Solvation simplified

The effects of solvents on chemical phenomena is complex because there are various solute-solvent interaction mechanisms. Solvatochromism refers to the effects of solvents on the spectra of probes. The study of this phenomenon sheds light on the relative importance of the solvation mechanisms. Solvation in pure solvents is quantitatively analyzed in terms of a multi-parameter equation. In binary solvent mixtures, solvation is analyzed by considering the organic solvent, S, water, W, and a 1:1 hydrogen bonded species (S-W). The applications of solvatochromism to understand distinct chemical phenomena, reactivity and swelling of cellulose, is briefly discussed.

Eletrodo de hidrogênio: o que há nos livros didáticos além de E¸ = 0?

The results of an exercise on electrochemistry for General Chemistry students are presented. The difficulty encountered by students in predicting the shift in the potential of the hydrogen electrode under non-standard conditions prompted a search in textbooks on how the subject is developed. Besides several instances of inconsistencies in defining the standard state, such as including the temperature in the definition, a number of incorrect depictions of the hydrogen electrode were discovered. Of the 28 General Chemistry books, 16 Physical Chemistry books and 24 Internet pages, 30, 20 and 46%, respectively, showed devices that would not work in practice.

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.

Headland-bay beach planform stability of Santa Catarina State and of the Northern Coast of São Paulo State

This paper presents the results of the planform stability classification for the headland-bay beaches of the State of Santa Catarina and of the Northern Coast of São Paulo, based on the application of the Parabolic Bay-Shape Equation (PBSE) to aerial images of the beaches, using the software MEPBAY®. For this purpose, georeferenced mosaics of the QuickBird2® satellite imagery (for the State of Santa Catarina) and vertical aerial photographs (for the northern coast of São Paulo State) were used. Headland-bay beach planform stability can be classified as: (1) in static equilibrium, (2) in dynamic equilibrium, (3) unstable or (4) in a state of natural beach reshaping. Static equilibrium beaches are the most frequent along the coast of the State of Santa Catarina and the Northern Shore of São Paulo, notably along the most rugged sectors of the coast and those with experiencing lower fluvial discharge. By comparison, dynamic equilibrium beaches occur primarily on the less rugged sectors of the coast and along regions with higher fluvial discharge. Beaches in a state of natural beach reshaping have only been found in SC, associated with stabilized estuarine inlets or port breakwaters. However, it is not possible to classify any of these beaches as unstable because only one set of images was used. No clear relation was observed between a beach's planform stability and other classification factors, such as morphodynamics or orientation.

Crescimento alométrico dos componentes da carcaça de cordeiros Texel × Ile de France confinados do desmame aos 35kg de peso vivo

Foi avaliado o crescimento alométrico de ossos, músculos e gordura, e das regiões da carcaça de cordeiros Texel × Ile de France, terminados em confinamento. Vinte cordeiros, machos não-castrados, foram desmamados aos 42 dias de idade (15,9 ± 2,1kg de peso vivo) e confinados em baias individuais recebendo alimentação ad libitum. Destes, cinco foram abatidos 10 dias após o desmame e, os remanescentes, aos 25, 30 ou 35kg de peso vivo. Para determinação do crescimento alométrico dos cortes e tecidos foi utilizada a equação exponencial Y = aXb, transformada logaritmicamente em um modelo linear. Observou-se crescimento precoce (b = 0,89) da paleta, ao passo que a perna, a costela e o pescoço apresentaram crescimento isogônico (b = 1,00, 1,03 e 1,11, respectivamente), ou seja, equivalente ao da carcaça. O aumento do peso da carcaça implicou em redução da taxa de crescimento de ossos e músculos (b = 0,60 e 0,92, respectivamente) e aumento da taxa de crescimento da gordura (b = 1,78). O crescimento muscular foi diferenciado nas distintas regiões da carcaça, sendo isogônico na paleta (b = 0,98) e na perna (b = 0,99) e precoce na costela (b = 0,90) e no pescoço (b = 0,79). Recomenda-se que o abate de cordeiros Texel × Ile de France seja realizado com, no máximo, 30kg de peso vivo.

Fracionamento dos carboidratos pelas equações do Cornell Net Carbohydrate and Protein System de três cultivares de girassol na presença ou não de irrigação

Objetivou-se quantificar as frações de carboidratos pelas equações do Cornell Net Carbohydrate and Protein System (CNCPS) de três cultivares de girassol (Helianthus annuus L.) cultivados na presença ou não de irrigação. A utilização de uma preparação fibrosa, denominada parede celular (PC), nas equações da CNCPS, em substituição à fibra em detergente neutro (FDN) não promoveu diferenças nas frações de carboidratos B1 e C, mas influenciou as frações A e B2. Como os valores da fração B1, obtidos pelo modelo CNCPS foram menores que os teores de amido e pectina determinados em laboratório, supõe-se que a pectina e outros oligossacarídeos da parede celular, solubilizados pela solução de detergente neutro (fibra solúvel), nunca fizeram parte da fração B1, e sim da fração A. Apesar de os carboidratos da fibra solúvel apresentarem elevadas taxas de degradação, não parece adequada a caracterização da fibra solúvel na fração A. Parece mais adequado que a fibra solúvel (que inclui a pectina) seja alocada a uma fração exclusivamente sua, que pode ser a fração B2, e que seja criada uma nova fração, a B3, para os carboidratos digeríveis da parede celular. Assim, a fração B1 seria composta apenas de amido. A equação da fração C, que estima os carboidratos indigeríveis da parede celular, pode ser simplificada, relacionando a fração indigerível ao teor de lignina na matéria seca, e não à FDN isenta de cinzas e proteína, como atualmente utilizado. Esta proposta tem implicações práticas, uma vez que a fração indigerível da parede celular tem sido expressa em relação à FDN, e não na MS, com base no fato de que os efeitos inibitórios da lignina ocorrem sobre os componentes fibrosos da parede celular vegetal, e não sobre o conteúdo celular.

Load Ratio Estimation Through Striation Height and Spacing Analysis of an Aerospace Al Alloy 7475-T7351

It is well known that striation spacing may be related to the crack growth rate, da/dN, through Paris equation, as well as the maximum and minimum loads under service loading conditions. These loads define the load ratio, R, and are considered impossible to be evaluated from the inter-spacing striations analysis. In this way, this study discusses the methodology proposed by Furukawa to evaluate the maximum and minimum loads based on the experimental fact that the relative height of a striation, H, and the striation spacing, s, are strongly influenced by the load ratio, R. Fatigue tests in C(T) specimens were conducted on SAE 7475-T7351 Al alloy plates at room temperature and the results showed a straightforward correlation between the parameters H, s, and R. Measurements of striation height, H, were performed using scanning electron microscopy and field emission gun (FEG) after sectioning the specimen at a large inclined angle to amplify the height of the striations. The results showed that for increasing R the values of H/s tend to increase. Striation height, striation spacing, and load ratio correlations were obtained, which allows one to estimate service loadings from fatigue fracture surface survey.

Effects of Variations in Nonlinear Damping Coefficients on the Parametric Vibration of a Cantilever Beam with a Lumped Mass

Uncertainties in damping estimates can significantly affect the dynamic response of a given flexible structure. A common practice in linear structural dynamics is to consider a linear viscous damping model as the major energy dissipation mechanism. However, it is well known that different forms of energy dissipation can affect the structure's dynamic response. The major goal of this paper is to address the effects of the turbulent frictional damping force, also known as drag force on the dynamic behavior of a typical flexible structure composed of a slender cantilever beam carrying a lumped-mass on the tip. First, the system's analytical equation is obtained and solved by employing a perturbation technique. The solution process considers variations of the drag force coefficient and its effects on the system's response. Then, experimental results are presented to demonstrate the effects of the nonlinear quadratic damping due to the turbulent frictional force on the system's dynamic response. In particular, the effects of the quadratic damping on the frequency-response and amplitude-response curves are investigated. Numerically simulated as well as experimental results indicate that variations on the drag force coefficient significantly alter the dynamics of the structure under investigation. Copyright (c) 2008 D. G. Silva and P. S. Varoto.

A new constitutive theory extending Hypoplasticity

The purpose of the present theory is to improve Hypoplasticity, especially in relation to reloading processes. This is done by means of two hypoplastic equations (a classical equation along with a new one containing a so-called mnemonic tensor), a cone in stress space and a criterion defining loading, unloading and reloading. (C) 2010 Elsevier Ltd. All rights reserved.

Quasiharmonic elastic constants corrected for deviatoric thermal stresses

The quasiharmonic approximation (QHA), in its simplest form also called the statically constrained (SC) QHA, has been shown to be a straightforward method to compute thermoelastic properties of crystals. Recently we showed that for noncubic solids SC-QHA calculations develop deviatoric thermal stresses at high temperatures. Relaxation of these stresses leads to a series of corrections to the free energy that may be taken to any desired order, up to self-consistency. Here we show how to correct the elastic constants obtained using the SC-QHA. We exemplify the procedure by correcting to first order the elastic constants of MgSiO(3) perovskite and MgSiO(3) postperovskite, the major phases of the Earth's lower mantle. We show that this first-order correction is quite satisfactory for obtaining the aggregated elastic averages of these minerals and their velocities in the lower mantle. This type of correction is also shown to be applicable to experimental measurements of elastic constants in situations where deviatoric stresses can develop, such as in diamond-anvil cells.

Combining Legendre's Polynomials and Genetic Algorithm in the Solution of Nonlinear Initial-Value Problems

This work develops a method for solving ordinary differential equations, that is, initial-value problems, with solutions approximated by using Legendre's polynomials. An iterative procedure for the adjustment of the polynomial coefficients is developed, based on the genetic algorithm. This procedure is applied to several examples providing comparisons between its results and the best polynomial fitting when numerical solutions by the traditional Runge-Kutta or Adams methods are available. The resulting algorithm provides reliable solutions even if the numerical solutions are not available, that is, when the mass matrix is singular or the equation produces unstable running processes.

AVERAGE CONTINUOUS CONTROL OF PIECEWISE DETERMINISTIC MARKOV PROCESSES

This paper deals with the long run average continuous control problem of piecewise deterministic Markov processes (PDMPs) taking values in a general Borel space and with compact action space depending on the state variable. The control variable acts on the jump rate and transition measure of the PDMP, and the running and boundary costs are assumed to be positive but not necessarily bounded. Our first main result is to obtain an optimality equation for the long run average cost in terms of a discrete-time optimality equation related to the embedded Markov chain given by the postjump location of the PDMP. Our second main result guarantees the existence of a feedback measurable selector for the discrete-time optimality equation by establishing a connection between this equation and an integro-differential equation. Our final main result is to obtain some sufficient conditions for the existence of a solution for a discrete-time optimality inequality and an ordinary optimal feedback control for the long run average cost using the so-called vanishing discount approach. Two examples are presented illustrating the possible applications of the results developed in the paper.

LOCAL HEAD LOSS OF NON-COAXIAL EMITTERS INSERTED IN POLYETHYLENE PIPE

The design of a lateral line for drip irrigation requires accurate evaluation of head losses in not only the pipe but in the emitters as well. A procedure was developed to determine localized head losses within the emitters by the formulation of a mathematical model that accounts for the obstruction caused by the insertion point. These localized losses can be significant when compared with tire total head losses within the system due to the large number of emitters typically installed along the lateral line. Air experiment was carried out by altering flow characteristics to create Reynolds numbers (R) from 7,480 to 32,597 to provide turbulent flow and a maximum velocity of 2.0 m s(-1). The geometry of the emitter was determined by an optical projector and sensor An equation was formulated to facilitate the localized head loss calculation using the geometric characteristics of the emitter (emitter length, obstruction ratio, and contraction coefficient). The mathematical model was tested using laboratory measurements on four emitters. The local head loss was accurately estimated for the Uniram (difference of +13.6%) and Drip Net (difference of +7.7%) emitters, while appreciable deviations were found for the Twin Plus (-21.8%) and Tiran (+50%) emitters. The head loss estimated by the model was sensitive to the variations in the obstruction area of the emitter However, the variations in the local head loss did not result in significant variations in the maximum length of the lateral lines. In general, for all the analyzed emitters, a 50% increase in the local head loss for the emitters resulted in less than an 8% reduction in the maximum lateral length.

Antecedentes do relacionamento e da performance em empresas da cadeia de suprimentos: estruturação e aplicação de modelos de equações estruturais

The relationship between companies is an important issue in the management of supply chains. Several aspects relating to the flow and exchange of information along the chain are considered as having a decisive influence on the success of this relationship. The main objective of this work was to structured and test models that link aspects of this nature with performance and the purchaser-supplier relationship in the supply chain. Aspects relevant to communication and the use do IT in relationships between companies were investigated. The importance of performance in this relationship was also investigated. The research were based on empirical data obtained by means of structural equation modeling. The results show that some aspects contribute in a significant way to the success of this relationship while others that, a priori, are considered important make no contribution.

GLOBAL SOLUTIONS FOR ABSTRACT FUNCTIONAL DIFFERENTIAL EQUATIONS WITH NONLOCAL CONDITIONS

In this paper we study the existence of global solutions for a class of abstract functional differential equation with nonlocal conditions. An application is considered.