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.

Hotelling-downs competition with free entry when voters have an option to contest

Osborne shows that for almost all distributions of voters' preferences, a pure strategy Nash equilibrium does not exist in the classical Hotelling-Downs model of electoral competition with free entry. We show that equilibrium is generically possible if in addition one allows voters an option to announce their candidacy to compete side-by-side with office-seeking players. The model studied in this paper renders Osborne and the celebrated citizen-candidate model à la Osborne and Slivinski as two extreme cases. We characterize the equilibrium set with two central questions: (i) can there be equilibria where only voters contest? and (ii) are equilibria with contesting office-seeking players possible? We also show that in our general setting, extremists are typically voter-candidates so that in every two-party contest, office-seeking politicians stay out of competition.

Aggregate uncertainty in the citizen candidate model yields extremist parties

We extend the citizen candidate model of electoral competition with sincere voting to allow for k ≥ 2 states of aggregate uncertainty. We discuss and characterize the equilibrium set in this framework. We provide conditions for the existence of two-party equilibria when k = 2 and show that the policies of the two parties in any such equilibrium are not only divergent but that the parties are extremist: when the political mood is left-wing, the left-wing party wins decisively with a platform that is to the left of the left-wing median voter, while when the political mood is right-wing, the right-wing party wins decisively with a platform that is to the right of the right-wing median voter. We then provide conditions under which such equilibria remain robust for an arbitrary value of k.

Liquid phase adsorption kinetics and equilibrium of toluene by novel modified-diatomite

The adsorption equilibria of toluene from aqueous solutions on natural and modified diatomite were examined at different operation parameters such as pH, contact time, initial toluene concentration was evaluated and optimum experimental conditions were identified. The surface area and morphology of the nanoparticles were characterized by SEM, BET, XRD, FTIR and EDX analysis. It was found that in order to obtain the highest possible removal of toluene, the experiments can be carried out at pH 6, temperature 25°C, an agitation speed of 200 rpm, an initial toluene concentration of 150 mg/L, a centrifugal rate of 4000 rpm, adsorbent dosage = 0.1 g and a process time of 90 min. The results of this work show that the maximum percentage removal of toluene from aqueous solution in the optimum conditions for NONMD was 96.91% (145.36 mg/g). Furthermore, under same conditions, the maximum adsorption of natural diatomite was 71.45% (107.18 mg/g). Both adsorption kinetic and isotherm experiments were carried out. The experimental data showed that the adsorption follows the Langmuir model and Freundlich model on natural and modified diatomite respectively. The kinetics results were found to conform well to pseudo-second order kinetics model with good correlation. Thus, this study demonstrated that the modified diatomite could be used as potential adsorbent for removal of toluene from aqueous solution.

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.

Difference-form persuasion contests

We explore the equilibrium properties of two types of "difference-form" persuasion contest functions derived in Skaperdas and Vaidya in which contestants spend resources to persuade an audience. We find that both types of functions generate interior pure strategy Nash equilibria unlike Baik and Che and Gale with characteristics different to existing literature. For one type of function, we find that the reaction function of each player is "flat" and nonresponsive to the level of resources devoted by the rival so that the "preemption effect" as defined by Che and Gale is absent. Further, the equilibrium is invariant to the sequencing of moves. For the second type of function, which applies when there is asymmetry among contestants with regard to the quality of evidence, we find that the reaction functions of the stronger and weaker players have gradients with opposite signs relative to Dixit and therefore their incentive to precommit expenditures in a sequential move game is also different. For both types of functions, the extent of rent dissipation is partial. From the equilibrium analysis, we are also able to establish the potential effects of some specific factors affecting persuasion such as evidence potency, the degree of truth, and bias on aggregate resource expenditures and welfare.

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.