Thermodynamics of liquid mixtures containing carboxylic acids.
Redhi, Gyanasivan Govindsamy.
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The thesis involves a study of the thermodynamics of ternary liquid mixtures involving carboxylic acids with nitriles, hydrocarbons including cycloalkanes, and water. Carboxylic acids are an important class of compounds with a great number of industrial uses and applications. In many parts ofthe world the separation of carboxylic acids (in particular acetic and propanoic acid) is an important and desirable task. In South Africa, these carboxylic acids together with many other oxygenates and hydrocarbons are produced by SASOL using the Fischer - Tropsch process. The separation of these acids from hydrocarbons and from water is a commercially lucrative consideration, and is the raison d' etre for this study. The work focussed on the use of nitriles in effecting separation by solvent extraction and not by the more common method of distillation. The nitrile compounds were chosen because of their high polarity. The carboxylic acids used in this study always refer to: acetic acid, propanoic acid, butanoic acid, 2-methylpropanoic acid, pentanoic acid and 3-methylbutanoic acid. The first part of the experimental programme is devoted to the determination of excess molar volumes of mixtures of (a carboxylic acid + nitrile compound), where the nitrile refers to acetonitrile, butanenitrile or benzonitrile, respectively. Densimetry was used to determine the excess molar volumes. The work was done in order to get some idea of the interactions involved between a carboxylic acid and a nitrile. The second part of the experimental study is concerned with the determination of excess molar enthalpies of mixtures of( a carboxylic acid + nitrile compound), where the nitrile refers to acetonitrile, butanenitrile or benzonitrile, respectively. The excess molar enthalpies were determined using flow microcalorimetry Again, this work was done in order to gain some insight into the interactions involved between a carboxylic acid and a nitrile. The third part of the experimental work consists ofternary liquid-liquid equilibria of mixtures of (acetonitrile + a carboxylic acid + heptane or cyclohexane), (benzonitrile + a carboxylic acid + water); and (butanenitrile + a carboxylic acid + water), at 298.15 K. The purpose was to investigate the use of nitriles as solvent extractors in separating carboxylic acids from hydrocarbons and also carboxylic acids from water. Ternary liquid-liquid equilibrium data are essential for the design and selection of solvents used in the liquid-liquid extraction process. The final section deals with the fitting of models of liquid mixtures to the experimental data collected in this work. The NRTL (Non-random, two liquid), UNIQUAC (Universal quasichemical), and FBT (Flory-Benson-Treszczanowicz) models were used. The modelling work served three purposes: • to summarise the experimental data • to test theories of liquid mixtures • prediction of related thermodynamic properties