A note on the effective medium theory of random resistive-reactive medium

The effective medium theory for a system with randomly distributed point conductivity and polarisability is reformulated, with attention to cross-terms involving the two disorder parameters. The treatment reveals a certain inconsistency of the conventional theory owing to the neglect of the Maxwell-Wagner effect. The results are significant for the critical resistivity and dielectric anomalies of a binary liquid mixture at the phase separation point.

Hydrolysis of elemental sulphur in a homogeneous medium

Elemental sulphur dissolved in organic solvents (such as chloroform, carbon tetrachloride and benzene) reacts rapidly and quantitatively, with aqueous alkali at room temperature, when this immiscible liquid mixture is homogenized by the addition of ethyl alcohol. The products of reaction under these experimental conditions are sulphide, thiosulphate and a small quantity of sulphite. A mechanism involving the intermediate formation and decomposition of dihydrogen sulphoxide, HSOH, is suggested for the reaction.

Electrical and Dielectric Behaviour at the Critical Point of Binary Liquids: Acetonitrile + Cyclohexane

The electrical capacitance and resistance of the binary liquid mixture cyclohexane + acetonitrile are measured in the one phase and two phase regions at spot frequencies between 5 kHz and 100 kHz. This sample has a very low gravity affected (∼0.6 mK) region. In one phase region the capacitance data show a sharp, ∼0.7% increase above background within 0.5 degrees of Tc whereas the resistance has a smooth increase of ∼1.5% above background in a (T−Tc) range of 4 degrees. Two phase values of capacitance and resistance from the coexisting phases are used to determine the critical parameters Tc (critical temperature), Rc (resistance at Tc) and Cc (capacitance at Tc). A precise knowledge of these parameters reduces the uncertainty on the critical exponent 0 for C and R. The one phase capacitance data fit to an (1 - α) exponent in a limited temperature range of 0.2 degrees. Resistance data strongly support an (1 - α) exponent over the entire 5 degree range.

Novel phase-transition behavior in an aqueous electrolyte solution

We have investigated the near-critical behavior of the susceptibility of a ternary liquid mixture of 3-methylpyridine. water, and sodium bromide as a function of the salt concentration. The susceptibility was determined from light-scattering measurements performed at a scattering angle of 90 degrees in the one-phase region near the locus of lower consolute points. A sharp crossover from asymptotic Ising behavior to mean-field behavior has been observed at concentrations ranging from 8 to 16.5 mass% NaBr. The range of asymptotic Ising behavior shrinks with increasing salt concentration and vanishes at a NaBr concentration of about 17 mass%. where complete mean-field-like behavior of the susceptibility is observed. A simultaneous pronounced increase in the background scattering at concentrations above 15 mass%, as well as a dip in the critical locus at 17 mass % NaBr, suggests that this phenomenon can be interpreted as mean-field tricritical behavior associated with the formation of a microheterogeneous phase due to clustering of the molecules and ions. An analogy with tri critical behavior observed in polymer solutions as well as the possibility of a charge-density-wave phase is also discussed. In addition, we, have observed a third soap-like phase an the liquid-liquid interface in several binary and ternary liquid mixtures.

Methyl ethyl ketone plus water plus secondary butyl alcohol: A potential system for the exploration of a quadruple critical point

We report preliminary experiments on the ternary-liquid mixture, methyl ethyl ketone (MEK)+water (W)+secondary butyl alcohol (sBA)-a promising system for the realization of the quadruple critical point (QCP). The unusual tunnel-shaped phase diagram shown by this system is characterized and visualized by us in the form of a prismatic phase diagram. Light-scattering experiments reveal that (MEK+W+sBA) shows near three-dimensional-Ising type of critical behavior near the lower critical solution temperatures, with the susceptibility exponent (gamma) in the range of 1.217 <=gamma <= 1.246. The correlation length amplitudes (xi(o)) and the critical exponent (nu) of the correlation length (xi) are in the ranges of 3.536 <=xi(o)<= 4.611 A and 0.619 <=nu <= 0.633, respectively. An analysis in terms of the effective susceptibility exponent (gamma(eff)) shows that the critical behavior is of the Ising type for MEK concentrations in the ranges of 0.1000 <= X <= 0.1250 and X >= 0.3000. But, for the intermediate range of 0.1750 <= X < 0.3000, the system shows a tendency towards mean-field type of critical behavior. The advantages of the system (MEK+W+sBA) over the system (3-methylpyridine+water+heavy water+potassium Iodide) for the realization of a QCP are outlined.

Effects of capillary waves on the thickness of wetting layers

The free energy contribution of capillary waves is calculated to show its significant dependence on the thickness of the liquid layer, when the thickness is very small. It is shown that these oscillations can play an important role in determining the thermodynamic stability of a wetting layer, close to the critical point of a binary liquid mixture in the case of both short range and long range forces. In particular, the thickness of the wetting layer goes to zero as the temperature T approaches Tc.

Dimple and nose coalescences in phase-separation processes

Coalescence processes are investigated during phase separation in a density-matched liquid mixture (partially deuterated cyclohexane and methanol) under near-critical conditions. As a result of the interplay between capillary and lubrication forces, ''nose'' coalescence appears to be always associated with the slow growth of isolated droplets (exponent almost-equal-to 1/3), whereas ''dimple'' coalescence corresponds to the fast growth of interconnected droplets (exponent almost-equal-to 1). At each stage of growth, the distribution of droplets trapped during dimple coalescence is reminiscent of all of the previous coalescence events.

Grain Floatation During Equiaxed Solidification of an Al-Cu Alloy in a Side-Cooled Cavity: Part II-Numerical Studies

In this article, a single-phase, one-domain macroscopic model is developed for studying binary alloy solidification with moving equiaxed solid phase, along with the associated transport phenomena. In this model, issues such as thermosolutal convection, motion of solid phase relative to liquid and viscosity variations of the solid-liquid mixture with solid fraction in the mobile zone are taken into account. Using the model, the associated transport phenomena during solidification of Al-Cu alloys in a rectangular cavity are predicted. The results for temperature variation, segregation patterns, and eutectic fraction distribution are compared with data from in-house experiments. The model predictions compare well with the experimental results. To highlight the influence of solid phase movement on convection and final macrosegregation, the results of the current model are also compared with those obtained from the conventional solidification model with stationary solid phase. By including the independent movement of the solid phase into the fluid transport model, better predictions of macrosegregation, microstructure, and even shrinkage locations were obtained. Mechanical property prediction models based on microstructure will benefit from the improved accuracy of this model.

Effects of melting temperature on the broadband infrared luminescence of bi-doped and Bi/Dy co-doped chalcohalide glasses

Bismuth (Bi)-doped and Bi/Dy co-doped chalcohalide glasses are investigated as promising materials for amplifiers in optical communication. The samples synthesized at lower melting temperatures (MTs) are characterized by more intensified infrared emissions. With respect to the redox process of a liquid mixture at different MTs, we attribute an emission at 1230 nm to low-valent Bi ions. The lower MT favors the formation of LVB ions, i.e. Bi+ or Bi2+, while the higher MT promotes the production of higher-valent Bi ions Bi3+. An enhanced broadband infrared luminescence with the full-width at half-maximum over 200 nm is achieved from the present Bi/Dy co-doped chalcohalide glasses.

Otimização de metodologia para determinação de hidrocarbonetos policíclicos aromáticos pela técnica de extração por líquido pressurizado e sua aplicação a diferentes solos brasileiros

Os hidrocarbonetos policíclicos aromáticos (HPA) representam hoje grande preocupação à comunidade científica devido a sua comprovada ação cancerígena e mutagênica, assim tornam-se necessárias metodologias mais eficientes para suas determinações. O presente trabalho desenvolveu a técnica de extração por líquido pressurizado com a etapa de clean-up simultânea a extração, com sílica e alumina como adsorventes dentro da cela do equipamento ASE-350. A metodologia desenvolvida foi comparada com a tradicional extração por Sohxlet através de material de referência certificado. A extração por Soxhlet, apesar de eficiente, mostrou-se dispendiosa pelo gasto enorme de tempo, solvente e adsorventes quando comparada a extração por líquido pressurizado. De maneira geral a extração por líquido pressurizado apresentou-se mais vantajosa que a tradicional extração por Soxhlet. A eficiência da metodologia desenvolvida também foi testada através de quatro diferentes tipos de solos brasileiros fortificados com solução padrão de HPA. Os solos utilizados foram dos seguintes locais: Nova Lima MG, Lavras MG, Casimiro de Abreu RJ e Luiz Eduardo Magalhães BA. Todos possuíam características granulométricas e químicas diferentes entre si. Dois solos foram classificados em latossolos vermelhos, um em vermelho-amarelo e um em planossolo. Houve diferença significativa na eficiência de recuperação de alguns HPA quando comparados os quatro tipos de solos, já para outros HPA não evidenciou-se influência da tipologia do solo

Carbon dioxide pressure induced heterogeneous and homogeneous Heck and Sonogashira coupling reactions using fluorinated palladium complex catalysts

The Heck reaction of iodobenzene and methyl acrylate was investigated with CO2-philic Pd complex catalysts having fluorous ponytails and the organic base triethylamine (Et3N) in the presence of CO2 under solventless conditions at 80 degrees C. The catalysts are not soluble in the organic phase in the absence Of CO2 and the reaction occurs in a solid-liquid biphasic system. When the organic liquid mixture is pressurized by CO2, CO2 is dissolved into the organic phase and this promotes the dissolution of the I'd complex catalysts. As a result, the Heck reaction occurs homogeneously in the organic phase, which enhances the rate of reaction. This positive effect Of CO2 pressurization competes with the negative effect that the reacting species are diluted by an increasing amount of CO2 molecules dissolved. Thus, the maximum conversion appears at a CO2 pressure of around 4 MPa under the present reaction conditions. The catalysts are separated in the solid granules by depressurization and are recyclable without loss of activity after washing with n-hexane and/or water.

Tunable ordered droplets induced by convection in phase-separating P2VP/PS blend film

Ordered hexagonal droplets patterns in phase-separating polymeric blend films of polystyrene and poly(2-vinylpyridine) (PS/PVP) formed due to the convection effect by solvent evaporation. The influences of PS molecular weight, solvent evaporation rate, and the weight ratio of PS to PVP on the PVP-rich domains pattern formation and distributions were investigated by atomic force microscope (AFM). Only in an appropriate range of molecular weight of PS, can the ordered pattern form. Too low or too high molecular weight of PS led no ordered pattern due to the viscosity effects. The increase of solvent evaporation rate decreased the mean radius of the PVP-rich domains and the intervals between the centers of the domains due to the enhancement of the viscosity on the top layer of the fluid film. The increase of the weight ratio of PS to PVP decreased mean radius of the PVP-rich domains whereas the intervals between the centers of droplets remained constant. Therefore, the size and the distributions of ordered patterns can be tuned by the polymer molecular weight, the weight ratio of the two components and the solvent evaporation rate.

Catalytic Hydrogenolysis of Aromatic Ketones in Mixed Choline-Betainium Ionic Liquids

The palladium-catalyzed hydrogenolysis of aromatic ketones to alkylbenzenes was studied in mixtures of ionic liquids to explore the promotional effect of these reaction media. Choline-based ionic liquids displayed complete miscibility with the aromatic ketone substrate at reaction temperature and a clear phase separation of the derived alkylbenzene product at room temperature. Selected ionic liquids were then assessed as reaction media in the hydrogenolysis of aromatic ketones over palladium catalysts. A binary mixture of choline and betainium bis(trifluoromethylsulfonyl)imide ionic liquids resulted in the highest conversion and selectivity values in the hydrogenolysis of acetophenone. At the end of the reaction, the immiscible alkylbenzene separates from the ionic liquid mixture and the pure product phase can be isolated by simple decantation. After optimization of the reaction conditions, high yields (>90%) of alkylbenzene were obtained in all cases. The catalyst and the ionic liquid could be used at least three times without any loss of activity or selectivity.

Estudo da papila mamária em fêmeas bovinas (Bos taurus - Linnaeus, 1758), mediante as características ultra-sonográficas em modo-B (tempo real)

Nesta pesquisa foram utilizadas vinte fêmeas bovinas, sem patologias aparentes nas glândulas mamárias, em lactação, objetivando avaliar estruturas anatômicas das papilas mamárias. Quatro técnicas ultra-sonográficas foram avaliadas. Utilizou-se transdutor linear de 7,5 MHz para uso endoretal, na obtenção das imagens, padronizando-se o lado direito do animal para visualização das papilas craniais e caudais, em dois planos anatômicos (sagital e transversal). Os animais foram divididos em quatro grupos (G1, G2, G3, G4) que representaram as diferentes técnicas empregadas em momentos distintos (antes e após ordenha). Os resultados indicaram que entre as técnicas estudadas, as de exame direto e com uso de almofadada de silicone, foram as que apresentaram maior aplicabilidade, quando considerada a sua facilidade de uso na rotina com complementação do exame clinico. Entretanto, pólipos e cálculos lácteos tem sua extensão e localização convenientemente visibilizados mediante uso da técnica de pressão de liquido. Já a técnica de imersão em água, mostrou-se mais eficiente quanto à qualidade das imagens obtidas e na caracterização das estruturas anatômicas. O experimento realizado, traz subsídios anatomo-topográfico que irão contribuir com a qualidade do diagnóstico em pacientes que possam ter indicação cirúrgica (telotomia) e levanta questões que poderão ser respondidas conforme a casuística e a experiência consolidada do cirurgião.

Determinação de dados de equilíbrio líquido-vapor a altas pressões para sistemas de hidrocarbonetos assimétricos

Crude oil is a complex liquid mixture of organic and inorganic compounds that are dominated by hydrocarbons. It is a mixture of alkanes from the simplest to more complex aromatic compounds that are present derivatives such as gasoline, diesel, alcohol, kerosene, naphtha, etc.. These derivatives are extracted from any oil, however, only with a very high quality, in other words, when the content of hydrocarbons of low molecular weight is high means that production of these compounds is feasible. The American Petroleum Institute (API) developed a classification system for the various types of oil. In Brazil, the quality of most of the oil taken from wells is very low, so it is necessary to generate new technology to develop best practices for refining in order to produce petroleum products of higher commercial value. Therefore, it is necessary to study the thermodynamic equilibrium properties of its derivative compounds of interest. This dissertation aims to determine vapor-liquid equilibrium (VLE) data for the systems Phenilcyclohexane - CO2, and Cyclohexane - Phenilcyclohexane - CO2 at high pressure and temperatures between 30 to 70oC. Furthermore, comparisons between measured VLE experimental data from this work and from the literature in relation to the Peng- Robinson molecular thermodynamic model, using a simulation program SPECS IVCSEP v5.60 and two adjustable interaction parameters, have been performed for modeling and simulation purposes. Finally, the developed apparatus for determination of phase equilibrium data at high pressures is presented