Thermodynamic analysis of direct steam reforming of ethanol in molten carbonate fuel cell

Fuel cell as MCFC (molten carbonate fuel cell) operate at high temperatures, and due to this issue, cogeneration processes may be performed, sending heat for own process or other purposes as steam generation in an industry. The use of ethanol for this purpose is one of the best options because this is a renewable and less environmentally offensive fuel, and cheaper than oil-derived hydrocarbons (in the case of Brazil). In the same country, because of technical, environmental and economic advantages, the use of ethanol by steam reforming process have been the most investigated process. The objective of this study is to show a thermodynamic analysis of steam reforming of ethanol, to determine the best thermodynamic conditions where are produced the highest volumes of products, making possible a higher production of energy, that is, a most-efficient use of resources. To attain this objective, mass and energy balances are performed. Equilibrium constants and advance degrees are calculated to get the best thermodynamic conditions to attain higher reforming efficiency and, hence, higher electric efficiency, using the Nernst equation. The advance degree of reforming increases when the operation temperature also increases and when the operation pressure decreases. But at atmospheric pressure (1 atm), the advance degree tends to the stability in temperatures above 700°C, that is, the volume of supplemental production of reforming products is very small for the high use of energy resources necessary. Reactants and products of the steam-reforming of ethanol that weren't used may be used for the reforming. The use of non-used ethanol is also suggested for heating of reactants before reforming. The results show the behavior of MCFC. The current density, at same tension, is higher at 700°C than other studied temperatures as 600 and 650°C. This fact occurs due to smaller use of hydrogen at lower temperatures that varies between 46.8 and 58.9% in temperatures between 600 and 700°C. The higher calculated current density is 280 mA/cm 2. The power density increases when the volume of ethanol to be used also increases due to higher production of hydrogen. The highest produced power at 190 mW/cm 2 is 99.8, 109.8 and 113.7 mW/cm2 for 873, 923 and 973K, respectively. The thermodynamic efficiency has the objective to show the connection among operational conditions and energetic factors, which are some parameters that describes a process of internal steam reforming of ethanol.

Low-temperature structural effects in the (TMTSF)2PF6 and AsF6 Bechgaard salts

We present a detailed low-temperature investigation of the statics and dynamics of the anions and methyl groups in the organic conductors (TMTSF) 2PF6 and (TMTSF)2AsF6 (TMTSF: tetramethyl-tetraselenafulvalene). The 4 K neutron-scattering structure refinement of the fully deuterated (TMTSF)2PF6-D12 salt allows locating precisely the methyl groups at 4 K. This structure is compared to the one of the fully hydrogenated (TMTSF)2PF6-H12 salt previously determined at the same temperature. Surprisingly, it is found that deuteration corresponds to the application of a negative pressure of 5×102 MPa to the H12 salt. Accurate measurements of the Bragg intensity show anomalous thermal variations at low temperature both in the deuterated PF 6 and AsF6 salts. Two different thermal behaviors have been distinguished. Small Bragg-angle measurements reflect the presence of low-frequency modes at characteristic energies θE = 8.3 K and θE = 6.7 K for the PF6-D12 and AsF6-D12 salts, respectively. These modes correspond to the low-temperature methyl group motion. Large Bragg-angle measurements evidence an unexpected structural change around 55 K, which probably corresponds to the linkage of the anions to the methyl groups via the formation of F...D-CD2 bonds observed in the 4 K structural refinement. Finally we show that the thermal expansion coefficient of (TMTSF)2PF6 is dominated by the librational motion of the PF6 units. We quantitatively analyze the low-temperature variation of the lattice expansion via the contribution of Einstein oscillators, which allows us to determine for the first time the characteristic frequency of the PF6 librations: θE ≈ 50 K and θE = 76 K for the PF6-D12 and PF6-H12 salts, respectively. © 2013 American Physical Society.

Effects of calcium salts of soybean oil on factors that influence pregnancy establishment in Bos indicus beef cows

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effects of supplementation of calcium salts of polyunsaturated fatty acids on serum concentrations of progesterone and insulin of pregnant dairy cows

Forty-five non-lactating, pregnant Holstein animals (18 heifers and 27 multiparous cows; BW = 561 +/- 114 kg; BCS = 2.9 +/- 0.3; days pregnant = 110 +/- 56 d) were stratified by initial BW and BCS, and randomly assigned to receive daily (as-fed basis) 0.50 kg of ground corn plus 0.22 kg of kaolin (CON), calcium salts of saturated fatty acids (SFA) or polyunsaturated fatty acids (PF) for 14 d. Blood samples were collected on days 0, 7 and 14, immediately prior to (0 h) and 3, 6, 9 and 12 h after feeding, to determine the serum concentrations of P 4 and insulin. No treatment effects were detected for serum concentrations of P 4 (5.52, 6.13 and 5.63 +/- 0.41 ng/mL for CON, SFA and PF, respectively). No treatment effects were detected for serum concentrations of insulin (11.5, 10.5 and 10.1 +/- 1.43 mu IU/mL for CON, SFA and PF, respectively). Heifers had greater serum concentrations of P 4 than multiparous cows (6.35 vs. 5.16 +/- 0.42 ng/mL), but lower serum concentrations of insulin (7.0 vs. 14.4 +/- 1.49 mu IU/mL). Feeding 0.22 kg of calcium salts of polyunsaturated fatty acids is not sufficient to increase the serum concentrations of P 4 and insulin of non-lactating, pregnant dairy cows.

Influence of salts on the coexistence curve and protein partitioning in nonionic aqueous two-phase micellar systems

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Hard X-ray photoemission study of the Fabre salts (TMTTF)(2)X (X = SbF6 and PF6)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Probing the Mott physics in kappa-(BEDT-TTF)(2)X salts via thermal expansion

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Improvement of the alcohol dehydrogenase from baker's yeast using polymers and salts for alcohol determinations in beverages

An alcohol dehydrogenase (ADH) was purified from dry baker’s yeast. This is a key enzyme of the primary short-chain alcohol metabolism in many organisms. In the present study, the obtained enzymatic preparation of baker’s yeast, containing 2.7 U/mg of ADH, was used in the reactions. The purified extract of the ADH obtained from Fermix commercial dry yeast, presented the highest activity and purification factor when ammonium sulfate was added in the precipitation of protein, in the range 35-60% (w/v). The enzymatic preparation was maintained for 2 months in the lyophilized form at 4ºC (retention of 96.2% of activity) in the presence of 1 mmol/L of sodium azide, and it maintained 47% of activity for 30 days at 30°C in the presence of 15% PEG. The assays of ethanol (detection range 5 mM -150 mM or 2.3 x 10-4 – 6.91 x 10-3g/L) in different samples in alcoholic beverages, presented a maximum deviation of only 2.1%. Assays of recovery of the substrate (99.25%) added in the wine showed that the methodology is viable for this sample type. The standard curve and the analytic curve of this method meet the conditions of precision, sensitivity, simplicity, and low cost, required for a useable analytical method.

Lamivudine salts with improved solubilities

To optimize solubility of drugs, current strategies mainly focus on engineering and screening of smart crystal phases. Two salts of the anti-human immunodeficiency virus (HIV) drug lamivudinenamely, lamivudine hydrochloride and lamivudine hydrochloride monohydrate, were prepared in the course of screening the crystallization conditions of lamivudine duplex, an uncommon DNA-mimic, double-stranded helical structure made up of partially protonated drug pairs. Here, water solubilities of lamivudine hydrochloride, lamivudine hydrochloride monohydrate, and lamivudine duplex are reported. The aqueous solubility of this anti-HIV drug was significantly increased in both salts and also in lamivudine duplex in relation to the water solubility of lamivudine form II. In comparison with the lamivudine form II incorporated into therapeutic formulations, the drug solubility was increased at a temperature of 299 +/- 2 K by factors of 1.2, 3.3, and 4.5 in lamivudine hydrochloride, lamivudine hydrochloride monohydrate, and lamivudine duplex, respectively, demonstrating that this solid-state property of lamivudine can be improved by crystal engineering strategies. Solubility profiles were understood on the basis of structural and solventsolute interaction approaches. At last, correlations between solubility and crystal structures allowed for a rational approach to understand how this physicochemical feature could be enhanced by engineering new salts of the drug. (C) 2012 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 101:21432154, 2012

Use of Chlorine to Remove Magnesium from Molten Aluminum

Removal of Mg from aluminum scraps, known as demagging, has been widely applied in the,aluminum industry. This work discusses bubble-formation theories and magnesium kinetic removal from aluminum scraps using chlorine and inert gas fluxing. The interfacial area of the bubbles and residence time were estimated using a mathematical model. To inject gaseous chlorine, three types of nozzles were used with varying internal diameter. In addition, a porous plug, as well as varying input chlorine flow and concentration were used. The use of lower chlorine concentration improves efficiency because the interfacial tension is reduced therefore, more and smaller bubbles are formed. The model proposed herein is consistent with the experimental data. [doi:10.2320/matertrans.M2011256]

Kinetic resolution of alpha-bromophenylacetamides using quinine or Cinchona alkaloid salts

The kinetic resolution of racemic alpha-bromophenylacetamides 1 was achieved in the presence of benzenethiolate and Cinchona alkaloid salts as phase-transfer catalysts or benzenethiol and quinine, yielding (S)-enantioenriched alpha-sulfanylated products. The observed stereoselection was rationalized on the basis of the best fitting of 1 and the resolving agent in the ternary complexes. (C) 2012 Elsevier Ltd. All rights reserved.

Salts of the anti-HIV drug lamivudine with phthalic and salicylic acids

Salts of the anti-HIV drug lamivudine, with phthalic acid and salicylic acid as counterions, were investigated in this study. Neither the packing of the (lamivudine)(+)(phthalic acid)(-) ion pairs nor the conformation of the lamivudine moiety itself were similar to those found in other multicomponent molecular salts of the drug, such as hydrogen maleate and saccharinate ones, even though all three salts crystallize in the same P2(1)2(1)2(1) orthorhombic space group with similar unit cell metrics. Lamivudine salicylate assumes a different crystal structure to those of the hydrogen maleate and saccharinate salts, crystallizing in the P2(1) monoclinic space group as a monohydrate whose (lamivudine)(+)(salicylic acid)(-) ion pair is assembled through two hydrogen bonds with cytosine as a dual donor to both oxygens of the carboxylate, such as in the pairing of lamivudine with a phthalic acid counterion. In lamivudine salicylate monohydrate, the drug conformation is related to the hydrogen maleate and saccharinate salts. However, such a conformational similarity is not related to the intermolecular interaction patterns. Lamivudine and water molecules alternate into helical chains in the salicylate salt monohydrate.

High Viscosity of Imidazolium Ionic Liquids with the Hydrogen Sulfate Anion: A Raman Spectroscopy Study

Ionic liquids based on 1-alkyl-3-methylimidazolium cations and the hydrogen sulfate (or bisulfate) anion, HSO4-, are much more viscous than ionic liquids with alkyl sulfates, RSO4-. The structural origin of the high viscosity of HSO4- ionic liquids is unraveled from detailed comparison of the anion Raman bands in 1-ethyl-3-methylimidazolium hydrogen sulfate and 1-butyl-3-methylimidazolium hydrogen sulfate with available data for simple HSO(4)(-) salts in crystalline phase, molten phase, and aqueous solution. Two Raman bands at 1046 and 1010 cm(-1) have been assigned as symmetric stretching modes nu(s)(S = O) of HSO4-, the latter being characteristic of chains of hydrogen-bonded anions. The intensity of this component increases in the supercooled liquid phase. For comparison purposes, Raman spectra of 1-ethyl-3-methylimidazolium ethyl sulfate and 1-butyl-3-methylimidazolium methyl sulfate have been also obtained. There is no indication of difference in the strength of hydrogen bond interactions of imidazolium cations with HSO4- or RSO4- anions. Raman spectra at high pressures, up to 2.6 GPa, are also discussed. Raman spectroscopy provides evidence that hydrogen-bonded anions resulting in anion-anion interaction is the reason for the high viscosity of imidazolium ionic liquids with HSO4-. If the ionic liquid is exposed to moisture, these structures are disrupted upon absorption of water from the atmosphere.

Experimental investigation into the effect of stress on dissolution and growth of very soluble brittle salts in aqueous solution

Das Studium der Auflösungs- und Wachstumsprozesse an Feststoff-Flüssigkeits-Grenzflächen unter nicht-hydrostatischen Beanspruchungen ist wesentlich für das Verständnis von Defor-mationsprozessen, die in der Erde ablaufen. Unter diesen genannten Prozessen gehört die Drucklösung zu den wichtigsten duktilen Deformationsprozessen, von der Diagenese bishin zur niedrig- bis mittelgradigen metamorphen Bedingungen. Bisher ist allerdings wenig darüber bekannt, welche mechanischen, physikalischen oder chemischen Potentialenergie-Gradienten die Drucklösung steuern. I.a. wird angenommen, daß die Drucklösung durch Un-terschiede kristallplastischer Verformungsenergien oder aber durch Unterschiede der Normal-beanspruchung an Korngrenzen gesteuert wird. Unterschiede der elastischen Verformungs-energien werden dabei allerdings als zu gering erachtet, um einen signifikanten Beitrag zu leisten. Aus diesem Grund werden sie als mögliche treibende Kräfte für die Drucklösung vernachlässigt. Andererseits haben neue experimentelle und theoretische Untersuchungen gezeigt, daß die elastische Verformung in der Tat einen starken Einfluß auf Lösungs- und Wachstumsmechanismen von Kristallen in einer Lösung haben kann. Da die in der Erdkruste vorherrschenden Deformationsmechanismen überwiegend im elastischen Verformungsbereich der Gesteine ablaufen, ist es sehr wichtig, das Verständnis für die Effekte, die die elastische Verformung verursacht, zu erweitern, und ihre Rolle während der Deformation durch Drucklösung zu definieren. Die vorliegende Arbeit beschäftigt sich mit Experimenten, bei denen der Effekt der mechanisch kompressiven Beanspruchung auf Lösungs- und Wachstumsprozesse von Einzelkristallen unterschiedlicher, sehr gut löslicher, elastisch/spröder Salze untersucht wurde. Diese Salze wurden als Analoga gesteinsbildender Minerale wie Quarz und Calcit ausgewählt. Der Einfluß von Stress auf die Ausbildung der Oberflächenmikrostrukturen in einer untersättigten Lösung wurde an Kaliumalaun untersucht.Lösungsrillen (20 – 40 µm breit, 10 – 40 µm tief und 20 – 80 µm Abstand) entwickelten sich in den Bereichen, in denen die Beanspruchung im Kristall am größten war. Sie verschwanden wieder, sobald der Kristall entlastet wurde. Diese Rillen entwickelten sich parallel zu niedrig indizierten kristallographischen Richtungen und sub-perpendikular zu den Trajektorien, die der maximalen, lokalen kompressiven Beanspruchung entsprachen. Die Größe der Lösungsrillen hing von der lokalen Oberflächenbeanspruchung, der Oberflächenenergie und dem Untersättigungsgrad der wässrigen Lösung ab. Die mikrostrukturelle Entwicklung der Kristalloberflächen stimmte gut mit den theoretischen Vorhersagen überein, die auf den Modellen von Heidug & Leroy (1994) und Leroy & Heidug (1994) basieren. Der Einfluß der Beanspruchung auf die Auflösungsrate wurde an Natriumchlorat-Einzelkristallen untersucht. Dabei wurde herausgefunden, daß sich gestresste Kristalle schneller lösen als Kristalle, auf die keine Beanspruchung einwirkt. Der experimentell beobachtete Anstieg der Auflösungsrate der gestressten Kristalle war ein bis zwei Größenordnungen höher als theoretisch erwartet. Die Auflösungsrate stieg linear mit dem Stress an, und der Anstieg war um so größer, je stärker die Lösung untersättigt war. Außerdem wurde der Effekt der Bean-spruchung auf das Kristallwachstum an Kaliumalaun- und Kaliumdihydrogenphosphat-Ein-zelkristallen untersucht. Die Wachstumsrate der Flächen {100} und {110} von Kalium-alaun war bei Beanspruchung stark reduziert. Für all diese Ergebnisse spielte die Oberflächenrauhigkeit der Kristalle eine Schlüsselrolle, indem sie eine nicht-homogene Stressverteilung auf der Kristalloberfläche verursachte. Die Resultate zeigen, daß die elastische Verformung eine signifikante Rolle während der Drucklösung spielen kann, und eine signifikante Deformation in der oberen Kruste verursachen kann, bei Beanspruchungen, die geringer sind, als gemeinhin angenommen wird. Somit folgt, daß die elastische Bean-spruchung berücksichtigt werden muß, wenn mikrophysikalische Deformationsmodelle entwickelt werden sollen.

Isoxazolidines and oxazines: preliminary studies for the synthesis of N,O-heterocyclic systems via an organocatalyzed 1,3-Dipolar Cycloaddiction and a tandem reaction mediated by TEMPO salts

This thesis is the result of the study of two reactions leading to the formation of important heterocyclic compounds of potential pharmaceutical interest. The first study concerns the reaction of (1,3)-dipolar cycloaddition between nitrones and activated olefins by hydrogen bond catalysis of thioureas derivatives leading to the formation of a five-membered cyclic adducts, an interesting and strategic synthetic intermediate, for the synthesis of benzoazepine. The second project wants to explore the direct oxidative C(sp3)-H α-alkylation of simple amides with subsequent addition of an olefin and cyclization in order to obtain the corresponding oxazine. Both reactions are still under development.