A study of adsorption equilibria of oxygen, nitrogen and oxygen-nitrogen mixtures on types 4A, 5A, 13X and Na-Mordenite molecular sieve pellets has been made. Pure component isotherms, using a volumetric apparatus, have been measured for each gas on each adsorbent at pressures up to 9 bar and for temperatures of 278.15,293.15 and 303.15 K. Curve fitting of the pure canponent isotherms has been attempted using the kinetic model of Gonzalez and Holland, the vacancy solution model, the statistical thermodynamic model and a mathematical equation similar to the Hill-de Boer model. With the exception of the kinetic model, good curve fitting was obtained. Binary equilibria data have been measured, using a constant volume method, for mixtures of oxygen and nitrogen at pressures of 1.7 and 4.4 bar and at temperatures of 278.15,293.15 and 303.15 K for each of the adsorbents. These results have been presented graphically as equilibrium phase compositions and corresponding total adsorption loadings. The binary experimental equilibria data have been examined against values predicted by mixture models (kinetic model, the extended vacancy solution model, the statistical thermodynamic model, the Cook and Basmadjian model, and the ideal adsorbed solution theory) using regression parameters obtained from the pure component isotherms. The statistical thermodynamic model and the ideal adsorbed solution theory gave the best representation of the experimental data. The activity coefficients of the adsorbed phase for the binary experimental data have been calculated and the results showed no appreciable deviation of the adsorbed phase from ideality. / British Council and the University of Gezira (Sudan)

<p> Phase equilibrium relations were determined in the system NaAlSiO8-NaAlSiO4-H2O on a P-T projection in the P-T range 0.5-10Kb and 150°-900°C, and on three isobaric (2Kb, 5.15Kb and 7. 32Kb) T-X projections. The T-X stability field of analcite determined in this study has a relatively large distorted pentagonal shape. The petrogenetic problem of analcite is fully discussed. On the composition join NaAlSiO4-H2O, the phase relation is not binary for the transition: nepheline hydrate I = nepheline + H2O; there exists a narrow three-phase zone for the transition. The true P-T curve was determined in terms of a ternary univariant reaction: nepheline hydrate I+ analcite = nepheline + H2O. Another univariant reaction (zeolite species P. = analcite + nepheline hydrate I+ H2O) was found at 2Kb/215°C and 5.15Kb/235°C and determined on a P-T projection. In the system NaAlSi3O8-SiO2-H2O, albite contains a maximum of about 5 Wt.% silica in solid solution at 5.15Kb/670°C.</p> <p> The equilibrium compositions of various univariant phases were determined essentially by phase boundary-location on several isobaric T-X projections. Three singular points were determined: two of them are approximately located at 0.8Kb/390°C and 9.4Kb/475°C on a univariant curve (N-h I+ Anl =Ne+ H2O). The other one is approximately located at 6Kb/655°C on the (Ab) univariant curve.</p> </p> A simple method for determining H2O-solubility in melts was developed and applied to the study of the system NaAlSi3O8-NaAlSiO4-H2O. Using this method, solubility data are simply obtained as by-products of the experimental runs made for the investigation of the phase equilibria. The amount of water required to make an H2O-saturated melt (from the total amount of water in the original charge) is taken as the dissolved water in the melt; the solubility value is corrected by determining the amount of moisture originally absorbed in the starting powder. The method is generally applicable to the determination of H2O-content in any hydrous phase. The H2O-solubility in a melt is not too sensitive to a variation in anhydrous composition of the melt (~ 6±1 Wt.% H2O at 2Kb and ~11±1 Wt.% H2O at ~5Kb in the range of compositions Ab100Ne0-An40Ne60). H2O-solubility in the (Anl) and (Ne) univariant melts was determined up to l0Kb (H2O contents: 4.7 Wt.%/1.1Kb and 850°C, 6.2 Wt. %/2Kb and 804°C, 10.8 Wt. %/5.2Kb and 672°C, l2.2 Wt.% /6.6Kb and 655°C, 13.2 Wt. %/7.3Kb and 652°C and 14(?) Wt.% /10Kb and 632°C ). The origin of water bubbles in quenched hydrous glasses is essentially attributed to the exsolution of the dissolved water in melts upon quenching.</p> <p> The sequence of P-T curves around a quaternary invariant point (~5Kb and ~635°C) in the system NaAlSiO4-KAlSiO4-SiO2-H2O was theoretically discussed. The most probable four P-T diagram types are proposed, one of which is expected to be the real one.</p> <p> Phase relations in the system NaAlSi3O3-NaAlSiO4-H2O are theoretically discussed up to ~15Kb. The discussion is largely based on the equilibrium compositions of invariant phases approximately estimated from data presented in Parts 1 and 2. Six invariant points are examined. Two of them, I5 and I6, have been predicted to occur; I5 is inferred to be located at ~13Kb/~500°C where five phases Jd, N-h I, Anl, Ne and V coexist, and I6 to be located at ~0.5Kb/-375°C where Ab, Ne, Anl, N-h I and V coexist. The phase relations around the other four are partly modified. The maximum P-T stability field of analcite is deduced. The stability field of solidus analcite is extremely large whereas that of liquidus analcite is very much limited. The maximum stability field of liquidus analcite is a small triangular area defined by three invariant points I1 (5.15Kb/657°C), I2 (11Kb/650°C) and I4 (12.5Kb/575°C).</p> / Thesis / Doctor of Philosophy (PhD)

Cette thèse se focalise sur les jeux de potentiel et une généralisation d'un jeu d'ordonnancement dans un graphe que nous avons appelé jeu de placement.Dans ce jeu, le coût d'un joueur est impacté par son voisinage.Nous pouvons illustrer cela avec un exemple : le placement de joueurs dans un train, pour lesquels la présence de voisins directs influe sur le bien-être.Les résultats de cette thèse se divisent en deux parties.Tout d'abord, nous étudions ces jeux en considérant l'existence et les propriétés de structure des équilibres.Nous nous posons la question fondamentale de savoir s'il existe des équilibres de Nash dans le jeu de placement.Si tel est le cas, nous tachons de déterminer si ces équilibres sont facilement calculables.Dans le cas où il n'existe pas d'équilibre nous prouvons la NP-complétude du problème.Dans un second temps nous nous intéressons à la notion de calcul distribué d'équilibre de Nash dans des jeux de placement.En particulier nous considérons un jeu basé sur le problème de Max-Cut, qui a été plus étudié en théorie des graphes.Cela nous a permis d'étendre nos travaux à une application aux réseaux mobiles pour la gestion d'interférences dans les réseaux sans fils.Nous avons pu, pour les différents jeux, mettre en place des algorithmes distribués de calcul d'équilibres et étudier leur convergence.Parallèlement, nous avons étendu les travaux de Max-Cut à un problème de sélection d'offre de qualité de service parmi divers fournisseurs d'accès.Nous comparons les performances d'algorithmes de calcul distribué d'équilibres et de minimisation de regret. / This thesis focuses on potential games and a generalized load balancing game in a graph we called placement game.In this game, the cost of a player is affected by its neighbors.We can illustrate this with an example: the placement of players on a train, where the presence of direct neighbors affects their well-being.The results of this thesis are divided into two parts.First, we study these games considering the existence and structural properties of equilibria.We ask ourselves the fundamental question of whether there are Nash equilibria in the placement game.If this is the case we aim to determine if they are easily calculable, if there is no such equilibria we prove the NP-completeness of the problem.Secondly we focus on the concept of distributed algorithms to compute Nash equilibria in placement games.In particular we consider a game based on the Max-Cut problem, which has been more frequently studied.This allowed us to expand our work to a mobile network application for managing interference in wireless networks.We were able, for those different games, to implement distributed algorithms to compute equilibria and study their convergence.Meanwhile, we have expanded the Max-Cut works with a selection of QoS offers problem from various network providers.We compare the performance of distributed algorithms and regret minimization.

We consider a wireless communication system in which there are N transmitter-receiver pairs and each transmitter wants to communicate with its corresponding receiver. This is modelled as an interference channel. We propose power allocation algorithms for increasing the sum rate of two and three user interference channels. The channels experience fast fading and there is an average power constraint on each transmitter. In this case receivers use successive decoding under strong interference, instead of treating interference as noise all the time. Next, we u se game theoretic approach for power allocation where each receiver treats interference as noise. Each transmitter-receiver pair aims to maximize its long-term average transmission rate subject to an average power constraint. We formulate a stochastic game for this system in three different scenarios. First, we assume that each user knows all direct and crosslink channel gains. Next, we assume that each user knows channel gains of only the links that are incident on its receiver. Finally, we assume that each use r knows only its own direct link channel gain. In all cases, we formulate the problem of finding the Nash equilibrium(NE) as a variational in equality problem. For the game with complete channel knowledge, we present an algorithm to solve the VI and we provide weaker sufficient conditions for uniqueness of the NE than the sufficient conditions available in the literature. Later, we present a novel heuristic for solving the VI under general channel conditions. We also provide a distributed algorithm to compute Pare to optimal solutions for the proposed games. We use Bayesian learning that guarantees convergence to an Ɛ-Nash equilibrium for the incomplete information game with direct link channel gain knowledge only, that does not require knowledge of the power policies of other users but requires feedback of the interference power values from a receiver to its corresponding transmitter. Later, we consider a more practical scenario in which each transmitter transmits data at a certain rate using a power that depends on the channel gain to its receiver. If a receiver can successfully receive the message, it sends an acknowledgement(ACK), else it sends a negative ACK(NACK). Each user aims to maximize its probability of successful transmission. We formulate this problem as a stochastic game and propose a fully distributed learning algorithm to find a correlated equilibrium(CE). In addition, we use a no regret algorithm to find a coarse correlated equilibrium(CCE) for our power allocation game. We also propose a fully distributed learning algorithm to find a Pareto optimal solution. In general Pareto points do not guarantee fairness among the users. Therefore we also propose an algorithm to compute a Nash bargaining solution which is Pareto optimal and provides fairness among the users. Finally, we extend these results when each transmitter sends data at multiple rates rather than at a fixed rate.

Thesis (MScEng)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Distillation is the most widely used separation technique in the chemical process industry and typically accounts for approximately one-third of the total capital cost and more than half of the total energy consumption of a typical petrochemical-chemical plant. Therefore, the design and optimization of the distillation sequence are of critical importance to the economics of the entire process. Azeotropic mixtures cannot be separated into their pure components via normal distillation. Enhanced distillation techniques such as heterogeneous azeotropic distillation should be considered for these mixtures. Isobaric vapour-liquid-liquid equilibrium (VLLE) data are highly important for the design and analysis of heterogeneous distillation columns. However, limited VLLE data are available in literature due to the difficulties involved with measuring such data. The objective of this work was to systematically evaluate and compare the performance of selected entrainers (including benzene, DIPE and cyclohexane) for the dehydration of C2 and C3 alcohols. To meet this objective, phase equilibrium data had to be measured. Isobaric VLLE at standard atmospheric conditions were measured with a dynamic Guillespie unit equipped with an ultrasonic homogenizer, which prevented liquid-liquid separation. Vapour-liquid equilibrium (VLE) and VLLE data were measured for ethanol/water/di-isopropyl ether (DIPE), n-propanol/water/DIPE and n-propanol/water/isooctane. The VLE data were found to be thermodynamically consistent according to the L-W (Wisniak 1993) and McDermott-Ellis consistency tests. No thermodynamic consistency test, specifically for VLLE data, could be found in literature, but the LLE part of the data followed a regular profile according to the Othmer-Tobias correlation. The binary DIPE/water and isooctane/water azeotropes, as well as ternary ethanol/DIPE/water and n-propanol/isooctane/water azeotropes, as measured in this work, agree well with those found in literature. Regressed parameters for the NRTL, UNIQUAC, and UNIFAC models, generally improved the model predictions compared with built-in Aspen parameters. This confirmed the importance of having actual measured VLLE data available for evaluation and improvement of estimations by thermodynamic models. NRTL predicted the ethanol/DIPE/water and n-propanol/DIPE/water VLLE most accurately. Despite the improved regressed parameters for n-propanol/isooctane/water predictions, the models are still considered unsuitable for accurate prediction of the VLLE behaviour of this system. Separation sequences were simulated in Aspen with built-in and regressed parameters, respectively, to illustrate the significant effect such inaccurate parameters have on these simulations. Phase diagram (VLLE data) evaluation of ethanol and isopropanol (IPA) with various entrainers, as found in literature, indicated that DIPE might be a good entrainer for the dehydration of these alcohols. Benzene and cyclohexane are generally used as entrainers in industry for these processes. Benzene is however carcinogenic and therefore an alternative has to be found (United States Department of Labour - Occupational Safety & Health Administration 2011). Separation sequences were simulated for ethanol dehydration with benzene and DIPE as entrainers, respectively. Taking cost and safety into account, DIPE can be considered an acceptable replacement for benzene as entrainer for ethanol dehydration. A separation sequence was also simulated for the dehydration of IPA with DIPE as entrainer and compared to a simulation with cyclohexane (Arifin, Chien 2007) as entrainer. DIPE was found to be a reasonable alternative to cyclohexane as entrainer for IPA dehydration. Two other separation sequences were simulated as practical examples where DIPE could be used as entrainer for the recovery of ethanol or n-propanol from aqueous Fischer Tropsch waste streams. DIPE is therefore found to be a feasible alternative entrainer to benzene and cyclohexane for the dehydration of ethanol and IPA via heterogeneous azeotropic distillation, based on pre-liminary cost considerations, separation ability and safety. Better entrainers than DIPE may exist, but from the data available in literature and the measurements made in this work DIPE appears to be superior to benzene, cyclohexane and isooctane. / AFRIKAANSE OPSOMMING: Distillasie is die mees algemeen-gebruikte skeidingstegniek in die chemiese proses-industrie. Dit is tipies verantwoordelik vir ʼn derde van die totale kapitaalkoste en meer as die helfte van die totale energie verbruik op ʼn tipiese petrochemiese chemiese aanleg. Daarom is die ontwerp en optimering van ʼn distillasie trein van kardinale belang vir die winsgewendheid van die proses. Azeotropiese mengsels kan nie slegs deur normale distillasie in suiwer komponente geskei word nie. Gevorderde distillasie tegnieke soos heterogene azeotropiese distillasie moet dus oorweeg word vir sulke mengsels. Isobariese damp-vloeistof-vloeistof ewewigsdata is een van die belangrikste fisiese eienskappe vir die ontwerp van heterogene distillasie kolomme. Die hoeveelheid damp-vloeistof-vloeistof ewewigsdata wat beskikbaar is in die literatuur is egter baie beperk omdat dit moeilik is om die data te meet. In hierdie werk is isobariese damp-vloeistof-vloeistof ewewigsdata met ʼn dinamiese Guillespie eenheid, by standaard atmosferiese druk gemeet. Die eenheid is toegerus met ʼn ultrasoniese homogeniseerder om vloeistof-vloeistof skeiding te voorkom. Temperatuur is gemeet met ʼn akkuraatheid van 0.03oC by 0oC. Die sisteem se druk is konstant gehou op 101.3 kPa met ʼn akkuraatheid van 0.35 % VSU (Vol Skaal Uitset). Die ewewigsamestellings is met ʼn relatiewe akkuraatheid van 2 % gemeet. Daar is damp-vloeistof en damp-vloeistof-vloeistof ewewigsdata van etanol/water/di-isopropiel eter (DIPE), npropanol/ water/ DIPE en n-propanol/water/iso-oktaan gemeet. Die damp-vloeistof ewewigsdata is deur die LW (Wisniak 1993) en McDermott-Ellis termodinamiese konsistensie toetse getoets en konsistent bevind. Geen termodinamiese konsistensie toets spesifiek vir damp-vloeistof-vloeistof ewewigsdata kon gevind word nie. Die Othmer-Tobias korrelasie dui egter aan dat die vloeistof-vloeistof ewewig gedeelte van die data ʼn reëlmatige gang volg. Die binêre DIPE/water en iso-oktaan/water azeotrope en ternêre etanol/DIPE/water en n-propanol/iso-oktaan/water fase-ewewigte wat in hierdie werk gemeet is, stem ooreen met die wat in die literatuur te vind is. Die parameters vir die modelle (NRTL, UNIQUAC en UNIFAC) wat in hierdie werk bestudeer is, is in die algemeen verbeter deur regressie van die eksperimentele data. Dit dui daarop dat dit belangrik is om eksperimentele damp-vloeistof-vloeistof ewewigsdata te hê om die voorspellings van termodinamiese modelle mee te evalueer en te verbeter. Die etanol/water/ DIPE en n-propanol/water/DIPE damp-vloeistof-vloeistof ewewigsdata is die akkuraatste deur NRTL voorspel. Ten spyte van die verbeteringe wat deur regressie behaal is met die NRTL en UNIQUAC parameters vir n-propanol/water/isooktaan, word hierdie modelle steeds nie as gepas vir die voorspelling van hierdie datastel beskou nie. Skeidingsreekse is gesimuleer met die ingeboude Aspen parameters en regressie parameters, onderskeidelik, om te illustreer dat onakkurate parameters ʼn beduidende effek op sulke simulasies het. Die evaluasie van fase diagramme van etanol en IPA met verskeie skeidingsagente, wat in die literatuur te vind is, dui aan dat DIPE ʼn goeie skeidingsagent kan wees vir die dehidrasie van hierdie alkohole. Skeidingsreekse vir die dehidrasie van etanol met benseen en DIPE, onderskeidelik, is gesimuleer. Met koste en veiligheid in ag geneem, is daar gevind dat DIPE ʼn aanvaarbare plaasvervanger vir benseen as skeidingsagent vir etanol dehidrasie kan wees. Daar is ook ʼn skeidingsreeks vir die dehidrasie van IPA met DIPE as skeidingsagent gesimuleer en met ʼn simulasie (Arifin, Chien 2007) wat sikloheksaan as skeidingsagent gebruik, vergelyk. Daar is bevind dat DIPE ʼn redelike alternatief vir sikloheksaan kan wees as skeidingsagent vir IPA dehidrasie. Nog twee skeidingsreekse is gesimuleer om as praktiese voorbeelde te dien van die gebruik van DIPE as skeidingsagent om etanol of n-propanol vanaf waterige Fischer-Tropsch afvalstrome te herwin. Daarom is daar bevind dat DIPE ʼn geldige alternatiewe skeidingsagent vir benseen en sikloheksaan is, gebaseer op koste, skeidingsvermoë en veiligheid. Daar kan beter skeidingsagente as DIPE bestaan, maar vanuit die data beskikbaar in literatuur en die metings geneem in hierdie werk, is DIPE die beste.

<p>Congestion charging is a now accepted means of influencing traffic to behave in a more socio-economic optimal way, like e.g. in the Stockholm project. Already early work, in the 1920’s, showed that road use can be inefficient due externalities, i.e. that users don’t experience their own (negative) effect on other users: an extra car on a traffic link causes delays for other cars, but the driver himself does not experience this cost.In the 1950’s it was further shown - for a congested road network with homogeneous users – that if each user is charged a toll equal to the total value of time loss incurred on other users of the network, then -if we have fixed travel demand - this will induce an equilibrium that is system optimal in the sense that the total cost of network usage is minimal (assuming that all users have fixed and identical time values).  But toll charges need to be levied in monetary units, and different travelers have different values of time. Therefore, to account for the effects of tolls, and to be able to compute equilibria, one needs to introduce different user classes, differing in their time values.</p><p>In this thesis, consisting of four papers, we study congestion pricing of road networks with users differing only in their time values. In particular, we analyze marginal social cost (MSC) pricing, a tolling scheme that charges each user a penalty corresponding to the value of the delays inflicted on other users, as well as its implementation through fixed tolls.</p><p>Paper III contains the main theoretical work of the thesis. In that paper we show that the variational inequalities characterizing the equilibria in question can be stated in symmetric or non-symmetric forms. The symmetric forms correspond to optimization problems, convex in the fixed-toll case and non-convex in the MSC case, which hence may have multiple equilibria. The objective of the latter problem is the total value of travel time, which thus is minimized at the global optima of that problem. Implementing close-to-optimal MSC tolls as fixed tolls leads to equilibria with possibly non-unique class specific flows, but with identical close-to-optimal values of the total value of travel time. Finally we give an adaptation, to the MSC setting, of the Frank-Wolfe algorithm, which is further applied to some test cases, including Stockholm.</p><p>Paper I is an early application using Frank-Wolfe, after having realized the possibility to symmetrize the problem.</p><p>Paper II gives a convexification of non-convex equilibrium problem for MSC tolls. We have used these convexifications to compute lower bounds when computing equilibria.</p><p>Paper IV is a short note commenting some flaws in two papers by Dial on MSC tolls.</p>

The effect of magnesium, strontium, and other alkaline earths on the formation and persistence of metastable carbonates in the natural environment was investigated to determine the nature of the controlling mechanism. Barium and beryllium were studied to evaluate the effect of ionic radius; magnesium and strontium, in order to determine if the results correlate with the usual order of stability for complexes and adsorbed species. Known weights of aragonite were placed in contact with solutions of beryllium, magnesium, calcium, strontium, and barium. Samples were covered and periodically both pH and percent composition of aragonite determined; supernatant liquids and precipitates were analyzed for cation concentrations by atomic absorption spectroscopy and titrimetric methods. Results indicated that the order of effectiveness of alkaline earth metals in inhibiting recrystallization is : Be > Mg > Sr > Ba. This is the expected order of effectiveness for both surface and solution effects. A solution effect (i.e., sequestration of bicarbonate ions) is strongly suggested by the chemical behavior of each cation.

Thesis advisor: Arthur Lewbel / The thesis includes two essays. The first essay, Inequality Moments in Estimation of Discrete Games with Incomplete Information and Multiple Equilibria, develops a method for estimation of static discrete games with incomplete information, which delivers consistent estimates of parameters even when games have multiple equilibria. Every Bayes-Nash equilibrium in a discrete game of incomplete information is associated with a set of choice probabilities. I use maximum and minimum equilibrium choice probabilities as upper and lower bounds on empirical choice probabilities to construct moment inequalities. In general, estimation with moment inequalities results in partial identification. I show that point identification is achievable if the payoffs are functions of a sufficient number of explanatory variables with a real line domain and outcome-specific coefficients associated with them. The second essay, Tenancy Rent Control and Credible Commitment in Maintenance, co-authored with Richard Arnott, investigates the effect of tenancy rent control on maintenance and welfare. Under tenancy rent control, rents are regulated within a tenancy but not between tenancies. The essay analyzes the effects of tenancy rent control on housing quality, maintenance, and rehabilitation. Since the discounted revenue received over a fixed-duration tenancy depends only on the starting rent, intuitively the landlord has an incentive to spruce up the unit between tenancies in order to show it well, but little incentive to maintain the unit well during the tenancy. The essay formalizes this intuition, and presents numerical examples illustrating the efficiency loss from this effect. / Thesis (PhD) — Boston College, 2009. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Economics.

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.

Neste trabalho, a complexação do sistema ferro-III/azoteto em meio áqüeo-orgânico foi estudada para avaliar a formação dessas espécies sob diferentes forças iônicas: 1,00; 2,00 e 3,00 mol L-1 e em presença de diferentes solventes: tetraidrofurano, acetona e p-dioxano (T = 20 °C). Além disso, em meio contendo tetraidrofurano, as constantes de formação condicionais (b) foram determinadas sob diferentes percentagens deste solvente: 20, 30 e 40 % (v/v). O método empregado na determinação de tais constantes baseia-se na competição entre o metal e o íon hidrogênio pelo azoteto, no sistema tampão formado entre o ligante e o ácido azotídrico (N3-/HN3). Os parâmetros necessários para o cálculo das constantes de formação foram obtidos potenciometricamente por meio de variações de pH, provocadas pela complexação após a introdução do metal à célula. Tais parâmetros foram tratados preliminarmente pelo método de Leden e, posteriormente, refinados com alguns programas computacionais visando à caracterização das espécies e a determinação dos valores das constantes de formação globais dos complexos coexistentes no sistema Fe (III)/N3-. Os resultados mostraram evidências de que até quatro espécies complexas estáveis: [Fe(N3)]2+, [Fe(N3)2]+, [Fe(N3)3] e [Fe(N3)4]- podem coexistir tanto em meio contendo acetona quanto naquele contendo p-dioxano. Porém, em meio contendo tetraidrofurano, somente as três primeiras espécies foram detectadas (evidenciadas). Isto indica que uma maior competição entre o solvente orgânico e o ligante azoteto, na esfera de coordenação do íon metálico, ocorre em meios contendo tetraidrofurano, nestas condições estudadas. Verificou-se ainda que tanto a percentagem de solvente orgânico quanto a força iônica do meio têm forte influência na formação dos complexos sucessivos investigados, sendo que os complexos de maior estabilidade foram obtidos em soluções contendo 40 % (v/v) de tetraidrofurano e força iônica de 1,00 mol L-1. Diante dos resultados obtidos, observa-se que o método competitivo adotado neste trabalho, usualmente empregado em estudos realizados em meio totalmente aquoso, também se mostrou apropriado para a determinação das constantes de formação nas condições experimentais investigadas (meios áqüeos-orgânicos). / In this work, the system the iron-III/azide in aqueous-organic media was studied in order to evaluate the formation of complexes under different conditions: ionic strengths in the range of 1.00 to 3.00 mol L-1 and effect of the presence of organic solvents (tetrahydrofuran, acetone and p-dioxan) at T = 20 °C. Besides, in medium containing tetrahydrofuran, the conditional formation constants (b) were determined under different proportions of this solvent (20-40 %, v/v). The method used in the determination of these constants is based on the competition between the metal and the hydrogen ion for the azide, in the buffered system formed between the ligand and the azotidric acid (N3-/HN3). The parameters for the determination of the formation constant of each complexe were obtained by potentiometric measurements, through changes on the solution pH, caused by complexation due the iron ions added into the cell. These parameters were initially analysed by using the Leden method and, subsequently, refined by computational simulation in order to characterize the different complexes in the Fe (III)/N3- system, as well as to determine the value for the global constant of formation for each coexistent species. The results showed the possible coexistence of following four stable complexes: [Fe(N3)]2+, [Fe(N3)2]+, [Fe(N3)3] e [Fe(N3)4]- in aqueous medium containing acetone or p-dioxan. However, in the presence of tetrahydrofuran, the [Fe(N3)4]- was not evidenced. This indicates that a larger competition between the molecules of this organic solvent and the azide ligand, into the coordination sphere of the metallic ion occurs under these experimental conditions. Besides, the organic solvent proportion and the experimental medium are important parameters affecting the formation of these complexes. It was observed that iron complexes with higher stability were produced in the presence of 40 % (v/v) tetrahydrofuran and 1.00 mol L-1 ionic strength. Before the obtained results, it is observed that the competitive method adopted in this work, usually employed in studies accomplished in totally aqueous medium, it was also shown appropriate for the determination of the formation constants in the experimental conditions (aqueous-organic media) investigated.