Evidences of the evolution from solid solution to surface segregation in Ni-doped SnO(2) nanoparticles using Raman spectroscopy

Ni-doped SnO(2) nanoparticles, promising for gas-sensing applications, have been synthesized by a polymer precursor method. X-ray diffraction (XRD) and transmission electron microscopy (TEM) data analyses indicate the exclusive formation of nanosized particles with rutile-type phase (tetragonal SnO(2)) for Ni contents below 10 mol%. The mean crystallite size shows a progressive reduction with the Ni content. Room-temperature Raman spectra of Ni-doped SnO(2) nanoparticles show the presence of Raman active modes and modes activated by size effects. From the evolution of the A(1g) mode with the Ni content, a solubility limit at similar to 2 mol% was estimated. Below that content, Raman results are consistent with the occurrence of solid solution (ss) and surface segregation (seg.) of Ni ions. Above similar to 2 mol% Ni, the redshift of A(1g) mode suggests that the surface segregation of Ni ions takes place. Disorder-activated bands were determined and their integrated intensity evolution with the Ni content suggest that the solid-solution regime favors the increase of disorder; meanwhile, that disorder becomes weaker as the Ni content is increased. Copyright (C) 2010 John Wiley & Sons, Ltd.

Selective corrosion of 550 degrees C aged Cu10Ni-3Al-1.3Fe alloy in NaCl aqueous solution

This work studied the electrochemical behavior of a solution treated or 550 degrees C aged Cu10Ni-3Al-1.3Fe alloy, in 0.01 M NaCl aqueous solution, through potentiodynamic polarization in both stagnant condition or under erosion process. Results showed the occurrence of a passivity break potential (E(pb)), related to the beginning of the denickelification process, which occurred as a localized attack under stagnant electrolyte. Under erosion conditions localized denickelification was not observed, despite of the presence of E(pb). This could indicate that selective corrosion of Ni, which caused the observed E(pb), occurred as a dissolution-redeposition process, with removal of the Cu deposits during erosion process. (C) 2011 Elsevier Ltd. All rights reserved.

Degradation of Poly(ethylene glycol) in Aqueous Solution by Photo-Fenton and H(2)O(2)/UV Processes

This article reports experimental results obtained in a laboratory-scale photochemical reactor on the photodegradation of poly(ethylene glycol) (PEG) in aqueous solutions by means of the photo-Fenton and H(2)O(2)/UV processes. Dilute water solutions of PEG were fed to a batch reactor, mixed with pertinent reactants, and allowed to react under different conditions. Reaction progress was evaluated by sampling and analyzing the concentration of the total organic carbon (TOC) in solution as a function of the reaction time. Organic acids formed during oxidation were determined by HPLC analyses. The main acids detected in both processes were acetic and formic. Glycolic acid was detected only in the photo-Fenton process, and malonic acid was detected only in the H(2)O(2)/UV treatment, indicating that different reaction paths occur in these processes. The characteristics of both processes are discussed, based on the evolution of the TOC-time curves and the concentration profiles of the monitored organic acids. The experimental results constitute a contribution to the design of industrial processes for the treatment of wastewaters containing soluble polymers with similar properties.

AN ASSESSMENT ON THE USE OF THE DEBYE-HUCKEL EQUATION FOR THE THERMODYNAMIC MODELING OF AQUEOUS SYSTEMS CONTAINING POLYMERS AND SALTS

In this work, a study on the role of the long-range term of excess Gibbs energy models in the modeling of aqueous systems containing polymers and salts is presented. Four different approaches on how to account for the presence of polymer in the long-range term were considered, and simulations were conducted considering aqueous solutions of three different salts. The analysis of water activity curves showed that, in all cases, a liquid-phase separation may be introduced by the sole presence of the polymer in the long-range term, regardless of how it is taken into account. The results lead to the conclusion that there is no single exact solution for this problem, and that any kind of approach may introduce inconsistencies.

Coalescence of Water Droplets in Crude Oil Emulsions: Analytical Solution

In petroleum refineries, water is used in desalting units to remove the salt contained in crude oil. Typically, 7% of the volume of hot crude oil is water, forming a water-and-oil emulsion. The emulsion flows between two electrodes and is subjected to an electric field. The electrical forces promote the coalescence of small droplets of water dispersed in crude oil, and these form bigger droplets. This paper calculates the forces acting on the droplets, highlighting particularly the mechanisms proposed for droplet-droplet coalescence under the influence of an applied electric field. Moreover, a model is developed in order to calculate the displacement speed of the droplets and the time between droplet collisions. Thus, it is possible to simulate and optimize the process by changing the operational variables (temperature, electrical field, and water quantity). The main advantage of this study is to show that it is feasible to increase the volume of water recycled in desalting processes, thus reducing the use of freshwater and the generation of liquid effluents in refineries.

On the solubility of proteins as a function of pH: Mathematical development and application

Thermodynamic relations between the solubility of a protein and the solution pH are presented in this work. The hypotheses behind the development are that the protein chemical potential in liquid phase can be described by Henry`s law and that the solid-liquid equilibrium is established only between neutral molecules. The mathematical development results in an analytical expression of the solubility curve, as a function of the ionization equilibrium constants, the pH and the solubility at the isoelectric point. It is shown that the same equation can be obtained either by directly calculating the fraction of neutral protein molecules or by integrating the curve of the protein average charge. The methodology was successfully applied to the description of the solubility of porcine insulin as a function of pH at three different temperatures and of bovine beta-lactoglobulin at four different ionic strengths. (C) 2011 Elsevier B.V. All rights reserved.

Thermodynamics of aqueous solutions of polyelectrolytes: Experimental results for the activity of water in aqueous solutions of (a single synthetic polyelectrolyte and sodium chloride)

Experimental results for the activity of water in aqueous solutions of 10 single, synthetic polyelectrolytes (polysodium acrylate, polysodium methacrylate, polyammonium acrylate, polysodium ethylene sulfonate, and polysodium styrene sulfonate) and sodium chloride at 298.2 K are presented. The experimental work was performed by applying the isopiestic method with sodium chloride as a reference substance. As expected, the activity of water decreases when the concentration of a polyelectrolyte and/or sodium chloride increases. At constant concentration of a polyelectrolyte and sodium chloride, the activity of water depends on the monomer unit and the molecular mass of the polyelectrolyte. The new data are to be used in future work to develop and test models for the Gibbs excess energy of aqueous solutions of polyelectrolytes.

An extension of the Pitzer equation for the excess Gibbs energy of aqueous electrolyte systems to aqueous polyelectrolyte solutions

Pitzer`s equation for the excess Gibbs energy of aqueous solutions of low-molecular electrolytes is extended to aqueous solutions of polyelectrolytes. The model retains the original form of Pitzer`s model (combining a long-range term, based on the Debye-Huckel equation, with a short-range term similar to the virial equation where the second osmotic virial coefficient depends on the ionic strength). The extension consists of two parts: at first, it is assumed that a constant fraction of the monomer units of the polyelectrolyte is dissociated, i.e., that fraction does not depend on the concentration of the polyelectrolyte, and at second, a modified expression for the ionic strength (wherein each charged monomer group is taken into account individually) is introduced. This modification is to account for the presence of charged polyelectrolyte chains, which cannot be regarded as punctual charges. The resulting equation was used to correlate osmotic coefficient data of aqueous solutions of a single polyelectrolyte as well as of binary mixtures of a single polyelectrolyte and a salt with low-molecular weight. It was additionally applied to correlate liquid-liquid equilibrium data of some aqueous two-phase systems that might form when a polyelectrolyte and another hydrophilic but neutral polymer are simultaneously dissolved in water. A good agreement between the experimental data and the correlation result is observed for all investigated systems. (c) 2008 Elsevier B.V. All rights reserved.

Thermodynamics of aqueous solutions of polyelectrolytes: Experimental results for the activity of water in aqueous solutions of some single synthetic polyelectrolytes

Experimental results for the activity of water in aqueous solutions of 10 single polyelectrolytes (two polysodium acrylates, two polysodium methacrylates, three polyammonium acrylates, two polysodium ethylene sulfonates, and one polysodium styrene sulfonate) at (298.2 and 323.2) K are reported. The isopiestic method was employed in these experiments with aqueous solutions of sodium chloride as references. The polyelectrolytes were characterized by three averaged molecular masses determined by gel permeation chromatography. Furthermore, the density and the refractive index increments of the aqueous polyelectrolyte solutions are reported. Although a similar pattern for the activity of water was observed for all systems (i.e., the osmotic coefficient increases with rising polyelectrolyte concentration), the experimental results show that this property depends on the monomer type as well as on the size of the polymer chain. The temperature (varied from (298.2 to 323.2) K) has only a small influence on the activity of water.

New Analytic Solution Related to the Richards, Philip, and Green-Ampt Equations for Infiltration

Based on physical laws of similarity, an analytic solution of the soil water potential form of the Richards equation was derived for water infiltration into a homogeneous sand. The derivation assumes a similarity between the soil water retention function and that of the soil water content profiles taken at fixed times. The new solution successfully described soil water content profiles experimentally measured for water infiltrating downward, upward, and horizontally into a homogeneous sand and agrees with that presented by Philip in 1957. The utility of this analysis is still to be verified, but it is expected to hold for soils that have a narrow pore-size distribution before wetting and that manifest a sharp increase of water content at the wetting front during infiltration. The effect of van Genuchten`s parameters alpha and n on the application of the solution to other porous media was investigated. The solution also improves and provides a more realistic description of the infiltration process than that pioneered by Green and Ampt in 1911.

New Analytic Solution of Boltzmann Transform for Horizontal Water Infiltration into Sand

The use of the Boltzmann transform function, lambda(theta), to solve the Richards equation when the diffusivity, D, is a function of only soil water content,., is now commonplace in the literature. Nevertheless, a new analytic solution of the Boltzmann transform lambda(h) as a function of matric potential for horizontal water infiltration into a sand was derived without invoking the concept or use of D(theta). The derivation assumes that a similarity exists between the soil water retention function and the Boltzmann transform lambda(theta). The solution successfully described soil water content profiles experimentally measured for different infiltration times into a homogeneous sand and agrees with those presented by Philip in 1955 and 1957. The applicability of this solution for all soils remains open, but it is anticipated to hold for soils whose air-filled pore-size distribution before wetting is sufficiently narrow to yield a sharp increase of water content at the wetting front during infiltration. It also improves and provides a versatile alternative to the well-known analysis pioneered by Green and Ampt in 1911.

Distribution and storage characterization of soil solution for drip irrigation

The increased use of marginal quality water with drip irrigation requires sound fertigation practices that reconcile environmental concerns with viable crop production objectives. We conducted experiments to characterize dynamics and patterns of soil solution within wet bulb formed by drip irrigation. Time-domain reflectometry probes were used to monitor the distribution of potassium nitrate (KNO(3)) and water distribution from drippers discharging at constant flow rates of 2, 4 and 8 L h(-1) in soil-filled containers. Considering results from different profiles, we observed greater solute storage near the dripper decreasing gradually towards the wetting front. About half of the applied KNO(3) solution (48%) was stored in the first layer (0-0.10 m) for all experiments, 29% was stored in the next layer (0.10-0.20 m). Comparing different dripper flow rates, we observed higher solution storage for 4 L h(-1), with 45, 53 and 47% of applied KNO(3) solution accumulating in the first layer (0-0.10 m) for dripper flow rates of 2, 4 and 8 L h(-1), respectively. The results suggest that based on the volume and frequency used in this experiment, it would be advantageous to apply small amounts of solution at more frequent intervals to reduce deep percolation losses of applied water and solutes.

Nickel adsorption in two Oxisols and an Alfisol as affected by pH, nature of the electrolyte, and ionic strength of soil solution

Background, aim, and scope The retention of potentially toxic metals in highly weathered soils can follow different pathways that variably affect their mobility and availability in the soil-water-plant system. This study aimed to evaluate the effects of pH, nature of electrolyte, and ionic strength of the solution on nickel (Ni) adsorption by two acric Oxisols and a less weathered Alfisol. Materials and methods The effect of pH on Ni adsorption was evaluated in surface and subsurface samples from a clayey textured Anionic `Rhodic` Acrudox ( RA), a sandy-clayey textured Anionic `Xantic` Acrudox (XA), and a heavy clayey textured Rhodic Kandiudalf (RK). All soil samples were equilibrated with the same concentration of Ni solution (5.0 mg L(-1)) and two electrolyte solutions (CaCl(2) or NaCl) with different ionic strengths (IS) (1.0, 0.1 and 0.01 mol L(-1)). The pH of each sample set varied from 3 to 10 in order to obtain sorption envelopes. Results and discussion Ni adsorption increased as the pH increased, reaching its maximum of nearly pH 6. The adsorption was highest in Alfisol, followed by RA and XA. Competition between Ni(2+) and Ca(2+) was higher than that between Ni(2+) and Na(+) in all soil samples, as shown by the higher percentage of Ni adsorption at pH 5. At pH values below the intersection point of the three ionic strength curves (zero point of salt effect), Ni adsorption was generally higher in the more concentrated solution (highest IS), probably due to the neutralization of positive charges of soil colloids by Cl(-) ions and consequent adsorption of Ni(2+). Above this point, Ni adsorption was higher in the more diluted solution (lowest ionic strength), due to the higher negative potential at the colloid surfaces and the lower ionic competition for exchange sites in soil colloids. Conclusions The effect of ionic strength was lower in the Oxisols than in the Alfisol. The main mechanism that controlled Ni adsorption in the soils was the ionic exchange, since the adsorption of ionic species varied according to the variation of pH values. The ionic competition revealed the importance of electrolyte composition and ionic strength on Ni adsorption in soils from the humid tropics. Recommendations and perspectives The presence of NaCl or CaCl(2) in different ionic strengths affects the availability of heavy metals in contaminated soils. Therefore, the study of heavy metal dynamics in highly weathered soils must consider this behavior, especially in soils with large amounts of acric components.

Novel and facile solution-phase synthesis of 2,5-diketopiperazines and O-glycosylated analogs

This work describes the synthesis in Solution of a series of related diketopiperazines with potential biological activities: cyclo(L-Pro-L-Ser), cyclo(L-Phe-L-Ser), cyclo(D-Phe-L-Ser) and the corresponding glycosylated analogs of the latter, cyclo[D-Phe-L-Ser(alpha GlcNAc)] and cyclo[D-Phe-L-Ser(beta GlcNAc)]. The synthetic approach involved coupling reactions of -OH or O-glycosylated serine benzyl esters with NFmoc-protected amino acids (Pro or Phe), followed by one-pot deprotection-cyclization reaction in the presence of 20% piperidine in DMF. (C) 2009 Elsevier Ltd. All rights reserved.

Computationally efficient solution techniques for adsorption problems involving steep gradients in bidisperse particles

A piecewise uniform fitted mesh method turns out to be sufficient for the solution of a surprisingly wide variety of singularly perturbed problems involving steep gradients. The technique is applied to a model of adsorption in bidisperse solids for which two fitted mesh techniques, a fitted-mesh finite difference method (FMFDM) and fitted mesh collocation method (FMCM) are presented. A combination (FMCMD) of FMCM and the DASSL integration package is found to be most effective in solving the problems. Numerical solutions (FMFDM and FMCMD) were found to match the analytical solution when the adsorption isotherm is linear, even under conditions involving steep gradients for which global collocation fails. In particular, FMCMD is highly efficient for macropore diffusion control or micropore diffusion control. These techniques are simple and there is no limit on the range of the parameters. The techniques can be applied to a variety of adsorption and desorption problems in bidisperse solids with non-linear isotherm and for arbitrary particle geometry.