Vapor–liquid equilibria for systems of diethyl carbonate and ketones and determination of group interaction parameters for the UNIFAC and ASOG methods

doi:10.1016/j.fluid.2005.06.024

Fluid Phase Equilibria

Volume 235, Issue 1, 18 August 2005, Pages 83-91

https://doi.org/10.1016/j.fluid.2005.06.024 Get rights and content

Abstract

Densities and speeds of sound for the binary mixtures acetone, 2-butanone and 2-pentanone + diethyl carbonate, over the whole composition range, at T = 298.15 K and atmospheric pressure have been measured. Excess molar volumes and deviations in isentropic compressibility for the binary systems were fitted to the Redlich–Kister polynomial. Isobaric vapor–liquid equilibria for the binary systems acetone + diethyl carbonate, 2-butanone + diethyl carbonate and 2-pentanone + diethyl carbonate at P = 101.3 kPa have been determined. The activity coefficients were calculated to be thermodynamically consistent and they were correlated with the Wilson, NRTL, UNIQUAC and Redlich–Kister equations. Interaction parameters related to the carbonate ( single bond OCOO) and ketone (CO) groups, in ASOG and UNIFAC methods, have been determined using our experimental VLE data.

Introduction

Recently a number of papers on diethyl carbonates [1], [2] have been published related to dialkyl carbonates due to the possible use of oxygenated volatile organic compounds as fuel additives. There is also a strong interest in applications of dialkyl carbonates [3] in batteries based on intercalation of lithium and bromine in graphite, that can be recharged thermally at relatively low temperatures.

In order to better define the thermodynamic properties of diethyl carbonate (DEC) with other components and as a continuation of our work on the study of the thermodynamic behavior of binary mixtures containing DEC [4], [5], we present experimental densities and speeds of sound of binary mixtures of some ketones and diethyl carbonate at T = 298.15 K and atmospheric pressure, and isobaric VLE of these mixtures.

Section snippets

Chemicals

Acetone (99.8 mass%), 2-butanone (99.5 mass%), 2-pentanone (99.5 mass%), and DEC (99.5 mass%) were supplied by Merck. These components were degassed ultrasonically, and stored in an inert argon atmosphere over molecular sieves type 0.4 nm (supplied by Aldrich) for several weeks before using to reduce the water content. After this treatment, the water content was determined using a Metrohm 737 KF coulometer, showing that the water content of the components was neglible. Chromatographic tests of the

Results and discussion

The experimental density, speed of sound, excess molar volume, isentropic compressibility (determined by means of the Laplace equation, κ_S = ρ⁻¹ u⁻²) and deviation in isentropic compressibility of the binary mixtures acetone + DEC, 2-butanone + DEC, 2-pentanone + DEC at T = 298.15 K are given in Table 2. Excess molar volumes and deviations in isentropic compressibility were calculated from experimental values, as follows: $V^{E} = \sum_{i = 0}^{N} x_{i} M_{i} (ρ^{- 1} - ρ_{i}^{\circ^{- 1}})$ $Δ κ_{S} = κ_{S} - \sum_{i = 1}^{N} x_{i} κ_{S, i}$ where ρ and $ρ_{i}^{\circ}$ are the density of the

Conclusions

In this paper, the experimental density and speed of sound of binary mixtures diethyl carbonate with acetone, 2-butanone and 2-pentanone at T = 298.15 K were determined. In order to test the quality of the experimental results, the excess molar volumes, isentropic compressibilities and deviations in isentropic compressibility for the above binary mixtures were calculated. Excess molar volumes are negative in the whole composition range. These values suggest that molecular packing of diethyl

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The type of LLE can be shown in the triangle phase diagrams in Figs. 3 and 4. Table 7 shows the binary parameters (a12 and a21), which were derived from VLE results [19,20] for completely miscible mixtures of (water + acetone), (acetone + DEC) and (2-butanone + DEC), whereas those were obtained from mutual solubility data measured in this work for partially miscible mixtures of (water + DEC) and (water + 2-butanone). Table 8 lists the ternary parameters along with the rmsd of the mole fraction for the measured ternary LLE.
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Study of volumetric and thermodynamic properties of binary mixtures 1,4-butanediol with methylpyridine isomers at different temperatures
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Densities, ρ and speeds of sound, u of {1,4-butanediol (1,4BD) + methylpyridine isomers (α-, or β-picoline)} binary mixtures have been measured over the entire composition range at a temperature of (303.15, 308.15, 313.15 and 318.15) K, and at atmospheric pressure (0.1 MPa). The measured densities and speeds of sound data have been utilized to determine excess molar volumes, V_m^E, excess isentropic compressibilities, κ_s^E, excess molar isentropic compressibilities, κ_s , m^E, excess speed of sound, u^E and excess isobaric coefficient of thermal expansion α_p^Eof the investigated mixtures. Excess parameters were correlated by the Redlich–Kister polynomials. Excess partial molar volumes ( ${\overset{̅}{V}}_{m, 1}^{E}$ and ${\overset{̅}{V}}_{m, 2}^{E}$ ) and their limiting values at infinite dilution ( ${\overset{̅}{V}}_{m, 1}^{0 E}$ and ${\overset{̅}{V}}_{m, 2}^{0 E}$ ) have been calculated from the experimental density measurements and were analytically obtained using Redlich–Kister and Legendre polynomials. The deviation in V_m^E were investigated by employing Prigogine–Flory–Patterson theory.
Influence of alkyl group and temperature on excess thermodynamic properties of diethyl carbonate and their binary mixtures at 0.1 MPa
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With these studies, some important factors responsible for the positive or negative deviations for binary polar–polar or non-polar–polar systems have been discussed. However, a survey of the literature [16–36] reveals that very few reports have been made on the excess quantities for binary solutions of DEC. The excess molar enthalpies of DEC + xylenes at 298.15 K were measured by Lien et al. [37].
In this work, the experimental densities, ρ, and speeds of sound, u, of binary mixtures of diethyl carbonate (DEC) with the three isomers of xylene (ortho-, meta- and para-xylenes) were measured over the entire composition range at T = (298.15–323.15) K, and at atmospheric pressure (0.1 MPa). From the experimental data, the excess molar volumes, V_m^E, excess isentropic compressibility, κ_s^E, excess molar isentropic compressibility, κ_s,m^E, and deviation in speed of sound, μ^D have been evaluated. Excess parameters were fitted to the Redlich–Kister polynomial equation to obtain the binary coefficients and the standard errors. Excess partial molar volumes ( ${\bar{V}}_{m, 1}^{E}$ and ${\bar{V}}_{m, 2}^{E}$ ) and their limiting values at infinite dilution ( ${\bar{V}}_{m, 1}^{0 E}$ and ${\bar{V}}_{m, 2}^{0 E}$ ) have been calculated from the experimental density measurements. Excess partial molar isentropic compressibilities, ${\bar{κ}}_{s, m, 1}^{E}$ and ${\bar{κ}}_{s, m, 2}^{E}$ of both components and their respective limits at infinite dilution, ${\bar{κ}}_{s, m, 1}^{0 E}$ and ${\bar{κ}}_{s, m, 2}^{0 E}$ , were analytically obtained using Redlich–Kister type equations.
Excess properties of diethyl carbonate + ketone binary mixtures at variable temperatures: Application of PFP theory to excess volumes
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Francesconi and Comelli [11] studied excess enthalpies and excess molar volumes for DEC + n-alkanol mixtures at 298.15 K. Ottani et al. [12] studied densities, viscosities, and refractive indices of poly(ethylene glycols) + DEC mixtures at 313.15 K. Likewise Rivas et al. [13] studied permittivity and density of DEC + dodecane at (298.15 to 328.15) K. Yang et al. [14] have determined density and viscosity for mixtures of DEC + alcohols at (293.15 to 363.15) K. However there are only a few studies on binary mixtures of DEC + ketones [15–18] reported in literature. In view of the increasing importance of DEC, and the lack of extensive knowledge about its behavior with ketones, it has created in us an interest to undertake this present research.
Measurements of densities ρ, viscosities η, and refractive indices n_D have been carried out for binary mixtures of diethyl carbonate (DEC) with acetophenone, cyclopentanone, cyclohexanone, and 3-pentanone over the entire composition range at the temperatures (303.15, 308.15 and 313.15) K and at atmospheric pressure. From these experimental data, the excess volumes V^E, deviation in viscosity Δη and deviation in molar refraction ΔR have been calculated. The Redlich–Kister polynomial equation has been used to estimate the binary fitting parameters and the standard errors. The Prigogine–Flory–Patterson (PFP) theory and its applicability in predicting V^E at (303.15, 308.15 and 313.15) K has been tested. The experimental viscosities were analyzed on the basis of Lobe and Auslaender models. Further different mixing rules have been applied to predict the refractive index values of the studied mixtures.

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Vapor–liquid equilibria for systems of diethyl carbonate and ketones and determination of group interaction parameters for the UNIFAC and ASOG methods

Abstract

Introduction

Section snippets

Chemicals

Results and discussion

Conclusions

Appl. Catal. A: Gen.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Energy Fuel.

J. Chem. Eng. Data

J. Chem. Eng. Data

J. Chem. Eng. Data

J. Chem. Eng. Data

J. Chem. Eng. Data