PRACTICAL STOCHASTIC MODEL FOR CHEMICAL KINETICS

The Practical Stochastic Model is a simple and robust method to describe coupled chemical reactions. The connection between this stochastic method and a deterministic method was initially established to understand how the parameters and variables that describe the concentration in both methods were related. It was necessary to define two main concepts to make this connection: the filling of compartments or dilutions and the rate of reaction enhancement. The parameters, variables, and the time of the stochastic methods were scaled with the size of the compartment and were compared with a deterministic method. The deterministic approach was employed as an initial reference to achieve a consistent stochastic result. Finally, an independent robust stochastic method was obtained. This method could be compared with the Stochastic Simulation Algorithm developed by Gillespie, 1977. The Practical Stochastic Model produced absolute values that were essential to describe non-linear chemical reactions with a simple structure, and allowed for a correct description of the chemical kinetics.

Uptake and translocation of nitrogen, phosphorus and calcium in soybean infected with Meloidogyne incognita and M. javanica

Two soybean (Glycine max) cultivars were used in this study, Ocepar 4, rated as moderately resistant to Meloidogyne incognita race 3 but susceptible to M. javanica, and 'BR 16', susceptible to both nematodes. The effect of nematodes infection on the uptake and transport of N, P and Ca to the shoot was studied in plants growing in a split root system. The upper half was inoculated with 0, 3,000, 9,000 or 27,000 eggs/plant while the lower half received 15N, 32P or 45Ca. Infected plants showed an increase of root but a decrease of shoot mass with increasing inoculum levels. In general, total endogenous nutrients increased in the roots and tended to decrease in the shoots with increasing inoculum levels. When concentrations were calculated, there was an increase in the three nutrients in the roots, and an increase of Ca but no significant variation of N and P was observed in the shoots. The total amount of 15N in the roots increased at the highest inoculum levels but 32P and 45Ca decreased. In the shoots there was a reduction of 32P and 45Ca. The specific concentrations of the labelled nutrients (abundance or radioactivity/tissue mass) also showed a decrease of 32P and 45Ca in the shoots and roots of infected plants and an increase of 15N in the shoots. Considering that overall nutrient concentrations reflect cumulative nutrient uptake and the data from labelled elements gave information at a specific moment of the infection, thus nematodes do interfere with nutrient uptake and translocation.

Photoinhibition of Photosystem II. Kinetics, Photoprotection and Mechanism

Photosystem II (PSII) is susceptible to light-induced damage defined as photoinhibition. In natural conditions, plants are capable of repairing the photoinhibited PSII by on-going degradation and re-synthesis of the D1 reaction centre protein of PSII. Photoinhibition is induced by both visible and ultraviolet light and photoinhibition occurs under all light intensities with the same efficiency per photon. In my thesis work, I studied the reaction kinetics and mechanism of photoinhibition of PSII, as well as photoprotection in leaves of higher plants. Action spectroscopy was used to identify photoreceptors of photoinhibition. I found that the action spectrum of photoinhibition in vivo shows resemblance to the absorption spectra of manganese model compounds of the oxygen evolving complex (OEC) suggesting a role for manganese as a photoreceptor of photoinhibition under UV and visible light. In order to study the protective effect of non-photochemical quenching, the action spectrum was measured from leaves of wild type Arabidopsis thaliana and two mutants impaired in nonphotochemical quenching of chlorophyll a excitations. The findings of action spectroscopy and simulations of chlorophyll-based photoinhibition mechanisms suggested that quenching of antenna excitations protects less efficiently than would be expected if antenna chlorophylls were the only photoreceptors of photoinhibition. The reaction kinetics of prolonged photoinhibition was studied in leaves of Cucurbita maxima and Capsicum annuum. The results indicated that photoinhibitory decrease in both the oxygen evolution activity and ratio of variable to maximum fluorescence follows firstorder kinetics in vivo. The persistence of first-order kinetics suggests that already photoinhibited reaction centres do not protect against photoinhibition and that the mechanism of photoinhibition does not have a reversible intermediate. When Cucurbita maxima leaves were photoinhibited with saturating single-turnover flashes and continuous light, the light response curve of photoinhibition was found to be essentially a straight line with both types of illumination, suggesting that similar photoinhibition mechanisms might function during illumination with continuous light and during illumination with short flashes.

About the kinetics and mechanism of the reactions of 4-(2-pyridylazo)-resorcinol, with Zn2+, Cu2+ and Zn2++Cu2+ equimolar mixtures, in aqueous solutions

The kinetics and mechanism of the reactions between 4(2pyridylazo)-resorcinol and Zn2+, Cu2+ and Zn2++Cu2+ equimolar mixtures were studied. The reactions were performed in aqueous solution (pH = 8.5, borate buffer) and monitored spectrophotometrically at 500 nm using stopped-flow technique. Spectral and kinetic data indicate that the Zn2++Cu2+ equimolar mixture behaves as an unique species and it can be attributed to the interactions of Zn2+ and of Cu2+ with water molecules in the aqueous solution. A mechanism is proposed and the rate constants are calculated.

Sorption kinetics and intrapaticulate diffusivity of As(III) bioremediation from aqueous solution, using modified and unmodified coconut fiber

The pollution and toxicity problems posed by arsenic in the environment have long been established. Hence, the removal and recovery remedies have been sought, bearing in mind the efficiency, cost effectiveness and environmental friendliness of the methods employed. The sorption kinetics and intraparticulate diffusivity of As (III) bioremediation from aqueous solution using modified and unmodified coconut fiber was investigated. The amount adsorbed increased as time increased, reaching equilibrium at about 60 minutes. The kinetic studies showed that the sorption rates could be described by both pseudo-first order and pseudo-second order process with the later showing a better fit with a value of rate constant of 1.16 x 10-4 min-1 for the three adsorbent types. The mechanism of sorption was found to be particle diffusion controlled. The diffusion and boundary layer effects were also investigation. Therefore, the results show that coconut fiber, both modified and unmodified is an efficient sorbent for the removal of As (III) from industrial effluents with particle diffusion as the predominant mechanism.

Polarographic study and electrode kinetics of [Zn(II) - antibiotics - cephaloglycin] system vis a vis kinetics of electrode reactions

Electrode kinetics and complex formation of Zn(II) using doxycycline, chlortetracycline, oxytetracycline, tetracycline, minocycline, amoxicillin, chloramphenicol and cephaloglycin were reported at pH = 7.30 ± 0.01 in = 1.0 molL-1 NaClO4 used as supporting electrolyte at 25.0°C. Kinetic parameters viz. transfer coefficient (α), degree of irreversibility (λ) and rate constant (k) were determined. The study showed that 'Transition state' behaves between reactant (O) and product (R) response to applied potential. The stability constants varied from 2.14 to 10.31 showing that these drugs or their complexes could be used against Zn toxicity.

Comparison of the dehydration kinetics of solid state compounds of 2-methoxybenzylidenepyruvate with some divalent metal ions

Divalent metal complexes of ligand 2-methoxybenzylidenepyruvate with Fe, Co, Ni, Cu and Zn as well as sodium salt were synthesized and investigated in the solid state. TG curves of these compounds were obtained with masses sample of 1 and 5mg under nitrogen atmosphere. Different heating rates were used to characterize and study these compounds from the kinetic point of view. The activation energy and pre-exponential factor were obtained applying the Wall-Flynn-Ozawa method to the TG curves. The obtained data were evaluated and the values of activation energy (Ea / kJ mol-1) was plotted in function of the conversion degree (α). The results show that due to mass sample, different activation energies were obtained. The results are discussed mainly taking into account the linear dependence between the activation energy and the pre exponential factor, where was verified the effect of kinetic compensation (KCE) and possible linear relations between the dehydrations steps of these compounds.

Intensidade da ferrugem asiática (Phakopsora pachyrhizi H. Sydow & P. Sydow) da soja [Glycine max (L.) Merr.] nas cultivares Conquista, Savana e Suprema sob diferentes temperaturas e períodos de molhamento foliar

A Ferrugem Asiática (Phakopsora pachyrhizi H. Sydow & P. Sydow), relatada em diversas regiões do globo terrestre de climas tropicais e subtropicais, causa redução significativa na produtividade da soja [Glycine max (L.) Merr.]. Fatores bióticos como interação patógeno-hospedeiro e abióticos influenciam o progresso da doença. Objetivou-se neste trabalho estudar os efeitos da temperatura e de períodos de molhamento foliar no progresso da Ferrugem Asiática nas cultivares Conquista, Savana e Suprema. O experimento foi conduzido no Departamento de Fitopatologia da Universidade Federal de Lavras, em junho de 2004, em câmaras de crescimento vegetal nas temperaturas de 15, 20, 25 e 30 °C e períodos de molhamento foliar de 0, 6, 12, 18 e 24 horas. A inoculação foi realizada pulverizando-se as plantas com suspensão de 10(4) uredósporos de P. pachyrhizi.mL-1 de água. Dados da incidência e da severidade foram utilizados para avaliar o progresso da doença e integrados por meio da área abaixo da curva de progresso da incidência (AACPI) e da severidade (AACPS). Modelos de regressão não-linear foram ajustados para a AACPI e AACPS. Foi calculado o volume abaixo da superfície de resposta para incidência (VASRI) e severidade (VASRS) em relação à temperatura e molhamentos foliares com o objetivo de detectar diferenças entre cultivares. Molhamentos foliares acima de 15 horas e temperaturas próximas a 20 ºC, nas 3 cultivares avaliadas, determinaram maior intensidade da Ferrugem Asiática. Temperaturas próximas a 30 e 15 ºC ocasionaram menor intensidade da doença. Períodos de molhamento foliar abaixo de 6 horas reduziram a intensidade da doença. Todas as cultivares testadas foram suscetíveis à doença, entretanto, a cultivar Conquista apresentou maior VASRI e VASRS da Ferrugem Asiática comparada às cultivares Savana e Suprema, as quais não diferiram estatisticamente. Houve diferença entre as cultivares para AACPI em cada temperatura e molhamento foliar.

Efeitos de sistemas de preparo do solo na cultura da soja (Glycine max (L.) Merrill)

Com o objetivo de avaliar o efeito de cinco equipamentos de preparo do solo sobre o desenvolvimento e a produtividade da cultura da soja (Glycine max L. (Merril)), foi conduzida uma pesquisa em Latossolo Vermelho distrófico, no município de Uberaba-MG, em delineamento experimental em blocos casualizados, com cinco tratamentos (escarificador, enxada-rotativa, arado de aivecas, arado de discos e grade aradora) e quatro repetições. Os sistemas de preparo do solo não mostraram diferenças para o número médio de dias para a emergência das plântulas, estande final, altura da primeira vagem e produtividade da cultura da soja. Os tratamentos com arado de disco, arado de aivecas e grade aradora proporcionaram as maiores populações iniciais da cultura. A altura das plantas foi afetada pelos sistemas de preparo utilizados, destacando-se o preparo com o arado de aivecas e com a enxada-rotativa, com os maiores e menores valores absolutos, respectivamente.

Mapeamento de semeaduras de soja (Glycine max (L.)Merr.) mediante dados MODIS/Terra E TM/Landsat 5: um comparativo

O objetivo deste trabalho foi comparar mapeamentos de semeadura da cultura da soja na região oeste do Paraná, realizados com imagens MODIS/Terra e TM/Landsat 5. Primeiramente, construiu-se máscara de referência, considerando seis imagens TM ao longo do ciclo da cultura, utilizando-se dos algoritmos Paralelepípedo e MaxVer com posterior análise visual. As imagens MODIS foram classificadas com o algorítimo Paralelepípedo, em quatro passagens referentes ao pico vegetativo. O desempenho das classificações foi avaliado por meio de Matrizes de Erros, calculadas pela análise de 100 pontos amostrais (soja ou não-soja), aleatoriamente distribuídos em cada um dos oito municípios da área de estudo. Os principais resultados mostraram que a Exatidão Global (EG) e o Índice Kappa (IK), que variaram entre 0,55 e 0,80, em ambos os sensores, são considerados bons a muito bons. Quando EG e IK dos sensores TM e MODIS foram comparados, não se encontrou diferença significativa. O mapeamento da soja utilizando o sensor MODIS produziu 70% de confiabilidade sob o ponto de vista do usuário. A principal conclusão é a viabilidade de mapear a soja pelo sensor MODIS com as vantagens de que as imagens MODIS têm melhor resolução temporal e são disponibilizadas gratuitamente na Internet.

Qualidade da aplicação aérea líquida com uma aeronave agrícola experimental na cultura da soja (Glycine Max L.)

Os avanços da tecnologia de aplicação aérea de agroquímicos têm-se dado na direção de redução do volume de calda, o que pode ocasionar má distribuição e consequente deposição irregular. O presente trabalho teve como objetivo avaliar a qualidade da aplicação de calda de pulverização em aplicação aérea, na cultura da soja (Glycine Max L.). Para a aplicação, foi utilizada uma aeronave agrícola experimental, aplicando um volume de calda de 20 L ha-1 . Para a determinação dos volumes depositados nas folhas do terço superior, médio e inferior das plantas de soja, foi utilizado corante alimentício azul brilhante adicionado à calda de pulverização. Estas folhas foram lavadas, e o volume determinado por espectrofotometria. Para a obtenção do espectro de gotas, foram utilizados alvos artificiais constituídos por papel hidrossensível, distribuídos no terço superior e médio das plantas. Os dados foram submetidos à análise de variância de fator único, considerando as diferentes posições na planta, e cartas de controle foram feitas a partir dos limites inferior e superior de controle. A aplicação aérea de calda de pulverização na cultura da soja apresentou menores valores de diâmetro da mediana volumétrica, amplitude relativa e cobertura no terço médio em relação ao terço superior da cultura da soja. Houve menor deposição da calda de pulverização no terço inferior. Os indicadores de cobertura da calda de pulverização demonstraram que a aplicação aérea com a aeronave agrícola experimental avaliada não se encontra sob controle estatístico de processo, ou seja, fora do padrão de qualidade.

Perfomance evaluation of a direct injection engine using different blends of soybean (Glycine max) methyl biodiesel

Diesel fuel is used widely in Brazil and worldwide. On the other hand, the growing environmental awareness leads to a greater demand for renewable energy resources. Thus, this study aimed to evaluate the use of different blends of soybean (Glycine max) methyl biodiesel and diesel in an ignition compression engine with direct injection fuel. The tests were performed on an electric eddy current dynamometer, using the blends B10, B50 and B100, with 10; 50 e 100% of biodiesel, respectively, in comparison to the commercial diesel B5, with 5% of biodiesel added to the fossil diesel. The engine performance was analyzed trough the tractor power take off (PTO) for each fuel, and the best results obtained for the power and the specific fuel consumption, respectively, were: B5 (44.62 kW; 234.87 g kW-1 h-1); B10 (44.73 kW; 233.78 g kW-1 h-1); B50 (44.11 kW; 250.40 g kW-1 h-1) e B100 (43.40 kW; 263.63 g kW-1 h-1). The best performance occurred with the use of B5 and B10 fuel, without significant differences between these blends. The B100 fuel showed significant differences compared to the other fuels.

Decomposition kinetics of gaseous ozone in peanuts

This study was conducted to evaluate the decomposition kinetics of gaseous ozone in peanut grains. This evaluation was made with 1-kg peanut samples, moisture contents being 7.1 and 10.5% wet basis (w.b.), placed in 3-liter glass containers. The peanut grains were ozonated at the concentration of 450 µg L-1, at 25 and 35 ºC, with gas flow rates of 1.0 and 3.0 L min-1. Time of saturation was determined by quantifying the residual concentration of ozone after the gas passed through the grains to constant mass. The decomposition kinetics of ozone was evaluated after the grain mass was ozone-saturated. For the peanut grains whose moisture content was 7.1% (w.b.), at 25 and 35ºC and with flow rates of 1.0 and 3.0 L min-1, the values obtained for time of saturation of gaseous ozone ranged between 173 and 192 min; the concentration of saturation was approximately 260 µg L-1. For the grains whose moisture content was 10.5% (w.b.), a higher residual concentration of gaseous ozone was obtained at 25 ºC, that of 190 µg L-1. As regards the half-life of ozone, the highest value obtained was equivalent to 7.7 min for grains ozonated at 25 ºC, while for those with moisture content of 10.5% at 35 ºC, half-life was 3.2 min. In the process of ozone decomposition in peanut grains, temperature was concluded to be the key factor. An increase of 10 ºC in the temperature of the grains results in a decrease of at least 43% in the half-life of ozone.

Material embodiment and energy flows as efficiency indicators of soybean (Glycine max) production in Brazil

As the requirement for agriculture to be environmentally suitable there is a necessity to adopt indicators and methodologies approaching sustainability. In Brazil, biodiesel addition into diesel is mandatory and soybean oil is its main source. The material embodiment determines the convergence of inputs into the crop. Moreover, the material flows are necessary for any environmental analysis. This study evaluated distinct production scenarios, and also conventional versus GMO crops, through the material embodiment and energy analysis. GMO crops demanded less indirectly applied inputs. The energy balance showed linearity with yield, whereas for EROI, the increases in input and yield were not affected.

KINETICS OF MASS LOSS OF ARABICA COFFEE DURING ROASTING PROCESS

ABSTRACT Roasting is one of the most complex coffee processing steps due to simultaneous transfers of heat and mass. During this process, beans lose mass because of fast physical and chemical changes that will set color and flavor of the commercial coffee beverage. Therefore, we aimed at assessing the kinetics of mass loss in commercially roasted coffee beans according to heating throughout the processing. For that, we used samples of 350-g Arabica coffee processed grains with water content of 0.1217 kga kg-1, in addition to a continuous roaster with firing gas. The roaster had initial temperatures of 285, 325, 345 and 380 °C, decreasing during the process up to 255, 285, 305 and 335 °C respectively. Mass loss was calculated by the difference between grain weight before and after roasting. We observed a linear variation directly dependent on roaster temperature. For each temperature during the process was obtained a constant mass loss rate, which was reported by the Arrhenius model with r2 above 0.98. In a roaster in non-isothermal conditions, the required activation energy to start the mass loss in a commercial coffee roasting index was 52.27 kJ mol -1.