Mechanistic aspects of the linear stabilization of non-stationary electrochemical oscillations

The problem of non-stationarity in experimentally recorded time-series is common in many (electro)chemical systems. Underlying this non-stationarity is the slow drift in some uncontrollable parameter, and it occurs in spite of the fact that all controllable parameters are kept constant. Particularly for electrochemical systems, some of us have recently suggested [J. Phys. Chem. C, 144, (2010), 22262–22268] an empirical method to stabilize experimental time-series. The method was exemplified for the electro-oxidation of methanol and different patterns were satisfactorily stabilized. In this paper we further elaborate some mechanistic aspects of this method and test it for the electro-oxidation of formaldehyde, a system that has some resemblance with the electro-oxidation of methanol, but produces a richer dynamics. In terms of the reaction mechanism, we were able to describe the coupling and to separate the surface processes of the two sub-systems: the fast one (or the core-oscillator) and the slow one, responsible for the drift

Phase diagram of two-dimensional hard rods from fundamental mixed measure density functional theory

A density functional theory for the bulk phase diagram of two-dimensional orientable hard rods is proposed and tested against Monte Carlo computer simulation data. In detail, an explicit density functional is derived from fundamental mixed measure theory and freely minimized numerically for hard discorectangles. The phase diagram, which involves stable isotropic, nematic, smectic, and crystalline phases, is obtained and shows good agreement with the simulation data. Our functional is valid for a multicomponent mixture of hard particles with arbitrary convex shapes and provides a reliable starting point to explore various inhomogeneous situations of two-dimensional hard rods and their Brownian dynamics

Photoelectrochemical oxidation of glycerol on hematite: thermal effects, in situ FTIR and long-term HPLC product analysis

Photoelectrochemical (PEC) oxidation of biomass is a profitable approach to produce hydrogen by substituting the water oxidation reaction in the electrolyzers’ photoanodes. Among the biomass-derived molecules, glycerol is an interesting alternative to water since its standard thermodynamic potential is considerably lower than that of water and because it is widely produced in the biodiesel industry. Herein, we performed a fundamental study of the PEC oxidation of glycerol on hematite. In situ FTIR experiments and long-term electrolysis followed by HPLC analysis revealed C1, C2 and C3 oxidation products showing the low selectivity of the reaction under these conditions. We explained this lack of selectivity by an electrooxidation mechanism involving highly reactive radicals as intermediates. [Figure not available: see fulltext.]

Bioavailability of phosphorus on highly weathered Oxisoils of the Brazilian Mid-West.

Soils from mid-west Brazil show strong phosphorus (P) fixation, which can reduce the efficiency of P fertilizers. Under this condition, soil competes with the plant for the applied P adsorbing it strongly in its mineral fraction. Nevertheless, in areas where crops are grown and fertilizers are added for many years, soil fertility status has increased over time, making these soils nonresponsive to P. The objective of this study was to evaluate how P availability changes with soil use. Forty soil samples were collected under different types of land use: native forest, pasture, no-tillage, and areas with periodic tillage. P fractionation was performed to determine the amount of P in the organic and inorganic fractions with high, medium, and low lability under each land use. Corn was cultivated in a greenhouse experiment to evaluate P uptake and values correlated with different P fractions. The results showed differences in the P fraction relations among different land uses. Cultivated areas (no tillage and periodic tillage) accumulated greater amounts of P in all fractions than pastures and the native forest. A higher proportion of labile organic P was observed under no tillage than under periodic tillage. NaHCO3 and NaOH 0.1 mol L-1were the most relevant P fractions for shoot P uptake. No tillage promoted the accumulation of available P fractions, suggesting that it is a good management strategy to ensure fertilizer use efficienc

Singularity theory and forced symmetry breaking in equations

A theory of bifurcation equivalence for forced symmetry breaking bifurcation problems is developed. We classify (O(2), 1) problems of corank 2 of low codimension and discuss examples of bifurcation problems leading to such symmetry breaking

HEP Applications Evaluation of the EDG Testbed and Middleware

Workpackage 8 of the European Datagrid project was formed in January 2001 with representatives from the four LHC experiments, and with experiment independent people from five of the six main EDG partners. In September 2002 WP8 was strengthened by the addition of effort from BaBar and D0. The original mandate of WP8 was, following the definition of short- and long-term requirements, to port experiment software to the EDG middleware and testbed environment. A major additional activity has been testing the basic functionality and performance of this environment. This paper reviews experiences and evaluations in the areas of job submission, data management, mass storage handling, information systems and monitoring. It also comments on the problems of remote debugging, the portability of code, and scaling problems with increasing numbers of jobs, sites and nodes. Reference is made to the pioneeering work of Atlas and CMS in integrating the use of the EDG Testbed into their data challenges. A forward look is made to essential software developments within EDG and to the necessary cooperation between EDG and LCG for the LCG prototype due in mid 2003.Comment: Talk from the 2003 Computing in High Energy and Nuclear Physics Conference (CHEP03), La Jolla, CA, USA, March 2003, 7 pages. PSN THCT00

Concentração de nutrientes minerais em acessos da Etiópia de Coffea arabica.

O sucesso do manejo nutricional em plantas depende de diversos fatores, como características químicas, biológicas e físicas do solo, além da influência do genótipo. Apesar do manejo agronômico visando à adequação do solo para a cultura do cafeeiro estar bem estabelecido, pouco se sabe sobre o efeito do genótipo na absorção e acúmulo de nutrientes minerais. Tradicionalmente, o melhoramento genético do cafeeiro foca-se em características morfológicas, resistência a doenças e na produtividade; dessa forma, a exigência nutricional foi deixada em plano secundário ao longo deste processo. Com a necessidade cada vez maior de variedades que apresentem boa produtividade com impactos menores ao meio ambiente, a introgressão de características de genótipos silvestres é uma relevante estratégia para incremento da eficiência nutricional. Neste contexto, o presente trabalho tem como objetivo caracterizar a concentração de nutrientes em 12 acessos silvestres de Coffea arabica provenientes da Etiópia, identificando genótipos de cafeeiro que apresentam acumulação diferencial de nutrientes minerais (N, P, K, Ca, Mg, Cu, Zn, B e Mn) com relação a três tecidos: folhas, caule e raiz. Entre os acessos da Etiópia, destacou-se a concentração diferencial de P em folhas do acesso CAF032, e o acúmulo em raiz de N (CAF009), Zn (CAF131) e Mn (CAF023). Bourbon teve acúmulo diferencialmente menor de P no caule e maior de Ca na raiz e Catuaí Vermelho apresentou concentração diferencial de Mg no caule. O presente trabalho é uma importante contribuição na definição de genótipos silvestres de Coffea arabica com potencial de introgressão de características relacionadas à eficiência nutricional