Submitted in fulfillment of the academic requirements for the degree of Master in Engineering, Durban University of Technology, Durban, South Africa, 2017. / Phase equilibrium data plays a significant role in the design and optimization of industrial separation schemes, such as distillation and absorption units. These separation processes are utilised for the purification of valuable chemicals, which play a pivotal role in daily human life. Separation units are operated at various conditions of temperature and pressure, however it is common for most units to operate in the moderate pressure region (100-500 kPa). On the contrary, there is a lack of phase equilibrium data available in the moderate pressure region, thus prompting an interest in this area. In this study, a new static synthetic cell was tested, and the experimental apparatus was successfully set up and commissioned. Some key features of this design include a total working cell volume of 60 cm3 (which reduces the amount of chemicals required compared to conventional static synthetic cells) and equilibrium is achieved faster. In addition, two high-accuracy Teledyne Isco pumps were utilised for the feed loading, as it is vital that the volume of chemicals dispensed into the cell be accurately determined. The necessary calibrations were conducted and the overall uncertainties were found to be 0.06 K, 0.36 kPa and 0.1 ml for temperature, pressure and volume respectively. The following test systems were measured to determine the reproducibility of the apparatus and to verify the experimental technique: • water (1) + 2-butanol (2) at 323.16 K • n-hexane (1) + 2-butanol (2) at 329.21 K • n-pentane (1) + 1-propanol (2) at 317.18 K • n-pentane (1) + 2-butanol (2) at 303.17 K • n-pentane (1) + ethanol (2) at 303.11 K The test systems measured produced a good fit with the literature data, and thus the experimental apparatus was commissioned. New systems, previously unmeasured in the open literature, were measured in this study. These systems include: • n-hexane (1) + perfluoro-n-heptane (2) at 313.21 and 333.12 K • n-pentane (1) + 2-propanol (2) at 313.11, 323.11 and 333.12 K The data was modelled on Aspen Plus®. Since the method of operation is of the static synthetic type, no analysis of the vapour and liquid phases took place, and instead an algorithm was developed using the combined method (γ-ϕ) together with the method of Barker (1953), to convert the overall composition (zi) to liquid mole fraction (xi). The Wilson and Non-Random Two-Liquid (NRTL) activity coefficient models together with the Ideal Gas law and Hayden O’Connell second virial coefficient were utilised to regress the data. For both the fluorinated and alkane + alcohol systems, the experimental i data produced an excellent fit with the activity coefficient models. For both systems, azeotropes were observed, indicating poor separation of these binary combinations at specific mole fractions. This is due to the boiling point of both components being similar under certain conditions. The calculated pressure residuals were well within the overall combined uncertainty for pressure, whilst the calculated temperature residuals were slightly above the overall combined uncertainty for temperature. / M

The fuel industry in many parts of the world is blending alcohols with motor fuel either to extend the fuel or to improve its octane rating or both. Unfortunately alcohols are hygroscopic and as a result, water becomes a component of the fuel. This can lead to phase separation and the formation of a water-rich layer which could have serious corrosion consequences. In an attempt to understand the phase-splitting in alcohol-petrol-water blends, phase equilibria in ternary systems (alcohol-hydrocarbon-water) have been determined by experiment. The phase equilibria in these ternary systems are also discussed in terms of modern theories of liquid mixtures and the UNIQUAC theory is applied to the "ethanol + benzene + water" ternary system. The alcohols are all the C₁, C₂, C₃ and C₄ alcohols, and the hydrocarbons include those typically found in petrol, e.g. cyclohexane, benzene and substituted benzenes.

Orientador : Antonio Jose de Almeida Meirelles / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-03T14:52:13Z (GMT). No. of bitstreams: 1 Alves_JoseGuilhermeLembiFerreira_D.pdf: 9466611 bytes, checksum: 5373bb06cd092c9f0cb3bd3b29df531f (MD5) Previous issue date: 2003 / Resumo: Neste trabalho foi estudada a pré-purificação da proteína de fusão precursora à insulina humana e produzida por Escherichia coli modificada, utilizando-se Sistemas Aquosos Bifásicos do tipo polietileno glicol (PEG)/sal/água. A proteína de fusão foi fornecida pela empresa farmacêutica Biobrás S.A (Montes Claros/MG) e foi dissolvida em uréia 8M. Os experimentos de partição da proteína de fusão foram conduzidos de forma a identificar condições para a separação da proteína de fusão de outras proteínas e componentes celulares de E. coli. Foram realizados dois planejamentos experimentais 32 para o estudo da partição da proteína de fusão precursora da insulina humana no sistema PEG/fosfato de potássio/água. tendo-se como variáveis a massa molar do polietileno glicol, a razão mássica PEG/fosfato do sistema (RPEG/FOS). OS níveis estudados foram 1500, 3350 e 8000 para a massa molar do PEG; 1,6, 1,636 e 1,67 para RPEG/FOS. No primeiro planejamento, os testes de partição foram conduzidos a pH 9, enquanto que no segundo planejamento, os testes foram conduzidos a pH 12. Concluídos os testes com o sistema PEG/fosfato de potássio/água, foi escolhida a melhor condição para a purificação da proteína de fusão, condição esta que foi também testada para o sistema PEG/citrato de sódio/água. Para o sistema PEG/fosfato de potássio/água, o melhor resultado foi obtido com o PEG de massa molar 1500, concentração de 16% p/p PEG/l0% p/p de fosfato e pH 9, com fator de purificação da ordem de 1,5 vez e recuperação de 99%. Nestas mesmas condições, mas utilizando citrato de sódio, o fator de purificação e a recuperação foram 1,8 vez e 50,0%, respectivamente. Para analisar a proteína de fusão precursora da insulina humana, desenvolveu-se uma metodologia de análise por Cromatografia de afinidade / FPLC, usando-se a coluna Chelating Sepharose para separar a proteína de fusão dos demais componentes celulares e o Método de Bradford para quantificá-1a. Diagramas de fase do sistema PE& Na3Cit/H2O, para 3 pesos moleculares de PEG (600, 1500 e 3000) foram medidos a 25°C e modelou-se o equilíbrio líquido-líquido deste sistema usando-se o modelo VERS, baseado na equação do virial e que usa como medida de concentração uma fração de superfície externa do componente. Um ajuste muito bom aos dados experimentais foi obtido e os erros absolutos médios entre as concentrações experimentais dos componentes e as calculadas pelo modelo VERS foram 1,16%, 1,05% e 1,19% para os sistemas PEG600/ Na3Cit/H2O, PEGl500/ Na3Cit/H2O e PEG3000/ Na3Cit/H2O, respectivamente. O modelo obtido apresentou boa capacidade preditiva para a influência da massa molar do PEG sobre o equilíbrio líquido-líquido do sistema estudado. Para fins de modelagem termodinâmica, também foi estudada a partição das insulinas humana e suína puras nos sistemas PEG600/ Na3Cit/H2O, PEG1450/Na3Cit/ H2O e PEG3350/Na3Cit/ H2O em pH 4,5, 7 e 9,5 a 25°C para modelar a partição da insulina no sistema PEG/ Na3Cit/ H2O, utilizando-se também o modelo VERS e bons resultados foram obtidos para a -predição do coeficiente de partição da insulina suína no sistema PEG/ Na3Cit/H2O a pH 7,0 / Abstract: In this work the primary purification of a fusion protein precursor of human insulin and produced by recombinant E. coli has been studied using aqueous two-phase systems. The fusion protein was provided by the pharmaceutical company Biobrás S.A (Montes Claros/Brazil) and was dissolved in 8M area. Partitioning essays of fusion protein were investigated in the poly(ethylene glycol) (PEG)/potassium phosphate and poly(ethylene glycol)/sodium citrate aqueous two-phase systems at 25°C. Two 32 experimental design were done to evaluate the effects of PEG molecular weight and the polymer/salt concentration ratio on the purification factor and on the recovery of the fusion protein in the top phase. The studied levels were 1500, 3350 and 8000 for PEG molecular weight and 1,6; 1,636 and 1,67 for the polymerlsaIt concentration ratio. The partitioning experiments were performed at pH 9 and 12. An analytical method for the fusion protein was developed using Immobilized Metal Affinity Chromatography and the Bradford method. Solids on the interface top were observed in all cases examined The fusion protein partitioned between the PEG-rich phase and the solids on interface. Contaminating proteins were eliminated to some extent, which resulted in an almost 2-fold fusion protein purification with good recoveries. Phase diagrams of the system poly(ethylene glycol)1 sodium citrate/water were determined for three different molecular weights of PEG ( 600, 1500, 3000) at 25°C. At least four tie-lines of each system were measured. The experimental results were correlated by applying a model for the excess Gibbs energy. This model is the Virial equation used by Pitzer for salt solutions, but concentrations are expressed by surface fraction. It is called Virial Equation with Relative Surface fractions (VERS). All phase equilibrium calculations were performed using this model and minimizing the Gibbs energy of the feed under the constraint that both phases are electroneutral. Agreement between the experimental and calculated results within the experimental uncertainty was obtained. The average percents of deviation between experimental and calculated values using VERS model for all components were 1,16%, 1,05% and 1,19% for the systems PEG6001 Na3Cit/H2O, PEGl500/ Na3Cit/H2O PEG30001 Na3Cít/ H2O respectively. Human and porcine insulin partitioning was investigated in the system PEG/sodium citrate/water for three pHs (4,5; 7 and 9,5) at 25°C. Human and porcine insulin showed great affinity for the PEG-rich phase and the partition coefficients were higher than 10. The human insulin partition coefficient is practically independent of the PEG molecular mass. However, there is a tendency for the porcine insulin partition coefficient to increase with the PEG molecular mass at pH 7 and 9,5, attaining values- above 50. The porcine insulin partition coefficient was predicted in the system PEG/sodium citrate/water at 25°C using VERS model and good results were obtained for the system at pH 7 / Doutorado / Mestre em Engenharia de Alimentos

Orientadores: Antonio Jose de Almeida Meirelles, Fabio Rodolfo Miguel Batista / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-27T18:12:26Z (GMT). No. of bitstreams: 1 Lucchesi_KarolynneWeber_M.pdf: 2545312 bytes, checksum: 924445a68faa88732383166e326ff7eb (MD5) Previous issue date: 2015 / Resumo: A biomassa de microalgas vem despertando grande interesse científico como matéria prima para produção de biodiesel, devido ao elevado teor de óleo de algumas espécies, além de ser uma importante fonte para a produção de diversos biocompostos. Seu cultivo não compete com a produção de alimentos e ainda auxilia na captura de CO2, tendo um impacto benéfico para o meio ambiente. Diante desta promissora potencialidade, este trabalho objetiva investigar a produção de ésteres etílicos a partir de óleo de microalgas, avaliando as propriedades físicas destes ésteres e do óleo, além de estudar o equilíbrio líquido-líquido de algumas misturas de interesse. Óleo comercial de microalga da espécie Chlorella protothecoides, obtido junto à empresa Solebyo, foi utilizado como matéria prima para a produção do biodiesel (etanol como álcool reagente), obtendo-se um biocombustível totalmente renovável. O óleo foi caracterizado em termos dos seus ácidos graxos, estimando-se sua composição em triacilgliceróis (TAG). A dependência da viscosidade e densidade com relação à temperatura, índice de acidez e teor de umidade, foram determinados para o óleo e seu respectivo biodiesel. Uma análise adicional de ponto de fulgor foi realizada exclusivamente para o biodiesel. Por fim, o estudo do equilíbrio líquido - líquido das misturas biodiesel de microalgas + glicerol + etanol e óleo de microalgas + biodiesel de microalga + etanol, foi realizado a 25, 40 e 55 °C. Estes sistemas têm importância nas diversas etapas da reação de transesterificação e nas etapas de purificação do biodiesel. A técnica de HPSEC foi utilizada para quantificar os componentes nas fases e a modelagem do equilíbrio foi realizada utilizando os modelos NRTL e UNIQUAC. Todos os sistemas apresentaram desvios de balanço menores que 0,5%, indicando uma boa qualidade dos dados experimentais e da técnica utilizada. A grande semelhança entre as propriedades do óleo e do biodiesel de microalgas com relação a óleos e biodieseis convencionais indica uma grande potencialidade desta matéria prima para a produção de biodiesel / Abstract: The biomass of microalgae has been attracting great scientific interest as raw material for biodiesel (fatty acid esters), due to the high oil content of some species, and its importance for biocompounds production. Its great advantage with respect to traditional raw materials (oil) is centered on the fact that the microalgae cultivation does not compete with the food production, especially regarding the production of biofuels, and aids in the capture of CO2, having a beneficial impact to the environment. Given this promising potential, this work aims to investigate the production of ethyl esters from microalgae oil, evaluating the physical properties of these esters and oil, as well as studying liquid-liquid equilibrium of mixtures of interest.For this purpose, commercial microalgae oil of the species Chlorella protothecoides, obtained from Soleybio company, was used as raw material for biodiesel production and ethanol as reagent alcohol, giving to this biofuel a completely renewable character. The oil was characterized in terms of their fatty acids and its composition in triglycerides (TAG) was estimated. The viscosity and density temperature dependence, acidity number and moisture content were determined for oil and its respective biodiesel. Analysis of flash point has been made exclusively for biodiesel. Finally, the study of the liquid - liquid equilibrium of mixtures biodiesel + glycerol + ethanol and microalgae biodiesel + ethanol + oil was performed at 25, 40 and 55 °C. These systems are important in various stages of transesterification reaction and in the steps of biodiesel purification. The HPSEC technique was used to quantify the components at equilibrium phases and the equilibrium modeling was performed using the NRTL and UNIQUAC models. All the systems studied in this work presented balance deviations lower than 0.5%, indicating a good quality of the experimental data and the technique used. The great similarity between the properties of microalgae oil and biodiesel with respect to conventional oils and biodiesels indicate a high potential of microalgae as alternative raw material for the production of biofuels / Mestrado / Engenharia de Alimentos / Mestra em Engenharia de Alimentos

Flash boiling may be defined as the finite-rate mechanism that governs phase change in a high temperature liquid that is depressurized below its vapor pressure. This is a transient and complicated phenomenon which has applications in many industries. The main focus of the current work is on modeling flash boiling in injectors used in engines operating on the principle of gasoline direct injection (GDI). These engines are prone to flash boiling due to the transfer of thermal energy to the fuel, combined with the sub-atmospheric pressures present in the cylinder during injection. Unlike cavitation, there is little tendency for the fuel vapor to condense as it moves downstream because the fuel vapor pressure exceeds the downstream cylinder pressure, especially in the homogeneous charge mode. In the current work, a pseudo-fluid approach is employed to model the flow, and the non-equilibrium nature of flash boiling is captured through the use of an empirical time scale. This time scale represents the deviation from thermal equilibrium conditions. The fuel composition plays an important role in flash boiling and hence, any modeling of this phenomenon must account for the type of fuel being used. In the current work, standard, NIST codes are used to model single component fluids like n-octane, n-hexane, and water, and a multi-component surrogate for JP8. Additionally, gasoline-ethanol blends are also considered. These mixtures are azeotropic in nature, generating vapor pressures that are higher than those of either pure component. To obtain the properties of these fuels, two mixing models are proposed that capture this non-ideal behavior. Flash boiling simulations in a number of two and three dimensional nozzles are presented, and the flow behavior and phase change inside the nozzles is analyzed in detail. Comparison with experimental data is performed in cases where data are available. The results of these studies indicate that flash boiling significantly affects the characteristics of the nozzle spray, like the spray cone angle and liquid penetration into the cylinder. A parametric study is also presented that can help understand how the two different time scales, namely the residence time in the nozzle and the vaporization time scale, interact and affect the phenomenon of flash boiling.

No description available.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第23535号 / エネ博第426号 / 新制||エネ||81(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 河本 晴雄, 教授 石原 慶一, 教授 川那辺 洋 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

A method has been developed for the quantitative extraction of nitrotoluenes (2,6-dinitrotoluene, 2,4-dinitrotoluene, and trinitrotoluene) from water. Three types of solid sorbents were investigated: two 47 mm Empore disks™ - octadecylsilane (C18) and styrene-divinylbenzene (SDVB); and one Bakerbond spe*™ Phenyl stationary phase. The phenyl sorbent yielded the highest recoveries. The average SPE recoveries for spike standards ranged from 80 to 95 percent for Millipore water and 55 to 95 percent from well and surface water in the low ppb and ppt levels. After the nitrotoluenes were trapped on the solid sorbents they were quantitatively eluted by first doping the bed with toluene and then extracting with supercritical carbon dioxide. Doping with toluene was found to increase the rate of extraction. The extracts were analyzed off-line via GC-ECD using an internal standard. Extraction losses are due to analyte break through, and not from poor SFE recoveries. This demonstrates that supercritical fluid extraction is a suitable elution technique for analytes trapped on solid phase extraction (SPE) cartridges. A method has also been developed and evaluated for the direct on-line coupling of SPE to GC. SPE-SFE-GC-ECD analysis eliminates off-line collection and subsequent handling of hazardous materials. SFE is an ideal means of directly coupling SPE to GC, since carbon dioxide is a gas at ambient temperatures and pressures and thus easily removed. One potential problem for SPE-SFE on-line GC is the presence of residual water trapped on the active sites of the bonded silica sorbent. The presence of water can interfere with the cryogenic trapping of the analytes on the capillary GC column. The water becomes ice at cryogenic temperatures and in large quantities blocks the GC column. This problem has been avoided by using a split injection interface previously described by Hawthorne. The quantitative reproducibility of this interface will be investigated for nanogram quantities of nitroaromatics. / Ph. D.

Orientador: Martin Aznar / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-05T00:40:21Z (GMT). No. of bitstreams: 1 Arce-Castillo_PedroFelipe_D.pdf: 4607592 bytes, checksum: 216de649e3febd33712f357f832e071f (MD5) Previous issue date: 2005 / Resumo: Durante a presente década, vários resultados experimentais sobre fenômenos críticos no equilíbrio de fases, tais como efeito de co-solvência, janelas de miscibilidade e regiões de duas fases LV em superfícies de três fases LLV em sistemas ternários foram obtidos experimentalmente por vários grupos de pesquisa. Estes fenômenos são de grande influência em aplicações industriais de tecnologia supercrítica ou quase crítica, já que eles são observados dentro do intervalo de pressão, temperatura e concentração onde acontecem estes processos tecnológicos. O presente trabalho de tese visou modelar computacionalmente o equilíbrio multifásico (ELL, ELV, ELLV) e predizer esses fenômenos, que acontecem perto da região crítica, em sistemas simples (CO2 + n-alcano + n-alcanol, CO2 + 2-nitrofenol + n-alcanol) e complexos, tais como polímero + CO2 + cosolvente [polipropileno (iPP) + CO2 + n-pentano; poliestireno (PS) + CO2 + ciclohexano e poli(D,L-lactida) + CO2 + dimetileter)], fazendo uso de equações de estado (EDE) não cúbicas, que possuem algum embasamento teórico, como modelos termodinâmicos. Esses modelos foram a equação da Teoria Estatística do Fluido Associado de Cadeia Perturbada (Perturbed Chain ¿ Statistical Associating Fluid Theory, PC-SAFT) e de Sanchez- Lacombe (SL). Os resultados obtidos na modelagem do equilíbrio de fases a altas pressões desses sistemas foram comparados com os obtidos pela tradicional EDE de Peng-Robinson (PR). Estes modelos termodinâmicos também foram usados na modelagem do ELV e ELL de sistemas binários compostos de copolímeros comuns e biodegradáveis com solventes a baixas e altas pressões. Cada modelo termodinâmico possui parâmetros de componente puro e um parâmetro de interação (na sua regra de cruzamento) para cada sistema binário. Em todos os modelos termodinâmicos foi usada uma regra de cruzamento convencional e uma regra de mistura de primeira ordem de van der Waals. Os parâmetros de componente puro foram obtidos ajustando por regressão os dados de pressão de vapor e do volume molar do líquido saturado para o componente simples e dados de densidade, pressão e temperatura para o polímero na fase líquida. A modelagem de cada sistema binário foi feita a partir de dados de ELL, ELV e ELLV obtendo um parâmetro de interação binária (que leva em conta as interações entre duas moléculas). A predição do comportamento de fases do sistema ternário foi feita usando os parâmetros de interação binária dos três sistemas binários envolvidos e os resultados foram comparados com os dados experimentais. A otimização foi feita usando o método modificado de Máxima Verossimilhança para determinar o ótimo global dos dois tipos de parâmetros. Em todas as modelagens do comportamento do equilíbrio multifásico dos sistemas apresentados acima, a EDE PC-SAFT teve a melhor performance em termos dos desvios relativos na pressão quando comparada à performance das EDEs SL e PR / Abstract: During the present decade, several experimental results on critical phenomena in phase equilibria, such as co-solvency effect, miscibility windows and two-phases LV regions in three phases LLV surfaces in ternary systems were obtained experimentally by several research groups. These phenomena are of great influence in industrial applications of near-critical and supercritical technology, since they are observed within the pressure, temperature and concentration intervals where these technological processes happen. The present thesis aimed for modeling computationally the phase equilibria (LLE, VLE, VLLE) and predict those phenomena that happen near to critical region in simple systems (CO2 + n-alkane + n-alkanol, CO2 + 2-nitrophenol + n-alkanol) and complex systems, such as polymer + CO2 + co-solvent [polypropylene (iPP) + CO2 + n-pentane; polystyrene (PS) + CO2 + cyclohexane and poly(D,L-lactide) + CO2 + dimethyl ether)] using non-cubic equations of state (EoS), with some theoretical base, as thermodynamic models. Those models were the Perturbed Chain - Statistical Associating Fluid Theory (PC-SAFT) and the Sanchez - Lacombe (SL) EoS. The results obtained in modeling of high-pressure phase equilibria of those systems were compared with those obtained by the traditional Peng- Robinson (PR) EoS. These thermodynamic models were also used in modeling the VLE and LLE of binary systems composed of common and biodegradable copolymers with solvents at low and high pressures. Each thermodynamic model has pure component parameters and one interaction parameter (in its combining rule) for each binary system. Conventional combining and van der Waals one-fluid mixing rules were used in all thermodynamic models. Pure component parameters were obtained by regression of liquid saturated vapor pressure and volume molar data for each simple component, and liquid density, pressure and temperature data for each polymer. The modeling of each binary system was made from LLE, VLE and VLLE data, obtaining one binary interaction parameter (which takes into account the interactions between two molecules). The prediction of phase behavior of ternary system was made using the binary interaction parameters of its three binary systems and the results were compared with experimental data. Optimization was made using the modified likelihood maximum method to determine the global optimum of the two types of parameters. In all the modeling of the multiphase equilibria behavior of the systems presented above, the PC-SAFT EoS had the best performance in terms of relative deviations in pressure when compared to performance of SL and PR EoS / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

For many years the problem of separating aliphatic and aromatic compounds has been at the forefront of the petroleum and oil refining industries. This separation is often effected using liquid-liquid extraction or extractive distillation. Both of these processes require the addition of a solvent to bring about separation. The aims of this work were to investigate the use of "mixed" solvents, such as those used in the Arosolvan process, for their application in liquid-liquid extraction and extractive distillation as well as to provide related thelmodynamic data for systems containing mixed solvents. In the last part of this work, a computer program was developed to theoretically predict the effectiveness of a number of solvents on a user-defined separation. The solvents used for liquid-liquid extraction were chosen based on their similarities to those in the Arosolvan process and were of the form, {N-methyl-2-pyrollidone (NMP) + glycerol, a glycol or water} where the glycol was either monoethylene glycol (MEG), diethylene glycol (DEG) or triethylene glycol (TEG). The additives were combined in various mixing ratios to NMP to determine a mixing ratio for which the effect of the solvent is possibly optimized (a list of all solvents and mixing ratios used are presented in this work). Solvent selectivity and the range of compositions over which separation could occur determined the effectiveness of the solvents. This work dealt with the separation of n-hexane and toluene. In order to determine the selectivity and range of compositions, the liquid-liquid equilibria (LLE) of systems containing n-hexane + toluene + solvent had to be determined. LLE was measured using a simple equilibrium cell at 298 K and 1 atm. The phase separation boundaries (binodal curves) were determined using a titration method. The results obtained in this work showed an increase in the range of compositions over which the mixture of n-hexane and toluene could be separated (i.e a larger range of mixing ratios over which these components could be separated from each other) from the pure NMP solvent to the mixed solvent cases. This implies that there is a The range of compositions over which separation could be affected is given (for the solvents) in descending order: NMP + 50% glycerol> NMP + 10% water > NMP + 30% MEG > NMP + 5% water > NMP + 30% glycerol> NMP + 10% glycerol > NMP + 10% MEG > NMP + 10% DEG > NMP + 10% TEG > NMP + 5% DEG > 100% NMP. The selectivities of the solvents showed a remarkable increase from the pure NMP case to the mixed solvent cases. The maximum selectivity obtained for the NMP + 10% DEG system was over 1200 compared to a maximum selectivity of just 6 for the pure NMP system. The maximum selectivities obtained in descending order were as follows: NMP + 10% DEG > NMP + 10% TEG > NMP + 10% glycerol > NMP + 10% MEG > NMP + 30% MEG > NMP + 50% glycerol > NMP + 10% water > NMP + 5% water > NMP + 30% glycerol > NMP + 5% DEG > 100% NMP. The binodal curves were modelled using the Hlavaty, ,8-density and log-y functions. The maximum standard deviations obtained were 0.075, 0.078 and 0.05 for each of the functions respectively. The equilibrium data was modelled using the UNIQUAC and NRTL thermodynamic models and showed excellent agreement. This work showed better agreement to the NRTL functions due to the fact that the non-randomness parameter, a ij , may be chosen arbitrarily. The results obtained in this work indicate that the use of mixed solvents greatly increases the effectiveness ofNMP used for the separation of n-hexane and toluene. It is suggested that further studies be performed on a wider range of aliphatic and aromatic compounds in order to determine whether this is a generic behaviour or just true for n-hexane and toluene. The effectiveness of each solvent for extractive distillation was determined by its separation factor. In order to determine separation factors, the activity coefficients at infinite dilution (IDACs) had to be measured. This was done using a gas-liquid chromatography technique. The solvents employed in this study were NMP, Glycerol, MEG, TEG, NMP + 10% glycerol, NMP + 10% MEG, NMP + 10% DEG, NMP + 10% TEG. The solutes used were: pentane, heptane, hexane, toluene and benzene. The separation factors were determined for each alkane/aromatic pair per solvent. The pure solvent cases were then compared to the mixed solvent cases. The mixed solvents did not show results as promising for extractive distillation applications as they did for liquid-liquid extraction. TEG displayed the best selectivities for each of the alkane/aromatic separations except for the heptane/benzene pair, for which NMP + 10% glycerol proved to be the most effective solvent. When compared to the results obtained from the original UNIF AC model, the IDACs obtained in this work showed up to a 99% deviation. This is due to the fact that the model does not work well for all types of molecules and does not predict the equilibrium of "unlike" molecules adequately. It is suggested that other mixing ratios and different solvents be used to further investigate the effectiveness of mixed solvents for extractive distillation applications. It is further recommended that a computer aided data logging system be developed to determine residence times. This would not only provide more accurate results, but also provide a database for future reference. The computer program that was developed using the original UNIF AC method contains a database of 28 commonly used industrial solvents. This program enables the user to compare graphically the effectiveness of each of the solvents on the desired separation. Due to the limitations of the original UNIF AC method, the program does not work well for all types of molecules. However, the model can be changed without altering the prografnming structure to include a modified version of the UNIFAC model depending on the users needs. The program although written from an extractive distillation standpoint can be extended to include liquid-liquid equilibrium predictions. The main benefit of such a program is to eliminate time-consuming experimental work required to narrow down a long list of solvents required for a particular separation by theoretically predicting the best solvents for the job. The solvent database can also be expanded when new solvents become available or the user needs change / Thesis (M.Sc. Eng)-University of Natal, Durban, 2003.