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Masters Degrees (Chemistry)

Permanent URI for this collectionhttps://hdl.handle.net/10413/6597

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Browsing Masters Degrees (Chemistry) by Subject "Activity coefficients."

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    The determination of activity coefficients at infinite dilution using gas liquid chromatography.
    (1991) Moollan, Warren Charles.; Letcher, Trevor M.
    The aim of this investigation was to develop and test a theory that allowed for the calculation of the activity coefficients at infinite dilutions (l' ~ 3) from G.L.C. measurements using moderately volatile solvents. The solvents chosen for study were straight chained (Cs to C7) and cyclic (Cs, C6 and benzene) liquid hydrocarbons using cis- and trans-decahydronaphthalene (decalin) as the stationary liquid phase (solvent). The systems were studied at two different temperatures, 283.15 K and 298.15 K. The solutes were n-pentane~ n-hexane, n-heptane, cyclopentane, cyclohexane and benzene. This method for the determination of activity coefficients has the advantage of being able to work at infinite dilution, whereas in other techniques, extrapolation to infinite dilution of finite-concentration data is necessary. In addition solutes are separated from impurities when chromatographed so that only very small quantities of moderately pure material need be· used. However the technique is also limited since the solute studied (injected reagent) needs to be volatile, while the solvent (liquid stationary phase) should be involatile. The solvents chosen in this experiment (cis- and transdecalin) are moderately volatile which introduces many limitations since the theory developed for the determination of activity coefficients at infinite dilution is restricted to involatile solvents. However a novel method for working with moderately volatile solvents is developed by relating the loss of solvent to its partial pressure and modifying the existing theory. In the past the use of precolumns and/or saturators, coarse packing, small pressure gradients, and internal standards were used when working with volatile solvents. However employing this new method excludes the use of precolumns, saturators, or internal standards, and allows any type of packing and pressure gradient to be used. The calculated activity coefficients are compared with literature values, where the wor~ers employed G.L.C. techniques, and with predicted values. The activity coefficients calculated at both temperatures are used in the calculation of excess partial molar enthalpies. These results are compared with values obtained from finite concentration data by other workers.
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    The determination of activity coefficients at infinite dilution using gas-liquid chromatography.
    (1996) Deenadayalu, Nirmala.; Letcher, Trevor M.
    Abstract available in PDF file.
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    Part 1: The determination of activity coefficients at infinite dilution ; Part 2: Investigations into the colour components of raw sugar.
    (1996) Whitehead, Paul Graham.; Letcher, Trevor M.
    PART I: This work is part of an investigation to determine activity coefficients at infinite dilution (1'73) of hydrocarbons dissolved in the industrially important polar solvent tetrahydrothiophene-l, l-dioxide (sulfolane), by medium pressure gas liquid chromatography (g.l.c.). In this work the activity coefficients at infinite dilution for a series of l-alkenes (C6-CS) , l-alkynes (C6-CS) , and cycloalkanes (C7 and Cs) have been measured in the polar solvent, sulfolane, at 303.15 K and 313.15 K. The activity coefficients of some of the solutes discussed in this work would be difficult to determine by any other method because of their low solubility in sulfolane. The mixed second virial coefficients used in this work were determined assuming the principle of corresponding states, the Hudson and McCoubrey combining rules for T~2' the Lorentz rule for V~2' and the McGlashan-Potter equation. PART II: Unrefined sugar contains organic colour material originating In the sugarcane or formed during the extraction and purification processes. Sugar colour must be within the limits of acceptability for direct or indirect consumption. In this work, a cost effective technique to separate colourants from sugar through a sucrose packed medium pressure chromatographic column was investigated. Three dimensional perspective plots of wavelength/absorbance/time were developed to provide insight into the nature of the sugar colourants and to provide a means of investigating various decolourisation systems. In addition to the above experiment a procedure was developed to remove colourant species from unrefined sugar samples and from samples taken during the refining process for chemical analysis. In this work only one technique - gas chromatography-mass spectroscopy was used to identify the species.