Viscosity of binary mixtures. I. mono-, di-, and tri-n-butyl and -n-octylamine with cyclohexane

Viscosities for six binary mixtures of n-butylamine, di-n-butylamine, tri-n-butylamine, n-octylamine, di-n-octylamine, and tri-n-octylamine with cyclohexane have been measured at 303.15 K with an Ubbelohde suspendedlevel viscometer. Deviations of viscosities from a rectilinear dependence on mole fraction are attributed to H-bonding and to the size of alkylamine compounds. The application of the Eyring's theory of activation energy is examined. The free volume theory of Prigogine-Flory-Patterson (PFP) and the experimental excess enthalpy have been used to estimate excess viscosity ln = (ln / ₁ ⁰ – x ₂ ln ₂ ⁰ / ₁ ⁰ ) and corresponding free volume, enthalpy, and entropy contributions for five binary mixtures of tri-n-alkylamine: triethyl, tripropyl, tributyl, trihexyl, and trioctylamine with cyclohexane. A comparison of experimental and theoretical excess viscosities indicates a failure of the PFP theory when two components of the mixture differ considerably in size. The size difference contribution to excess viscosity is related to (V ₂ ^*1/2 – V ₁ ^*1/2 ), where V ₁ ^* and V ₂ ^* are hard-core volumes of two components of the mixture.     

Viscosity of binary mixtures. II. n-butyl,n-hexyl,n-octyl,n-decyl,and n-dodecylamine with benzene and n-hexyl,n-decyl,and n-dodecylamine with cyclohexane

Viscosities of eight binary systems of n-butylamine, n-hexylamine, n-octylamine, n-decylamine, and n-dodecylamine with benzene and n-hexylamine, n-decylamine, and n-dodecylamine with cyclohexane have been measured at 303.15 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 H-bonding and to the size of alkylamine molecules. The free volume theory of Prigogine-Flory-Patterson in combination with the work of Bloomfield-Dewan has been used to estimate the excess viscosity In and the terms corresponding to enthalpy, entropy, and free volume contributions for 10 binary mixtures containing n-butyl, n-hexyl, n-octyl, n-decyl, and n-dodecylamine with benzene and cyclohexane.     

Correlation of dense fluid self-diffusion,shear viscosity,and thermal conductivity coefficients

A general procedure has been developed for simultaneously fitting any two of the self-diffusion coefficient, the viscosity (as the fluidity), and the thermal conductivity (as its reciprocal) as Dymond reduced coefficients, (D*,*,*), to a simple function of the volume and the temperature for dense fluids. For example,D*=₁+₂ V _r/(1+₃,/V _r), whereV _r=V[1-₁(T–T _r)-₂(T–T _r)²].T _r is any convenient temperature, here 273.15 K. AsV _r is common to the two properties, only eight coefficients, _j and _k are required. Such reduced transport-coefficient curves are geometrically similar for members of groups of closely related compounds. The procedure has been extended to give family curves for such groups by fitting a pair of transport properties for three substances from the group in a single regression. Overall, fewer coefficients are required than for other schemes in the literature, and the fitting functions used are simpler. The curves so constructed can be used for the correlation of data obtained from different sources, as well as interpolation and, to a limited extent, extrapolation. A comparison is made for a number of compotmd groups between simultaneous fits of the pairs (D– ), (D–), and (–)Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

Prediction of Kinematic Viscosities for Binary and Ternary Liquid Mixtures with an ASOG-VISCO Group Contribution Method

The kinematic viscosities for 273 binary and 11 ternary systems were predicted with a new model (ASOG-VISCO) developed by combining the ASOG group contribution method and Eyrings theory of absolute reaction rates. The ASOG-VISCO group pair parameters were determined from literature kinematic viscosity data for group pairs of CH₂, ArCH, CyCH, OH, H₂O, CO, COO, CCl₃, and CCl₄ in the temperature range of 283.15 to 333.15 K. The overall average deviations between experimental and predicted kinematic viscosities for the binary and ternary systems were 4.15 and 5.03%, respectively. The predicted results using ASOG-VISCO were better than those determined with the UNIFAC-VISCO group contribution method.Paper presented at the Sixteenth European Conference on Thermophysical Properties, September 1–4, 2002, London, United Kingdom.     

Excess volumes and excess viscosities of binary mixtures of 1-bromo-2-methylpropane + an isomer of butanol at 298.15 and 313.15 K

Excess volumesV ^E, excess viscosities ^E, and excess free energies of activation of flow G^*E at 298.15 and 313.15 K are reported for binary mixtures of 1-bronw-2-methypropane and each of the alcoholic isomers of I-butanol. The results were obtained from density and viscosity measurements and show positive values forV ⁴ and negative for both ^E andG ^*E for all mixtures over the entire composition range.     

Viscosity Studies on Polypropylene Glycol and Its Blend

Viscosity studies have been made on polypropylene glycol (PPG) of different molar masses [500, 1000, 2000] in both low and medium concentration ranges [lower concentration range 0 to 1% (w/v) and medium concentration range 1 to 10% (w/v)] in toluene, in the temperature range of 303 to 333 K. The effect of concentration on the activation energy of flow was calculated. It was observed that the activation energy of flow is greater for molar masses of 1000 and 2000 than that of the solvent. The effect of molar mass was also analyzed, and it was indicated that in PPG, a molar mass of 1000 might represent a transition state for the molecule from one shape to another shape. An attempt has also been made to blend PPG 2000 with PPG 500 (concentration 1% (w/v)), for various compositions of the blend. The miscibility nature of the blend was analyzed through viscosity studies and other techniques. The blend showed immiscibility. In this study the activation energy of flow for PPG in toluene was calculated and also the miscibility of two molar masses of PPG was investigated through viscosity studies. This work clearly shows that a viscosity study can be used for analyzing the miscibility of two polymers.Paper presented at the Seventh Asian Thermophysical Properties Conference, August 23–28, 2004, Hefei and Huangshan, Anhui, P. R. China.     

A four-parameter corresponding-states method for prediction of Newtonian,pure-component viscosity

The extended Lee-Kesler (ELK) method, introduced for calculating thermodynamic properties of polar as well as nonpolar fluids and their mixtures, has been adapted to the calculation of Newtonian, pure-fluid viscosity. The method is a four-parameter, corresponding-states technique requiring as input the critical temperature, critical pressure, a size/shape parameter , and a polar interaction parameter . Because and have been previously tabulated for many fluids (for calculation of thermodynamic properties) and may also be obtained directly from the radius of gyration and a single liquid density, respectively, the method contains no adjustable parameters and is predictive in nature. ELK viscosity predictions were compared to experimental data for nonpolar and polar fluids. For 36 different nonpolar fluids and a total of 5748 different points, the comparison yielded an absolute average deviation (AAD) of 7.88% with a bias of –4.45%. Similarly, the AAD was 10.62% with a bias of –5.34% for a comparison of 15 different polar fluids involving 1500 different points. With this method, viscosities can be calculated within the range 0.55 T _r2.00 and 0<P _r10.     

Isotope effect on the viscosity of benzene and cyclohexane mixtures under high pressures

Viscosities of binary mixtures of cyclohexane with protiobenzene, C₆H₆, or deuteriobenzene, C₆D₆, have been measured at 298 and 323 K and at pressures up to 50 MPa using a capillary viscometer. The viscosities of these mixtures obtained were represented by a empirical Tait-type equation within the experimental uncertainty of ±2%. The effect of the isotopic substitution on the viscosity has been discussed.     

Correlation of high-pressure thermal conductivity,viscosity, and diffusion coefficients for n-alkanes

Thermal conductivity, viscosity, and self-diffusion coefficient data for liquid n-alkanes are satisfactorily correlated simultaneously by a method based on the hard-sphere theory of transport properties. Universal curves are developed for the reduced transport properties ^*, ^*, and D ^* as a function of the reduced volume. A consistent set of equations is derived for the characteristic volume and for the parameters R , R , and R _D, introduced to account for the nonsphericity and roughness of the molecules. The temperature range of the above scheme extends from 110 to 370 K, and the pressure range up to 650 MPa.     

Influence of additives on melt viscosity,surface tension,and film formation of dry powder coatings

Background: Limited information on thermally cured dry-powder coatings used for solid dosage forms has been available in the literature. Aim: The aim of this study was to characterize the film formation process of Eudragit® L 100-55 dry-powder coatings and to investigate the influence of film additives on melt viscosity and surface tension. Methods: The coating process employed no liquids and the plasticizer was combined with the polymer using hot melt extrusion. Thermoanalytical methods including differential scanning calorimetry and thermogravimetric analysis (TGA) were used to investigate the thermal properties of the dry-coating formulations. The rheological behavior of the coating formulations were characterized with the extrusion torque, and the surface energy parameters were determined from contact angle measurements. The influence of the level of triethyl citrate (TEC) as plasticizer and polyethylene glycol (PEG) 3350 in the polymer film on film formation was investigated using a digital force tester. Results: TGA confirmed thermal stability of all coating excipients at the investigated curing conditions. Increasing TEC levels and the addition of PEG 3350 as a low melting excipient in the coating reduced the viscosity of the polymer. Plasticization of the polymer with TEC increased the surface free energy, whereas the admixture of 10% PEG 3350 did not affect the surface free energy of Eudragit® L 100-55. The spreading coefficient of the polymers over two sample tablet formulations was reduced with increasing surface free energy. During the curing process, puncture strength, and elongation of powder-cast films increased. The effect of curing time on the mechanical properties was dependent on the plasticizer content. Conclusions: The incorporation of TEC and PEG 3350 into the Eudragit® L 100-55 powder coating formulation improved film formation. Mechanical testing of powder-cast films showed an increase of both elongation and puncture strength over the curing process as criterion for polymer particle fusion, where film formation progressed faster at high plasticizer levels.     

An improved extended corresponding states method for estimation of viscosity of pure refrigerants and mixtures

The extended corresponding states method for calculating the viscosity of pure refrigerants and mixtures is investigated. The accuracy of pure fluid viscosity values is significantly improved by introducing a third shape factor evaluated using available pure fluid viscosity data. A modification to the method of Huber and Ely (Fluid Phase Equilibria, 1992, 80, 45–46) is proposed for estimation of the viscosity of mixtures; this modification eliminates the possibility of discontinuities at the critical point, ensures that the pure component viscosity is provided in the limit of a component mole fraction approaching 1, and improves the overall accuracy of the method. The method has been applied to 12 pure refrigerants including three hydrocarbons and mixtures. The average absolute deviations between the calculated and experimental viscosity values are within 4% for all of the pure fluids and most of the mixtures investigated.     

Correlation of high-pressure diffusion and viscosity coefficients for n-alkanes

Self-diffusion coefficient and viscosity coefficient data for liquid n-alkanes over the whole pressure range at different temperatures are satisfactorily correlated simultaneously by a method which is just an extension of that previously used to apply the smooth hard-sphere theory of transport properties to individual transport coefficients. Universal curves are developed for reduced quantities D ^* and ^* as a function of reduced volume. A consistent set of values is derived for the characteristic volume V ₀ and for parameters R _D and R , introduced to account for effects of nonspherical molecular shape and molecular roughness. On this basis, accurate calculation can be made of self-diffusion and viscosity coefficients for other members of the n-alkane series, for which data are at present limited.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

Group Contributions for an Estimation of Partial Molar Volumes at Infinite Dilution for Aqueous Organic Solutes at Extended Ranges of Temperature and Pressure

Experimental data on the partial molar volume at infinite dilution in water for two groups of organic solutes (derivatives of benzene and aliphatic hydroxyl derivatives) measured using a vibrating-tube densimeter in the temperature and pressure ranges 298 to 573K and 0.1 to 30MPa are summarized. Smoothed values of partial molar volume as a function of temperature and pressure are employed for the evaluation of group and structural contributions. The contributions are used to estimate the partial molar volumes at infinite dilution in water for various solutes. The average deviation between partial molar volumes calculated from the contributions and the experimental data employed for the evaluation of the contributions is less than 1cm³mol^–1 in most cases. Predictions of partial molar volumes of solutes not included in the evaluation of the contributions are performed and results are compared with experimental data.     

Simultaneous measurement of surface tension and kinematic viscosity using thermal fluctuations

We have developed a surface laser-light scattering apparatus to measure simultaneously surface tension and kinematic viscosity. In this method, we can obtain the surface properties by the laser heterodyne detection of light scattered from thermally excited capillary waves (called ripplon), which are typically of low amplitude (1 nm) and a characteristic wavelength (100m). Two gratings (d=100 and 200m) were employed to select the wave number of the capillary waves and to produce a reference beam for heterodyne detection. It was found through an experimental study on water that this contact-free method has considerable potential for application to measurements under extreme conditions such as high temperatures and high pressures.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, 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.     

Linking the Viscous and Vacancy Behavior of Mixtures of High-Molecular-Weight Hydrocarbons

A zero-shear viscosity model has now been extended to mixtures of three-branch alkanes with and without cyclopentyl or cyclohexyl attachments. The model links the equilibrium theory of Simha–Somcynsky (SS) statistical thermodynamics of liquids and the Eyring significant structure (ESS) transport theory. The predicted quantity of the hole fraction as a measure of the free volume, computed from the SS equation of state, plays a primary role in the approach to combine both theories. Experimental PVTη data from 310 to 408 K and 0.1 to 344.5 MPa have been used. The proportionality constant of the activation energy and the transmission coefficient have been calculated for each species separately, and they are in the expected trend with the fraction of mixtures. Satisfactory agreement in the prediction of viscosity from the hole fraction has been obtained. The volumetric and viscous data of physical mixtures are predicted from and compared with their chemical correspondence.     

变温条件下HDPE/CB的正电子湮灭特性

对掺杂了25份（phr）导电炭黑（CB）的样品进行了正电子湮灭寿命谱的变温测量，在玻璃化转变温度以上，随着温度的增加，自由体积的大小线性增加，在玻璃化转变温度以下，自由体积的大小基本不变，o-Ps的强度在－40℃下基本不变，从－40℃以上开始增加，但在50℃以上上升有加快的趋势，与PTC材料的PTC现象和导电性能有一定的关联。     

The shear viscosity and mutual diffusion coefficients of binary mixtures using the modified Enskog Theory

We use an extended form of the modified Enskog Theory (MET) to calculate viscosity and mutual diffusion coefficients for several binary mixtures. Second and third virial coefficients are required for the calculations. We find that the extended MET provides predictions of the shear viscosity for He-Ar and Ne-Ar mixtures with an accuracy of 2% at densities up to 6 mol · L^–1. Extended MET values of mutual diffusion coefficients of binary mixtures in which the mole fraction of one component approaches zero were calculated for He-Ar and Kr-Ar mixtures. The MET values fall within 10–15% of the experimental data at densities up to 11 mol · L^–1.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

Study of non-isothermal kinetics, electrical and optical properties of (GaSeTe) films

Ternary Ga_xSe_86−xTe₁₄ amorphous films (x=15 and 36) were prepared by thermal evaporation. The results of differential scanning calorimetry (DSC) at different heating rates are reported and discussed. The glass transition activation energy, E_t, and the crystallization activation energy, E_c, were evaluated by measuring the heating rate dependence of the glass transition, crystallization onset and peak crystallization temperatures. The average calculated values of E_t and E_c are 140.29 and 97.89 kJ/mol, respectively. The electrical conductivity of amorphous Ga_xSe_86−xTe₁₄ thin films with different thickness has been measured in the temperature range (263.2-333.3 K) and this allows the effect of introducing a metallic impurity to be observed. It was observed that conductivity increases with increasing activation energy and with a lowering of the pre-exponential factor, which suggests the results can be explained in terms of hopping conduction. The optical constants of these films were determined by transmission and reflection measurements at normal incidence in the spectral range of 500-800 nm. The refractive index has anomalous behavior in the spectral range 400-500 nm. The refractive index dispersion can be fitted to a single oscillator model.