirical scheme for the correlation and prediction of these mixture properties from those of the pure components.     

Viscosity and Liquid Density of Asymmetric Hydrocarbon Mixtures

Although a large body of viscosity data exists for simple mixtures of lighter n-alkanes, available information for heavy or asymmetric systems is scarce. Experimental measurements of viscosity and liquid densities were performed, at atmospheric pressure, in pure and mixed n-heptane, n-hexadecane, n-eicosane, n-docosane, and n-tetracosane from 293.15 K, or above the melting point, up to 343.15 K. The measured densities were correlated using the Peng–Robinson equation of state, and viscosities were modelled using the friction theory.     

Correlation and prediction of dense fluid transport coefficients. III. n-alkane mixtures

Viscosity and thermal conductivity coefficients for binary, ternary, and quaternary n-alkane mixtures are predicted over extended ranges of temperature and pressure, in excellent agreement with experiment, by extension of a method recently described for the correlation of n-alkane transport coefficients. The outstanding advantage of this approach is that there are no adjustable parameters. Furthermore, in contrast with other mixture viscosity equations, this scheme does not require experimental viscosity coefficient data for the pure components under the same conditions of temperature and pressure.     

Mutual diffusivity in binary mixtures of n-heptane with n-hexane isomers

This paper presents a study of the influence of branching in the binary diffusion coefficients of n-heptane + n-hexane isomers, in the liquid state. The measurements have been made with the Taylor dispersion technique, at several compositions, at 283 and 298 K, for the X + n-heptane mixtures, where X= n-hexane, 3-methylpentane, 2, 3-dimethylbutane, and 2, 2-dimethylbutane. The results show a very interesting behavior of the composition dependence of the binary diffusion coefficients, presenting a maximum, for compositions about a molar fraction of n-heptane of 0.5, which increases with the increase in the degree of branching, suggesting the possibility of order-disorder effects caused by stereochemically favored packing in the liquid phase and energetically favored segment interaction in the liquid mixtures. An attempt to apply the van der Waals model to these data could not predict the experimental binary diffusion coefficients of these systems within the experimental accuracy.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

Viscosity of biniary mixtures. III. Tri-n-butylamine with alkanes and monoalkylamines at 303.15 and 313.15 K

Viscosities of seven binary systems of n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-hexane, n-octane, and isoctane (2,2,4-trimethylpentane) with tributylamine have been measured at 303.15 and 313.15 K with an Ubbelohde suspended-level viscometer. Based on Eyring's theory, values of excess Gibbs energy of activation G ^*E of viscous flow have been calculated. Deviations of viscosities from linear dependence on the mole fraction and values of G ^*E are attributed to the H-bonding and to the size of alkylamine and alkane molecules. The free volume theory of Prigogine-Flory-Patterson in combination with work by Bloomfield-Dewan has been used to estimate the excess viscosity ln and the terms corresponding to enthalpy, entropy, and free volume contributions for the present binary mixtures.     

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.