Dynamic viscosities of binary mixtures of cycloalkanes with primary alcohols at T = (293.15, 298.15, and 303.15) K: New UNIFAC-VISCO interaction parameters

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Abstract

In this work, dynamic viscosities, densities, and speed of sound have been measured over the whole composition range and 0.1 MPa for the binary mixtures (cyclopentane and cyclohexane with ethanol, 1-propanol, and 1-butanol) at several temperatures (293.15, 298.15, 303.15) K along with the properties of the pure components. Excess molar volumes, molar isentropic compression, excess molar isentropic compression, and excess free energy of activation for the binary systems at the above mentioned temperatures, were calculated and fitted to the Redlich–Kister equation to determine the fitting parameters and the root-mean-square deviations. The UNIQUAC equation was used to correlate the experimental viscosity data. The UNIFAC-VISCO method and ASOG-VISCO method, based on contribution groups, were used to predict the dynamic viscosities of the binary mixtures. The interaction parameters of cycloalkanes with primary alcohol (CHcy/-OH) have been determined for their application in the predictive UNIFAC-VISCO method.

Introduction

Among all physical properties, the knowledge of the viscosity of liquid mixtures and their dependence with composition and temperature is very important for design the industrial processes. Indeed, viscosity is a fundamental characteristic of substances such as adhesives, lubricants, paintings, etc. As an extension of our work concerning dynamic viscosity of binary systems alkanes with alcohols [1], [2], [3], in this paper, we show experimental dynamic viscosity, density, and speed of sound data of {x1 cyclohexane + (1  x1) ethanol}, {x1 cyclohexane + (1  x1) 1-propanol}, {x1 cyclohexane + (1  x1) 1-butanol}, {x1 cyclopentane + (1  x1) ethanol}, {x1 cyclopentane + (1  x1) 1-propanol}, and {x1 cyclopentane + (1  x1) 1-butanol} at T = (293.15, 298.15, and 303.15) K. Experimental data were used to calculate excess molar volumes, molar isentropic compression, excess molar isentropic compression, and excess free energy of activation over the entire mole fraction range. Viscosity data were correlated using the UNIQUAC [4] equation.

The UNIFAC-VISCO [5], [6] and ASOG-VISCO [7] methods have been applied to predict the viscosity of these systems and the results were compared with the experimental data. Both methods are based on the Eyring theory [8] and on group contributions methods. To improve the results of the prediction of the UNIFAC-VISCO method, the interaction parameter CHcy/-OH have been determined.

Section snippets

Chemicals

The pure components were supplied by Fluka (cyclohexane and cyclopentane) and Merck (1-propanol, 1-butanol, and 1-pentanol). The components were degassed ultrasonically, and dried over molecular sieves Type 4 Å, 4 · 10−8 cm, that were supplied by Aldrich, and kept in inert argon with a maximum content in water of 2 · 10−6 by mass fraction. The maximum water contents of the liquids were determined using a Metrohm 737 KF coulometer. Their mass fraction purities were >0.998 for cyclohexane, ethanol, and

Results and discussion

Dynamic viscosity, density, speed of sound, excess molar volume and molar isentropic compression, excess molar isentropic compression, and excess free energy of activation for the binary systems {x1 cyclohexane + (1  x1) ethanol}, {x1 cyclohexane + (1  x1) 1-propanol}, {x1 cyclohexane + (1  x1) 1-butanol}, {x1 cyclopentane + (1  x1) ethanol}, {x1 cyclopentane + (1  x1) 1-propanol}, and {x1 cyclopentane + (1  x1) 1-butanol} at T = (293.15, 298.15 and 303.15) K and atmospheric pressure are reported in TABLE 2, TABLE 3

Correlation and prediction

The UNIQUAC equation is used for calculating of the excess molar free energy of activation for flow, ΔG∗E, which is related to the viscosity by:ln(νM)=ixiln(νiMi)+ΔGE/R·T,where ν is the kinematic viscosity and M and Mi are the molar mass of the mixture and the pure component, respectively.

The correlation has been performed with experimental data using the UNIQUAC equation for calculating of the excess molar free energy, minimizing the following objective function:O.F.=1Ni=1N|ηi,exp-ηi,calc|ηi

Conclusions

In this work, the dynamic viscosities, densities, and speed of sound of cyclohexane (1) and cyclopentane (1) with ethanol (2), 1-propanol (2), and 1-butanol (2) at several temperatures T = (273.15, 298.15, and 303.15) K over the whole composition range have been determined.

Excess molar volume, excess molar isentropic compression, and excess free energy of activation were calculated and fitted to the Redlich–Kister equation to test the quality of the experimental values. The correlation of the

References (32)

  • B. Gonzalez et al.

    J. Chem. Thermodyn.

    (2004)
  • J.L. Chevalier et al.

    J. Chem. Eng. Sci.

    (1988)
  • Y. Gaston-Bonhomme et al.

    J. Chem. Eng. Sci.

    (1994)
  • A. Rodriguez et al.

    J. Chem. Thermodyn.

    (2003)
  • H. Iloukhani et al.

    J. Chem. Thermodyn.

    (2006)
  • J. Peleteiro et al.

    J. Chem. Thermodyn.

    (2005)
  • C.A. Cerdeiriña et al.

    Fluid Phase Equilibr.

    (1999)
  • G.C. Benson et al.

    J. Chem. Thermodyn.

    (1979)
  • M.N.M. Al-Hayan et al.

    J. Chem. Thermodyn.

    (2006)
  • B. Gonzalez et al.

    J. Chem. Thermodyn.

    (2006)
  • B. Gonzalez et al.

    J. Chem. Eng. Data

    (2004)
  • B. Gonzalez, A. Dominguez, J. Tojo, J. Chem. Thermodyn. (in press), doi:...
  • D.S. Abrams et al.

    AIChE J.

    (1975)
  • K. Tochigi, K. Yoshino, V.K. Rattan, in: The Sixteenth European Conference on Thermophysical Properties, 1–4 September,...
  • H. Eyring

    J. Chem. Phys.

    (1936)
  • P.J. Petrino et al.

    J. Chem. Eng. Data

    (1995)
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