Densities, speeds of sound, and refractive indices of the ternary mixtures (toluene + methyl acetate + butyl acetate) and (toluene + methyl acetate + methyl heptanoate) at 298.15 K

doi:10.1016/j.jct.2006.07.013

The Journal of Chemical Thermodynamics

Volume 39, Issue 2, February 2007, Pages 218-224

https://doi.org/10.1016/j.jct.2006.07.013 Get rights and content

Abstract

Density, ρ, speed of sound, u, and refractive index, n_D, at 298.15 K and atmospheric pressure have been measured over the entire composition range for (toluene + methyl acetate + butyl acetate) and (toluene + methyl acetate + methyl heptanoate) systems. Excess molar volumes, V^E, isentropic compressibility, κ_s, isentropic compressibility deviations, Δκ_s, and changes of refractive index on mixing, Δn_D, for the above systems, have been calculated from experimental data and fitted to Cibulka, Singh et al., and Nagata and Sakura equations, standard deviations from the regression lines are shown. Geometrical solution models, Tsao and Smith, Kholer, Jacob and Fitzner, Rastogi et al. were also applied to predict ternary properties from binary contributions.

Introduction

This paper is part of a thermodynamic study of lineal esters with aromatics hydrocarbons that were done in ours laboratories. In this work, the densities, speeds of sound, and refractive indices of ternary mixtures (toluene + methyl acetate + butyl acetate) and (toluene + methyl acetate + methyl heptanoate) at 298.15 K and atmospheric pressure have been measured. The thermodynamics of ternary mixtures of non-electrolytes has not received as much attention as the thermodynamics of binary mixtures. It is therefore interesting to estimate excess properties with more than two components.

The experimental values of physical properties were used to calculate excess molar volumes, isentropic compressibilities, isentropic compressibility deviations, and changes of refractive index on mixing over the entire mole fraction range for the ternary mixtures. The binary contribution calculated from the Redlich and Kister [1] equation, was used to correlate the experimental ternary results with the Cibulka [2], Singh et al. [3], and Nagata and Sakura [4] equations. The standard deviations between experimental and calculated values are shown.

Assuming that interactions in a ternary mixture are closely dependent on the interactions in binary systems, we consider the application of geometrical solutions models, Tsao and Smith [5], Kohler [6], Jacob and Fitzner [7], and Rastogi et al. [8], to predict the properties for these ternary systems from binary contributions.

No experimental data corresponding to density, speed of sound, and refractive index have been found in the literature on the ternary mixtures studied in this paper.

Section snippets

Experimental

Toluene (>99.8%) and butyl acetate (>98.0%) were supplied by Aldrich, methyl acetate (>99.0%) was provided by Merck and methyl heptanoate (>99.0%) by Fluka. Its properties compared with those found in the literature are gathered in table 1. All the liquids were dried with 0.4 nm Union Carbide molecular sieves from Fluka and partially degassed before use with an ultrasonic bath.

The mixtures were prepared by adding known masses of the pure liquids into stoppered bottles with a syringe to prevent

Results and discussion

Density, excess molar volume, speed of sound, isentropic compressibility, isentropic compressibility deviation, refractive index, and change of refractive index on mixing for the ternary mixtures (toluene + methyl acetate + butyl acetate) and (toluene + methyl acetate + methyl heptanoate) are reported in TABLE 2, TABLE 3. Excess molar volumes, V^E, isentropic compressibility, κ_s, isentropic compressibility deviations, Δκ_s, and changes of refractive index on mixing, Δn_D, for the ternary mixtures were

References (15)

P. Singh et al.
Fluid Phase Equilibr.
(1984)
K.T. Jacob et al.
Thermochim. Acta
(1977)
J.P.E. Grolier et al.
J. Chem. Thermodyn.
(1974)
O. Redlich et al.
Ind. Eng. Chem.
(1948)
I. Cibulka
Coll. Czech. Commun.
(1982)
M. Nagata et al.
J. Chem. Soc. Faraday Trans. I
(1987)
C.C. Tsao et al.
Chem. Eng. Prog. Symp.
(1953)

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Citation Excerpt :
In Table 1, purity, CAS and source of reagents used in this study are presented. Table 2 [25–48] represents the comparative list of measured and reported values of density and sound velocity for toluene and dodecane. The ionic liquids, trioctylmethylammonium bis-(2-ethylhexyl)phosphate and trioctylmethylammonium bis-(2-ethylhexyl)diglycolamate were synthesized following the procedure reported in the literature [9,16].
The structural variance ability of ionic liquids (ILs) provides an opportunity to fine tune the thermophysical properties for given application. For effective extraction of metal ion from water, the applied ILs should be hydrophobic and preferably containing non fluorinated anions. The hydrophobicity of ILs can be further manipulated by the addition of diluents. To understand extraction of metal ion using binary mixtures of ILs + diluent, it is utmost important to explore different types of interactions exist in the binary mixtures using thermophysical properties. For this purpose, we present experimentally measured data of densities, ρ and speeds of sound, u for binary solutions of aprotic ionic liquids (APILs) namely trioctylmethylammonioum bis-(2-ethylhexyl) phosphate [TOMA][DEHP], trioctylmethylammonioum bis-(2-ethylhexyl) diglycolamate [TOMA][DGA], trioctylmethylammonioum bis-(2-ethyhexyl)sulfosuccinate [TOMA][DEHS] in toluene and dodecane (diluents) at T = 293.15 K to 328.15 K. The apparent molar properties like volume V_ϕ, isentropic compressibility K_s,ϕ and limiting expansivity E_ϕ^∞ were calculated and explained in terms of temperature, size of anion, and nature of solvent. The both V_ϕ and K_s,ϕ were increased with rise in temperature and replacing toluene with dodecane whereas decreased with increase in concentration of APIL. The Redlich-Mayer type equation was used to correlate apparent molar volume, V_ϕ^∞ and apparent molar isentropic compressibility, K_ϕ^∞ at infinite dilution. The influence of interactions (IL-IL or IL-solvent) in studied binary mixtures was elucidated by S_v and S_k parameters. It was observed that ion-solvent interactions are dominating in APILs + toluene than in APILs + dodecane.

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¹: CONICET scholarship holder.

²: CONICET member.

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Densities, speeds of sound, and refractive indices of the ternary mixtures (toluene + methyl acetate + butyl acetate) and (toluene + methyl acetate + methyl heptanoate) at 298.15 K

Abstract

Introduction

Section snippets

Experimental

Results and discussion

Fluid Phase Equilibr.

Thermochim. Acta

J. Chem. Thermodyn.

Ind. Eng. Chem.

Coll. Czech. Commun.

J. Chem. Soc. Faraday Trans. I

Chem. Eng. Prog. Symp.