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- Binary mixtures; Solid liquid equilibrium; Saturated and unsaturated fatty acids; Phase diagram; DSC (1)
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Enrichment of natural unsaturated fractions by melt crystallization processes has already been proved to be effective in prior investigations [1]–[3]. Palmitic, stearic, oleic, linoleic and linolenic acid are the five main fatty acids present in most of these plant based natural oils. There is quite a bit of information about the liquid solid phase behavior of binary mixtures such as palmitic-oleic, stearic-oleic and palmitic-stearic acid mixtures in literature [4]–[6]. Recent investigations have shown phase diagrams of real natural oil based fatty acid systems containing up to 19% saturated content (11% stearic acid and 8% palmitic acid) [7]. Yet, there is hardly any information regarding ternary systems as those of palmitic-stearic-oleic and palmitic-stearic-linoleic acids.
In this work, synthetic mixtures have been used in order to obtain a complete overview of the liquid solid phase diagrams of these ternary mixtures. To imitate naturally occurring mixtures, a mixture with 1:1 ratio of palmitic stearic acid was prepared. Varying amounts of either oleic or linoleic acids were added to this mixture in order to obtain the entire range required for the phase diagrams. These mixtures were then subjected to a specific profile with a wide temperature range in a Differential Scanning Calorimeter (DSC) so as to record every phase transition.
This study successfully concludes that these complex mixtures could be treated as binary mixtures of their saturated and unsaturated contents. This is because there were essentially two main peaks noted in the DSC thermograms. It is to be noted that there was a third peak, assumed to represent the solid transition, in mixtures containing oleic acid. This has already been shown in detail and discussed in prior investigations [6], [7]. Another major discovery was that the solidus line depends on the type of the unsaturated content, that is, the degree of unsaturation, in the mixture.
The solid liquid phase diagrams of binary mixtures of the five main saturated and unsaturated fatty acids present in most edible plant oils have been determined in this paper. These binary mixtures comprise of a saturated fatty acid, either palmitic (C16:0) or stearic (C18:0) and an unsaturated one, oleic (C18:1), linoleic (C18:2) or linolenic (C18:3) acid. Differential scanning calorimetry (DSC) was used to obtain an overview of the solid liquid transition behaviour including the metastable ranges of these mixtures. In order to describe all the phase transformations in these systems, the boundary functions have been determined and compared. Phase diagrams determined, illustrate characteristic behaviour in accordance to literature. This work specifically focuses on to describe the solid liquid transitions of the mixtures and not on every single transition or reaction. This paper contributes to the elucidation of the phase behaviour of these important mixtures which are applied in diverse industries.
In this paper, binary phase diagrams of the five main fatty acids present in edible oil based mixtures are shown. While previously the binary systems of one saturated and one unsaturated acid were investigated, in this work the binary mixtures comprise of palmitic (C16:0) and stearic acid (C18:0) or a binary mixture of oleic (C18:1), linoleic (C18:2) or linolenic acid (C18:3). In order to obtain the phase diagrams with all the solid liquid and solid phase transitions, the mixtures were analyzed by means of Differential Scanning Calorimetry (DSC). Phase change boundary functions based on thermodynamic models and experimental values were fitted and compared. The phase diagrams obtained show behaviors in good agreement to literature. The paper contributes to the deeper understanding of the essential phase change effects during industrial crystallization processes.
A mathematical model for the prediction of phase change temperatures and crystallization paths for mixtures consisting of palmitic (P), stearic (S), oleic (O), linoleic (L) and linolenic acid (Ll) in any distribution is presented in this paper. This model is based on the information gathered from modeled ternary phase diagrams, namely PSO, PSL, PSLl and OLLl, that were based on experimental binary phase diagrams of all possible combinations of these fatty acids. These experimental binary phase diagrams were obtained by means of differential scanning calorimetry and mathematical function fitting, within which the eutectic region of binary palmitic/stearic with oleic/linoleic/linolenic acid was investigated in detail. The basic mathematical model used was previously shown in literature which delivered good results for such systems. The importance of the developed model was then justified by investigations on real and composed synthetic fatty acid mixtures, where a high accuracy of the predicted temperatures could be shown for the technically relevant liquidus and solidus temperatures. A satisfying prediction for thermal events below the first solidus line could be reached as well. This work directly contributes to an enhanced understanding of the thermodynamic and kinetic background of such important mixtures applied in diverse products and industries, thereby showing a large optimization potential for crystallization technologies.