This thesis describes the results of two process system engineering studies: (1) hydrogen pinch analysis; and (2) application of COSMO-SAC (conductor-like screening model – segment activity coefficient) to electrolytes. Part (1) presents an automated spreadsheet method that can quickly help minimize fresh hydrogen consumption and maximize hydrogen recovery and reuse in petroleum refineries and petrochemical complexes. Part (1) has appeared as a featured article on engineering practice in the Chemical Engineering Magazine, volume 115, pp. 56-61, June 2008. We present an automated spreadsheet on our research group website (www.design.che.vt.edu) and describe procedures for using the spreadsheet in this thesis. Part (2) discusses the application of the conductor-like screening model – segment activity coefficient (COSMO-SAC), a liquid-phase activity-coefficient model, to electrolytes. We offer detailed procedure for obtaining sigma profiles for electrolytes. A sigma profile is a molecular-specific probability distribution of the surface-charge density, which enables the application of solvation-thermodynamic models to predict vapor-liquid and solid-liquid equilibria, and other properties. We propose to add an additional term to the exchange energy to account for ion-ion attractive and repulsive forces. We also look at the resulting exchange energy behavior. Although accurate numerical results are not achieved, we are able to produce results that match literature data by adding an adjustment factor. / Master of Science

In this work, we present two open literature databases, the VT-2005 Sigma Profile Database and the VT-2006 Solute Sigma Profile Database, that contain sigma profiles for 1,645 unique compounds. A sigma profile is a molecular-specific distribution of the surface-charge density, which enables the application of solvation-thermodynamic models to predict vapor-liquid and solid-liquid equilibria, and other properties. The VT-2005 Sigma Profile Database generally focuses on solvents and small molecules, while the VT-2006 Solute Sigma Profile Database primarily consists of larger, pharmaceutical-related solutes. We design both of these databases for use with the conductor-like screening model−segment activity coefficient (COSMO-SAC), a liquid-phase activity-coefficient model. The databases contain the necessary information to perform binary and multicomponent VLE and SLE predictions. We offer detailed tutorials and procedures for use with our programs so the reader may also use their own research on our research group website (www.design.che.vt.edu). We validate the VT-2005 Sigma Profile Database by pure component vapor pressure predictions and validate the VT-2006 Solute Sigma Profile Database by solid solubility predictions in pure solvents compared with literature data from multiple sources. Using both databases, we also explore the application of COSMO-SAC to solubility predictions in mixed solvents. This work also studies the effects of conformational isomerism on VLE and SLE property prediction. Finally, we compare COSMO-SAC solubility predictions to solubility predictions by the Non-Random Two-Liquid, Segment Activity Coefficient (NRTL-SAC) model. We find UNIFAC is a more accurate method for predicting VLE behavior than the COSMO-SAC model for many of the systems studied, and that COSMO-SAC predicts solute mole fraction in pure solvents with an average root-mean-squared error (log10(xsol)) of 0.74, excluding outliers, which is greater than the RMS error value of 0.43 using the NRTL-SAC model. / Master of Science

En plein essor, le marché des vernis à ongles représente plusieurs milliards de flacons vendus chaque année à travers le monde. Malgré un durcissement de la réglementation au cours des vingt dernières années, la composition des vernis reste problématique d’un point de vue environnemental. L’agent filmogène secondaire, ou résine, qui permet d’apporter le supplément d’adhésion, de brillance et de stabilité faisant défaut à la nitrocellulose, est le principal obstacle à l’obtention d’un vernis 100 % biosourcé. Dans ce contexte, nous nous sommes attachés à comprendre la physicochimie de ces systèmes complexes, en vue d'orienter la conception de nouvelles résines biosourcées compatibles par l'établissement de relations structures-propriétés. En premier lieu, des caractérisations physicochimiques complètes (état de surface, composition, perméabilité) ont été menées sur l’ongle et deux modèles semi-synthétiques. Un test d’adhésion a été mis au point afin d’évaluer l’adhérence de formulations sur ces substrats. La corrélation des résultats a permis d’identifier le meilleur modèle de l’ongle natif et mis en évidence les mécanismes d’adhésion vernis-ongle. Parallèlement, les résines benchmarks ont été caractérisées afin de définir un cahier des charges précis. L’adaptation d’outils de prédiction aux polymères a permis de relier des modifications structurales à la solubilité et a été validée à l’aide d’oligoesters modèles synthétisés. L’impact de certains motifs structuraux sur la brillance ou la dureté des résines a été mis en évidence et les relations structures-propriétés identifiées ont été confirmées via l'évaluation des performances de nouvelles résines polyesters biosourcées. / Several billion nail polishes are sold every year throughout the world, and the market is still fast-growing. Despite a tightening of regulations over the past twenty years, the composition of varnishes remains problematic from an environmental point of view. The main obstacle to reach a 100% bio-based varnish is the secondary film-forming agent, or resin, which provides the additional adhesion, the gloss and the stability that nitrocellulose lacks. In this context, we have focused on understanding the physicochemistry of these complex systems in order to assist the design of new compatible biosourced resins through the establishment of structures-properties relationships. First, complete physicochemical characterizations (surface aspect and surface energy, composition, permeability) were carried out on native nails and two semi-synthetic models. An adhesion test was developed to evaluate the adhesion of formulations onto substrates. Correlated to physicochemical characterizations, these results allowed to identify the best model of the native nail and highlighted the adhesion mechanisms at the varnish-nail interface. In parallel, the "benchmarks" resins were characterized in order to define precise specifications according to their application performances. Thanks to the adaptation of prediction tools to polymers, we managed to link structural modifications to solubility and was validated using synthesized model oligoesters. The impact of some structural features on the gloss or the hardness of resins has been highlighted and the identified structures-properties relationships were confirmed through the evaluation of the performances of new bio-based polyester resins.

Solvation-thermodynamics models based on computational quantum mechanics, such as the conductor-like screening model (COSMO), provide a good alternative to traditional group-contribution methods for predicting thermodynamic phase behavior. Two COSMO-based thermodynamic models are COSMO-RS (real solvents) and COSMO-SAC (segment activity coefficient). The main molecule-specific input for these models is the sigma profile, or the probability distribution of a molecular surface segment having a specific charge density. Generating the sigma profiles represents the most time-consuming and computationally expensive aspect of using COSMO-based methods. A growing number of scientists and engineers are interested in the COSMO-based thermodynamic models, but are intimidated by the complexity of generating the sigma profiles. This thesis presents the first free, open-literature database of 1,513 self-consistent sigma profiles, together with two validation examples. The offer of these profiles will enable interested scientists and engineers to use the quantum-mechanics-based, COSMO methods without having to do quantum mechanics. This thesis summarizes the application experiences reported up to October 2004 to guide the use of the COSMO-based methods. Finally, this thesis also provides a FORTRAN program and a procedure to generate additional sigma profiles consistent with those presented here, as well as a FORTRAN program to generate binary phase-equilibrium predictions using the COSMO-SAC model. / Master of Science

This research project aims to determine whether fully subsidised BNG house developed within an integrated development such as Cosmo City can fetch sufficient value to bridging the ‘gap’ between BNG house and an affordable house and thereby assisting a house hold to leverage itself up the housing ladder. Based on Cosmo City as a case study the research investigates real value verse perceived value of BNG houses within an integrated development. The information and data collected includes; the replacement cost of a BNG house, Cosmo City’s BNG residents perception of value, professional commentary on BNG house value, capital growth within the entire development of Cosmo City, a comparable analysis of three houses within Cosmo City and official Municipal Valuations. The literature review reveals that the creation of integrated developments are the way forward to urban and community sustainability, as they provide a platform for social and economic development by alleviating poverty and assist with wealth creation. This is achieved by constructing environments which have better access to amenities and work opportunities and which provide for lifestyle and income changes. The analysis of the research determined that a BNG house has real value (replacement cost), perceived value, (BNG and professional interviews) and market value (Municipal Valuation) and should command sufficient value as a result of the attributes associated with integrated development’s, which include mobility, accessibility, service levels and locality. The conclusion is that my hypothesis cannot be substantiated as yet as a BNG house cannot be sold or purchased due to the pre-emptive clause which restricts the sales of BNG houses for a period that is no sales of BNG houses have as yet taken place. However, the research does determine that BNG house has both perceived and real value.

The main aim of the study was to investigate the extent to which the implementation of Cosmo City Project has accomplished the aims of housing policy. The main areas of housing policy which were explored are: partnerships, public participation, tenure security, and integration (spatial, institutional, economic, and social). In order for this study to be successful, primary data was collected from ten residents from Cosmo City, Cosmo Environmental Control Officer, and the Project Manager. A research questionnaire was administered to each of the identified respondents. In addition, secondary data was collected from books, journal articles and relevant policy documents. The analysis of findings used research questions as themes to ensure that the data collected respond to the objectives of the research. The findings of the study revealed that the implementation of Cosmo City achieved most of its objectives such as tenure security, environmental sustainability, spatial integration and institutional integration. However, economic and social integration were not achieved by the project. These findings led the researcher to conclude that an attempt by South African government to create socially and economically viable human settlements did not succeed in Cosmo City. This was due to lack of effective public participation. Consequently, it was recommended that there was a need to strengthen the capacity of the Local Authorities in terms of housing policy formulation and implementation. Again, thorough research on urban poverty and urban integration processes were to be clearly incorporated into housing policy.

'Cosmo House' is a new idea of living. The people are leaving their home for different life purpose and setting up a temporary home in a new place in a new city. The world has already many cosmopolitan cities. What if there is a new housing type named 'Cosmo House'. It is not a permanent house to live, not so temporary living as like hotel and dorms. It is something in between, it must have some certain design considerations which serve the purpose of those new nomads. 'Cosmo House' is an experience of living where people come to live for few years and can engage with other people, events and experiences and such way they feel it is their new home away from home. The site is in Newark downtown in New Jersey which is a perfect location for international students who study in nearby universities and for international professionals who commute to work in Manhattan and nearby areas. The thesis seeks for an experiential living system in 50000 square feet of a lot where a complex housing mass generates from a concept. It has many grounds, roofs, and neighborhood blocks within the 28-story building. 'Cosmo House' has many small, medium and large social spaces for its many users' group to carefully generate engagements among them and experiences of home. It also connects the tenants to the neighboring people with shared experiences and thus makes the building an integral part of the city too. The experiences of 'Cosmo House' can be universal and adjustable depending on the context where it is built. A new nomad will search for a 'Cosmo House' when he moves from Newark to another city in this world and will always live at home. The concept of home is not restricted to a place where he thinks he belongs but he can carry his home from one place to another place and will always feel at home. / Master of Architecture / Imagine, one is moving to a new country leaving his home behind. Once lands in a new country, he has to adapt himself in a new living condition. Very soon he gets homesick. What if, he could just live in a similar home as like he used to live in his country. Practically, it is not possible to live in the exact same house in a completely different contextual condition. One can not live a house like Saudi Arabia in cold weather like New York City. But maybe he can expect a house which can make himself feel home. Human should not adjust himself, rather home should adapt to the need for Human. A cosmo-house is the concept of new housing typology which accommodates the needs of this neo-nomad in a new city. Their scale can be changed depending on the contexts of different cosmo-cities. But the idea is same the cosmo-house is for the cosmo-people where certain programs of a building are present. It is diversified living by diversified demographic who start to live here for a temporary period but can engage in many interactions and experiences. When there are interactions, experiences, memories are created there. The new memory should help the neo-nomad people to feel the cosmo-house as their home away from home. Who once lives in a cosmo-house carries the concept of home. If he moves to a new cosmo-house to a new city, he actually carries his home with him. He will be always in his home any part of the world in a cosmo-house.

Les milieux biologiques et alimentaires sont généralement des mélanges contenant un nombre élevé de constituants (eau, solvants organiques, solides dissous, gaz dissous, espèces ioniques, macromolécules). La prédiction des propriétés d’équilibre de tels milieux requiert l’utilisation d’un modèle thermodynamique entièrement prédictif. Ce modèle doit également permettre d’assurer la cohérence entre des données expérimentales et garantir la robustesse de la représentation simultanée des équilibres physiques (liquide-vapeur, solubilité, etc.) et chimiques (dissociation, oxydo-réduction, complexation, etc.). Le potentiel chimique est une donnée indispensable pour modéliser ces équilibres. Sa connaissance dépend de la prédiction de deux variables : l’enthalpie libre de formation dans un état de référence choisi, et le coefficient d’activité qui dépend aussi de l’état de référence choisi. Le modèle COSMO-RS est un excellent modèle de prédiction des coefficients d’activité très largement utilisé dans le domaine du génie chimique où on s’intéresse essentiellement à des molécules neutres. Ce travail de thèse a permis d’étendre les performances du modèle COSMO-RS au traitement des milieux biologiques et alimentaires dans lesquels on trouve systématiquement des électrolytes en solution (en plus des molécules neutres). Un nouvel outil utilisant les récentes avancées de la mécanique quantique a été développé pour prédire les propriétés de formation à l’état gaz. En combinant des concepts de la thermodynamique, de la mécanique quantique, de l’électrostatique, et de la physique statistique, il a été démontré qu’il est possible d’utiliser le modèle COSMO-RS pour faire la transition entre l’état gaz et la phase condensée. Partant de là, ce travail démontre qu’il est maintenant possible de traiter simultanément les équilibres physiques et chimiques et donc de prédire les propriétés physico-chimiques (aW, pH, Eh) dans les milieux biologiques et alimentaires par le modèle COSMO-RS. / Food and biological systems are generally multicomponent mixtures (including water, organic solvents, dissolved solids, dissolved gases, ionic species, macromolecules). The prediction of the equilibrium properties of such environments requires the use of a fully predictive thermodynamic model. This model must be able to ensure the consistency between experimental data and to ensure the robustness of the simultaneous representation of physical equilibria (liquid-vapour, solubility, etc.) and chemical equilibria (dissociation, redox, complexation, etc.). The chemical potential is an essential property for modelling such equilibria. Its determination depends on two variables: the Gibbs free energy of formation in a chosen reference state, and the prediction of the activity coefficient which also depends on the chosen reference state. The COSMO-RS model is an excellent model for predicting activity coefficients that is widely used in chemical engineering where the studied molecules are generally neutral. This PhD study enabled to extend the performance of the COSMO-RS model toward the treatment of food and biological systems where there are systematically electrolytes in solution (in addition to neutral molecules). A new tool based on the recent advances of quantum mechanics has been developed in order to predict gas phase formation properties. By combining concepts of thermodynamics, quantum physics, electrostatics and statistical physics, it has been demonstrated that it is possible to use the COSMO-RS model to ensure the transition between the gas phase and the condensed phase. In this context, this work demonstrates that it is possible to treat simultaneously physical and chemical equilibria and thus to predict physico-chemical properties (aW, pH, Eh) in food and biological systems using the COSMO-RS model.

A travers les tâches de perception et de production, les humains peuvent manipuler non seulement des mots et des phrases mais également des unités de plus bas niveau tels des syllabes et des phonèmes. Les études en phonétique sont principalement focalisées sur ces seconds types d'unitées. Un des objectif majeur dans ce domaine et de comprendre comment les humains acquiert et manipulent ces unités.Dans cette thèse, nous nous intéressons à cette question à travers l'utilisation de la modélisation computationnelle en réalisant des simulation informatiques à l'aide d'un modèle bayésien de la communication nommé COSMO (“Communicating Objects using Sensory-Motor Operations”). Nos études s'étendres à trois aspects.Dans une première partie, nous étudions les représentations cognitives des unités phonétiques. Il est maintenant bien établie que les unités sont caractérisées par des représentations auditives et motrices. En examinant leur rôle respectifs durant le développement, nous établissons leur complémentarité à travers ce que nous nommons la propriété <<bande étroite/bande large>>.Dans une seconde partie, nous nous intéressons à la variabilité des unités phonétiques, notamment à travers l'étude de la corrélation des idiosyncrasies en perception et en production. En comparant plusieurs conditions de développement, nous établissons qu'elles s'acquiert à travers un processus de reproduction des catégories plutôt qu'à une répétition des sons.Dans une troisième partie, nous analysons la nature des catégories phonétiques. En phonétique, il y a un débat autour du statut des syllabes vs. des phonèmes dans la communication de la parole. Dans nos simulations, nous examinons leurs acquisitions respectives à travers un apprentissage non supervisée et montrons les particularités nécessaires à la communication. / Through perception and production tasks, humans are able to manipulate not only high-level units like words or sentences but also low-level units like syllables and phonemes. Studies in phonetics mainly focus on the second type of units. One of the main goal in this field is to understand how humans acquire and manipulate these units and how they are stored in the brain. In this PhD thesis, we address this set of issues by using computer modeling, performing computer simulations with a Bayesian model of communication, named COSMO (“Communicating Objects using Sensory-Motor Operations”). Our studies extend in three ways.In a first part, we investigate the cognitive content of phonetic units. It is well established that phonetic units are characterized by both auditory and motor representations. It also seems that these representations are both used during speech processing. We question the functional role of a double representation of phonetic units in the human brain, specifically in a perception task. By examining their respective development, we show that these two representations have a complementary role during perception: the auditory representation is tuned to recognize nominal stimuli whereas the motor representation has generalization properties and can deal with stimuli typical of adverse conditions. We call this the “auditory-narrow/motor-wide” property.In a second part, we investigate the variability of phonetic units. Despite the universality of phonetic units, their characterization varies from one person to another, both in their articulatory/motor and acoustic content. This is called idiosyncrasies. In our study, we aim at understanding how they appear during speech development. We specifically compare two learning algorithms, both based on an imitation process. The first version consists in sound imitation while the second version exploits phoneme imitation. We show that idiosyncrasies appear only in the course of a phoneme imitation process. We conclude that motor learning seems rather driven by a linguistic/communication goal than motivated by the reproduction of the stimulus acoustic properties.In a third part, we investigate the nature of phonetic units. In phonetics, there is a debate about the specific status of the syllable vs phoneme in speech communication. In adult studies, a consensus is now found: both units would be stored in the brain. But, in infant studies, syllabic units seem to be primary. In our simulation study, we investigate the acquisition of both units and try to understand how our model could “discover” phonemes starting from purely syllabic representations. We show that contrary to syllables and vowels, consonants are poorly characterized in the auditory representation, because the categories overlap. This is due to the influence of one phoneme on its neighbors, the well-known “coarticulation”. However, we also show that the representation of consonants in the motor space is much more efficient, with a very low level of overlap between categories. This is in line with classical theories about motor/articulatory invariance for plosives. In consequence, phonemes, i.e. vowels and consonants, seem well displayed and likely to clearly emerge in a sensory-motor developmental approach such as ours.Through these three axes, we implemented different versions of our model. Based on data from the literature, we specifically cared about the cognitive viability of its variables and distributions and of its learning phases. In this work, modeling computation has been used in two kinds of studies: comparative and explanatory studies. In the first ones, we compared results of two models differing by one aspect and we selected the one in accordance with experimental results. In the second ones, we interpreted a phenomenon observed in literature with our model. In both cases, our simulations aim at better understanding data from the literature and provide new predictions for future studies.

Optimisation of molecular structures in solvation is important in many fields, such as drugdesign. In order to optimise geometries, one needs nuclear energy gradients. To optimisestructures efficiently, analytical gradients are required. In this work, the analytical nucleargradients within the Conductor-like Screening Model (COSMO) for modelling solvation arederived and implemented in the quantum chemistry software VeloxChem. By validation withnumerical gradients of varying accuracy, agreement with the implemented analytical gradientwas found, demonstrating internally consistent analytical expressions. / Optimering av molekylära strukturer i lösning är viktigt inom många områden, såsomläkemedelsdesign. För att optimera geometrier behöver man energigradienter med avseendepå atomkärnorna, och för att optimera strukturer effektivt krävs analytiska gradienter. Idetta arbete härleds och implementeras de analytiska gradienterna inom COSMO-ramverketför lösning av molekyler i kvantkemimjukvaran VeloxChem. Genom jämförelser med numeriskagradienter av varierande noggrannhet fanns en överensstämmelse gentemot den implementer-ade analytiska gradienten, vilket visar på inbördes konsekventa analytiska uttryck.