Abstract: This work focused on the interactions which occur between ester solvents and alcohol solutes. The alcohols selected ranged from the simplest alcohol (methanol) to C10-alcohols, and solubility predictions in the form of infinite dilution activity coefficients were made using the Modified UNIFAC Dortmund group contribution model. The model computation was set up on a Microsoft Excel spreadsheet specifically designed for this purpose. It was found that alcohol/ ester interactions yielded an increase in activity coefficients (i.e. became less soluble) with an increase in the size of the ester solvent molecule. Furthermore, activity coefficients decreased with an increase in the size of the alcohol solute. The activity coefficients also decreased with an increase in the degree of unsaturation of the ester hydrocarbon tail. Tertiary alcohols yielded lower activity coefficients than primary alcohols. Finally, cyclic alcohols yielded higher activity coefficients than straight-chain alcohols until a point is reached where the trend is reversed, referred to as the ‘crossover’ point.
Abstract: The aim of this study was to compare the solubility of selected volatile organic compounds in water and silicon oil using the simple static headspace method. The experimental design allowed equilibrium achievement within 30 – 60 minutes. Infinite dilution activity coefficients and Henry-s law constants for various organics representing esters, ketones, alkanes, aromatics, cycloalkanes and amines were measured at 303K. The measurements were reproducible with a relative standard deviation and coefficient of variation of 1.3x10-3 and 1.3 respectively. The static determined activity coefficients using shaker flasks were reasonably comparable to those obtained using the gas liquid - chromatographic technique and those predicted using the group contribution methods mainly the UNIFAC. Silicon oil chemically known as polydimethysiloxane was found to be better absorbent for VOCs than water which quickly becomes saturated. For example the infinite dilution mole fraction based activity coefficients of hexane is 0.503 and 277 000 in silicon oil and water respectively. Thus silicon oil gives a superior factor of 550 696. Henry-s law constants and activity coefficients at infinite dilution play a significant role in the design of scrubbers for abatement of volatile organic compounds from contaminated air streams. This paper presents the phase equilibrium of volatile organic compounds in very dilute aqueous and polymeric solutions indicating the movement and fate of chemical in air and solvent. The successful comparison of the results obtained here and those obtained using other methods by the same authors and in literature, means that the results obtained here are reliable.