Excess molar enthalpies for binary mixtures of cyclopentanone, cyclohexanone, or cycloheptanone with n-nonane at T = 298.15 K and atmospheric pressure

https://doi.org/10.1016/j.jct.2014.03.007Get rights and content

Highlights

  • HE for binary systems of cycloalkanones with n-nonane have been measured.

  • Experimental data were well represented by the Redlich–Kister equation.

  • The experimental results have been used to test the applicability of the Wilson, NRTL and UNIQUAC models.

Abstract

Excess molar enthalpies, HE, for the binary mixtures of cyclopentanone, cyclohexanone, or cycloheptanone with n-nonane were measured at T = 298.15 K and 0.1 MPa, by means of a Setaram Tian-Calvet MS80 microcalorimeter. All the binary systems investigated show endothermic behaviour (positive values) over the whole mole fraction range. The molar excess enthalpies decrease as the size of the cycloalkanone increases. The experimental results of HE are fitted to the Redlich–Kister equation to correlate the composition dependence. The experimental HE data are also used to test the suitability of the Wilson, NRTL, and UNIQUAC models. The correlation of excess enthalpy data in these binary systems using the UNIQUAC model provides relatively the most appropriate results.

Introduction

From a theoretical point of view, the excess molar enthalpies can be used to study the energetic interactions between the molecules present in a mixture, such as the three van der Waals forces (orientation, induction, dispersion), and hydrogen bonding interactions, etc. Moreover, in modern separation design, an important part of many phase-equilibrium calculations is the mathematical representation of pure-component and mixture enthalpies. Mixture enthalpy data are important not only for determination of heat loads, but also for the design of distillation units. Furthermore, mixture enthalpy data, when available, are useful for extending (vapour + liquid) equilibria to higher (or lower) temperatures, through the use of the Gibbs–Helmholtz equation [1], [2].

This work reports the experimental excess molar enthalpies of cyclopentanone, cyclohexanone, or cycloheptanone with n-nonane, respectively, at T = 298.15 K and 0.1 MPa. As far as we know, no previous HE measurements for the binary mixtures investigated were found in the literature despite their great theoretical and technical interest. The measured values were fitted by the Redlich–Kister equation. Thermodynamic models (the Wilson, NRTL, and UNIQUAC) based on the local composition theory were also examined for the suitability by correlating experimental HE data with compositions.

Section snippets

Materials

All chemicals of cyclopentanone, cyclohexanone, cycloheptanone, and n-nonane were supplied by J&K Scientific Company (Beijing, China). The mass fraction purity of substances, checked by gas chromatography, was not less than 0.996. Evidence of chemical purity was also provided by comparison of measured refractive indices, nD298.15K and densities, ρ298.15K with the literature values, in table 1. Densities were measured using a vibrating-tube densimeter and a sound analyser, Mettler-Toledo model

Results and discussion

Experimental values of molar excess enthalpies at T = 298.15 K and atmospheric pressure are given in table 2 and shown graphically in figure 1. In all the binaries, x1 is the mole fraction of the n-nonane.

The excess enthalpies for cyclopentanone, cyclohexanone, or cycloheptanone with n-nonane are large and positive over the entire range of mole fractions. The curves of excess molar enthalpies vs. composition vary almost symmetrically and maximum positive values are (1430 J · mol−1 at x1 = 0.5556), (1334

Conclusions

Excess molar enthalpies for several binary mixtures involving cycloalkanones with n-nonane have been measured at the temperature 298.15 K and atmospheric pressure, over the whole mole fraction range. It was found that mixing process is endothermic for all binary systems. The values of HE for the mixtures containing n-nonane increase in the sequence:cyclopentanone>cyclohexanone>cycloheptanon.

The Redlich–Kister equation successfully correlated the experimental excess molar enthalpy values of

References (30)

  • H. Dong et al.

    J. Chem. Thermodyn.

    (2006)
  • S.K. Jangra et al.

    Thermochim. Acta

    (2012)
  • D. Dragoescu et al.

    Fluid Phase Equilib.

    (2008)
  • A. Barhala et al.

    J. Chem. Thermodyn.

    (2006)
  • M.M. Piñeiro et al.

    Fluid Phase Equilib.

    (2006)
  • J.G. Baragi et al.

    J. Chem. Thermodyn.

    (2006)
  • K.N. Marsh et al.

    J. Chem. Thermodyn.

    (1969)
  • J. Ortega et al.

    Fluid Phase Equilib.

    (2004)
  • A. Amigo et al.

    J. Chem. Thermodyn.

    (1990)
  • O. Kiyohara et al.

    J. Chem. Thermodyn.

    (1979)
  • J.-L.M. Abboud et al.

    Pure Appl. Chem.

    (1999)
  • C. Bermúdez-Salguero et al.

    J. Chem. Eng. Data

    (2011)
  • O. Ciocirlan et al.

    J. Chem. Eng. Data

    (2010)
  • P. Brocos et al.

    J. Chem. Eng. Data

    (2002)
  • M.V. Rathnam et al.

    J. Chem. Eng. Data

    (2010)
  • Cited by (9)

    • Topological investigations of molecular interactions in binary and ternary mixtures at varying temperatures and atmospheric pressure: Excess molar volumes and excess isentropic compressibilities

      2021, Chemical Data Collections
      Citation Excerpt :

      Liquids with their provenance, purification, analysis methods, initial as well as final mass fraction purities with water content are specified in Table 1. Purity of the liquids was assessed by comparing ρ, u of liquids [26-48] with literature data. ρ, u of binary/ternary mixtures were measured by vibrating tube density, speed of sound analyzer (Anton Paar, DSA-5000) at 3 MHz in a manner as described earlier [49,50].

    • Densities, speeds of sound and molar heat capacities of multicomponent liquid mixtures containing 1-methylpiperidine, pyrrolidin-2-one and cycloalkanones at varying temperatures

      2021, Journal of Chemical Thermodynamics
      Citation Excerpt :

      The specifications of the chemicals are summarised in Table 1. Purity of samples after purification was further checked by comparing densities, speeds of sound and molar heat capacities of pure liquids with the literature data, results being shown in Table 2 [17–52]. Despite of the fact that melting point of 2-py is around (298–299) K, no crystallization of the compound was observed at 293.15 K and 298.15 K, so the data at these temperatures are for supercooled liquid 2-py.

    • Effect of temperature on the equilibrium solubility of dimethylolpropionic acid: Measurement, correlation, thermodynamic analysis and solvent selection

      2021, Journal of Molecular Liquids
      Citation Excerpt :

      Excess enthalpy (HE) is a vital thermodynamic property of solutions. The values of HE represent molecular interactions: namely, van der Waals forces and hydrogen bonding interactions which occur during the mixing process [46,47]. As illustrated in Fig. 6, due to the breaking of strong interactions of ketone molecules, large positive HE values for MIBK are observed [47].

    • Experimental data and modeling for excess enthalpies of 2-Pentanol with n-alkanes (C7–C9) at T = (293.15, 298.15 and 303.15) K

      2020, Chinese Journal of Chemical Engineering
      Citation Excerpt :

      Excess molar enthalpies were measured at (293.15, 298.15 and 303.15) K and 0.1 MPa, with a microcalorimeter of the Tian-Calvet MS80 model by Setaram. The high sensitivity isothermal calorimeter used for the measurements and the experimental procedure were same as described previously [22–24]. The uncertainty of HE values estimates to be (0.01·HE) J·mol−1 (0.95 level of confidence).

    View all citing articles on Scopus
    View full text