Isobaric vapor–liquid equilibrium and isothermal surface tensions of 2,2′-oxybis[propane] + 2,5-Dimethylfuran

doi:10.1016/j.fluid.2013.02.005

Fluid Phase Equilibria

Volume 345, 15 May 2013, Pages 60-67

https://doi.org/10.1016/j.fluid.2013.02.005 Get rights and content

Abstract

Isobaric vapor–liquid equilibrium (VLE) data have been measured for the binary system 2,2′-oxybis[propane] + 2,5-Dimethylfuran at 50, 75, and 94 kPa and over the temperature range 321–364 K using a vapor–liquid equilibrium still with circulation of both phases. Atmospheric surface tension (ST) data have been also determined at 283.15 and 330.15 K using a maximum bubble pressure tensiometer. Experimental results show that the mixture is zeotropic and exhibits slight positive deviation from ideal behavior over the experimental range. Surface tensions, in turn, exhibit negative deviation from the linear behavior. For each isothermal condition, it is observed that the surface tension decreases as the mole fraction of 2,2′-oxybis[propane] increases, whereas at a fixed mole fraction, the surface tension decreases as the temperature increases.

The VLE data of the binary mixture satisfy the Fredenlund's consistency test, and the dependence of ST on mole fraction was satisfactorily smoothed using the Redlich–Kister equation.

The experimental VLE and ST data were accurately described by applying the square gradient theory to the Cubic-Plus-Association equation of state. This theoretical model was also applied to describe the surface activity of species along the interfacial region, from which it is possible to conclude that only the 2,2′-oxybis[propane] presents an interfacial accumulation which decreases as the concentration of DIPE or temperature increases.

Introduction

During the last years renewable source of fuels have gained importance due to the need to find environmental friendly and sustainable fuels. One promising new fuel is 2,5-Dimethylfuran (or DMF). Technically, DMF exhibits some interesting fuel features, such as an energy density similar to gasoline and 40% superior to ethanol [1], a Research Octane Number (RON) similar to gasoline and ethanol [2], and a stoichiometric air/fuel ratio lower than the stoichiometric air/fuel ratio of gasoline. In practice, DMF has been successfully tested as a fuel in a direct-injection spark-ignition engine, showing an excellent performance [3], [4], [5]. Additionally, among its attributes, DMF can be obtained from fructose through a high yield chemical or biochemical route (catalytic biomass-to-liquid process) where the raw material is fructose, which can be obtained from fruit, some root vegetables or sucrose [2].

In order to explore DMF applications as a fuel or as a gasoline additive, it is necessary to characterize its thermo-physical properties, such as the vapor–liquid equilibrium, density, and surface tension as a pure fluid as well as mixed with hydrocarbons or other gasoline additives, such as ethers and alcohols. In spite of their importance, experimental and theoretical investigations concerning key properties such as vapor–liquid equilibrium (VLE) and surface tension (ST) are scarce and limited to narrow experimental conditions. To the best of our knowledge, the available experimental data for DMF is scarce and limited to pure fluid vapor pressures [6], densities [6], [7] and surface tensions [8]. For the case of DMF based mixtures, only VLE, mixing volumes and ST data have been reported by us for DMF + hexane [8].

Consequently, and as part of our ongoing research program devoted to the characterization of the thermo-physical properties of DMF mixtures, this work is undertaken to determine VLE and ST data of 2,2′-oxybis[propane] (or DIPE) + DMF and to analyze its phase and interface behavior under the light of molecular theories. Specifically, a primary goal of this contribution is to report isobaric VLE data at 50, 75 and 94 kPa for DIPE + DMF, together with their atmospheric ST at 283.15 and 330.15 K. An additional goal is to simultaneously describe both bulk phase (VLE) and interfacial properties (ST and surface activity) of the mixture. For that purpose, bulk phases are described by using the Cubic-Plus-Association (CPA) EoS [9], [10], [11], [12], [13] while the corresponding interfacial properties are predicted by applying the square gradient theory (SGT) [14] to that EoS model. As we have demonstrated in previous works ([15], [16], [17], [18], [19], [20], [21], [22], and references therein), such a modeling approach provides a full predictive scheme both for bulk and interfacial properties from experimental VLE values and surface tensions of the pure components.

Section snippets

Purity of materials

2,2′-Oxybis[propane] and 2,5-Dimethylfuran were purchased from Merck and Aldrich, respectively. Both chemicals were used without further purification. Table 1 reports the purity of the components (as determined by gas chromatography, GC), together with the normal boiling points (T_b), the mass densities ( $\hat{ρ}$ ), the refractive indexes (n_D) at 298.15 K and the surface tensions (σ) of pure fluids at 303.15 K. The reported values are also compared with those previously reported [8], [23].

Vapor–liquid equilibrium cell

An all-glass

Experimental data treatment and consistency

Isobaric VLE measurements have been used to predict the activity coefficients (γ_i) and then to evaluate their consistency. γ_i are calculated from the following equation: [26] $\ln γ_{i} = \ln \frac{y_{i} p}{x_{i} p_{i}^{0}} + \frac{(B_{i i} - V_{i}^{L}) (p - p_{i}^{0})}{R T} + y_{j}^{2} \frac{δ_{i j} p}{R T}$ where p is the total pressure and $p_{i}^{0}$ is the pure component vapor pressure. R is the universal gas constant. T is the equilibrium temperature. x_i and y_i are the mole fraction of the liquid and the vapor-phase of component i, respectively. $V_{i}^{L}$ is the liquid molar volume of

Vapor–liquid equilibrium

The experimental VLE or vapor pressures for DIPE, $p_{1}^{0}$ , are reported in Table 2, whereas the corresponding p⁰ values for DMF, $p_{2}^{0}$ , have been previously reported elsewhere [8]. For DIPE and DMF, the temperature dependence of $p_{i}^{0}$ was correlated using the Antoine Eq. (4), where the corresponding A_i, B_i, C_i constants have been summarized in Table 3. In both cases, Eq. (4) correlated the vapor pressure data of the pure fluids within a maximum absolute percentage deviation (ADP) of 0.13%. Comparing

Conclusions

Vapor–liquid equilibrium and interfacial properties (concentration profile in the interfacial region, surface activity and surface tension) for the binary system DIPE + DMF have been described over the whole mole fraction range. According to experimental VLE results, the mixture exhibits slight positive deviation from the ideal behavior and does not present azeotropic behavior over the studied experimental range. The phase equilibrium data of the binary mixture satisfies the Fredenlund's

Funding sources

This work was financed by FONDECYT, Santiago, Chile (Project 1120228), and FCT–Fundação para a Ciência e a Tecnologia, through the project Pest-C/CTM/LA0011/2011. M.B.O. also acknowledges to postdoctoral grant SFRH/BPD/71200/2010.

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Isobaric vapor–liquid equilibrium and isothermal surface tensions of 2,2′-oxybis[propane] + 2,5-Dimethylfuran

Abstract

Introduction

Section snippets

Purity of materials

Vapor–liquid equilibrium cell

Experimental data treatment and consistency

Vapor–liquid equilibrium

Conclusions

Funding sources

Combust. Flame

Fuel

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Am. Chem. Soc.

Nature

Energy Fuels

Struct. Chem.

Justus Liebigs Ann. Chem.

J. Chem. Eng. Data

Ind. Eng. Chem. Res.

Ind. Eng. Chem. Res.

Ind. Eng. Chem. Res.

Thermodynamic Models for Industrial Applications: From Classical and Advanced Mixing Rules to Association Theories