On the solid–liquid equilibrium of binary mixtures of fatty alcohols and fatty acids

• Published in: Fluid phase equilibria 2014-03, Vol.366, p.88-98
• Main Authors: Maximo, Guilherme J., Carareto, Natália D.D., Costa, Mariana C., dos Santos, Adenilson O., Cardoso, Lisandro P., Krähenbühl, Maria A., Meirelles, Antonio J.A.
• Format: Article
• Language: English
• Subjects: Differential scanning calorimetry; Fatty systems; Solid–liquid equilibrium; Thermodynamic modeling; X-ray diffraction
• ISSN: 0378-3812; 1879-0224
• DOI: 10.1016/j.fluid.2014.01.004

•SLE phase diagrams of three fatty alcohol+fatty acid systems.•Experimental measurements by DSC and thermodynamic modeling for γiL calculation.•Liquid phase activity coefficients’ evaluation.•Micrographs of the solid–liquid transition and X-ray diffraction of the solid-phase. Fatty alcohols and fatty acids are used in the cosmetic, pharmaceutical and food industries as surfactants. They are also considered phase change materials for thermal storage processes. Information on their thermal properties is required for optimizing production processes as well as for improving their industrial and home use. In the present study, the solid–liquid phase diagrams of three binary systems of 1-tetradecanol+dodecanoic acid, 1-hexadecanol+tetradecanoic acid and 1-octadecanol+hexadecanoic acid were determined by differential scanning calorimetry. The phase-transition phenomena were further investigated by optical micrographs and X-ray diffraction patterns. The experimental data showed that the systems present eutectic transitions and some of them exhibit partial solid phase miscibility. The liquid phase activity coefficients were calculated by Margules 2 and 3-suffix and by UNIFAC and UNIFAC-Dortmund methods. The modeling approach resulted in an accurate prediction, with average absolute deviations from experimental data lower than 1.16K. The values of excess Gibbs free energy present an unusual behavior, with positive deviations at very low alcohol concentrations and negative ones at high concentrations of this component. This occurs due to changes in the H-bonding interactions along the concentration range of the mixture.