Evaluation of thermodynamic properties of fluid mixtures by PC-SAFT model

doi:10.1016/j.tca.2014.07.022

Thermochimica Acta

Volume 591, 10 September 2014, Pages 75-80

https://doi.org/10.1016/j.tca.2014.07.022 Get rights and content

Highlights

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Densities and viscosities of the mixtures (MIK + 2-alkanols) were measured.
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PC-SAFT model was applied to correlate the volumetric properties of binary mixtures.
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Agreement between experimental data and calculated values by PC-SAFT model is good.

Abstract

Densities and viscosities of binary mixtures of methyl isobutyl ketone (MIK) with polar solvents namely, 2-propanol, 2-butanol and 2-pentanol, were measured at 7 temperatures (293.15–323.15 K) over the entire range of composition. Using the experimental data, excess molar volumes $V_{m}^{E}$ , isobaric thermal expansivity $α_{p}$ , partial molar volumes ${\bar{V}}_{m, i}$ and viscosity deviations $Δ η$ , have been calculated due to their importance in the study of specific molecular interactions. The observed negative and positive values of deviation/excess parameters were explained on the basis of the intermolecular interactions occur in these mixtures. The Perturbed Chain Statistical Association Fluid Theory (PC-SAFT) has been used to correlate the volumetric behavior of the mixtures.

Graphical abstract

Experimental and calculated partial molar volumes ( ${\bar{V}}_{m, 1}$ ) of MIK with (♦) 2-PrOH, (♢) 2-BuOH, (●) 2-PenOH at T = 298.15 K. (—) PC-SAFT model.

Introduction

Thermodynamic properties of binary non-electrolyte mixtures are very valuable in the study of the type and nature of molecular interactions. Experimental densities and viscosities for binary mixtures are necessary to develop the equations of state. The aims of this study are to understand the intermolecular interactions between the methyl isobutyl ketone and 2-alkanols with different alkyl chain length. As a part of our systematic studies on the thermodynamic and transport properties of liquid mixtures containing 2-alkanols in previous papers [1], [2], [3], here, densities, viscosities, excess molar volumes and viscosity deviations of mixing for the binary mixtures of methyl isobutyl ketone with 2-propanol, 2-butanol and 2-pentanol at temperature intervals 293.15–323.15 K are reported. A survey of literature shows that there are few data about this kind of mixtures [4], [5]. Also prediction or correlation of volumetric properties with the PC-SAFT model is other background of this work. PC-SAFT model is able to predict the effects of molecular weight and hydrogen bonding on the thermodynamic properties of complex fluids and mixtures. In this paper PC-SAFT model has been applied to correlate and predict the values of isobaric thermal expansibility and partial molar volumes. Complete description of these systems requires three physically meaningful temperature-independent parameters: the segment number (m), the hard-core segment diameter (σ), and the segment-segment interaction energy parameter ( $ϵ / k$ ) for each pure non-associating fluid. They are typically fitted to vapour pressure and liquid density data. Associating fluids require two additional compound parameters, the association energy ( $ϵ^{A B}$ ), and the association volume (κ^AB).

Section snippets

Experimental section

Methyl isobutyl ketone, 2-propanol, 2-butanol and 2-pentanol were obtained from Merck with mass purity >99%. All of the materials were used without further purification. In Table1, we compared the measured densities and viscosities at T = 298.15 K with values available in the literature [6], [7]. Density and viscosity measurements were performed with a fully automated SVM 3000 Anton-Paar rotational Stabinger viscometer. The viscometer is based on a modified Couette principle with a rapidly

Densities and excess molar volumes

Excess molar volumes, $V_{m}^{E}$ for studied mixtures, were calculated at different temperatures by use of the following equation: $V_{m}^{E} = \sum_{i = 1}^{N} x_{i} M_{i} (ρ^{- 1} - ρ_{i}^{- 1})$ where ρ is the density of the mixture, ρ_i is the density of pure component i, x_i is the mole fraction, M_i is the molar mass of component i, and N stands for the number of components in the mixture. Excess molar volumes for binary mixtures of MIK + 2-alkanols at T = 298.15 K are plotted in Fig. 1. Values of densities are reported in Table 2. The $V_{m}^{E}$ values

Conclusions

This paper reports the densities and viscosities for binary mixtures of MIK and 2-alkanol. Excess molar volumes, isobaric thermal expansivity, partial molar volumes, and viscosity deviations were calculated from experimental data. Excess molar volumes are positive and viscosity deviations are negative over the whole composition range. The ability of the PC-SAFT equations of state to reproduce the volumetric behavior of the mixtures was also tested at various temperatures. Overall, PC-SAFT

Acknowledgments

The author thanks the University authorities for providing the necessary facilities to carry out this research project (Tarhe Pajooheshi).

References (14)

M. Almasi
Densities and viscosities of binary mixtures of ethylmethylketone and 2-alkanols; application of the ERAS model and cubic EOS
Thermochim. Acta
(2013)
M. Almasi
Densities and viscosities of the mixtures (formamide + 2-alkanol): experimental and theoretical approaches
J. Chem. Thermodyn.
(2014)
R. Privat et al.
Are safe results obtained when the PC-SAFT equation of state is applied to ordinary pure chemicals
Fluid Phase Equilib.
(2010)
M. Almasi et al.
Densities, viscosities, and refractive indices of binary mixtures of acetophenone and 2-alkanols
J. Chem. Eng. Data
(2010)
R. Riggio et al.
Mixtures of methyl isobutyl ketone with three butanols at various temperature
Can. J. Chem.
(1981)
R. Riggio et al.
Densities, viscosities, and refractive indexes for the methyl, isobutyl ketone + pentanols systems. Measurements and correlations
J. Chem. Eng. Data
(1986)
J.A. Riddick et al.
Organic Solvents, Physical Properties and Methods of Purification
(1986)

There are more references available in the full text version of this article.

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Evaluation of thermodynamic properties of fluid mixtures by PC-SAFT model

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Experimental section

Densities and excess molar volumes

Conclusions

Acknowledgments

Thermochim. Acta

J. Chem. Thermodyn.

Fluid Phase Equilib.

Densities, viscosities, and refractive indices of binary mixtures of acetophenone and 2-alkanols

J. Chem. Eng. Data

Mixtures of methyl isobutyl ketone with three butanols at various temperature

Can. J. Chem.

Densities, viscosities, and refractive indexes for the methyl, isobutyl ketone + pentanols systems. Measurements and correlations

J. Chem. Eng. Data

Organic Solvents, Physical Properties and Methods of Purification