Thesis (Ph. D.)--University of Chicago, 1933. / "Private edition, distributed by the University of Chicago libraries, Chicago, Illinois."

Thesis (Ph. D.)--University of Chicago, 1933. / "Private edition, distributed by the University of Chicago libraries, Chicago, Illinois."

Thesis--Catholic University of America. / Bibliography: p. 26-27.

Thesis (Ph. D.)--Catholic University of America, 1933. / At head of title: The Catholic University of America. Vita. Bibliography: p. 23-24.

Thesis (Ph. D.)--Catholic University of America, 1933. / At head of title: The Catholic University of America. Vita. Bibliography: p. 23-24.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1963. / Typescript. Vita. With this is bound: The diffusion coefficient of formamide in dilute aqueous solutions at 25⁰C as measured with the Gouy diffusiometer / by John G. Albright and Louis J. Gosting, reprinted from Journal of physical chemistry, v. 64 (1960), p. 1537-1539. Includes bibliographical references.

The determination of limiting activity coefficients in liquid mixtures has become an important tool in chemical engineering. It has been investigated intensively during the past in order to find new alternatives and improved methods for its accurate detennination. The limiting activity coefficient is a fundamental thermodynamic quantity which measures the solution non-ideality and acts as a correction factor to deviations from Raoult's Law. This dissertation involves the determination of limiting activity coefficients using the inert gas stripping (IGS) technique only. It is considered to be the best method as it is a direct method involving exact concentrations of components in the mixtures encountered in industry. A comprehensive study of activity coefficients at infinite dilution for various systems, using the inert gas stripping (IGS) method has been undertaken. Various other methods and their suitability have also been discussed but preference is given to the superior quality of measurements obtained using the inert gas stripping technique. Extensive research has been conducted into the background and origination of the technique. Various improvements of the equilibrium cell designed by various authors for different types of systems have been outlined along with the various equations derived by the authors. The equipment was designed for use with the double-cell technique as well as the single-cell technique and in some cases both techniques were used. The techniques involve the use of a dilutor cell in which the highly diluted, volatile solute is stripped from a liquid solution using the inert gas nitrogen, introduced into the cell through capillaries and dispersed through the solution as small bubbles, at a constant flow rate. Analysis of the stripped solution is accomplished through the use of a gas chromatograph; the peak areas obtained from these analyses as well as the residence times and other system data such as temperature, pressure, mass and flow rate were used to compute the infinite dilution activity coefficient through the use of the various equations available in literature. The original equipment was designed for the use of the single cell technique by Soni (2004). Various modifications have been made to the equipment in order to measure limiting activity coefficients of more diverse systems with high accuracy. A major change to the equipment was the introduction of a second saturation cell of similar design to the dilutor cell. This enabled the determination of activity coefficients at infinite dilution of difficult systems i.e. systems where the solvent volatility is high and for higher order systems. The equipment was redesigned and built using ideas and improvements by previous researchers in the field and commissioned using test systems that have been classed as easy systems for this technique. The new equipment is now applicable to almost all systems, however good separation in the GC column could be a problem for complex systems. The determination of infinite dilution activity coefficients for one-component solute + onecomponent solvent systems and multi-component solvent systems were accomplished. The systems that were investigated consisted of a mixture of components of alkanes, alkenes, phenols and ketones, mostly in binary mixtures. Multi-component mixtures have also been investigated in the form of ternary systems involving a binary solvent mixture at varying concentrations, and a solute in order to show the diversity, uniqueness and efficiency of the IGS technique. Major variables affecting the system (the dilutor cell), namely the stripping gas flow rate and the dilutor cell temperature, were also investigated for all systems. Two test systems, cyclohexane in 1-methyl-2-pyrrolidone (NMP) and n-heptane in NMP were used to determine if the equipment is operating properly by comparing values obtained, to literature values where the inert gas stripping technique was used to determine the activity coefficients at infinite dilution. Another test system n-hexane in NMP was used to compare the two techniques, Le. the results of the single cell technique with the results of the double cell technique. The experimental results were thereafter compared to published literature values. Systems where the inert gas stripping technique has not been used to determine activity coefficients at infinite dilution were also investigated. These systems include 1-hexene in 0- cresol as well as the ternary systems '-hexene in various concentrations of NMP + o-cresol. A thorough literature survey has been completed and the relevant theory has been summarized. The validity of the equations proposed by Bao and Han (1995), Duhem and Vidal (1978), Leroi et a!. (1977), Hovorka and Dohnal (1997) and Krummen et al. (2000) for the determination of activity coefficients at infinite dilution were investigated. The experimental values obtained were consistent with literature values, with percentage errors of less than 1 % where the same equation was used to determine the limiting activity coefficient. Comparing limiting activity coefficients with the values obtained from other equations proposed by other authors mentioned above resulted in deviations no greater than 2.5 %, and where possible limiting activity coefficients were compared to values obtained from the single-cell technique. The theory section of this thesis covers all the various formulae (and where possible a summary of their derivation) used in the analysis of results. Some limiting activity coefficients for the systems involving n-heptane, n-hexane, n-hexene, cyclohexane, o-cresol and n-methyl-2-pyrrolidone under various experimental conditions have been reported making it readily available for use in other works. The effect of two major variables temperature and inert gas flow rate on the limiting activity coefficients with regard to all the systems studied have also been investigated and reported. This was also done in order to check that the data was reproducible. A sensitivity analysis was also performed in order to check the effect that certain measured variables would have on the limiting activity coefficient. These errors are estimated possible errors and may not exist at all, so not much consideration was given to this when reporting limiting activity coefficients for the various systems. The maximum error range for any given limiting activity coefficient as determined by the sensitivity analysis is ±11 %. The inert gas stripping technique is also extended to the determination of Hendry's constants. The actual values for the Hendry's constants were not determined but a comprehensive study of its determination was undertaken by Miyano et al. (2003) and summarized here. In addition the suitability and diversity of the inert gas stripping technique has been outlined, along with the advantages and disadvantages of the technique. The various designs of equilibrium cells have been outlined taking into account mass transfer considerations as proposed by Richon et al. (1980). The assumptions and limits of the method have also been outlined and must be taken into consideration when using the technique. A detailed description of the equipment setup and experimental procedure has been provided. The purpose, suitability, operation and applicability, of the various pieces of equipment used to make up the final equipment have been discussed in detail. Details for consideration when designing the equilibrium cells have also been provided. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2008.

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. / Thesis (M.Sc.)-University of Natal, Durban, 1992.

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. / Thesis (Ph.D.)-University of Natal, 1995.

Thesis (Ph.D.) OGI School of Science & Engineering at OHSU, March 2008. / Includes bibliographical references (leaves 98 - 99).