Hydrolysis of acetic anhydride: Non-adiabatic calorimetric determination of kinetics and heat exchange

A simple calorimetric method to estimate both kinetics and heat transfer coefficients using temperature-versus-time data under non-adiabatic conditions is described for the reaction of hydrolysis of acetic anhydride. The methodology is applied to three simple laboratory-scale reactors in a very simple experimental setup that can be easily implemented. The quality of the experimental results was verified by comparing them with literature values and with predicted values obtained by energy balance. The comparison shows that the experimental kinetic parameters do not agree exactly with those reported in the literature, but provide a good agreement between predicted and experimental data of temperature and conversion. The differences observed between the activation energy obtained and the values reported in the literature can be ascribed to differences in anhydride-to-water ratios (anhydride concentrations). (C) 2010 Elsevier Ltd. All rights reserved.

Toluene and naphthalene sorption by iron oxide/clay composites

Commercial bentonite (BFN) and organoclay (WS35), as well as iron oxide/clay composite (Mag_BFN) and iron/oxide organoclay composite (Mag_S35) were prepared for toluene and naphthalene sorption. Mag_BFN and Mag_S35 were obtained, respectively, by the precipitation of iron oxide hydrates onto sodium BFN and S35 clay particles. The materials were characterized by powder X-ray diffraction (XRD), X-ray Fluorescence (XRF), and TG and DTA. From XRF results and TG data on calcined mass basis, a quantitative method was developed to estimate the iron compound contents of the composites, as well as the organic matter content present in WS35 and Mag_S35.

Investigation of Cationic Polymerization of beta-Pinene Using Calorimetric Measurements

An experimental investigation of the kinetics of cationic polymerization of beta-pinene was performed using two different initiator systems under two different operating conditions (shot additions of initiator, and continuous feeding of monomer). The experiments were done using calorimetric measurements under isoperibolic conditions. The heat of polymerization of beta-pinene was found to be -30.6 kcal . mol(-1). A simple kinetic model was tentatively proposed, and the model fit reasonably well to the different experimental runs. Different values of the fitting parameters were obtained for runs carried out under different conditions, which can probably be ascribed to the presence of adventitious impurities in the commercial-grade monomer used.

Synthesis and characterization of semiconductor polymers having different phenylene-vinylene conjugation lengths

We have synthesized phenylene-vinylene (PV) polymers containing segments with different conjugation lengths interspaced by random distributed aliphatic segments. Infrared (IR) and ultraviolet-visible (UV-vis) spectroscopies, hydrogen nuclear magnetic resonance ((1)H NMR) spectrometry and differential scanning calorimetry (DSC) were used to characterize the prepared copolymers` structures. Polymers molecular weights were determined by gel permeation chromatography (GPC). The effect of polymer structure and composition on emission properties was studied by fluorescence (PL) spectroscopy under different irradiation wavelength. The emission energy shift due to segments with longer conjugation lengths was minor owed to the low polymerization degree achieved.

Lightning-Induced Voltages on Overhead Lines-Application of the Extended Rusck Model

Lightning-induced overvoltages have a considerable impact on the power quality of overhead distribution and telecommunications systems, and various models have been developed for the computation of the electromagnetic transients caused by indirect strokes. The most adequate has been shown to be the one proposed by Agrawal et al.; the Rusck model can be visualized as a particular case, as both models are equivalent when the lightning channel is perpendicular to the ground plane. In this paper, an extension of the Rusck model that enables the calculation of lightning-induced transients considering flashes to nearby elevated structures and realistic line configurations is tested against data obtained from both natural lightning and scale model experiments. The latter, performed under controlled conditions, can be used also to verify the validity of other coupling models and relevant codes. The so-called Extended Rusck Model, which is shown to be sufficiently accurate, is applied to the analysis of lightning-induced voltages on lines with a shield wire and/or surge arresters. The investigation conducted indicates that the ratio between the peak values of the voltages induced by typical first and subsequent strokes can be either greater or smaller than the unity, depending on the line configuration.

Sensory Stability of Ultra-High Temperature Milk in Polyethylene Bottle

The objective of this study was to evaluate the sensory stability of ultra-high temperature (UHT) milk subjected to different heat treatments and stored at room temperature in white high density polyethylene bottles (HDPE) pigmented with titanium dioxide. Two lots of 300 units each were processed, respectively, at 135 and 141 degrees C/10 s using indirect heating and subsequently aseptically filled in an ISO class 7 clean room. These experimental lots were evaluated for appearance, aroma, flavor, and overall appreciation and compared to samples of commercial UHT milk purchased from local commercial stores. The time-temperature combinations investigated did not affect either the acceptability or the shelf life of the milk. Despite the limited light barrier properties of HDPE bottles, the product contained in the package tested exhibited good stability, with a shelf life ranging from 4 to 11 wk. Within this time period, the acceptability of the experimental lots was similar to that of the commercial products. The results achieved in this study contribute to turn the low-cost UHT system investigated into a technically viable option for small-size dairy processing plants.

Drying and autogenous shrinkage of pastes and mortars with activated slag cement

Activated slag cement (ASC) shows significantly higher shrinkage than ordinary Portland cement agglomerates. Cracking generated by shrinkage is one of the most critical drawbacks for broader applications of this promising alternative binder. This article investigates the relationship between ASC hydration, unrestrained drying and autogenous shrinkage of mortar specimens. The chemical and microstructure evolution due to hydration were determined on pastes by thermogravimetric analysis, conduction calorimetry and mercury porosimetry. Samples were prepared with ground blast furnace slag (BFS) activated with sodium silicate (silica modulus of 1.7) with 2.5, 3.5 and 4.5% of Na2O, by slag mass. The amount of activator is the primary influence on drying and autogenous shrinkage, and early hydration makes a considerable contribution to the total result, which increases with the amount of silica. Drying shrinkage occurred in two stages, the first caused by extensive water loss when the samples were exposed to the environment, and the second was associated with the hydration process and less water loss. Due to the refinement of ASC porous system, autogenous shrinkage is responsible for a significant amount of the total shrinkage. (C) 2007 Elsevier Ltd. All rights reserved.

A hybrid commodity price-forecasting model applied to the sugar-alcohol sector

Accurate price forecasting for agricultural commodities can have significant decision-making implications for suppliers, especially those of biofuels, where the agriculture and energy sectors intersect. Environmental pressures and high oil prices affect demand for biofuels and have reignited the discussion about effects on food prices. Suppliers in the sugar-alcohol sector need to decide the ideal proportion of ethanol and sugar to optimise their financial strategy. Prices can be affected by exogenous factors, such as exchange rates and interest rates, as well as non-observable variables like the convenience yield, which is related to supply shortages. The literature generally uses two approaches: artificial neural networks (ANNs), which are recognised as being in the forefront of exogenous-variable analysis, and stochastic models such as the Kalman filter, which is able to account for non-observable variables. This article proposes a hybrid model for forecasting the prices of agricultural commodities that is built upon both approaches and is applied to forecast the price of sugar. The Kalman filter considers the structure of the stochastic process that describes the evolution of prices. Neural networks allow variables that can impact asset prices in an indirect, nonlinear way, what cannot be incorporated easily into traditional econometric models.

Comparative physical-chemical characterization of encapsulated lipid-based isotretinoin products assessed by particle size distribution and thermal behavior analyses

Isotretinoin is the drug of choice for the management of severe recalcitrant nodular acne. Nevertheless, some of its physical-chemical properties are still poorly known. Hence, the aim of our study consisted to comparatively evaluate the particle size distribution (PSD) and characterize the thermal behavior of the three encapsulated isotretinoin products in oil suspension (one reference and two generics) commercialized in Brazil. Here, we show that the PSD, estimated by laser diffraction and by polarized light microscopy, differed between the generics and the reference product. However, the thermal behavior of the three products, determined by thermogravimetry (TGA), differential thermal (DTA) analyses and differential scanning calorimetry (DSC), displayed no significant changes and were more thermostable than the isotretinoin standard used as internal control. Thus, our study suggests that PSD analyses in isotretinoin lipid-based formulations should be routinely performed in order to improve their quality and bioavailability. (C) 2010 Elsevier B.V. All rights reserved.

CALCINED SLUDGE SINTERING EVALUATION BY HEATING MICROSCOPY THERMAL ANALYSIS

Aiming the use of the sewage sludge produced in one of the largest Brazilian wastewater treatment stations as a raw material for the ceramic industry, the sintering process of the ashes produced from its calcination was evaluated by heating microscopy thermal analysis (HMTA). From the microprocessed images, a method was developed to obtain HMTA dimensional change curves as a function of temperature, equivalent to those usually obtained from dilatometers or by thermomechanical analysis (TMA). The final product after sintering at 1050 degrees C, characterized by X-ray fluorescence spectrometry, scanning electron microscopy and X-ray dispersive energy, indicates the presence of a vitreous phase containing phosphorus, which explains the good sintering properties of the studied calcined sludge, as shown from its HMTA dimensional change curve.

Contribution of soil organic carbon to the ion exchange capacity of tropical soils

Highly weathered soils represent about 3 billion ha of the tropical region. Oxisols represent about 60% of the Brazilian territory (more than 5 million km 2), in areas of great agricultural importance. Soil organic carbon (SOC) can be responsible for more than 80% of the cation exchange capacity (CEC) of highly weathered soils, such as Oxisols and Ultisols. The objective of this study was to estimate the contribution of the SOC to the CEC of Brazilian soils from different orders. Surface samples (0.0 to 0.2 m) of 30 uncultivated soils (13 Oxisols, 6 Ultisols, 5 Alfisols, 3 Entisols, I Histosol, 1 Inceptisol. and I Molisol), under native forests and from reforestation sites from Sao Paulo State, Brazil, were collected in order to obtain a large variation of (electro)chemical, physical, and mineralogical soil attributes. Total content of SOC was quantified by titulometric and colorimetric methods. Effective cation exchange capacity (ECEC) was obtained by two methods: the indirect method-summation-estimated the ECECi from the sum of basic cations (Ca+ Mg+ K+ Na) and exchangeable Al; and the direct ECECd obtained by the compulsive exchange method, using unbuffered BaCl2 solution. The contribution of SOC to the soil CEC was estimated by the Bennema statistical method. The amount of SOC var ied from 6.6 g kg(-1) to 213.4 g kg(-1). while clay contents varied from 40 g kg(-1) to 716 g kg(-1). Soil organic carbon contents were strongly associated to the clay contents, suggesting that clay content was the primary variable in controling the variability of SOC contents in the samples. Cation exchange capacity varied from 7.0 mmol(c) kg(-1) to 137.8 mmol(c) kg(-1) and had a positive Correlation with SOC. The mean contribution (per grain) of the SOC (1.64 mmol(c)) for the soil CEC was more than 44 times higher than the contribution of the clay fraction (0.04 mmol(c),). A regression model that considered the SOC content as the only significant variable explained 60% of the variation in the soil total CEC. The importance of SOC was related to soil pedogenetic process, since its contribution to the soil CEC was more evident in Oxisols with predominance of Fe and Al (oxihydr)oxides in the mineral fraction or in Ultisols, that presented illuviated clay. The influence of SOC in the sign and in the magnitude of the net charge of soils reinforce the importance of agricultural management systems that preserve high levels of SOC, in order to improve their sustainability.

Environmental, land-use and economic implications of Brazilian sugarcane expansion 1996-2006

Governments are promoting biofuels and the resulting changes in land use and crop reallocation to biofuels production have raised concerns about impacts on environment and food security. The promotion of biofuels has also been questioned based on suggested marginal contribution to greenhouse gas emissions reduction, partly due to induced land use change causing greenhouse gas emissions. This study reports how the expansion of sugarcane in Brazil during 1996-2006 affected indicators for environment, land use and economy. The results indicate that sugarcane expansion did not in general contribute to direct deforestation in the traditional agricultural region where most of the expansion took place. The amount of forests on farmland in this area is below the minimum stated in law and the situation did not change over the studied period. Sugarcane expansion resulted in a significant reduction of pastures and cattle heads and higher economic growth than in neighboring areas. It could not be established to what extent the discontinuation of cattle production induced expansion of pastures in other areas, possibly leading to indirect deforestation. However, the results indicate that a possible migration of the cattle production reached further than the neighboring of expansion regions. Occurring at much smaller rates, expansion of sugarcane in regions such as the Amazon and the Northeast region was related to direct deforestation and competition with food crops, and appear not to have induced economic growth. These regions are not expected to experience substantial increases of sugarcane in the near future, but mitigating measures are warranted.

Thermal analysis of vitamin PP Niacin and niacinamide

Vitamin PP includes two vitamers, niacin and niacinamide which are essential for energy production. Vitamins are sensitive and losses can occur during shelf life and heating processes. Thermal analysis can provide information about thermal behavior of each vitamer relating them with time and/or temperature exposure. The vitamers thermal behavior were studied by TG/DTG and DSC under air and nitrogen atmosphere and the results showed that niacin is more stable than the niacinamide and the decomposition happens by volatilization at 238 A degrees C while niacinamide melts at 129 A degrees C and volatilize at 254 A degrees C when there is the total mass loss in the TG/DTG curves.

Thermal properties and resistant starch content of green banana flour (Musa cavendishii) produced at different drying conditions

The objective of this research was to verify the effect of drying conditions on thermal properties and resistant starch content of green banana flour (Musa cavendishii). The green banana flour is a complex-carbohydrates source, mainly of resistant starch, and quantifying its gelatinization is important to understand how it affects food processing and the functional properties of the flour. The green banana flour was obtained by drying unripe peeled bananas (first stage of ripening) in a dryer tunnel at 52 degrees C, 55 degrees C and 58 degrees C and air velocity at 0.6 m s(-1), 1.0 m s(-1) and 1.4 m s(-1). The results obtained from differential scanning calorimetry, (DSC) curves show a single endothermic transition and a flow of maximum heating at peak temperatures from (67.95 +/- 0.31)degrees C to (68.63 +/- 0.28) degrees C. ANOVA shows that only drying temperature influenced significantly (P < 0.05) the gelatinization peak temperature (Tp). Gelatinization enthalpy (Delta H) varied from 9.04 J g(-1) to 11.63 J g(-1) and no significant difference was observed for either temperature or air velocity. The resistant starch content of the flour produced varied from (40.9 +/- 0.4) g/100 g to (58.5 +/- 5.4) g/100 g, on dry basis (d. b.), and was influenced by the combination of drying conditions: flour produced at 55 degrees C/1.4 m s(-1) and 55 degrees C/1.0 m s(-1) presented higher content of resistant starch. (c) 2009 Elsevier Ltd. All rights reserved

Obtention and Evaluation of Inclusion Complexes of Furosemide with beta-ciclodextrin and hidroxipropil-beta-ciclodextrin: Effects on Drug`s Dissolution Properties

Obtention and Evaluation of Inclusion Complexes of Furosemide with beta-ciclodextrin and hidroxipropil-beta-ciclodextrin: Effects on Drug`s Dissolution Properties. The purpose of this study was to prepare, characterize and evaluate the dissolution behavior of inclusion complexes of furosemide with beta-cyclodextrin (beta-CD) and hydroxypropyl-beta-cyclodextrin (HP-beta-CD). Solid complexes of furosemide with P-CD and-HP-beta-CD were prepared by using a freeze-drying method. Physical mixtures were prepared for comparison. The inclusion complexes were characterized by differential scanning calorimetry (DSC), Infrared (IR) and dissolution test. ""In vitro"" dissolutions assays were performed at pH 1,2; pH 4,5 and pH 6,8 media for a 60 min period. Statistical analysis employing ANOVA and Tukey`s Test, for the dissolution efficiency values (ED%), showed that complexation of furosemide with both cyclodextrins improved significantly ED% of the drug in all tested media, suggesting a minor pH influence on dissolution properties of the drug.