The guided wave method is one of the non-destructive testing methods with the ability to inspect long length of pipeline. The presence of defects and pipe features can be indicated by analyzing the reflected echoes and the mode conversion phenomena of guided waves. To provide the profile of defects, the signals of guided wave are usually processed to form a B-scan or C-scan image. As for the characteristics of multimodes and dispersion, the C-scan image of defect shows a poor resolution both in the axial and cricumferential directions. Therefore, this study uses the synthetic aperture focusing technique (SAFT) to improve the resolution of the C-scan image. The propagation and scattering of the fundamental torsional mode T(0,1) in pipes are analyzed by the transient analysis of finite element method. Furthermore, the reflected signals are processed by SAFT to form a C-scan image with better resolution. Three types of defects including circumferential crack, axial crack and pitting were discussed in this study both by finite element method and experimental method. In the numerical study, the modification of the C-scan image of the circumferential crack showed a better consequent than the axial crack and pitting. The SAFT was also used to separate the images of two circumferential cracks with different axial location on the pipe succesfully. In the experimental study, the signals of the axisymmetric weld and non-axisymmetric defects were processed by SAFT to form the C-scan image. The results showed a nice resolution of circumferential cracks and the circumferential distribution of the weld in the modified C-scan image at the same time. The application of SAFT to guided wave on a pipe is valid to overcome the effects of guide wave multimode and dispersion characteristics, it provides a new way to defects identification.

Techn. Universiẗat, Diss., 2002--Berlin.

Nesse trabalho, a equação de estado PC-SAFT é combinada com um método de contribuição de grupos (GC) para estimação dos seus parâmetros. Para tanto, foram utilizados dados experimentais dos componentes puros (pressão de vapor e volume específico do líquido) e em mistura (equilíbrio líquido-vapor - VLE e coeficiente de atividade em diluição infinita - IDAC). Através de uma análise de sensibilidade, verificou-se que o parâmetro volume de associação poderia ser mantido constante, reduzindo o número de parâmetros a serem estimados. O objetivo principal foi estudar misturas que apresentassem associação cruzada ou forte interação entre os compostos. Com os parâmetros estimados, avaliou-se o desempenho do modelo GC-PC-SAFT no cálculo de propriedades de n-alcanos, 1-álcoois, aminas, clorofórmio e acetona. Os desvios médios obtidos no cálculo do equilíbrio líquido-vapor (VLE), entre as diferentes misturas estudadas, mostraram que a estratégia adotada para a estimação do parâmetro energia de associação apresentou bons resultados, com desvios relativamente baixos para a maioria dos casos estudados. Para IDAC, as predições foram muito semelhantes àquelas obtidas por outros modelos. Os resultados de VLE são importantes, pois fornecem informações sobre as concentrações intermediárias de uma mistura, enquanto que o IDAC fornece uma medida eficiente do grau de não-idealidade da mistura. Essas propriedades foram escolhidas com o objetivo de conseguir uma melhor representação das misturas, buscando eliminar a necessidade de parâmetros de interação binária. Os resultados obtidos revelam que o modelo GC-PC-SAFT proposto pode ser utilizado para predizer o equilíbrio líquido-vapor com uma precisão satisfatória para sistemas binários entre os diferentes compostos estudados, sem nenhum parâmetro de interação binária. / In this work, the PC-SAFT EoS is combined with a group contribution method (GC) for parameter estimation. To achieve this, experimental data for pure components (vapor pressure and liquid volume) and mixtures (vapor-liquid equilibria - VLE and infinite dilution activity coefficient -IDAC) has been used. Through sensitivity analysis, it has been found that the association volume parameter could be set constant, thus reducing the amount of parameters that needed to be estimated. The aim of this work was to study mixtures that presented cross association or strong component interaction. With the estimated parameters, GC-PC-SAFT performance in properties calculation of n-alkanes, 1-alcohols, amines, chloroform and ketone has been evaluated. The average deviations obtained in the calculation of vapor-liquid equilibria (VLE), in the different mixtures considered, have shown that the strategy for association energy parameter estimation has presented good results, with relatively low deviations for most of the cases. For IDAC, the predictions presented very similar results to those obtained by other models. VLE results are important because they provide information about mixtures’ intermediary concentrations, whereas IDAC offers an efficient measure of mixtures’ degree of non-ideality. These properties have been chosen with the aim of getting a better representation of the mixtures, seeking to eliminate the need for binary interaction parameters. The obtained results show that GC-PC-SAFT can be used to predict vapor-liquid equilibria for binary systems among the different studied components with satisfactory accuracy with no binary interaction parameter.

A modelagem termodinâmica do equilíbrio de fases e a determinação de propriedades termodinâmicas de sistemas em que as moléculas apresentam associação é um problema desafiador na indústria química. Embora o uso de equações de estado tenha sido durante muito tempo restrito aos sistemas de fluidos simples, há uma crescente demanda por modelos que também sejam adequados a compostos complexos e macromoleculares. O avanço teórico mais aparente para equações de estado com tais capacidades foi conseguido por aplicação dos princípios da mecânica estatística, o qual considera as forças de associação entre as moléculas em sua teoria molecular. Um exemplo desta categoria é a equação de estado PC-SAFT (Perturbed Chain-Statistical Associating Fluid Theory), cuja formulação requer apenas um pequeno conjunto de parâmetros para cada componente e estas interações são computadas através de regras de mistura. Desta forma, os objetivos deste trabalho foram a implementação do termo de associação desta equação e o desenvolvimento de ferramentas para o cálculo de propriedades termodinâmicas de sistemas contendo fluidos associados e não-associados, bem como para o cálculo do equilíbrio de fases. Todas as funções foram desenvolvidas no software MATLAB e a verificação da implementação foi feita através de comparação entre os resultados obtidos com estas ferramentas e dados experimentais e/ou outras equações de estado presentes na literatura. Através da comparação com dados de equilíbrio de fases disponíveis na literatura, foi analisado o desempenho da equação PC-SAFT com associação para diferentes sistemas multicomponentes e múltiplas fases envolvendo substâncias polares e apolares. Os resultados obtidos foram satisfatórios quando comparados a dados experimentais e aqueles obtidos através de outras equações de estado. / Modeling the phase equilibrium and thermodynamic properties of systems in which molecules exhibit associating interactions remains a challenging problem in chemical industry. Although the use of equations of state has for a long time been restricted to systems of simple fluids, there is an increasing demand for models that are also suitable for complex and macromolecular compounds. Progress toward this goal has been achieved by applying principles of statistical mechanics, which takes molecular theories into account. One example of such approach is the PC-SAFT (Perturbed Chain-Statistical Associating Fluid Theory) equation of state, which requires only a small set of parameters for each component and whose interactions are obtained by mixing rules. The goals of this work have been the implementation of the PC-SAFT association term and the development of tools for thermodynamic properties calculation of associating and non-associating systems, as well as for phase equilibria calculation. All the functions have been developed using MATLAB software and their implementation analysis has been made by comparing obtained results to experimental data and those obtained by other equations of state available in literature. Through these comparisons, PC-SAFT performance has been analyzed for different multicomponent and multiphase systems involving polar and non-polar substances. The obtained results have shown good correlation to both experimental data and those obtained by other equations of state.

A modelagem termodinâmica do equilíbrio de fases e a determinação de propriedades termodinâmicas de sistemas em que as moléculas apresentam associação é um problema desafiador na indústria química. Embora o uso de equações de estado tenha sido durante muito tempo restrito aos sistemas de fluidos simples, há uma crescente demanda por modelos que também sejam adequados a compostos complexos e macromoleculares. O avanço teórico mais aparente para equações de estado com tais capacidades foi conseguido por aplicação dos princípios da mecânica estatística, o qual considera as forças de associação entre as moléculas em sua teoria molecular. Um exemplo desta categoria é a equação de estado PC-SAFT (Perturbed Chain-Statistical Associating Fluid Theory), cuja formulação requer apenas um pequeno conjunto de parâmetros para cada componente e estas interações são computadas através de regras de mistura. Desta forma, os objetivos deste trabalho foram a implementação do termo de associação desta equação e o desenvolvimento de ferramentas para o cálculo de propriedades termodinâmicas de sistemas contendo fluidos associados e não-associados, bem como para o cálculo do equilíbrio de fases. Todas as funções foram desenvolvidas no software MATLAB e a verificação da implementação foi feita através de comparação entre os resultados obtidos com estas ferramentas e dados experimentais e/ou outras equações de estado presentes na literatura. Através da comparação com dados de equilíbrio de fases disponíveis na literatura, foi analisado o desempenho da equação PC-SAFT com associação para diferentes sistemas multicomponentes e múltiplas fases envolvendo substâncias polares e apolares. Os resultados obtidos foram satisfatórios quando comparados a dados experimentais e aqueles obtidos através de outras equações de estado. / Modeling the phase equilibrium and thermodynamic properties of systems in which molecules exhibit associating interactions remains a challenging problem in chemical industry. Although the use of equations of state has for a long time been restricted to systems of simple fluids, there is an increasing demand for models that are also suitable for complex and macromolecular compounds. Progress toward this goal has been achieved by applying principles of statistical mechanics, which takes molecular theories into account. One example of such approach is the PC-SAFT (Perturbed Chain-Statistical Associating Fluid Theory) equation of state, which requires only a small set of parameters for each component and whose interactions are obtained by mixing rules. The goals of this work have been the implementation of the PC-SAFT association term and the development of tools for thermodynamic properties calculation of associating and non-associating systems, as well as for phase equilibria calculation. All the functions have been developed using MATLAB software and their implementation analysis has been made by comparing obtained results to experimental data and those obtained by other equations of state available in literature. Through these comparisons, PC-SAFT performance has been analyzed for different multicomponent and multiphase systems involving polar and non-polar substances. The obtained results have shown good correlation to both experimental data and those obtained by other equations of state.

A modelagem termodinâmica do equilíbrio de fases e a determinação de propriedades termodinâmicas de sistemas em que as moléculas apresentam associação é um problema desafiador na indústria química. Embora o uso de equações de estado tenha sido durante muito tempo restrito aos sistemas de fluidos simples, há uma crescente demanda por modelos que também sejam adequados a compostos complexos e macromoleculares. O avanço teórico mais aparente para equações de estado com tais capacidades foi conseguido por aplicação dos princípios da mecânica estatística, o qual considera as forças de associação entre as moléculas em sua teoria molecular. Um exemplo desta categoria é a equação de estado PC-SAFT (Perturbed Chain-Statistical Associating Fluid Theory), cuja formulação requer apenas um pequeno conjunto de parâmetros para cada componente e estas interações são computadas através de regras de mistura. Desta forma, os objetivos deste trabalho foram a implementação do termo de associação desta equação e o desenvolvimento de ferramentas para o cálculo de propriedades termodinâmicas de sistemas contendo fluidos associados e não-associados, bem como para o cálculo do equilíbrio de fases. Todas as funções foram desenvolvidas no software MATLAB e a verificação da implementação foi feita através de comparação entre os resultados obtidos com estas ferramentas e dados experimentais e/ou outras equações de estado presentes na literatura. Através da comparação com dados de equilíbrio de fases disponíveis na literatura, foi analisado o desempenho da equação PC-SAFT com associação para diferentes sistemas multicomponentes e múltiplas fases envolvendo substâncias polares e apolares. Os resultados obtidos foram satisfatórios quando comparados a dados experimentais e aqueles obtidos através de outras equações de estado. / Modeling the phase equilibrium and thermodynamic properties of systems in which molecules exhibit associating interactions remains a challenging problem in chemical industry. Although the use of equations of state has for a long time been restricted to systems of simple fluids, there is an increasing demand for models that are also suitable for complex and macromolecular compounds. Progress toward this goal has been achieved by applying principles of statistical mechanics, which takes molecular theories into account. One example of such approach is the PC-SAFT (Perturbed Chain-Statistical Associating Fluid Theory) equation of state, which requires only a small set of parameters for each component and whose interactions are obtained by mixing rules. The goals of this work have been the implementation of the PC-SAFT association term and the development of tools for thermodynamic properties calculation of associating and non-associating systems, as well as for phase equilibria calculation. All the functions have been developed using MATLAB software and their implementation analysis has been made by comparing obtained results to experimental data and those obtained by other equations of state available in literature. Through these comparisons, PC-SAFT performance has been analyzed for different multicomponent and multiphase systems involving polar and non-polar substances. The obtained results have shown good correlation to both experimental data and those obtained by other equations of state.

Orientador: Liliane Lona / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-09T09:29:23Z (GMT). No. of bitstreams: 1 Pereira_YuriGuerrieri_M.pdf: 1827964 bytes, checksum: 8c6635139bee2d39bd01aba8b6a2c335 (MD5) Previous issue date: 2007 / Resumo: Os sistemas poliméricos, sejam eles reacionais ou não-reacionais, são em geral bastante complexos, devido à própria estrutura das cadeias das suas moléculas e pela existência de diversas interações entre elas. No que se refere à termodinâmica de sistemas poliméricos, este é um aspecto fundamental em muitos processos de polimerização, uma vez que têm impacto direto nas características dos materiais formados. Neste sentido, este trabalho tem como objetivo investigar o comportamento de sistemas poliméricos em duas plantas industriais de produção de polietileno, denominadas aqui como Planta PEBD, onde é produzido polietileno de baixa densidade (PEBD), e Planta PEL, onde são produzidos polietileno linear de baixa densidade (PELBD) e polietileno alta densidade (PEAD). Na Planta PEBD foi estudado o equilíbrio líquido-líquido a alta pressão, presente no reator, e o equilíbrio líquido-vapor presente no separador de baixa pressão (flash). Para este estudo foram utilizadas 8 resinas produzidas comercialmente. Na Planta PEL foi estudado o equilíbrio líquido-vapor presente no separador de pressão intermediaria (flash). Para este estudo foram utilizadas 25 resinas produzidas comercialmente. De um modo geral foram feitas as modelagens de sistemas binários e multicomponentes constituídos por: etileno, etano, propeno, propano, 1-buteno, cicloexano, 1-octeno e polímero. Os dados experimentais utilizados foram gerados a partir de medições disponíveis e balanços de massa e energia em ambas as plantas industriais. Para a modelagem dos equilíbrios de fases investigados neste trabalho foi utilizada a equação de estado PC-SAFT (Perturbed-Chain Statistical Associating Fluid Theory, Teoria Estatística de Fluidos Associativos com Cadeia Perturbada), que tem apresentado desempenho superior ao das suas antecessoras. Após a implementação computacional, o modelo foi validado para ambas as plantas industriais. Os resultados mostram que, para alguns sistemas, os parâmetros binários encontrados na literatura são suficientes para uma boa modelagem; para outros, quando os parâmetros de interação binária são ajustados na equação, o modelo apresenta-se capaz de representar melhor os dados experimentais / Abstract: Polymeric systems, with or without chemical reactions, are in general much complex due to molecules structure and due to the existence of many interactions between them. Thermodynamics of polymeric systems, and more specifically phase equilibria, is a fundamental aspect in many polymerization processes, since they influence directly in the characteristics of the material produced. In this way, the objective of this work is to investigate the behavior of polymeric systems in two industrial plants of polyethylene production, called here as PEBD Plant, where low density polyethylene (LDPE) is produced, and PEL Plant, where linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) are produced. In PEBD Plant liquid-liquid equilibria in the reactor unit and vapor-liquid equilibria in the low pressure separator (flash) were studied. For this study 8 resins produced commercially were used. In PEL Plant vapor-liquid equilibria present in the intermediate pressure separator (flash) was studied. For this study 25 resins produced commercially were used. In a general way binary and multicomponent systems were modeled, with the following components: ethylene, ethane, propylene, propane, 1butene, ciclohexane, 1-octene and polymer. The experimental data used has been generated through a few measurements at disposal and though mass and energy balance calculations in both industrial plants. In modeling phases equilibria investigated in this work, PC-SAFT (Perturbed-Chain Statistical Associating Fluid Theory) equation of state was used, since it has presented superior performance when compared with its predecessors. After the computational implementation, the model was validated for both industrial plants. The results show that, for some systems, the binary parameters found in literature had been good enough for modeling purposes. In others systems, when binary interaction parameters were adjusted in the equation, the model had presented a better capability in representing the experimental data / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

En la presente tesis se plantea el modelado del equilibrio entre fases de mezclas de importancia en biorrefinerías, y el desarrollo de módulos de simulación de procesos y productos. El modelo termodinámico empleado es la Ecuación de Estado a Contribución Grupal con Asociación (gca-eos) que ha sido desarrollada y exitosamente aplicada al procesamiento de mezclas derivadas de sustratos vegetales y de sistemas a alta presión por el grupo de Termodinámica de Procesos de plapiqui. La gca-eos es robusta para la representación, tanto a baja como alta presión, de sistemas altamente no ideales que presenten asimetría en tamaño y energética y con presencia de interacciones de tipo puente hidrógeno, generalmente presentes en mezclas procedentes del procesamiento de productos naturales. Su carácter a contribución grupal facilita la predicción de compuestos complejos y mezclas a los que se les desconoce sus propiedades, como también frecuentemente ocurre con los de origen natural. Dadas las características favorables de este modelo se propone su extensión para cubrir un número mayor de grupos funcionales típicos del procesamiento en biorrefinerías y una mejor descripción de las interacciones asociativas que pueden presentar el agua, alcoholes, compuestos nitrogenados y aromáticos. Teniendo en cuenta esta premisa se implementaron algoritmos de cálculo termodinámico que fueron incorporados a simuladores de procesos, con énfasis en equipos involucrados en la purificación de biocombustibles, como por ejemplo equipos de destilación flash, columnas de destilación y extractores líquido-líquido. La presente tesis se desarrolla en 8 capítulos. Luego de un apartado introductorio, el capítulo 2 describe el modelo termodinámico gca-eos, destacando leyes físicas que lo sustentan ya que resultan una herramienta sólida para generar las estrategias de parametrización desarrolladas en esta tesis. Los siguientes capítulos, muestran la extensión del modelo a las distintas familias de compuestos orgánicos estudiados. Específicamente, el capítulo 3 trata la extensión la gca-eos, a hidrocarburos aromáticos en sistemas que involucren alcoholes alifáticos y agua. El capítulo 4 por su parte, discute una nueva definición de los grupos fenólicos en sistemas con hidro - carburos aromáticos, alifáticos y agua. Los capítulos 5 y 6 discuten la parametrización de sistemas nitrogenados: el primero define los nuevos grupos amino, y si interacción con hi - drocarburos y alcoholes, mientras que en el segundo se incluye mezclas acuosas de estos compuestos y se prueba la capacidad predictiva de la gca-eos en soluciones acuosas de alcanolaminas. Siendo estas últimas un reconocido solvente para la remoción de gases ácidos también presentes en el procesamiento, tanto bio- como termo-químico, de biomasa. Por último, el capítulo 7 trata el desarrollo de un módulo de simulación de columnas trifásicas. Se desarrollan las ecuaciones básicas que permiten adaptar un algoritmo tradicional de destilación líquido-vapor para considerar la posible existencia de dos fases líquidas. Como caso de estudio, se analiza una columna de remoción de metanol en el contexto del proceso supercrítico de producción de biodiesel. / Phase equilibrium modeling of mixtures of importance in biorefineries, and the development of process simulation modules and products are presented in this thesis. The thermodynamic model chosen is the Group Contribution with Association Equation of State (gca-eos). This model has been developed by the group of Process Thermodynamics in plapiqui and successfully applied to model processes of mixtures of vegetable substrates and high-pressure systems. The gca-eos is capable to model systems of highly non-ideal mixtures, at low or high pressures, which exhibit important energetic and size asymmetry. Also the model is able to handle molecules that present h-bond interactions, characteristic of natural products mixtures. Moreover, its group contribution formulation allows the predictions of unknown properties of complex compounds and mixtures, as in the case of natural compounds. These characteristics encourage an extension of its parameter table to cover a greater number of functional groups that are common in biorefineries processes. Another goal of this thesis was to obtain a better description of associative interactions present in mixtures of water, alcohols, with aromatic and nitrogen compounds. With this premise, thermodynamic calculation algorithms were incorporated into process simulators, with emphasis on equipment involved in the purification of biofuels, such as flash distillation equipment, distillation columns and liquid–liquid extractors. This thesis is presented in eight chapters. After an introductory section, Chapter 2 describes the mathematical formulation of the gca-eos, with emphasis on underlying physical laws which generate robust parameterization strategies developed in this dissertation. The following chapters show the extension of this model to different families of organic compounds studied in this work. Chapter 3 addresses the extension of the model to aromatic hydrocarbons in systems with water and aliphatic alcohols. Chapter 4 discuss a new definition of the phenolic group present in systems with aromatic and aliphatic hydrocarbons and water. Chapters 5 and 6 discuss the parameterization of amine groups: the first one defines new amine groups and its interaction with aliphatic hydrocarbons and alcohols, while the second one includes aqueous amine mixtures, and the predictive capability of the gca-eos is tested with aqueous alkanolamine solutions. Finally, Chapter 7 shows the development of a simulation module of a three phase distillation column. Basic equations that enable a typical vapor–liquid distillation algorithm to represent the existence of two liquid phases are presented. Furthermore, a methanol stripping column in the context of supercritical biodiesel production is analyzed as a case of study.

No description available.

Thesis (MEng)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Thermodynamic models have been investigated extensively since Johannes van der Waals first devised a mathematical relation capable of predicting both vapour and liquid phases for a mixture at equilibrium. With the advent of modern computing power, these equations of state have gone from their humble empirical beginnings to the comprehensive and fundamentally derived models we have today. One such physically sound model is the Statistical Associating Fluid Theory (SAFT) family of equations, derived from the molecular perturbation theories of the 1980’s. The relative youth of this thermodynamic framework has meant that much work has gone into modification and optimisation of the model recently. The variants of particular interest to this work are the simplified perturbed chain SAFT equations with the Jog & Chapman (sPC-SAFTJC) and Gross & Vrabec (sPC-SAFTGV) polar terms. Each of the polar terms supports one adjustable polar parameter that relates to the quantity of polar segments in the reference fluid but not necessarily its position in the carbon chain. The strength of polar interactions is known to decrease as the functional group moves away from the terminal methyl group and the effects of steric hindrance increase. Thus, in question here is whether the models can account for the change in polar interactions associated with the changing position of the polar group, by only adjusting the values of the existing pure component parameters; that is, in lieu of a position specific parameter. The carbonyl group in ketone molecules is one such polar group, and it is this homologous series that is the focus of this study. The decrease in polar interactions as the carbonyl group in a ketone molecule shifts centrally is apparent from the lower boiling points of the isomers where the polar group is central as compared to those where the functional group is nearer the terminal methyl group. The effect of this functional group shift on binary phase behaviour has not previously been assessed for any system however, as the lack of experimental data attests. Thus, experiments had to be conducted to generate phase equilibrium data for systems comprising each structural isomer of a mid-length ketone with a common second component with no functionality. This limitation was imposed to isolate the cause of experimentally observed phenomena to the shifting polar group alone. The generated data could then be appropriately modelled using the polar sPC-SAFT variants and the capabilities of each model, as outlined above, assessed. To this end, isobaric binary vapour-liquid equilibrium data were measured for 2-, 3- & 4-heptanone with three separate normal alkanes of similar length (n-octane, n-nonane & n-decane) at 40kPa. The apparatus used was a dynamic Gillespie VLE still with temperature and pressure accuracies of 0.03°C and 1.6mbar respectively. Equipment verification was achieved through the reproduction of experimental data for the ethanol/1-butanol system at 1.013bar. The vapour and liquid samples for all nine systems were analysed by gas chromatography with a maximum compositional error of ±0.022 mole fraction. All reported data were found to be thermodynamically consistent using both the L/W and McDermott-Ellis consistency tests. When paired with a common n-alkane, all three structural heptanone isomers displayed similar qualitative trends in phase behaviour. Minimum boiling azeotropes were measured in all nine systems; in the high alkane region for n-octane systems (~98 mole%), the equal concentration region for n-nonane systems (34 mole% to 53 mole%) and in the very dilute n-alkane region for n-decane systems (~3 mole%). The n-nonane systems in particular highlighted the effect of shifting functional group, with completely separate phase envelopes away from the pure alkane composition space evident in a particularly small temperature range. Modelling was performed using in-house developed software, with pure component parameters generated for each system using five different regression procedures. The first was traditional fitting of the segment diameter (σ), segment number (m), segment energy (є/k) and the respective polar parameter (xp, np) to DIPPR correlations of pure component saturated vapour pressure, liquid density and the heat of vaporisation. The latter four procedures included the fixing of the polar parameter according to functional group correlations and the three instances of including the binary VLE data set for each of the three alkanes considered in this work. When applied to the nine binary ketone-alkane systems measured in this work, excellent predictions of the experimental data were in evidence in most cases and only small binary interaction parameters were necessary to correlate the data where pure predictions were poor. The performance of the parameter sets based on the fixing of the polar parameter and the inclusion of VLE data were consistent and of a high quality for both models, with near identical parameters generated in all four cases for each of the nine systems. The parameter sets generated in this fashion were shown to be applicable not only to the systems measured in this work, but also successfully predicted the independently measured experimental data of the n-hexane/4-heptanone system. It was thus concluded that either of these regression alternatives are viable for the generation of accurate component parameters, and the choice of VLE data set included is trivial. The pure predictions of the sPC-SAFTGV model were generally better than its sPC-SAFTJC counterpart, particularly in the case of the traditionally regressed parameter sets. sPC-SAFTGV displayed constant qualitative agreement with the experimental data for each of the heptanone isomers with a given n-alkane. The quality of the predictions of sPC-SAFTJC, however, worsened significantly as the polar interactions diminished from 2- to 4-heptanone, with no predictions even possible for the least polar isomer. This was attributed to the different perturbation theories used in the development of these terms, but a more detailed study would be necessary to confirm this. This work thus shows an apparent inability of the sPC-SAFTJC equation of state to account for the decreasing polar interactions associated with the carbonyl group in a ketone molecule shifting centrally, while sPC-SAFTGV produces qualitatively good fits for all three isomers. These flaws can be overcome through the incorporation of VLE data in the regression procedure if such data is available, or otherwise through the use of group specific correlations for fixing the polar parameter value. / AFRIKAANSE OPSOMMING: Sedert Johannes van der Waals die eerste wiskundige verhouding ontwikkel het wat beide die damp- en vloeibare fases van 'n mengsel by ewewig kon voorspel, is die veld van termodinamiese modellering al deeglik ondersoek. Na die koms van die moderne rekenaars het hierdie vergelykings van hul nederige empiriese wortels gegroei tot die omvattende, fundamentele modelle wat ons vandag het. Een so 'n fundamenteel gebaseerde familie van vergelykings is die ‘Statistical Associating Fluid Theory’ (SAFT) modelle, wat afgelei is vanaf molekulêre versteuringsteorieë, ontwikkel in die 1980s. Hierdie relatiewe jong modelle het in die afgelope ruk aansienlike aanpassing en optimering ondervind. Modelvariante van besondere belang tot hierdie werk, is die vereenvoudigde versteurde ketting of ‘simplified perturbed chain’ SAFT vergelykings, met Jog & Chapman (sPC- SAFTJC) en Gross & Vrabec (sPC- SAFTGV) polêre terme. In die sPC-SAFT toestandsvergelyking word elkeen van die polêre terme ondersteun deur een polêre veranderlike. Hierdie veranderlike is afhanklik van die aantal polêre segmente in die verwysingsvloeistof, maar nie noodwendig hul posisie in die koolstofketting nie. Daarteen is dit bekend dat die polêre interaksies tussen molekules swakker word soos die polêre groep wegbeweeg van die terminale metielgroep, en steriese hindernis ʼn groter rol begin speel. Dus is die vraag of die model die verandering in die polêre interaksie, as gevolg van veranderende posisie van die polêre groep, kan voorspel deur in plek van ʼn posisie afhanklike parameter, slegs ʼn aanpassing van die polêre waardes van die suiwer komponente te maak. Die karbonielgroep in ketoon molekules is een so 'n polêre groep, en ʼn homoloë reeks ketone word in hierdie studie ondersoek. Die afname in die polêre interaksie soos wat die karbonielgroep in 'n ketoon molekule weg skuif vanaf die terminale metiel groep is sigbaar deur die afname in kookpunt van die verskillende isomere. Hierdie effek van die funksionele groepsposisie op binêre fasegedrag is nog nie voorheen vir enige stelsels geëvalueer nie en geen eksperimentele data is vrylik beskikbaar nie. Om hierdie tekortkoming in die literatuur aan te spreek, is eksperimentele fase ewewig data gemeet. ʼn Reeks stelsels is ondersoek wat elk bestaan uit ʼn struktuurisomeer van ʼn mid-lengte ketoon en ʼn tweede komponent met geen funksionele bydrae. Eksperimente is so opgestel om die effek van die skuiwende polêre groep op die fasegedrag te isoleer en kwalitatief te ondersoek. Die gegenereerde data is dan gemodelleer met behulp van die polêre sPC- SAFT variante, soos hierbo gespesifiseer, en die vermoëns van elke model is beoordeel. Isobariese binêre fase ewewig data is by 40kPa gemeet vir damp-vloeistof stelsels bestaande uit 2, 3 & 4 heptanoon, gemeng met drie verskillende normaal alkane van vergelykbare kettinglengte (n-oktaan, n-nonaan & n-dekaan). Die apparaat wat gebruik was is 'n dinamiese Gillespie VLE eenheid met temperatuur- en drukakkuraatheid van 0,03°C en 1.6mbar, onderskeidelik. Die akkuraatheid van die toerusting is bevestig deur eksperimentele data vir ʼn etanol/1-butanol stelsel by 1.013bar te reproduseer. Die damp en vloeibare monsters vir al nege stelsels is ontleed deur gaschromatografie met 'n maksimum komposisionele fout van ± 0,022 (molfraksie). Alle data is as termodinamies konsekwent gevind deur van beide die L/W en McDermott-Ellis konsekwentheidstoetse gebruik te maak. Mengsels van die drie strukturele isomere van heptanoon met ʼn gemene n-alkaan het tydens eksperimente soortgelyke kwalitatiewe tendense in fasegedrag getoon. Gedurende eksperimente is die lae kookpunt asiotrope gemeet vir al nege stelsels. Die asiotrope verskyn in die hoë alkaan konsentrasies (~98 mol%) vir n-oktaan stelsels, medium konsentrasies (34 mol% tot 53 mol%) vir n-nonaan stelsels en baie verdunde konsentrasies (~ 3 mol%) vir n-dekaan stelsels. Die n-nonaan stelsels beeld veral die effek van die verskuiwing van die funksionele groep uit, met diskrete fasegrense wat duidelik apart staan van die suiwer alkaan ruimte, binne ʼn klein temperatuurverskil. Modellering van die stelsels is uitgevoer met behulp van sagteware wat in-huis ontwikkel is. Suiwer komponent data is gegenereer vir elke stelsel deur van vyf verskillende regressie prosedures gebruik te maak. Die eerste is die tradisionele passing van die segment deursnee (σ), segment nommer (m), segment energie (є/k) en die onderskeie polêre parameters (xp, np) op DIPPR korrelasies van die suiwer komponent versadigde dampdruk, vloeistof digtheid en die hitte van verdamping. Die oorblywende vier prosedures sluit in die bepaling van die polêre parameter deur funksionelegroep korrelasies, en drie gevalle waar die binêre VLE data vir elk van die drie alkane ingesluit is. Deur hierdie prosedures op die modellering van die nege binêre ketoon/alkaan stelsels toe te pas, is uitstekende passings van die eksperimentele data verkry met slegs baie klein binêre interaksie parameters nodig waar voorspellings minder akkuraat was. Die prestasie van die parameter stelle, gebaseer op die bepaling van die polêre parameter en die insluiting van VLE data, is konsekwent en van 'n hoë gehalte vir albei modelle, met 'n byna identiese parameters gegenereer in al vier gevalle vir elk van die nege stelsels. Die parameter stelle wat op hierdie metode gegenereer is, is nie net toepaslik gevind op eksperimentele data gemeet in hierdie werk nie, maar ook op onafhanklike data vir die n-heksaan/4-heptanoon stelsel. Daar is tot die gevolgtrekking gekom dat beide van die regressie alternatiewe lewensvatbaar is vir die generasie van akkurate suiwer komponent parameters, en dat die insluiting van die VLE data triviaal is. Die suiwer sPC - SAFTGV voorspelling was oor die algemeen beter as die suiwer sPC- SAFTJC model met die voorspelling van data, veral in die geval van passings gedoen met parameters verkry vanaf tradisionele regressie metodes. sPC- SAFTGV het ʼn voortdurende, kwalitatiewe ooreenkoms met eksperimentele data getoon vir elk van die nege stelsels. Daarteen het voorspellings deur sPC- SAFTJC beduidend verswak soos die polêre interaksies afgeneem het vanaf 2- na 4- heptanoon, met geen akkurate voorspelling moontlik vir die minste polêre isomeer nie. Die verskynsel kan toegeskryf word aan die verskil in versteuringsteorieë wat gebruik word in die ontwikkeling van die onderskeie toestandsvergelykings, maar ʼn meer in-diepte ondersoek is nodig om hierdie teorie te bevestig. Hierdie werk toon dus 'n skynbare onvermoë van die sPC - SAFTJC toestandsvergelyking om die verandering in polêre interaksie, as gevolg van die veranderende posisie van die polêre groep, vir die karbonielgroep in ʼn ketoon te voorspel, terwyl die sPC-SAFTGV toestandsvergelyking goeie kwalitatiewe passings vir al drie isomere bied. Hierdie tekortkominge kan oorkom word deur VLE data, indien beskikbaar, in die regressie prosedure in te sluit, of deur die gebruik van groep spesifieke korrelasies vir die aanpassing van die polêre parameter.