Volumetric and viscometric properties of binary mixtures of {methyl tert-butyl ether (MTBE) + alcohol} at several temperatures and p = 0.1 MPa: Experimental results and application of the ERAS model

doi:10.1016/j.jct.2011.02.018

The Journal of Chemical Thermodynamics

Volume 43, Issue 8, August 2011, Pages 1104-1134

https://doi.org/10.1016/j.jct.2011.02.018 Get rights and content

Abstract

Densities and viscosities of binary mixtures of {methyl tert-butyl ether (MTBE) + methanol, or +ethanol, or +1-propanol, or +2-propanol, or +1-butanol, or +1-pentanol, or +1-hexanol} have been determined as a function of composition at several temperatures and atmospheric pressure. The temperatures studied were (293.15, 298.15, 303.15, and 308.15) K. The experimental results have been used to calculate the excess molar volume $(V_{m}^{E})$ and viscosity deviation (Δη). Both $V_{m}^{E}$ and Δη values were negative over the entire range of mole fraction for all temperatures and systems studied. Moreover, the $V_{m}^{E}$ values have been used to test the applicability of the Extended Real Associated Solution (ERAS) model.

Highlights

► Binary mixtures of MTBE + alcohol have been studied. ► Volumetric and viscometric properties have been determined at several temperatures. ► Excess molar volumes have been used to test the applicability of the ERAS model. ► The results are discussed in terms of chemical and structural effects.

Introduction

Excess properties have been a qualitative and quantitative way to predict the deviation from ideal behaviour of liquid binary mixtures compared to experimental data. These properties can provide information about intermolecular interactions between components. Density and viscosity data are required in many chemical engineering calculations involving fluid flow, heat and mass transfer. Knowledge of dependency of volumetric and viscometric properties at different temperatures is required for process design and operation [1]. Moreover, there is interest in using volumetric data to test molecular theory and models of solution.

As a continuation of our studies on excess properties of binary liquid mixtures and to understand the interactions between ether and alcohols, in this work we report volumetric and viscometric properties of {methyl tert-butyl ether (MTBE) + methanol, or +ethanol, or +1-propanol, or +2-propanol, or +1-butanol, or +1-pentanol, or +1-hexanol} over the complete composition range at the temperatures of (293.15, 298.15, 303.15, and 308.15) K and atmospheric pressure. In addition, the ERAS model has been used to predict the excess molar volumes for the systems studied.

Oxygenated compounds (ether and alcohol) have been important additives for gasoline over the past decade. The importance of MTBE is based primarily on its exceptionally good octane-enhancing properties when used as a gasoline blend stock. Addition of MTBE cuts down exhaust emissions, particularly carbon monoxide, unburned hydrocarbons, polycyclic aromatics, and particulate carbon [2]. Methanol is used in chemical syntheses in the following order of importance: formaldehyde, MTBE, acetic acid, methyl methacrylate, and dimethyl terephthalate. Only a small proportion is utilized for energy production and it is also used as an antifreeze in heating and cooling circuits [3]. Ethanol is an organic chemical with many applications, mainly in alcoholic beverages, as a solvent and a raw material in chemical synthesis and fuel [4]. The alcohols, 1-propanol is used principally as a solvent in printing inks, paint, cosmetics, pesticides, and insecticides [5], 2-propanol primarily as a solvent in inks and surfactants [5], 1-butanol in the field of surface coating [6], 1-pentanol as a solvent, extracting agent, and starting material for lubricant additives and for auxiliaries in flotation [7], and finally 1-hexanol as a solvent, as a basic material for the perfume industry, and for the production of plasticizers [8].

Thermodynamic and physicochemical properties of binary liquid mixtures of ethers with alcohols have been studied by Farkova et al. [9] (methanol + butyl methyl ether, or +tert butyl methyl ether, or +ethyl propyl ether, or +diisopropyl ether, or +butyl ethyl ether), Toghiani et al. [10] (methanol + methyl tert-butyl ether, or +tert-amyl methyl ether), Coto et al. [11] (methanol + methyl tert-butyl ether, or +tert-amyl methyl ether), Canosa et al. [12] (diethyl ether + methanol, or +ethanol), Kammerer et al. [13] (ethanol + ethyl tert-butyl ether), Rezanova et al. [14] (diisopropyl ether, or dibutyl ether + methanol, or +ethanol, or +2-propanol, or +1-butanol, or +2-butanol), Gonzalez et al. [15] (methyl tert-butyl ether, or tert-amyl methyl ether, or ethyl tert-butyl ether + methanol, or +ethanol, or +1-propanol, or +2-propanol or +1-butanol), Rezanova et al. [16] (tert-amyl methyl ether + ethanol, or +1-propanol, or +2-propanol, or +1-butanol, or +2-butanol, or +1-octanol), Rezanova and Lichtenthaler [17] (butyl-vinyl ether, or iso-butyl-vinyl ether + ethanol, or +1-butanol, or +iso-butanol), Segade et al. [18] (methyl tert-butyl ether + 1-propanol), Piñeiro [19] (diisopropyl ether + alcohol from methanol to 1-undecanol), Aznarez et al. [20] (tetraethylene glycol dimethyl ether + 2-propanol, or +2-butanol, or +2-pentanol), and Gómez-Marigliano et al. [21] (methyl tert-butyl ether, or tert-amyl methyl ether, or diisopropyl ether + 1-propanol).

Nevertheless, to the best of our knowledge, there is no published study of excess molar and viscosity deviation with application of ERAS model at several temperatures for the systems studied in the present work.

Section snippets

Experimental

Methyl tert-butyl ether (Sigma–Aldrich, mole fraction purity > 0.998), methanol (Merck, mole fraction purity > 0.999), ethanol (Merck, mole fraction purity > 0.999), 1-propanol (Merck, mole fraction purity > 0.995), 2-propanol (JT Baker, mole fraction purity > 0.999), 1-butanol (Merck, mole fraction purity > 0.995), 1-pentanol (Riedel-de Haen AG, mole fraction purity > 0.99), 1-hexanol (Fluka Chemika, mole fraction purity > 0.98) were used without further purification. The water content in the MTBE and

Results

The excess molar volume is defined by $V_{m}^{E} = V_{m} - x_{1} V_{1}^{o} - x_{2} V_{2}^{o},$ in which V_m represents the volume of a mixture containing one mole of (MTBE + alcohol), x₁ and x₂ are the mole fractions of components 1 (MTBE) and 2 (alcohol), respectively, and $V_{1}^{o}$ and $V_{2}^{o}$ are the molar volumes of pure components.

The $V_{m}^{E}$ can be expressed by the following equation: $V_{m}^{E} = x_{1} M_{1} (1 / ρ - 1 / ρ_{1}) + x_{2} M_{2} (1 / ρ - 1 / ρ_{2}),$ in which M₁, M₂, ρ₁, ρ₂ represent the molar masses and densities of the pure components, respectively, and ρ is the density of

Discussion

Figure 1 shows the values of $V_{m}^{E}$ for the systems studied together with the smoothing curves using equation (4) at T = 298.15 K. For all systems studied, the $V_{m}^{E}$ is negative over the entire composition range and around 0.50 to 0.55 mole fraction of MTBE it becomes more negative in the sequence: 2-propanol < ethanol < methanol ≈ 1-propanol < 1-butanol < 1-pentanol < 1-hexanol. Negative values of $V_{m}^{E}$ may be attributed to strong specific or chemical interactions between the components present in the mixtures or

The ERAS model

Experimental results of the $V_{m}^{E}$ have been used to test the applicability of ERAS model [62] for all (MTBE + alcohol) systems studied. The relevant equations of the model have been given elsewhere [63]. The version of the model used here has been simplified using the following assumptions: alcohols auto-associate through hydrogen bond; MTBE does not auto-associate but it can form cross association through the hydrogen bond with molecules of alcohols. The parameters of pure components used in the

Acknowledgements

This work has been supported by the Fundação Educacional Inaciana Padre Sabóia de Medeiros (FEI) and Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP), Process No. 2009/14556-5.

References (75)

J. Farkova et al.
Fluid Phase Equilib.
(1995)
R.K. Toghiani et al.
Fluid Phase Equilib.
(1996)
B. Coto et al.
Fluid Phase Equilib.
(1997)
J. Canosa et al.
Fluid Phase Equilib.
(1999)
K. Kammerer et al.
Fluid Phase Equilib.
(1999)
E.N. Rezanova et al.
J. Chem. Thermodyn.
(2000)
E.N. Rezanova et al.
J. Chem. Thermodyn.
(2000)
Á. Piñeiro
Fluid Phase Equilib.
(2004)
S. Aznarez et al.
J. Mol. Liq.
(2006)
T.M. Letcher et al.
Fluid Phase Equilib.
(1997)

U. Domanska

Fluid Phase Equilib.

(1997)

R.B. Tôrres et al.

Fluid Phase Equilib.

(2003)

D.M. Jain et al.

J. Mol. Liq.

(2009)

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^☆: Presented at the 21st International Conference on Chemical Thermodynamics held in Tsukuba Science City, Japan, 1–6 August 2010.

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Volumetric and viscometric properties of binary mixtures of {methyl tert-butyl ether (MTBE) + alcohol} at several temperatures and p = 0.1 MPa: Experimental results and application of the ERAS model☆

Abstract

Highlights

Introduction

Section snippets

Experimental

Results

Discussion

The ERAS model

Acknowledgements

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