Interactions of pyridinium, pyrrolidinium or piperidinium based ionic liquids with water: measurements and COSMO-RS modelling

Looking for a better knowledge concerning water and ionic liquids (ILs) interactions, a systematic study of the activity coefficients of water in pyridinium, pyrrolidinium and piperidinium-based ILs at 298.2 K is here presented based on water activity measurements. Additionally, the study of the structural effects of the pyridinium-based cation is also pursued. The results show that non-aromatic ILs are interacting more with water than aromatic ones, and among the ortho, meta and para isomers of 1-butyl-methylpyridinium chloride, the ortho position confers a more hydrophilic character to that specific IL. The physicalchemistry of the solutions was interpreted based on dissociation constants, natural bond orbitals and excess enthalpies providing a sound basis for the interpretation of the experimental observations. These results show that hydrogen bonding controls the behavior of these systems, being the anion-water one of the most relevant interactions, but modulated by the anionecation interactions.

Solubility and solvation of monosaccharides in ionic liquids

Herein, solubility experimental data for six monosaccharides, viz. D-(+)-glucose, D-(+)-mannose, D-(-)-fructose, D-(+)-galactose, D-(+)-xylose and L-(+)-arabinose, in four ionic liquids (ILs), at temperatures ranging from 288.2 to 348.2 K, were obtained aimed at gathering a better understanding of their solvation ability and molecular-level mechanisms which rule the dissolution process. To ascertain the chemical features that enhance the solubility of monosaccharides, ILs composed of dialkylimidazolium or tetra-alkylphosphonium cations combined with the dicyanamide, dimethylphosphate or chloride anions were investigated. It was found that the ranking of the solubility of monosaccharides depends on the IL; yet, D-(+)-xylose is always the most soluble while D-(-)-fructose is the least soluble monosaccharide. The results obtained show that both the IL cation and the anion play a major role in the solubility of monosaccharides. Finally, from the determination of the respective thermodynamic properties of solution, it was found that enthalpic contributions are dominant in the solubilization process. However, the observed differences in the solubilities of monosaccharides in 1-butyl-3-methylimidazolium dicyanamide are ruled by a change in the entropy of solution.

The economics of credit markets: theory and evidence.

Doutoramento em Economia.

Effects of solid poly (ethylene glycols) addition to the solutions of aniline or N,N-dimethylaniline with water:experimental measurements and modelling

In this work, the liquid-liquid and solid-liquid phase behaviour of ten aqueous pseudo-binary and three binary systems containing polyethylene glycol (PEG) 2050, polyethylene glycol 35000, aniline, N,N-dimethylaniline and water, in the temperature range 298.15-350.15 K and at ambient pressure of 0.1 MPa, was studied. The obtained temperature-composition phase diagrams showed that the only functional co-solvent was PEG2050 for aniline in water, while PEG35000 even showed a clear anti-solvent effect in the N,N-dimethylaniline aqueous system. The experimental solid-liquid equilibria (SLE) data have been correlated by the non-random two-liquid (NRTL) model, and the correlation results are in accordance with the experimental results.

Pareto Dominance of Deferred Acceptance through Early Decision

An early decision market is governed by rules that allow each student to apply to (at most) one college and require the student to attend this college if admitted. This market is ubiquitous in college admissions in the United States. We model this market as an extensive-form game of perfect information and study a refinement of subgame perfect equilibrium (SPE) that induces undominated Nash equilibria in every subgame (SPUE). Our main result shows that this game can be used to define a decentralized matching mechanism that weakly Pareto dominates student-proposing deferred acceptance.

Pareto Dominance of Deferred Acceptance through Early Decision

An early decision market is governed by rules that allow each student to apply to (at most) one college and require the student to attend this college if admitted. This market is ubiquitous in college admissions in the United States. We model this market as an extensive-form game of perfect information and study a refinement of subgame perfect equilibrium (SPE) that induces undominated Nash equilibria in every subgame (SPUE). Our main result shows that this game can be used to define a decentralized matching mechanism that weakly Pareto dominates student-proposing deferred acceptance.

Dynamics of undeactuated cable-driven parallel robots

This thesis focuses on the dynamics of underactuated cable-driven parallel robots (UACDPRs), including various aspects of robotic theory and practice, such as workspace computation, parameter identification, and trajectory planning. After a brief introduction to CDPRs, UACDPR kinematic and dynamic models are analyzed, under the relevant assumption of inextensible cables. The free oscillatory motion of the end-effector (EE), which is a unique feature of underactuated mechanisms, is studied in detail, from both a kinematic and a dynamic perspective. The free (small) oscillations of the EE around equilibria are proved to be harmonic and the corresponding natural oscillation frequencies are analytically computed. UACDPR workspace computation and analysis are then performed. A new performance index is proposed for the analysis of the influence of actuator errors on cable tensions around equilibrium configurations, and a new type of workspace, called tension-error-insensitive, is defined as the set of poses that a UACDPR EE can statically attain even in presence of actuation errors, while preserving tensions between assigned (positive) bounds. EE free oscillations are then employed to conceive a novel procedure aimed at identifying the EE inertial parameters. This approach does not require the use of force or torque measurements. Moreover, a self-calibration procedure for the experimental determination of UACDPR initial cable lengths is developed, which consequently enables the robot to automatically infer the EE initial pose at machine start-up. Lastly, trajectory planning of UACDPRs is investigated. Two alternative methods are proposed, which aim at (i) reducing EE oscillations even when model parameters are uncertain or (ii) eliminate EE oscillations in case model parameters are perfectly known. EE oscillations are reduced in real-time by dynamically scaling a nominal trajectory and filtering it with an input shaper, whereas they can be eliminated if an off-line trajectory is computed that accounts for the system internal dynamics.

Aquivion-based spray freeze-dried composite catalysts for the cascade conversion of furfural to γ-valerolactone

Furfural is one of the most promising biomass derived platform molecules. It is to this day produced in volumes above 300 ktons per year from the hydrolysis and dehydration of hemicellulose, one of the main components of lignocellulosic biomass. While the majority of the yearly production is destined to selective reduction to furfuryl alcohol for the production of furan resins, these molecules hold great potential for the production of more valuable chemicals, fuels, fuel additives and solvents. Among these products are alkyl levulinates and γ-valerolactone. To convert furfural to these target products, a cascade process involving Lewis acidity-catalysed reduction steps and Brønsted acidity-catalysed steps. In order to develop catalysts capable of promoting the one-pot domino reaction from furfural to γ-valerolactone, the two kinds of acidity must both be present. To this end, in this work, the spray freeze-drying technique is employed to combine the high activity and strong Brønsted acidity of Aquivion with the structural properties and Lewis acidity of different supporting metal oxide, forming composite catalysts. The flexibility of the spray freeze-drying technique and the modulable composition of the catalysts allowed a thorough study of the complex network of equilibria underlying the cascade reaction, while achieving high selectivities towards the final product.