School of Chemistry and Physics
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Browsing School of Chemistry and Physics by Subject "Activity coefficients."
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Item 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.Item The determination of activity coefficients at infinite dilution using gas-liquid chromatography.(1996) Deenadayalu, Nirmala.; Letcher, Trevor M.Abstract available in PDF file.Item The determination of activity coefficients at infinite dilution.(1995) Moollan, Warren Charles.; Letcher, Trevor M.The aim of this work was to extend the theory of Everett and Cruickshank, for the determination of activity coefficients at infinite dilution, Y 13 (where 1 refers to the solute and 3 to the solvent), to accommodate solvents of moderate volatility, using the gas liquid chromatography (GLC) method. A novel data treatment procedure is introduced to account for the loss of solvent off the column, during the experiment. The method also allows us to determine the vapour pressure of the solvent. No auxiliary equipment is required, and the method does not employ the use of a presaturator. Further, the effect of a polar involatile solute is examined using various types of solutes. The activity coefficient was found to be independent of column packing and flowrate. Considering the volatile solvent, the systems investigated by the GLC method were straight chain hydrocarbons, (n-pentane, n-hexane and n-heptane), cyclic hydrocarbons (cyclopentane, and cyclohexane) and an aromatic compound, benzene. The systems were investigated at 2 temperatures, 280.15 K and 298.15 K. The results indicate a clear dependence of the activity coefficient on temperature. For the polar nonvolatile solvent, sulfolane (tetrahydrothiophene, 1,1 dioxane) was used. The systems studied were sulfolane + n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane, benzene, tetrahydrofuran, and tetrahydropyran. The systems were studied at one temperature, 303.15 K, due to the low melting point of sulfolane i.e. 301.60 K. Part of this study into the thermodynamics of solutions'\vas conducted at the Technical University of Warsaw, where the equilibria of sulfolane was studied using· two techniques, a dynamic solid-liquid equilibrium method (SLE), and an ebulliometriGI vapor-liquid method (VLE) . The main purpose of this was to apply solution theories to this data in order to predict the.activity coefficient at infinite dilution for the sulfolane mixtures. The systems measured using solid liquid equilibrium are sulfolane + tetrahydrofuran, or, 1,4-dioxane, or, I-heptyne, or, 1, 1, l,-trichloroethane, or, benzene, and cyclohexane. The results of these measurements were then described using various solution theories, and· new interaction parameters obtained. The vapour liquid equilibrium systems measured were sulfolane + I-heptyne, or, tetrahyrdofuran, or, 1,1, I-trichloroethane, and tetrachloromethane. Here as in SLE the results were described using solution theories. The results of both the VLE and SLE measurements were used in a multiple optimization procedure to produce new parameters for the interaction of sulfolane with various groups, using two group contribution method, DISQUAC and modified UNIFAC. The predicted activity coefficients compare well with the measured values using GLC.Item 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.