Avaliação de laboratórios brasileiros na determinação de alguns parâmetros de qualidade de biocombustíveis

This work shows the results of a Proficiency Testing performed by a partnership between INMETRO and ANP. The performance of 49 Brazilian laboratories (using the z-score statistical test) in determining 10 quality parameters of ethanol fuel and biodiesel was evaluated. The certified reference values were provided by INMETRO, allowing a more rigorous assessment of the laboratories. For hydrous ethanol, the acidity parameter showed the lowest number of laboratories with satisfactory results (48%), while 85% of the laboratories presented satisfactory results for ethanol content. For biodiesel, the percentage of laboratories with satisfactory results ranged from 46% (kinematic viscosity) to 92% (acid number).

Síntesis química, estudios de caracterización y reactividad de un material catalítico a base de ZrO2-H3PW12O40

In this work, the preparation and characterization of materials such as zirconium oxide (ZrO2) and phosphotungstic acid promoted zirconium oxide (ZrO2-H3PW12O40) is presented. Physico-chemical characterization results showed that addition of H3PW12O40 acted as both a textural and chemical promoter of zirconium oxide. The incorporation of phosphotungstic acid into the ZrO2 matrix delayed the sintering of the material and stabilized ZrO2 in the tetragonal phase. ZrO2 acidity was also enhanced, developing strong acid sites on its surface. The Pt/ZrO2-H3PW12O40 catalyst was active for n-pentane isomerization at 250 °C, exhibiting high selectivity to iso-pentane (95%). This result is probably due to its suitable acidity.

Isomerization-cracking of n-octane on catalysts based on heteropolyacid H3Pw12O40 and heteropolyacid supported on zirconia and promoted with Pt and Cs

Isomerization - cracking of n-octane was studied using H3PW12O40 (HPA) and HPA supported on zirconia and promoted with Pt and Cs. The addition of Pt and Cs to the supported HPA did not modify the Keggin structure. The Pt addition to the supported HPA did not substantially modify the total acidity; however, the Brönsted acidity increased significantly. Cs increased the total acidity and Brönsted acidity. A linear relation was observed between the n-C8 total conversion and Brönsted acidity. The most adequate catalysts for performing isomerization and cracking to yield high research octane number (RON) are those with higher values of Brönsted acidity.

Caracterização potenciométrica de substâncias húmicas extraídas de solos da Antártica Marítima

Monitoring of soil carbon storage may indicate possible effects of climate change on the terrestrial environment and it is therefore necessary to understand the influence of redox potential and chemical characteristics of humic substances (HS) of Antarctic soil. Five soils from King George Island were used. HS were extracted, quantified and characterized by potentiometry and the content of total carbon and nitrogen determined. HS of these soils had greater aliphatic character, low content of phenolic groups, lower acidity and lower formal standard electrode potential, compared to HS of soils from other regions, suggesting they are more likely to be oxidized.

Redes metalorgânicas e suas aplicações em catálise

Metal-organic frameworks (MOFs) form a new class of materials with well-defined yet tunable properties. These are crystalline, highly porous and exhibit strong metal-ligand interactions. Importantly, their physical and chemical properties, including pore size, pore structure, acidity, and magnetic and optical characteristics, can be tailored by choosing the appropriate ligands and metal precursors. Here we review the key aspects of synthesis and characterization of MOFs, focusing on lanthanide-based and vanadium-based materials. We also outline some of their applications in catalysis and materials science.

Equilibrium studies of 2,2'-(5-bromo-6-methylpyrimidine-2,4-diyl)bis(azanediyl)dipropanoic acid with some transition-metal ions in aqueous solution

The stability constants of the 1:1 complexes formed between M2+ (M2+: Mn2+, Ni2+, Cu2+, or Cd2+) and BMADA2- (BMADA: 2,2'-(5-bromo-6-methylpyrimidine-2,4 diyl)bis(azanediyl)dipropanoic acid) were determined by potentiometric pH titration in aqueous solution (I = 0.1 mol L-1, NaNO3, 25 °C). The stability of the binary M - BMADA complexes is determined by the basicity of the carboxyl or amino groups. All the stability constants reported in this work exhibit the usual trend, and the order obtained was Mn2+< Ni2+ < Cu2+ > Cd2+. The observed stability order for BMADA approximately follows the Irving - Williams sequence. In the M - BMADA complexes, the M ion is able to form a macrochelate via the pyrimidine group of BMADA.

A direct potentiometric titration study of the dissociation of humic acid with selectively blocked functional groups

A direct potentiometric titration method was applied to commercial and soil humic acids in order to determine their carboxyl and phenol group concentrations and apparent and intrinsic pK. In that context, acid-base properties of humic acids are interpreted by selective blocking of carboxylic and phenolic groups by esterification and acetylation. Differences in underivatized and derivatized HA's acid-base properties are ascribed to carboxyl and phenol groups influence on total humic acidity. Potentiometric data were treated with the modified Henderson-Hasselbalch equation. Infra red results, the acidic group contents and the average values of apparent and intrinsic pK for underivatized and derivatized HAs confirmed the selectivity of esterification derivatization method. After blocking of the functional groups, the values of acidic group contents decreased, while the value of apparent pK increased after derivatization. Phenol groups cannot be specifically identified by the acetylation method, due to low selectivity of the acetylation method.

Determination of Alkalinity and dissociation constants of high salinity waters: use of F5BC titration function

Measurements of parameters expressed in terms of carbonic species such as Alkalinity and Acidity of saline waters do not analyze the influence of external parameters to the titration such as Total free and associated Carbonic Species Concentration, activity coefficient, ion pairing formation and Residual Liquid Junction Potential in pH measurements. This paper shows the development of F5BC titration function based on the titrations developed by Gran (1952) for the carbonate system of natural waters. For practical use, samples of saline waters from Pocinhos reservoir in Paraiba were submitted to titration and linear regression analysis. Results showed that F5BC involves F1x and F2x Gran functions determination, respectively, for Alkalinity and Acidity calculations without knowing "a priori" the endpoint of the titration. F5BC also allows the determination of the First and Second Apparent Dissociation Constant of the carbonate system of saline and high ionic strength waters.

Chitosan and fungicides on postharvest control of Guignardia citricarpa and on quality of 'Pêra Rio' oranges

Citrus fruits are affected by the black spot disease caused by the fungus Guignardia citricarpa. Chitosan can be used as covering for fruits and may delay the ripening process and inhibit the growth of some fungi. Thus, the control of citrus black spot using chitosan and the fungicides thiabendazole and imazalil was assessed in addition to the physicochemical quality of 'Pêra Rio' oranges. The oranges were immersed into chitosan, thiabendazole or imazalil, and in chitosan mixed with both fungicides. The fruits were then stored at 25 °C, 80% RH, for 7 days and, after this storage period, subjected to physicochemical analyses. Chitosan in association with the fungicides reduced black spot in 'Pêra Rio' oranges and delayed the change in the orange skin colour from green to yellow during the postharvest storage. Total soluble solids, titratable acidity, pH, ascorbic acid content and ratio were not influenced by the treatments. Thus, chitosan applied with the fungicides thiabendazole and imazalil showed potential to control the development of black spot lesions on 'Pêra Rio' oranges during the postharvest period.

Distribution of tree species in a geomorphological and pedological gradient of submontane semidecidual seasonal forest in the vicinity of Rio Doce state park, Minas Gerais

The objective of this study was to test the hypothesis that the distribution of tree species in a fragment of submontane seasonal semideciduous forest, a buffer zone in the Parque Estadual do Rio Doce, Minas Gerais, is influenced by geomorphological and weather and soil variables, therefore it can represent a source of information for the restoration of degraded areas where environmental conditions are similar to those of the study area. A detailed soil survey was conducted in the area by sampling three soil profiles per slope segment, totaling 12 profiles. To sample the topsoil, four composite samples were collected from the 10-20 cm layers in each topographic range totaling 16 composite samples. In the low ramp and the lower and upper concave slopes, the texture ranged from clay to sandy-clay. The soil and topographic gradient was characterized by changes in the soil physical-chemical properties. The soil in the 10-20 cm sampled layer was sandier, slightly more fertile and less acid in the low ramp than the clayer soil, nutrient-poor and highly acid soil at the top. The soil conditions in the lower and upper slope of the sampled layers, in turn, were intermediate. The P levels were limiting in all soils. The species distribution along the topographic gradient was associated with variations in chemical fertility, acidity and soil texture. The distribution of Pera leandri, Astronium fraxinifolium, Pouteria torta, Machaerium brasiliense and Myrcia rufipes was correlated with high aluminum levels and to low soil fertility and these species may be indicated for restoration of degraded areas on hillsides and hilltops in regions where environmental conditions are similar. The distribution of Pouteria venosa, Apuleia leiocarpa and Acacia polyphylla was correlated with the less acid and more fertile soil in the environment of the low ramps, indicating the potential for the restoration of similar areas.

Performance during post-harvest storage of banana cv. 'prata', 'maçã' and 'nanica' exposed to physical and chemical treatments

Banana is the most consumed fruit in the world and Brazil is the second largest producer. Despite its global position, Brazil has an average of 40% losses during the post-harvest period. So, this experiment aimed at evaluating the efficiency of post-harvest treatments to improve the storage of banana cultivars cv. 'Prata', 'Maçã' and 'Nanica'. The fruits were acquired at CEASA with green peel, and were submitted to six different treatments: T- immersion in drinking water for 3 minutes (control), H3 - hot water (50 °C for 3 minutes), H8 - hot water (50 °C for 8 minutes), HP - immersion in hypochlorite 0.2% for 3 minutes, OS - immersion in soybean oil 10% for 3 minutes, and OM - immersion in mineral oil 10% for 3 minutes. The fruits were stored at room temperature at about 21 °C for 14 days and evaluated in three periods (1, 7 and 14 days) comparing peel color, flesh/peel ratio, titratable acidity (TA), soluble solids (SS), SS/TA ratio, and pH. The fruits of cv. 'Prata' and 'Maçã' submitted to the treatments H3, H8 and HP ripened at the same time as the control for peel color, which showed increased soluble solids, flesh/peel ratio, acidity and a decrease in pH. On the other hand, the cv. 'Nanica' did not respond significantly different when compared to the applied treatments and the control. The fruits treated with OM and OS were kept green for a longer time for the cultivars 'Prata' and 'Nanica', but there were some changes on peel color due dark spots in 'Prata' banana and a softening aspect in 'Nanica', indicating some level of toxicity of these treatments. Fruits of the 'Maçã' cultivar continued green with the application of mineral oil, without toxicity symptoms. In conclusion, the treatments applied did not show any advantage for storage of these fruits.

Rheological behavior of mixed drink of annona and milk

In this study the rheological behavior in different temperatures (0; 6; 18 e 24 ºC) and physicochemical parameters of integral annona (Annona squamosa) pulp and the annona pulp with milk in different percentages pulp/milk (75g of annona pulp/25g of milk, 50g of annona pulp/50g of milk, 25g of annona pulp/75g of milk) have been availed, in order to verify the effect of temperature and pulp concentration in the rheological behavior of these beverages. To obtain the rheological parameters a concentric cylinder rheometer has been used and the rheograms were analyzed using the Ostwald-de-Wael (power Law) and Herschel-Bulkley models. The physicochemical parameters (sugars, pH, ash, acidity and soluble solids) were determined in order to establish correlations with the rheological behavior. Finally, the best results had been obtained using the Herschel-Bulkley model; the low values for the behavior index (n <1) obtained confirm the pseudoplastic behavior of all samples.

Anaerobic reactors with biofilter and different diameter-length ratios in cassava starch industry wastewater treatment

The use of anaerobic reactors with media support in the treatment of wastewater from the cassava starch industry has emerged as a viable option because it allows the application of high organic loads and a significant reduction of the HDT needed for the treatment. This research aimed at studying the process of biodigestion in two anaerobic reactors with bamboo support, in the treatment of effluent of cassava starch, by evaluating their performance. The two reactors used present the following diameter: length ratio, 1:6 and 1:3. The organic loads applied to the systems were 0.519, 1.156, 1.471, 3.049, 4.347, 4.708 and 5.601g.L-1.d-1. Regarding the efficiency of removal of COD, TS and TVS, no statistically significant differences were obtained between the reactors. The two systems evaluated showed a stable behavior with respect to the VA/TA (volatile acidity/total alkalinity) for all submitted loads. The reactors tended to the maintenance of biogas production as a function of consumed COD for the last three organic loads applied, indicating an ability to withstand higher organic loads.

Quality of papaya hybrid grown under different irrigation depths

Irrigation is a practice widely used in fruit production in the Brazilian Northeast region, including in the papaya crop in order to increase their productivity. For the purpose of knowing the productive potential of papaya hybrid irrigated, an experiment was carried out in order to evaluate the performance of a papaya hybrid under different irrigations depths. Four irrigation depths (50, 75, 100 and 125% of ETo) were tested and the reference evapotranspiration was calculated by the Penman-Monteith model. The hybrid papaya used was UENF/Caliman 01, which was planted in single rows, spaced 4 x 2m from each other, and irrigated by dripping. The experimental design in randomized blocks was used with six replications and three plants per plot. The following variables were evaluated: transversal diameter, longitudinal diameter, pulp thickness, external and internal appearances, soluble solids, titratable acidity, pulp pH and soluble solids/titratable acidity relation. The higher transversal and longitudinal diameters of the fruit were obtained applying an irrigation depth of about 108% of evapotranspiration. The UENF/Caliman 01 hybrid can be cultivated in the semiarid region of the State of Paraiba, Brazil, with replacement rate of 100% ETo, without compromising the quality of the fruits.

Adaptation of "Niagara Rosada" grape must to winemaking by partial cluster dehydration

This study aimed to verify the influence of partial dehydration of "Niagara Rosada" grape clusters in physicochemical quality of the pre- fermentation must. In Brazil, during the winemaking process it is common to need to adjust the grape must when the physicochemical characteristics of the raw material are insufficient to produce wines in accordance with the Brazilian legislation for classification of beverages, which establishes the minimum alcohol content of 8.6 % for the beverage to be considered wine. Therefore, given that the reduction in the water content of grape berries allows the concentration of chemical compounds present in its composition, especially the concentration of total soluble solids, we proceeded with the treatments that were formed by the combination of two temperatures (T1-37.1ºC and T2-22.9 ºC) two air speeds (S1: 1.79 m s-1 and S2: 3.21 m s-1) and a control (T0) that has not gone through the dehydration treatment. Analysis of pH, Total Titratable Acidity (TTA) were performed in mEq L-1, Total Soluble Solids (TSS) in ºBrix, water content on a dry basis and Concentration of Phenolic Compounds (CPC) in mg of gallic acid per 100g of must. The average comparison test identified statistically significant modifications for the adaptation of must for winemaking purposes, having the treatment with 22.9 ºC and air speed of 1.79 m s-1 shown the largest increase in the concentration of total soluble solids, followed by the second best result for concentration of phenolic compounds.