Thermodynamic and transport properties of acetonitrile + alkanediols liquid mixtures at different temperatures, experimental measurements and modeling

https://doi.org/10.1016/j.jct.2017.06.004Get rights and content

Highlights

  • Densities, viscosities and refractive indices of acetonitrile + diols were measured.

  • The negative excess molar volumes and excess viscosities were calculated.

  • Different models were applied to correlate and predict the experimental data.

  • The molecular interaction in the mixtures were discussed using obtained results.

Abstract

In this paper, experimental values of densities, viscosities and refractive indices of acetonitrile + 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol and poly (ethylene glycol) 200 binary liquid mixtures were measured at temperatures of 293.15, 298.15 and 303.15 K and atmospheric pressure (0.1 MPa) over the whole composition range. From the experimental measurements, different thermophysical properties including the excess molar volume, partial molar volume, partial molar volume at infinite dilution, thermal expansion coefficient, excess thermal expansion coefficient, molar refraction, refractive index deviation and viscosity deviation were calculated. Interactions between molecules in the mixtures are discussed using the obtained thermodynamic results. Moreover, to report the adjustable parameters and determine the prediction and correlation accuracy, models including the Peng-Robinson, Redlich-Kister, Prigogine–Flory–Patterson, Rackett, Lorentz-Lorentz, Andrade and two parameters McAllister equations were applied.

Introduction

Thermophysical properties of multicomponent liquid mixtures, such as density, viscosity and refractive index along with their derived excess or deviation quantities are essential for the industrial process design, extent of models, and understanding the molecular interactions in the mixtures. These properties change by the variation of composition, temperature and pressure, which can be investigated without any reference to assumption models. The sign and value of these quantities depend on the physical and chemical nature of the components of a mixture, the structural accommodation of the components, and the solute-solute, solvent-solvent, solute-solvent interactions.

This paper is focused on the analysis of thermodynamic, transport and optical properties of associating systems including the acetonitrile + alkanediols binary liquid mixtures. Acetonitrile possesses an interesting structure with two sites for accepting a hydrogen bond. One site is the lone electron pairs of the nitrogen atom (σ bonding) and the other site is the Ctriple bondN triple bond (π bonding). Moreover, it has a high polarity index of 5.8 and hydrogen bond basicity (nucleophilicity). Alkanediols can form intra and intermolecular H-bonds due to the presence of -OH groups in their structures. Because of H-bonding systems in the mixtures of acetonitrile and alkanediols, it is expected that these mixtures exhibit strongly negative deviations from the Raoult’s law characterized by large and negative values of the excess molar enthalpies and excess molar volumes. The type and extent of the hydrogen bonding in these mixtures depend on the alkanediols’s properties, such as length, degree of branching of molecules and number and positions of the functional groups. The objective of this research is to quantify the effect of the single bondOH groups in alkanediols on the volumetric and viscometric properties of the studied mixtures. Moreover, these studied systems have found noticeable applications in the chemical industries [1], [2], [3], [4].

Survey of scientific literature shows that the numerous thermodynamic and transport data have been reported for the mixtures consisting acetonitrile and alcohols or diols. However, comprehensive study on volumetric, viscometric and optical properties of mixtures including the acetonitrile + 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol or poly (ethylene glycol) 200 is rare. Tahery et al. [5], Tôrres et al. [6] and Nikam et al. [7] investigated the excess thermodynamic properties of acetonitrile + methanol, ethanol, 1-propanol and 1-butanol binary liquid mixtures. The results show that negative values of excess molar volume shift to positive values and positive values of excess surface tension and negative values of viscosity deviation shift to more negative values with increasing length of the diol carbon chain. Due to the same hydroxyl group in alcohols, the reported excess results could be ascribed to structural effects. Prasad et al. [8] calculated the negative excess Gibbs energy of acetonitrile + 1-butanol binary mixtures using the vapor pressure measurements. The obtained excess results indicate that strong molecular interactions take place in the liquid phase between unlike molecules. For acetonitrile + 2-alkanols binary mixtures, the positive excess molar volumes and negative viscosity deviations were obtained [9] and the explanation provided for such results was the domination dispersion forces between unlike components in the mixtures. Experimental measurements of surface tension and surface tension deviation of acetonitrile + 1,2-ethanediol, 1,2-propanediol and 1,4-butanediol binary mixtures were reported by Bagheri et al. [10]. Their research shows that surface tension decreases with increasing mole fraction of diols and the negative values of surface tension deviation varies in the order ACN + 1,2-propanediol > ACN + 1,4-butanediol > ACN + 1,2-ethanediol. Ilukhani and coworkers [11] reported the densities and excess molar volumes of acetonitrile + 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol and 1,2-hexanediol binary mixtures over the entire composition range at T = 293.15 K. The obtained negative excess molar volumes values were ascribed to dissociation of the self-associated 1,2-alkanediol molecules and the formation of aggregates between unlike molecules through the Osingle bondH…Ntriple bondC hydrogen bonding. Nain and coworkers [12] reported the experimental values of densities, refractive indices, ultrasonic speed of sound and calculated values of excess molar volume and excess molar isentropic compressibility of acetonitrile + PEG 200, PEG 300 and PEG 400 binary mixtures at different temperatures. Negative excess molar volume and excess molar isentropic compressibility were obtained for ACN + PEG binaries and the negative excess values were reported to the increase with increase of PEG molar mass.

In this research, experimental measurements of densities, viscosities and refractive indices of acetonitrile (ACN) + 1,2-ethanediol (1,2-ED), 1,2-propanediol (1,2-PD), 1,3-propanediol (1,3-PD) and poly (ethylene glycol) 200 gr.mol−1 (PEG 200) are reported over the entire composition range and temperatures of 293.15, 298.15 and 303.15 K at atmospheric pressure (0.1 MPa). From the experimental measurements, thermal expansion coefficient, excess thermal expansion coefficient, excess molar volumes, partial molar volume, partial molar volume at infinite dilution, molar refraction, refractive index deviation, and viscosity deviation were calculated and the excess molar volume and refractive index deviation have been correlated to Redlich-Kister polynomial equation. Moreover, the experimental values of density, viscosity and refractive index have been predicted and correlated with Rackett, Peng-Robinson, Prigogine–Flory–Patterson, Lorentz-Lorentz, McAllister, Heric, Arrhenius-like and Andrade models. Finally, the obtained information was used to discuss the nature and strength of molecular interactions and phase behavior of these studied liquid mixtures.

Section snippets

Experimental

Chemicals. All used liquids including the Acetonitrile, poly (ethylene glycol) 200, 1,2-ethanediol, 1,2-propanediol and 1,3-propanediol were supplied by Merck. The purity of these chemicals was higher than 98% and their water content was less than 0.25%. All these chemicals were used without further purification. The water content of the chemicals was measured with Kyoto mks-210 Karl Fischer instrument to be aware of the effect of water on temperature control. Table 1 shows the specifications

Results and discussion

Thermodynamic properties. The experimental values of densities ρ, dynamic viscosities η, and calculated values of thermal expansion coefficients αp, excess molar volumes VmE, and viscosities deviation Δη, of acetonitrile (x1) + 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol and PEG 200 binary mixtures at T = 293.15, 298.15 and 303.15 K and atmospheric pressure (0.1 MPa·s) are listed in Table 3, Table 4, Table 5, Table 6, respectively.

The variation of density against ACN composition for binary

Conclusions

In this work, experimental values of densities, refractive indices and viscosities of acetonitrile and 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol or poly (ethylene glycol) 200 binary liquid mixtures were measured over the whole composition range and temperatures of 293.15, 298.15 and 303.15 K. To understand how the position and number of hydroxyl groups of diols affect the molecular interactions and structural arrangements in the ACN + diols systems, different excess and deviation quantities

Acknowledgment

The instrumental support from Shomal University is gratefully acknowledged.

References (52)

  • E. Zorębski et al.

    Thermodynamic and transport properties of (1,2-ethanediol+1-nonanol) at temperatures from (298.15 to 313.15) K

    J. Chem. Thermodyn.

    (2009)
  • H. Zarei et al.

    Experimental studies on volumetric and viscometric properties of binary and ternary mixtures of N, N-dimethylacetamide, N-methylformamide and propane-1,2-diol at different temperatures

    J. Mol. Liq.

    (2013)
  • D.M. Bajić et al.

    Experimental measurements and modelling of volumetric properties, refractive index and viscosity of selected binary systems with butyl lactate at 288.15-323.15 K and atmospheric pressure. New UNIFAC-VISCO interaction parameters

    Thermochim. Acta

    (2013)
  • M. Moosavi et al.

    Investigation on some thermophysical properties of poly(ethylene glycol) binary mixtures at different temperatures

    J. Chem. Thermodyn.

    (2013)
  • M. Moosavi et al.

    Isobaric, isothermal theoretical investigation and examination of different prediction equations on some physicochemical properties in PEG liquid polymer system

    J. Chem. Thermodyn.

    (2014)
  • M. Atilhan et al.

    PρT measurements and derived properties of liquid 1,2-alkanediols

    J. Chem. Thermodyn.

    (2013)
  • M. Hou et al.

    Determination and modeling of solubility of CO2 in PEG200+1-pentanol and PEG200+1-octanol mixtures

    Fluid Phase Equilib.

    (2007)
  • M. Hemmat et al.

    Study on volumetric and viscometric properties of 1,4-dioxane and 1,2-ethanediol/1,3-propanediol binary liquid mixtures, measurement and prediction

    J. Mol. Liq.

    (2017)
  • I. Demeter, E. Itsov, Acetonitrile: Properties, applications and health effects, 2012....
  • F. Van Bambeke et al.

    Glycopeptide antibiotics: from conventional molecules to new derivatives

    Drugs

    (2004)
  • N.A. Peppas, Principles of Polymer Science and Technology in Cosmetics and Personal Care, 2000. doi:...
  • R. Tahery et al.

    Density and surface tension of binary mixtures of acetonitrile + 1-alkanol at 293.15 K

    J. Chem. Eng. Data

    (2006)
  • P.S. Nikam et al.

    Density and viscosity studies of binary mixtures of acetonitrile with methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, 2-methylpropan-1-ol, and 2-methylpropan-2-ol at (298.15, 303.15, 308.15, and 313.15) K

    J. Chem. Eng. Data

    (1998)
  • T.E.V. Prasad, A. Kumar, S. Naresh, D.H.L. Prasad, Excess Gibbs free energies of the binary mixtures of acetonitrile...
  • A. Bagheri et al.

    Prediction of the surface tension, surface concentration and the relative gibbs adsorption isotherm of non-ideal binary liquid mixtures

    J. Solution Chem.

    (2013)
  • H. Iloukhani et al.

    Volumetric properties of acetonitrile with 1,2-alkanediols (C2–C6) at 20 °C

    J. Solution Chem.

    (2001)
  • Cited by (7)

    • Volumetric, acoustic and viscometric properties of binary mixtures containing acetonitrile with glycols at several temperatures: Experimental study and correlations

      2022, Journal of Chemical Thermodynamics
      Citation Excerpt :

      Thermodynamic properties of binary mixtures of acetonitrile, glycols or similar substances have been studied by many authors: Iulian and Ciocirlan [2], Laavi et al. [3], Geppert-Rybczynska and Sitarek [4], Varfolomeev et al. [5], Nain [6], Singh et al. [7], Ouaar et al. [8], Anwar and Riyazuddeen [9], Droliya and Nain [10], Kaur et al. [11], Francesconi and Ottani [12], Kinart et al. [13], Sastry et al. [14], Rani and Maken [15], Rani et al. [16], Singh et al. [17]. After several reports on binary liquid mixtures including acetonitrile or glycols, a paper by Moosavi et al. [18] measured experimental values of density, viscosity and refractive index of acetonitrile + ethylene glycol. However, data about acetonitrile and other glycols are scarce and this explains the importance to study these systems.

    View all citing articles on Scopus
    View full text