Excess molar enthalpies for binary mixtures of cyclopentanone, cyclohexanone, or cycloheptanone with n-nonane at T = 298.15 K and atmospheric pressure
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, 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:
The Redlich–Kister equation successfully correlated the experimental excess molar enthalpy values of
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