Zone trapping/merging zones in flow analysis: A novel approach for rapid assays involving relatively slow chemical reactions

A novel strategy for accomplishing zone trapping in flow analysis is proposed. The sample and the reagent solutions are simultaneously inserted into convergent carrier streams and the established zones merge together before reaching the detector, where the most concentrated portion of the entire sample zone is trapped. The main characteristics, potentialities and limitations of the strategy were critically evaluated in relation to an analogous flow system with zone stopping. When applied to the spectrophotometric determination of nitrite in river waters, the main figures of merit were maintained, exception made for the sampling frequency which was calculated as 189h(-1), about 32% higher relatively to the analogous system with zone stopping. The sample inserted volume can be increased up to 1.0 mL without affecting sampling frequency and no problems with pump heating or malfunctions were noted after 8-h operation of the system. In contrast to zone stopping, only a small portion of the sample zone is halted with zone trapping, leading to these beneficial effects. (C) 2011 Elsevier B.V. All rights reserved.

Luz: um raro produto de reação

The production of visible light by chemical reactions constitutes interesting and fascinating phenomena and several reaction mechanisms are discussed to rationalize excited state formation. Most efficient chemiluminescence reactions are thought to involve one or more electron transfer steps and chemiexcitation is believed to occur by radical annihilation. A brief introduction to the general principles of light production and the main known chemiexcitation mechanisms will be given here. Subsequently, recent results on the mechanistic elucidation of efficient chemiluminescence systems, as the peroxyoxalate reaction, the induced decomposition of phenoxy-substituted 1,2-dioxetanes and the catalyzed decomposition of new a-peroxylactones will be discussed.

A Equação-Mestra: atingindo o equilíbrio

In the last years, a great interest in nonequilibrium systems has been witnessed. Although the Master Equations are one of the most common methods used to describe these systems, the literature about these equations is not straightforward due to the mathematical framework used in their derivations. The goals of this work are to present the physical concepts behind the Master Equations development and to discuss their basic proprieties via a matrix approach. It is also shown how the Master Equations can be used to model typical nonequilibrium processes like multi-wells chemical reactions and radiation absorption processes.

Hydrogen bond interactions between acetone and supercritical water

Hydrogen bond interactions between acetone and supercritical water are investigated using a combined and sequential Monte Carlo/quantum mechanics (S-MC/QM) approach. Simulation results show a dominant presence of con. gurations with one hydrogen bond for different supercritical states, indicating that this specific interaction plays an important role on the solvation properties of acetone in supercritical water. Using QM MP2/aug-cc-pVDZ the calculated average interaction energy reveals that the hydrogen-bonded acetone-water complex is energetically more stable under supercritical conditions than ambient conditions and its stability is little affected by variations of temperature and/or pressure. All average results reported here are statistically converged.

A critical evaluation of a long pathlength cell for flow-based spectrophotometric measurements

Coupling of a flow cell based on a liquid core waveguide (LCW) to flow systems for spectro photometric measurements was critically evaluated. Flow-based systems with and without chemical reactions were exploited to estimate the increase in analytical signal in comparison to those obtained with a conventional I cm cell under different experimental conditions. The Schlieren effect associated to intense concentration gradients in the sample zone was investigated with model solutions that do not absorb visible electromagnetic radiation. The effect of radiation scattering was lower than the expected by considering the increase in the optical path, being the magnitude of the perturbation up to 40% higher for the 100-cm LCW cell. Several alternatives for compensation of the Schlieren effect were experimentally investigated. The potentiality of the LCW for turbidimetric measurements and coupling to monosegmented flow analysis was also evaluated. (C) 2008 Elsevier B.V. All rights reserved.

Evidences of turbulent mixing in multi-pumping flow systems

Multi-pumping flow systems exploit pulsed flows delivered by Solenoid pumps. Their improved performance rely on the enhanced radial mass transport inherent to the pulsed flow, which is a consequence of the establishment of vortices thus a tendency towards turbulent mixing. This paper presents several evidences of turbulent mixing in relation to pulsed flows. such as recorded peak shape, establishment of fluidized beds, exploitation of flow reversal, implementation of relatively slow chemical reactions and/or heating of the reaction medium. In addition, Reynolds number associated with the GO period of a pulsed flow is estimated and photographic images of dispersing samples flowing under laminar regime and pulsed flow conditions are presented. (C) 2009 Elsevier B.V. All rights reserved.

Infiltration of Al2O3/Y2O3 mix into SiC ceramic preforms

Silicon carbide ceramics are very interesting materials to engineering applications because of their properties. These ceramics are produced by liquid phase sintering (LPS), where elevated temperature and time are necessary, and generally form volatile products that promote defects and damage their mechanical properties. In this work was studied the infiltration process to produce SiC ceramics, using shorter time and temperature than LPS, thereby reducing the undesirable chemical reactions. SiC powder was pressed at 300 MPa and pre-sintered at 1550 degrees C for 30 min. Unidirectional and spontaneous infiltration of this preform by Al2O3/Y2O3 liquid was done at 1850 degrees C for 5, 10, 30 and 60 min. The kinetics of infiltration was studied, and the infiltration equilibrium happened when the liquid infiltrated 12 mm into perform. The microstructures show grains of the SiC surrounded by infiltrated additives. The hardness and fracture toughness are similar to conventional SiC ceramics obtained by LPS. (c) 2007 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Design and assembly of an experimental laboratory for the study of atmosphere-plant interactions in the system of fumigation chambers

An experimental laboratory was designed and assembled at the Botanical Institute of So Paulo, Brazil, in order to research atmosphere-plant interactions through the use of a system of fumigation chambers. A system of three ""closed"" fumigation chambers was designed to be used inside or outside the laboratory. The system was built to be used with a single pollutant or a mix of them. The innovation in this system is to allow chemical reactions inside the chambers that simulate atmospheric chemistry, especially photochemical processes involving high levels of ozone. Assessment of the performance and applicability of the system was based on the response of Nicotiana tabacum Bel W3 exposed to ozone produced alternatively by a generator and inside the chamber by reactions of its precursors. The results showed that the system can be well applied to the study of atmospheric chemistry interactions and the effects on plants.

Gas flow analysis in a Kraft recovery boiler

Demands for optimal boiler performance and increased concerns in lowering emission have always been the driving force in the reevaluation and evolution of the Kraft boiler: specifically the air distribution strategies that are directly related to achieving increased residence time of flue gas combustion inside the furnace which in turn lowers atmosphere emission levels and enhances boiler operation. This paper presents the results of a study that analyzes the interaction of the different multilevel air injections have on flue gas flow patterns including various quaternary air supply arrangements. Additionally, this study assesses the performance of the CFD (Computational Fluid Dynamics) model against data available in literature. Simulations were performed considering isothermal and incompressible flows, and did not take into account thermal phenomena or chemical reactions. The numerical solutions generated proved to be coherently related to the data available in literature, and provided proof of the efficiency of tertiary level air injection, as well as revealed that quaternary air injection ports arranged in a symmetrical configuration is most suitable for optimal equipment operation. (C) 2010 Elsevier B.V. All rights reserved.

A simplified description of the evolution of organic aerosol composition in the atmosphere

Organic aerosol (OA) in the atmosphere consists of a multitude of organic species which are either directly emitted or the products of a variety of chemical reactions. This complexity challenges our ability to explicitly characterize the chemical composition of these particles. We find that the bulk composition of OA from a variety of environments (laboratory and field) occupies a narrow range in the space of a Van Krevelen diagram (H: C versus O:C), characterized by a slope of similar to-1. The data show that atmospheric aging, involving processes such as volatilization, oxidation, mixing of air masses or condensation of further products, is consistent with movement along this line, producing a more oxidized aerosol. This finding has implications for our understanding of the evolution of atmospheric OA and representation of these processes in models. Citation: Heald, C. L., J. H. Kroll, J. L. Jimenez, K. S. Docherty, P. F. DeCarlo, A. C. Aiken, Q. Chen, S. T. Martin, D. K. Farmer, and P. Artaxo (2010), A simplified description of the evolution of organic aerosol composition in the atmosphere, Geophys. Res. Lett., 37, L08803, doi: 10.1029/2010GL042737.

CASPT2 Study of the Potential Energy Surface of the HSO(2) System

The importance of the HSO(2) system in atmospheric and combustion chemistry has motivated several works dedicated to the study of associated structures and chemical reactions. Nevertheless controversy still exists in connection with the reaction SH + O(2) -> H + SO(2) and also related to the role of the HSOO isomers in the potential energy surface (PES). Here we report high-level ab initio calculation for the electronic ground state of the HSO(2) system. Energetic, geometric, and frequency properties for the major stationary states of the PES are reported at the same level of calculations:,CASPT2/aug-cc-pV(T+d)Z. This study introduces three new stationary points (two saddle points and one minimum). These structures allow the connection of the skewed HSOOs and the HSO(2) minima defining new reaction paths for SH + O(2) -> H + SO(2) and SH + O(2) -> OH + SO. In addition, the location of the HSOO isomers in the reaction pathways have been clarified.

MEH-PPV photobleaching control by femtosecond pulse shaping

In the work reported here we were able to control the photobleaching of poly[2-methoxy-5-(2`-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV), excited by two-photon absorption, using femtosecond pulse shaping. By applying a cosine-like spectral phase mask, we observe a reduction of three times in the photobleaching rate, while the fluorescence intensity decreases by 20%, in comparison to the values obtained with a Fourier-transform-limited pulse. These results demonstrate an interesting trade-off between photobleaching rate and nonlinear fluorescence intensity. The possible mechanism behind this process is discussed in terms of the pulse spectral profile and the absorbance band of MEH-PPV. (C) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Er : YAB nanoparticles and vitreous thin films by the polymeric precursor method

The synthesis of Y(0.9)Er(0.1)Al(3)(BO(3))(4) crystalline powders and vitreous thin films were studied. Precursor solutions were obtained using a modified polymeric precursor method using D-sorbitol as complexant agent. The chemical reactions were described. Y(0.)9Er(0.1)Al(3)(BO(3))(4) composition presents good thermal stability with regard to crystallization. The Y(0.9)Er(0.1)Al(3)(BO(3))(4) crystallized phase can be obtained at 1,150 degrees C, in agreement with other authors. Crack- and porosity-free films were obtained with very small grain size and low RMS roughness. The films thickness revealed to be linearly dependent on precursor solution viscosity, being the value of 25 mPa s useful to prepare high-quality amorphous multi-layers (up to similar to 800 nm) at 740 degrees C during 2 h onto silica substrates by spin coating with a gyrset technology.

Synthesis optimization, structural evolution and optical properties of Y(0.9)Er(0.1)Al(3)(BO(3))(4) nanopowders obtained by soft chemistry methods

This paper describes the structural evolution of Y(0.9)Er(0.1)Al(3)(BO(3))(4) nanopowders using two soft chemistry routes, the sol-gel and the polymeric precursor methods. Differential scanning calorimetry, differential thermal analyses, thermogravimetric analyses, X-ray diffraction, Fourier-transform infrared, and Raman spectroscopy techniques have been used to study the chemical reactions between 700 and 1200 degrees C temperature range. From both methods the Y(0.9)Er(0.1)Al(3)(BO(3))(4) (Er:YAB) solid solution was obtained almost pure when the powdered samples were heat treated at 1150 degrees C. Based on the results, a schematic phase formation diagram of Er:YAB crystalline solid solution was proposed for powders from each method. The Er:YAB solid solution could be optimized by adding a small amount of boron oxide in excess to the Er:YAB nominal composition. The nanoparticles are obtained around 210 nm. Photoluminescence emission spectrum of the Er:YAB nanocrystalline powders was measured on the infrared region and the Stark components of the (4)I(13/2) and (4)I(15/2) levels were determined. Finally, for the first time the Raman spectrum of Y(0.9)Er(0.1)Al(3)(BO(3))(4) crystalline phase is also presented. (C) 2008 Elsevier Masson SAS. All rights reserved.

HYDROTHERMAL REE FLUOROCARBONATE MINERALIZATION AT BARRA DO ITAPIRAPUA, A MULTIPLE STOCKWORK CARBONATITE, SOUTHERN BRAZIL

The Barra do Itapirapua ( BIT) carbonatites in southern Brazil belong to the final stages of the Early Cretaceous alkaline rock - carbonatite magmatism of the Ponta Grossa Arch Province. The BIT complex is a dyke and vein stockwork in which four main carbonatitic phases are recognized, mainly magnesiocarbonatites and ferrocarbonatites. These carbonatites are generally overprinted by pervasive hydrothermal events. The C-O stable isotopic data indicate re-equilibration under hydrothermal conditions at temperatures between 375 and 80 degrees C. Significant amounts of REE fluorocarbonate minerals, relatively Sr- and Th-rich, were deposited. Syntaxy between synchysite-(Ce) and parisite-(Ce) is very common owing to the similarity in structures, with alternating (001) layers of (CeF), (CO3) and (Ca). However, bastnasite-(Ce) occurs as individual crystals, overgrown by the synchysite and parisite polycrystals. Textural and chemical reactions between the REE fluorocarbonates provide insights into the mobility of rare-earth elements during fluid-rock interaction. The BIT complex is considered to be of potential economic interest for production of the rare-earth concentrates.