Excess molar enthalpies of R-fenchone + butan-1-ol or + pentan-1-ol. Modeling with COSMO-RS and UNIFAC
Graphical abstract
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, , 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 equationwhere 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)
- et al.
J. Chem. Thermodyn.
(2014) - et al.
J. Chem. Thermodyn.
(2015) - et al.
Fluid Phase Equilib.
(2000) - et al.
J. Chem. Thermodyn.
(2012) J. Chem. Thermodyn.
(2002)- et al.
J. Chem. Thermodyn.
(2011) - et al.
J. Chem. Thermodyn.
(1989) Thermochim. Acta
(1994)- et al.
Thermochim. Acta
(1994) - et al.
J. Chem. Thermodyn.
(1992)
J. Chem. Thermodyn.
J. Chem. Thermodyn.
J. Chem. Thermodyn.
Supercritical Fluid Extraction
J. Appl. Entomol.
J. Agric. Food Chem.
Urolithiasis
Desalin. Water Treat.
Ind. Eng. Chem. Res.
J. Phys. Chem.
J. Phys. Chem. A.
Cited by (4)
Comparison of excess molar enthalpies predicted by UNIFAC model and COSMO-SAC theory with experimental data for some binary mixtures
2023, Journal of Molecular StructureSpanish Satureja montana L. hydrolate: Ecotoxicological study in soil and water non-target organisms
2022, Industrial Crops and ProductsCitation Excerpt :The pre-optimised three-dimensional chemical structures of carvacrol and thymol were procured from the PubChem database. A continuum model provided with density functional theory (parametrisation bvp86/dga1) was used to carry out the calculations (parametrisation bvp86/dga1) following the procedures described by (Martinez-Lopez et al., 2018). Water solubility, boiling temperature, octanol-water partition coefficient and vapour pressure were also estimated.
Ecotoxicity of a novel biopesticide from Artemisia absinthium on non-target aquatic organisms
2019, ChemosphereCitation Excerpt :Taken into account that physics and chemical properties for this monoterpene diol are not been reported, the quantum continuum method COSMO-RS (Eckert and Klamt, 2002; Klamt et al., 1998) has been chosen for predicting water solubility, pka and log P of the monoterpene diol. Calculations were performed using a continuum model with DFT in a two-step procedure as described before (Martinez-Lopez et al., 2018). The water solubility of the monoterpene diol was 715 mg/L, pka = 20.5 and log P = 3.1.
Supercritical antisolvent fractionation of antioxidant compounds from salvia officinalis
2021, International Journal of Molecular Sciences