Thermodynamics properties of binary mixtures of aqueous solutions of glycols at several temperatures and atmospheric pressure

doi:10.1016/j.jct.2018.02.022

The Journal of Chemical Thermodynamics

Volume 122, July 2018, Pages 38-64

https://doi.org/10.1016/j.jct.2018.02.022 Get rights and content

Highlights

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Binary mixtures of (water + glycols) mixtures.
•
Volumetric, acoustic and viscometric properties were determined.
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Temperature range was T = (293.15 to 308.15) K.

Abstract

Densities (ρ), speeds of sound (u) and viscosities (η) for binary mixtures of {water + ethanol, or + ethylene glycol (EG), or + diethylene glycol (DEG), or + triethylene glycol (TEG), or + polyethylene glycol (PEG) 200, or + polyethylene glycol (PEG) 300, or + polyethylene glycol (PEG) 400, or + polyethylene glycol (PEG) 600, or + glycerol} have been determined as a function of composition at T = (293.15, 298.15, 303.15 and 308.15 K) and atmospheric pressure. From these results, excess molar volume ( $V_{m}^{E}$ ), deviation in isentropic compressibility (Δκ_S), deviation in viscosity (Δη), and excess Gibbs energy of activation for viscous flow (ΔG^∗E) were calculated and fitted by the Myers-Scott equation, as a function of mole fraction. Values of $V_{m}^{E}$ and Δκ_S were negative over the entire composition range for all mixtures studied. The values of Δη were negative for the systems containing ethylene glycol and glycerol and positive for the systems containing ethanol, PEG 400 and PEG 600. For other systems, the deviation of viscosity presented an S-shape, with negative values at high water concentration. For all mixtures studied, the values of ΔG^∗E were positive over the entire composition range. The results obtained were discussed in terms of structural effects and intermolecular interactions between like and unlike molecules.

Introduction

Experimental data of density, speed of sound and viscosity of liquid mixtures and the derived properties are very important in many industrial processes where fluid flow is important. Moreover, knowledge of the dependence of volumetric, acoustic and viscometric properties of mixtures liquid is a powerful tool in understanding the physicochemical properties of liquid systems.

Poly(ethylene glycol) (PEGs) include a class of compounds with molar mass ranging from (200 to 10,000) g·mol⁻¹. These compounds have been used in many areas of science, with wide application in chemistry, biochemistry, pharmaceutical, industrial fields, in the extraction-crystallization of inorganic salts, among others [1]. PEGs also have important clinical uses because of low toxicity and solubility in water and in organic solvents. As examples of the wide application of PEGs, we can mention: in cosmetics (such as surfactants, cleaning agents, emulsifiers, skin conditioners and moisturizers) [2] in toothpastes as a dispersant, in gas chromatography as polar stationary phase, in wood preservation by replacing water in wooden objects, in the production of non-ionic surfactants by coupling with hydrophobic molecules, in edible film preparation in which PEGs act as plasticizers and their applications to foods [3]. Mixtures of PEGs with water also find many applications in biochemical and biomedical processes, such as biomaterial separation and purification, cell fusion, as well as glucose sensors [4].

Thermodynamics properties of binary mixtures containing glycols have been studied by Hamam et al. [5] (excess enthalpies of binary mixtures of diethylene glycol and triethylene glycol with water), Aminabhavi and Gopalakrishna [6] (densities, viscosities, refractive indices and speeds of sound of binary mixtures of water with ethylene glycol and diethylene glycol), Pal and Singh [7] (speeds of sound and viscosities of binary mixtures of ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol with water), Kirincic and Klofutar [8] {densities of aqueous solutions of poly(ethylene glycol)s 300, 400, 600, 900, 1000, 1500, 2000, 3000, 4000, 6000, 10,000, 12,000, 15,000, 20,000, 35,000}, Kirincic and Klofutar [9] {viscosities of aqueous solutions of poly(ethylene glycol)s 300, 400, 600, 900, 1000, 1500, 2000, 3000, 4000, 6000, 10,000, 12,000, 15,000, 20,000, 35,000}, Eliassi et al. [10] {activities of water for aqueous solution of poly(ethylene glycol)s 300, 400, 4000 and 6000}, Aucouturier et al. [11] {densities and heat capacities of aqueous solutions of poly(ethylene glycol)s 300, 400 and 600}, Yang et al. [12] (densities, viscosities and heat capacities of binary mixture of ethylene glycol with water), Rahbari-Sisakht et al. [13] {densities and viscosities of binary mixtures of poly(ethylene glycol) 200, 300 and 600 and poly(propylene glycol) with water and ethanol}, Valtz et al. [14] (densities of binary mixtures of triethylene glycol with water), Bigi and Comeli [1] {excess molar enthalpies of binary mixtures of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and poly(ethylene glycol)s 200, 300, 400 and 600 with ethanol}, Zafarani-Moattar and Tohidifar [15] {vapor-liquid equilibria, densities and speeds of sound of binary system of poly(ethylene glycol) 400 with methanol}, Kinart et al. [16] {densities of binary mixtures of poly(ethylene glycol) 300 with 2-ethoxyethanol, 2-(2-ethoxyethoxy)ethanol, 2-[2-(2-ethoxyethoxy)ethoxy]ethanol}, Hanke et al. [4] {densities and speeds of sound of binary mixtures of poly(ethylene glycol) 200, 400 and 600 with water}, Kinart et al. [17] (densities and relative permittivities of binary mixtures of ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol with sulfolane), Sastry et al. [18] (densities, viscosities, speeds of sound and relative permittivities of binary mixtures of diethylene glycol with nitrobenzene and triethylene glycol with chlorobenzene, bromobenzene and nitrobenzene), Zafarani-Moattar and Tohidifar [19] {vapor-liquid equilibria, densities, speeds of sound and viscosities of binary system of poly(ethylene glycol) 400 with ethanol}, Han et al. [20] {densities and viscosities of binary system of poly(ethylene glycol) 400 with water}, Ayranci and Sahin [3] {densities and speeds of sound of aqueous solutions of ethylene glycol and poly(ethylene glycol)s 200, 300, 400, 550, 600, 1000, 1450, 3350, 8000 and 10,000}, Trivedi et al. [21] {densities of aqueous solution of poly(ethylene glycol)s 200, 400, 600 and 1500}, Yasmin and Gupta [22] {densities, viscosities, speeds of sound and refractive indices of binary mixtures of poly(ethylene glycol) 200 with ethanolamine, m-cresol and aniline}, Vural et al. [23] (densities, viscosities and refractive indices for binary mixtures of glycerol with water and methanol), Zhang et al. [24] {densities and viscosities of binary mixtures of poly(ethylene glycol) 400 with dimethylsulfoxide and poly(ethylene glycol) 600 with water}, Zhang et al. [25] {densities and viscosities for binary system of poly(ethylene glycol) 300 with water}, Egorov and Makarov [26] (densities of binary mixture of glycerol with tert-butanol), Kijevcanin et al. [27] (densities, viscosities and refractive indices of binary mixture pyridine with glycerol), Aniya et al. [28] (densities, refractive index and isobaric vapor-liquid equilibrium for the binary system of water with triethylene glycol), Begum et al. [29] {densities, refractive indices and viscosities for aqueous solution of poly(ethylene glycol)s 300 and 400} and Ebrahimi and Sadeghi [30] {densities, speeds of sound and viscosities of aqueous solution of poly(ethylene glycol)s 600 and 10,000}.

The purpose of this work was to study aqueous binary mixtures containing glycols reporting new experimental values of densities (ρ), speeds of sound (u) and viscosities (η) for binary mixtures of {water + ethanol, or + ethylene glycol (EG), or + diethylene glycol (DEG), or + triethylene glycol (TEG), or + polyethylene glycol (PEG) 200, or + polyethylene glycol (PEG) 300, or + polyethylene glycol (PEG) 400, or + polyethylene glycol (PEG) 600, or + glycerol} as a function of composition at T = (293.15, 298.15, 303.15 and 308.15 K) and atmospheric pressure. From these results, excess molar volume ( $V_{m}^{E}$ ), deviation in isentropic compressibility ( $Δ κ_{S}$ ), deviation in viscosity ( $Δ η$ ), and excess Gibbs energy of activation of viscous flow ( $Δ G^{* E}$ ) were calculated and fitted by the Myers-Scott equation. The results were analyzed in terms of structural effects and intermolecular interactions between like and unlike molecules.

Section snippets

Materials

Ethanol (Merck, mass fraction purity >0.999), ethylene glycol (Oxiteno, mass fraction purity >0.999), diethylene glycol (Synth, mass fraction purity >0.99), triethylene glycol (Sigma-Aldrich, mass fraction purity >0.99), poly(ethylene glycol) 200 (Oxiteno, ULTRAPEG 200), poly(ethylene glycol) 300 (Oxiteno, ULTRAPEG 300), poly(ethylene glycol) 400 (Oxiteno, ULTRAPEG 400), poly(ethylene glycol) 600 (Oxiteno, ULTRAPEG 600), glycerol (Synth, mass fraction purity >0.999) were used without further

Results and discussion

The experimental results of mole fraction (x₁), densities (ρ), speeds of sound (u), excess molar volumes ( $V_{m}^{E}$ ) and deviations in isentropic compressibility ( $Δ κ_{S}$ ) for the binary mixtures studied at different temperatures are listed in Table 3. Figs. S1–S18 also show the values of densities and speeds of sound over the entire composition range for the binary mixtures studied at different temperatures. The experimental results of densities (ρ), viscosities (η), deviation in viscosity ( $Δ η$ ) and

Conclusions

This paper reports experimental values of densities (ρ), speeds of sound (u) and viscosities (η) for binary mixtures of {water + ethanol, or + ethylene glycol (EG), or + diethylene glycol (DEG), or + triethylene glycol (TEG), or + polyethylene glycol (PEG) 200, or + polyethylene glycol (PEG) 300, or + polyethylene glycol (PEG) 400, or + polyethylene glycol (PEG) 600, or + glycerol} have been determined as a function of composition at T = (293.15, 298.15, 303.15 and 308.15) K and atmospheric

Acknowledgements

The authors wish to express their gratitude to Fundação Educacional Inaciana Padre Sabóia de Medeiros (FEI) and Fundação de Amparo à Pesquisa do Estado de São Paulo – Brazil (FAPESP) for their financial support (Process N^o 2010/17442-7 and Process N^o 2009/14556-5).

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Thermodynamics properties of binary mixtures of aqueous solutions of glycols at several temperatures and atmospheric pressure

Highlights

Abstract

Introduction

Section snippets

Materials

Results and discussion

Conclusions

Acknowledgements

Thermochim. Acta

Toxicology

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Fluid Phase Equilibr.

Fluid Phase Equilibr.

J. Chem. Thermodyn.

Fluid Phase Equilibr.

J. Chem. Thermodyn.

Fluid Phase Equilibr.

J. Chem. Thermodyn.

Fluid Phase Equilibr.

J. Chem. Thermodyn.

Fluid Phase Equilibr.

J. Mol. Liq.

J. Chem. Thermodyn.

Fluid Phase Equilibr.

J. Chem. Thermodyn.