Excess molar enthalpies of R-fenchone + butan-1-ol or + pentan-1-ol. Modeling with COSMO-RS and UNIFAC

https://doi.org/10.1016/j.jct.2018.01.005Get rights and content

Highlights

  • HmE, of the binary liquid mixtures R-fenchone + butan-1-ol or pentan-1-ol, were measured.

  • HmE maxima range from 1119 (283.15 K) to 1457 J·mol−1(328.15 K) for (R-fenchone + butan-1-ol).

  • HmE maxima range from 1154 (283.15 K) to 1459 J·mol−1(328.15 K) for (R-fenchone + pentan-1-ol).

  • UNIFAC provides better predictions for HmE than COSMO-RS for both mixtures.

  • UNIFAC provides fair predictions of HmE for both mixtures (maximum ΔAAD of 10.4).

Abstract

In this paper, experimental isobaric excess molar enthalpies for the binary mixtures of R-fenchone with butan-1-ol or pentan-1-ol at four temperatures (283.15, 298.15, 313.15 and 328.15) K and atmospheric pressure are reported over the entire composition range. They have been fitted to the Redlich–Kister equation at each temperature. Excess molar enthalpies are positive in all cases, being slightly greater for the mixture with pentan-1-ol than for the mixture with butan-1-ol. These positive values of the excess molar enthalpy suggest the predominance of both the effect due to hydrogen bond breaking and physical interactions over the interaction between dissimilar molecules in the mixture. Finally UNIFAC (Dortmund) method and the Quantum Continuum Method COSMO-RS have been used to predict the excess molar enthalpies. Better predictions are obtained in the case of the UNIFAC model. These experimental and modeling results obtained for excess molar enthalpies together with our previously reported ones are jointly discussed to cover binary mixtures containing R-fenchone with short chain alkan-1-ols (C2–C5).

Introduction

Extracts of plants or components of these extracts are widely used in pharmaceutical, food and cosmetic industries. There are several techniques of extraction including hydrodistillation, soaking in organic solvents or supercritical fluid extraction (SCFE). In this respect, low molar mass alkanols (C1–C6) can be used as solvents in conventional extractions of organic substances. They can be also employed as cosolvents in SCFE [1]. Then, the knowledge of the thermodynamic behavior of the mixtures (extract + alkanol) could be useful in order to improve these processes. As the extracts of plants commonly consist of a mixture of several compounds, a rigorous thermodynamic study of mixtures of the multicomponent extract with the solvent is difficult to carry out. For this reason, it is usual to consider binary mixtures of a major component of an extract with the alkanol.

One substance susceptible to this treatment is R-fenchone or (1R, 4S)-1,3,3-trimethylbicycle [2.2.1] heptan-2-one, a terpenoid that appears as the major component in the extracts of several plants such as fennel (Phoeniculum vulgare) and wormwood (Artemisia absinthium). It is used in perfumery and also as flavor in foods [2], but it has also potential uses in a variety of different fields. For example, its bio-activity as a toxic repellent and inhibitor of reproduction for insects [3] as well as an acaricidal agent [4] have been reported. Moreover, R-fenchone has been also tested as a compound drug in medical therapy for ureterolithiasis [5]. The presence of R-fenchone in the extract from seeds of fennel can justify in part the properties of these extract as green steel corrosion inhibitor in hydrochloric solution [6].

The present work is a continuation of previous studies of thermophysical properties of mixtures of R-fenchone with ethanol [7] and propanol isomers [8] with the aim of establishing a reliable physico-chemical database for biogenic compounds with industrial interest. This time, excess molar enthalpies have been measured for the binary mixtures of R-fenchone with butan-1-ol or pentan-1-ol at several temperatures between 283.15 and 328.15 K and atmospheric pressure. Additionally and considering the special molecular structure of R-fenchone, its mixtures with other compounds can constitute a demanding test to check the predictive capacity of thermodynamic models. In this case, UNIFAC (Dortmund version) method [9] and the Quantum Continuum Method COSMO-RS [10], [11], [12], [13], [14], widely applied to similar systems and that were also tested in our previous works, have been used in the present study for predicting the isobaric excess molar enthalpies.

Section snippets

Materials

Butan-1-ol, pentan-1-ol and R-fenchone were used as chemicals and their description can be found in Table 1. Water, also included in Table 1, was used to check the correct operation of the densimeter. Experimental values of density for the pure components and its comparison with literature data [15], [16], [17], [18], [19], [20] are reported in Table 2. In general, a good agreement can be observed between both sets of values.

Equipment and procedure

Excess enthalpies were determined experimentally by means of a

Experimental excess molar enthalpies for the binary mixtures {R-fenchone (1) + butan-1-ol (2)} and {R-fenchone (1) + pentan-1-ol (2)}

The experimental values of excess molar enthalpies, HmE, for the binary mixtures {R-fenchone (1) + butan-1-ol (2)} and {R-fenchone (1) + pentan-1-ol (2)} at the temperatures (283.15, 298.15, 313.15, and 328.15) K and atmospheric pressure are listed in Table 3 and are graphically represented in Fig. 1. Excess molar enthalpies were fitted, at every temperature, to the usual Redlich–Kister equationHmE=x1(1-x1)i=1nAi(2x1-1)i-1,where Ai are adjustable coefficients and n is the number of

Conclusions

Experimental excess molar enthalpies have been determined over the entire composition range for the binary mixtures of R-fenchone with butan-1-ol or pentan-1-ol at atmospheric pressure and at four temperatures (283.15, 298.15, 313.15 and 328.15) K. Excess molar enthalpies show positive values in the entire composition range at all working temperatures. The binary mixtures with pentan-1-ol have excess molar enthalpy values slightly higher than those mixtures with butan-1-ol at the same

Acknowledgements

The authors are grateful for the financial support to MINECO-FEDER (CTQ2015-64049-C3-2-R); and to Departamento de Ciencia, Tecnología y Universidad; del Gobierno de Aragón-Fondo Social Europeo (Grupo E52).

References (45)

  • J.F. Martínez-López et al.

    J. Chem. Thermodyn.

    (2014)
  • J.F. Martínez-López et al.

    J. Chem. Thermodyn.

    (2015)
  • A. Klamt et al.

    Fluid Phase Equilib.

    (2000)
  • G.A. Torín-Ollarves et al.

    J. Chem. Thermodyn.

    (2012)
  • O. Hiroyuki

    J. Chem. Thermodyn.

    (2002)
  • H. Liu et al.

    J. Chem. Thermodyn.

    (2011)
  • J.P. Chao et al.

    J. Chem. Thermodyn.

    (1989)
  • I. Nagata

    Thermochim. Acta

    (1994)
  • I. Nagata et al.

    Thermochim. Acta

    (1994)
  • G. Prieto et al.

    J. Chem. Thermodyn.

    (1992)
  • J. Iñarrea et al.

    J. Chem. Thermodyn.

    (1988)
  • J.L. Legido et al.

    J. Chem. Thermodyn.

    (1986)
  • B.A. Coomber et al.

    J. Chem. Thermodyn.

    (1976)
  • L.T. Taylor

    Supercritical Fluid Extraction

    (1996)
  • J. Lawless, The Encyclopedia of Essential Oils: The Complete Guide to the Use of Aromatic Oils In Aromatherapy,...
  • E.N. Nukenine et al.

    J. Appl. Entomol.

    (2010)
  • H.-S. Lee

    J. Agric. Food Chem.

    (2004)
  • M.E. Chua et al.

    Urolithiasis

    (2013)
  • A.S. Fouda et al.

    Desalin. Water Treat.

    (2014)
  • U. Weidlich et al.

    Ind. Eng. Chem. Res.

    (1987)
  • A. Klamt

    J. Phys. Chem.

    (1995)
  • A. Klamt et al.

    J. Phys. Chem. A.

    (1998)
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