Yes / The extraction of bioactive compounds, produced by plant cell cultures, directly from their culture medium, which contains other by-products, is a great challenge. Resveratrol extraction from its grapevine cell cultures is considered here as an example to improve the extraction processes from plant cell cultures using solubility parameters. Successive liquid-liquid extraction (LLE) processes were exploited to extract resveratrol from the culture medium with an extraction ratio approaching 100%, high selectivity and minimum amounts of solvents. The calculations of partition coefficients as a function of solubility parameters demonstrated that benzyl benzoate is the most suitable intermediate solvent to extract resveratrol from its aqueous medium. The calculations also illustrated the high ability of methanol and ethanol to extract resveratrol from benzyl benzoate. The physicochemical properties of benzyl benzoate and processing conditions were exploited to separate it from aqueous media and organic solvents. The agitation method, component ratios and extraction time were studied to maximize the extraction yield. Under the best studied conditions, the recovery of resveratrol from different culture media approached ∼100% with a selectivity of ∼92%. Ultimately, the improved extraction processes of resveratrol are markedly efficient, selective, rapid and economical. / Mohammad Amin Mohammad gratefully acknowledges CARA (The Council for At-Risk Academics, Stephen Wordsworth and Ryan Mundy) for providing the financial support for an academic fellowship.

Le couplage fonctionnel des opérations de séparation et de réaction ainsi que les bio-procédés sont deux axes de recherche largement explorés. Cependant, l’industrie du génie des procédés a du mal à se tourner vers des technologies de ce type car il demeure un réel manque de connaissances et d’outils de conception pour ce genre de procédés. Une méthodologie de conception générale pour l'extraction liquide-liquide réactive est introduite dans cette étude. Elle est composée de trois étapes différentes: l'analyse de faisabilité, la synthèse ou dimensionnement du procédé et la validation par simulation. Cette méthodologie conduit à des paramètres structuraux et opératoires de la colonne étudiée à partir seulement des informations concernant le comportement physico-chimique du système étudié, en exploitant les équations d’équilibre chimique et entre phase ainsi que les bilans matières. Les résultats de cette méthode sont un bon point de départ pour une étude d'optimisation ou d'un processus de calcul d'investissement. Cette méthodologie a été appliquée à différentes études de cas: regroupant deux stratégies différentes d'extraction avec plusieurs solvants pour récupérer l'acide succinique dans un milieu de fermentation / The functional coupling of separation and reaction operations and bioprocesses are two widely explored areas of research. However, process engineering industry is struggling to turn to these technologies because it remains a real lack of knowledge and design tools for this kind of processes. A general design methodology for reactive liquid-liquid extraction is introduced in this study. It is composed of three different steps: feasibility analysis, pre-design determination and simulation validation. This methodology leads to the design specifications of the units from the information concerning the physicochemical behaviour of the studied system, exploiting the equilibrium and material balance equations. The results of this methodology are a good starting point for an optimization study or for an investment calculation process. This methodology has been applied to different case studies: two different strategies of extraction and several solvents to recover succinic acid in fermentation broth.

Dans le cadre de la séparation sélective pour le traitement et la valorisation des combustibles nucléaires usés, l’extraction liquide/liquide est largement utilisée au niveau industriel. Néanmoins, ce procédé est encore mal compris en ce qui concerne les phénomènes physico-chimiques qui se produisent à l’interface liquide/liquide. Ce travail porte sur la compréhension de la dynamique de l’interface liquide nanométrique durant le transfert d’une espèce entre une phase aqueuse et une phase organique. Deux techniques expérimentales ont principalement été utilisées: la mesure de tension interfaciale et l’optique non linéaire. Ce travail a également donné lieu au développement d’un modèle numérique de dynamique de transfert de phase prenant en compte à la fois des phénomènes de transport diffusif proche de l’interface et une cinétique chimique sur l’interface décrivant les processus d’adsorption/désorption. Des systèmes modèles constitués de molécules surfactantes et/ou chromophores et/ou complexantes ont été étudiés aux interfaces air/liquide et liquide/liquide. L’adsorption/désorption, l’agrégation en surface, la complexation d’ion à une interface liquide et la structuration des systèmes ont ainsi pu être étudiées tant d’un point de vue des états d’équilibre que de la dynamique. Enfin, ces études ont été appliquées à un système d’intérêt industriel utilisé dans le procédé de dépollution DIAMEX / Liquid-liquid extraction processes are widely used in the industrial fields of selective separation. Despites its numerous applications, the microscopic mechanisms which occur during a liquid liquid extraction processes are really unknown specially at the liquid/liquid interface. Thus, this work deals on the understanding of the phenomena which drive the mass transfer across a liquid/liquid interface. Two experimental techniques were used in this work: dynamic interfacial tension measurement and non-linear optical experiments. Along with the use of this experimental approach, a numerical model describing the mass transfer dynamic has been developed. This model works under the assumption that both diffusion and a chemical step describing adsorption and desorption processes contribute to the global transfer kinetics. Model systems of surfactant molecules, chromophore molecules and complexing molecule were investigated at liquid/liquid and air/liquid interface. Interfacial phenomena like adsorption, surface aggregation and ion complexing were studied. Finally, the methodology developed in this work was applied to studied an extractant molecule with potential industrial application

La gazéification de la biomasse par voie thermochimique constitue une ressource en énergie renouvelable ayant un grand potentiel de développement. Parmi les différentes techniques possibles, la voie cogénération Chaleur/bio-SNG (Substitute Natural Gaz) est proche de la maturité technologique. Un des verrous technologique de cette technologie est l’élimination des goudrons contenu dans le gaz issu du gazéifieur. Le présent travail de recherche constitue une contribution à la levée de ce verrou. La technique d’élimination des goudrons par lavage au moyen d’un solvant non miscible à l’eau ayant été sélectionnée pour un pilote de démonstration, le présent travail de recherche s’est principalement focalisé sur l’acquisition de données d’équilibre bi et triphasique des composés modèles des goudrons - eau – solvant de lavage. De telles données sont en effet indispensable pour la mise au point du modèle thermodynamique permettant la modélisation et l’optimisation du lavage. Les analyses des phases liquides en équilibre on été réalisées par CPG-FID ou CPG-SM. Dans certains cas les niveaux de concentration étaient particulièrement faibles. Les concentrations réciproque obtenues et les coefficients de partage qui s’en déduisent vérifie respectivement la corrélation empirique de Hands et la relation de Van’t Hoff. L’équilibre liquide-liquide-vapeur des binaires eau – solvant de lavage ont été étudiés par la méthode statique. Les concentrations des phases en équilibres ont été corrélées par les modèles NRTL et UNIQUAC au moyen du logiciel commercial ‘Simulis Thermodynamic’. Les paramètres d’interaction ainsi ajustés permettent une bonne restitution des données expérimentales. / Gasification of biomass is a promising thermochemical renewable energy resource. Among all biomass conversion processes, gasification by heat cogeneration / bio-SNG (Substitute Natural Gas) is the promising one. But still, one of the deadlocks to be raised is the reduction of the high level of tar present in the product gas. The objective of this work is to perform a data base which will be useful at the operation of tar removal from aqueous medium. The present work has mainly focused on the acquisition of bi and triphasic equilibrium data model molecules of tars - water - washing solvent. Such data are indeed essential for the development of the thermodynamic model for the modeling and the optimization of the washing process. Analyses of liquid phases in equilibrium have been performed by GC-FID or GC-MS. In some cases the concentration levels were particularly low (up to 10-10 mole fraction of anthracene in the aqueous phase). Reciprocal concentrations obtained and the partition coefficients which are deduced from the empirical correlation satisfy each of Hands and the Van't Hoff relationship. Liquid-liquid-vapor equilibrium of binary systems (water-extracting solvent) was studied with the static method. The concentrations of the phases in equilibrium were correlated by the NRTL and UNIQUAC models using the commercial software 'Thermodynamic Simulis'. The interaction parameters adjusted allow a good reproduction of experimental data.

Heightened concerns for cleaner air and increasingly more stringent regulations on sulphur content in transportation fuels will make desulphurization more and more important. The sulphur problem is becoming more serious in general, particularly for diesel fuels as the regulated sulphur content is getting an order of magnitude lower, while the sulphur contents of crude oils are becoming higher. This thesis aimed to develop a desulphurisation process (based on oxidation followed by extraction) with high efficiency, selectivity and minimum energy consumption leading to minimum environmental impact via laboratory batch experiments, mathematical modelling and optimisation. Deep desulphurization of model sulphur compounds (di-n-butyl sulphide, dimethyl sulfoxide and dibenzothiophene) and heavy gas oils (HGO) derived from Libyan crude oil were conducted. A series of batch experiments were carried out using a small reactor operating at various temperatures (40-100 °C) with hydrogen peroxide (H2O2) as oxidant and formic acid (HCOOH) as catalyst. Kinetic models for the oxidation process are then developed based on 'total sulphur approach'. Extraction of unoxidised and oxidised gas oils was also investigated using methanol, dimethylformamide (DMF) and N-methyl pyrolidone (NMP) as solvents. For each solvent, the 'measures' such as: the partition coefficient (KP), effectiveness factor (Kf) and extractor factor (Ef) are used to select the best/effective solvent and to find the effective heavy gas oil/solvent ratios. A CSTR model is then developed for the process for evaluating viability of the large scale operation. It is noted that while the energy consumption and recovery issues could be ignored for batch experiments these could not be ignored for large scale operation. Large amount of heating is necessary even to carry out the reaction at 30-40 °C, the recovery of which is very important for maximising the profitability of operation and also to minimise environmental impact by reducing net CO2 release. Here the heat integration of the oxidation process is considered to recover most of the external energy input. However, this leads to putting a number of heat exchangers in the oxidation process requiring capital investment. Optimisation problem is formulated using gPROMS modelling tool to optimise some of the design and operating parameters (such as reaction temperature, residence time and splitter ratio) of integrated process while minimising an objective function which is a coupled function of capital and operating costs involving design and operating parameters. Two cases are studied: where (i) HGO and catalyst are fed as one feed stream and (ii) HGO and catalyst are treated as two feed streams. A liquid-liquid extraction model is then developed for the extraction of sulphur compounds from the oxidised heavy gas oil. With the experimentally determined KP multi stage liquid-liquid extraction process is modelled using gPROMS software and the process is simulated for three different solvents at different oil/solvent ratios to select the best solvent, and to obtain the best heavy gas oil to solvent ratio and number of extraction stages to reduce the sulphur content to less than 10 ppm. Finally, an integrated oxidation and extraction steps of ODS process is developed based on the batch experiments and modelling. The recovery of oxidant, catalyst and solvent are considered and preliminary economic analysis for the integrated ODS process is presented.

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.

La récupération assistée du pétrole implique la progression dans unmilieu poreux d'une phase aqueuse qui pousse une phase organique. Al'échelle du pore, les forces visqueuses et la gravité sontnégligeables, et la capillarité joue un rôle prépondérant : ledéplacement des fluides est gouverné par leur affinité avec lessurfaces et par les hétérogénéités de canaux. Les films liquidesexistent dans les pores d'une roche. Trois systèmes microfluidiquessont mis en place pour étudier le rôle des films microscopiques (demouillage) ou des films macroscopiques (de coins). Le premier consisteen un capillaire de section circulaire dans lequel on suit lemouvement d'un ménisque dans des conditions de mouillage variées. Enparticulier, en mouillage pseudo-partiel, un hystérésis d'angle decontact est observé, mais les films de mouillage présents dans cesystème conduisent à un accrochage de ligne de contact beaucoup plusfaible qu'en absence de film. Les deuxième et troisième systèmesmettent en évidence l’influence des films de coins dans un canalrectangulaire sur l'avancée du ménisque. Le couplage de l'écoulemententre la phase du coin et la phase du milieu entraîne le drainage del’huile piégée. Les propriétés de ce nouveau mécanisme sontcaractérisées par des expériences et s’accordent avec le modèleconstruit. / Enhanced oil recovery involves the displacement of an organic fluid byan aqueous one in the pores of the rocks. At the pores scale. Thedisplacement of fluids is governed by wetting condition of the system.The viscous and gravity forces are negligible and the capillarityplays a dominant role heterogeneities of channel sizes. Threemicrofluidic systems are designed to study experimentally the role ofmicroscopic liquid films (wetting) or macroscopic ones (corners) inthe pores level. The first one consists of the displacement of ameniscus in a circular capillary with various wetting conditions. Inparticular, for pseudo-partial wetting systems, a contact anglehysteresis is observed but with a weak pinning as compared to partialwetting systems where there are non wetting films. The second andthird ones show the influences of liquid films in the corners of asquare channel. The coupling between the corner flows and the mainflow involves the drainage of the trapped oil cluster. The propertiesof this new mechanism are consistent with the theoretical model, andalso characterized by experiments.

Ce travail est consacré à l'étude expérimentale des écoulements diphasiques et triphasiques d'inclusions (bulles, gouttes, sphères) en milieux tant newtoniens que non newtoniens à l'échelle microscopique et mésoscopique, en utilisant la visualisation par une caméra rapide, la vélocimétrie par images des particules (PIV) ainsi que la micro-vélocimétrie par images des particules. Des bulles et des gouttes ont été étudiées expérimentalement depuis leur formation, en passant par leur déformation jusqu'à leur coalescence. La formation de bulles dans des micro-mélangeurs a été étudiée et caractérisée par l'obtention de champs de vitesses. Différents paramètres, tels que le cisaillement, la géométrie de la zone de formation, les débits ou encore les propriétés physiques ont été testés afin de développer des lois d'échelles. La traversée d'une interface liquide-liquide par une inclusion a été abordée par des expériences originales, permettant de décrire la dynamique du phénomène, de définir des nombres adimensionnels et de mettre en évidence des instabilités interfaciales. L'effet Weissenberg a également été étudié aux différentes échelles afin de comprendre les phénomènes conduisant à son amplification. Enfin, en milieu viscoélastique et rhéofluidifiant, nous avons caractérisé l'écoulement autour d'une inclusion isolée solide par l'obtention de champs de vitesses. Ces résultats ont permis de confirmer l'origine viscoélastique du sillage négatif et de prédire ses caractéristiques / The present work was devoted to the experimental study of the multiphase flow around inclusions in both Newtonian and non-Newtonian media at respectively microscopic and mesoscopic scales, by means of the Particle Image Velocimetry (both PIV and µ-PIV) and fast camera visualization. Bubbles and drops were experimentally studied starting from their formation, the rising and up to their coalescence and fragmentation. Bubble formation in micro-mixers was also investigated and characterized by measuring the liquid velocity fields. Different parameters, such as the shear rate, the geometry of the micro-mixer, the flow rates or the physical properties were tested to develop correlations of power-law kind. The deformation of a liquid-liquid interface due to the passage of an inclusion was investigated by original experiments in order to observe and describe the dynamics of the phenomenon, to define the reliable dimensionless numbers and also to highlight several interfacial instabilities. The Weissenberg effect was also studied at different scales in various non-Newtonian fluids in comparison with Newtonian fluids to understand the amplification phenomena under the combining effects of instability and normal forces. Finally, the flow around an isolated solid inclusion was characterized by performing the measurements of velocity fields in viscoelastic and shear-thinning fluids. These results were used to confirm the viscoelastic origin of the negative wake behind the solid sphere and to model its characteristics

Cette étude s'inscrit dans la problématique de l'extraction minière de l'uranium. L'étape plus spécifiquement visée est celle de l'extraction liquide-liquide au cours de laquelle l'uranium en solution aqueuse de lixiviation est transféré dans une phase organique par une complexation avec une amine tertiaire (Alamine 336®). L'étude porte sur cette étape de séparation par le biais d'un contact liquide-liquide sans dispersion assuré au travers d'une membrane macroporeuse organique (pertraction). Cette technologie permet l'utilisation de phases de densités proches. Ainsi, l'extraction de l'uranium et du molybdène, co-extrait industriellement par l'Alamine 336, ont été étudiées pour différentes concentrations élevées en molécules extractantes. Pour cela, l'ensemble des paramètres physico-chimiques influents du système chimique (courbe de distribution, viscosité, densité, tension de surface, coefficient de diffusion à l'infini, etc.) et de la membrane (porosité, dimensions, tortuosité, etc.) sont caractérisés. Des essais de pertraction sur un dispositif unitaire de fibre creuse, développé dans le cadre de cette étude, sont réalisés et les résultats sont modélisés par une approche de résistances du transfert de matière en séries. Un seul paramètre ajustable est retenu : le coefficient de diffusion en phase organique. Cette modélisation permet de mettre en évidence les limitations au transfert de l'uranium de la phase aqueuse vers la phase organique lors du processus d'extraction à travers la membrane liées au système chimique, aux débits et à la membrane. / This study is falls within the framework of uranium mining. The step more specifically aimed is the solvent extraction during which the uranium is transferred from a lixiviation aqueous solution to an organic phase by a complexation with a tertiary amine (Alamine 336®). The study focuses on this step of separation using a liquid-liquid contact without dispersal guaranteed by an organic macroporous membrane (pertraction). This technology allows the use of phases with close densities. So, uranium and molybdenum extraction, co-extracted industrially by Alamine 336, were studied for various high extractantes molecules concentrations. For that purpose, all the influential physical chemical parameters of the chemical system (distribution curve, viscosity, density, surface tension, infinite diffusion coefficient, etc.) and of the membrane (porosity, size, tortuosity, etc.) are characterized. Pertraction essays on a single hollow fibre, developed within the framework of this study, are performed and the results are modelized by an approach of mass transfer resistances in series. A single adjustable parameter is retained: the diffusion coefficient in organic phase. This modelling allows highlighting the limitations of uranium transfer from the aqueous phase towards the organic phase during the extraction process through the membrane function of chemical system, the flows and the membrane.

Neste trabalho estudou-se a modelagem termodinâmica do equilíbrio de fases de sistemas aquosos bifásicos formados por um polímero neutro, especificamente o poli(etileno glicol), e um sal. O modelo implementado é baseado na equação de Pitzer para soluções de eletrólitos, dele diferindo ao considerar a influência das propriedades do polímero no cálculo da constante dielétrica e da densidade do meio, presentes no cálculo do termo relativo às interações de longo alcance da energia de Gibbs excedente. Além disso, procurou-se também considerar a dependência dos parâmetros relativos ao polímero com respeito ao tamanho de sua cadeia. Dados experimentais obtidos da literatura foram utilizados para a obtenção dos parâmetros ajustáveis do modelo, em cuja implementação foi utilizada a linguagem FORTRAN. A alteração nas propriedades do meio modificou o estado de equilíbrio calculado, fato que pôde ser observado por meio da análise de fatores como o desvio entre a composição calculada pelos modelos e os valores experimentais em cada fase e a inclinação da linha de amarração. Em alguns sistemas o desempenho do modelo modificado foi superior nesses parâmetros, mas em termos gerais a modificação no cálculo da constante dielétrica e da densidade não resultou em melhora no cálculo do equilíbrio de fases, por vezes piorando-o, de modo que investigações específicas sobre o termo de longo alcance foram conduzidas para verificar a razão deste comportamento. A inclusão de parâmetros ternários aumentou a capacidade de correlação de ambos os modelos. No que diz respeito à possibilidade de correlação dos parâmetros de interação como função do tamanho da cadeia polimérica, que poderia levar a um modelo preditivo, observou-se que somente para tamanhos grandes de cadeia foi possível estabelecer uma dependência direta e inequívoca. / The thermodynamic modeling of phase equilibrium in aqueous two phase systems containing the neutral polymer poly(ethylene glycol) and a salt was studied in this work. The implemented model is based on the Pitzer equation for electrolytes solutions, modified in order to account for the influence of polymer properties in both the medium dielectric constant and the medium density, values which are present in long range term of the excess Gibbs energy. The dependence of the adjustable parameters on the polymer molecule size was also investigated. Experimental data from literature were used to obtain the adjustable parameters of the model, in whose implementation the FORTRAN computer language was used. The changes introduced into the long range term resulted in a shift of the calculated equilibrium compositions, which could be observed by analyzing the deviation between calculated and experimental compositions and tie-line slopes. For some systems the performance of the modified model was superior, but in most cases the changes introduced did not result in a significant improvement in phase equilibrium calculations, and even worsened them. Specific investigations on the long range term were carried out to verify the reason for such behavior. The insertion of ternary parameters increased the correlation capacity of both models. Concerning the hypothesis that the interaction parameters can be directly related to the polymer chain size, which might eventually lead to a predictive model, it was noticed that a direct dependency holds only for larger chain sizes.