Preparation and thermal decomposition of solid state cinnamates of alkali earth metals, except beryllium and radium

Solid state compounds of general formula ML2.nH2O [where M is Mg, Ca, Sr or Ba; L is cinnamate (C6H5 -CH=CH-COO-) and n = 2, 4, 0.8, 3 respectively], have been synthetized. Thermogravimetry (TG), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC) and X-ray diffraction powder patterns have been used to characterize and to study the thermal stability and thermal decomposition of these compounds.

Thermal behavior studies of solid state compounds of 4-dimethylaminocinnamylidenepyruvate with alkali earth metals, except beryllium and radium

Solid state compounds of general formula M(DMCP)2.nH2O, where M represents Mg, Ca, Sr, Ba, and DMCP is 4-dimethylaminocinnamylidenepyruvate, and n = 1, except for Ca, where n = 2.5, have been prepared. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC), X-ray diffraction powder patterns and complexometry were used to characterize and to study the thermal decomposition of these compounds.

Electrochemical and physical characterization of Ni-Cu-Fe alloy for chlor-alkali hydrogen cathodes

This work describes the development of an alternative acetate bath for the electrochemical codeposition of Ni-Cu-Fe electrodes at low pH that is stable for several weeks and produces electrodes with good performance for chlor-alkali electrolysis. Physical characterization of the electrode surface was made using X ray absorption spectroscopy (XAS), scanning electron microscopy (SEM) and energy dispersive analysis (EDX). The evaluation of the material as electrocatalyst for the hydrogen evolution reaction (her) was carried out in brine solution (160 g L-1 NaCl + 150 g L-1 NaOH) at different temperatures through steady-state polarization curves. The Ni-Cu-Fe electrodes obtained with this bath have shown low overpotentials for the her, around 0.150 V at 353 K, and good stability under continuous long-term operation for 260 hours. One positive aspect of this cathode is that the polarization behavior of the material shows only one Tafel slope over the temperature range of 298 - 353 K.

Dose-dependent in vitro inhibition of rabbit corneal matrix metalloproteinases by an extract of Pothomorphe umbellata after alkali injury

The in vitro ability of Pothomorphe umbellata ethanolic crude extract to inhibit matrix metalloproteinase (MMP) in normal cornea and in cornea after alkali injury was demonstrated. Corneas of albino rabbits were injured with 1 N NaOH for 20 s. After 48 h the corneas were excised, homogenized and analyzed for MMP-9 (92 kDa), pro-MMP-2 (72 kDa) and MMP-2 (67 kDa) activity by gelatin zymography. The activity was also measured in untreated corneas. After electrophoresis of 20 µg protein, gels were incubated with 50, 100, or 250 µg/mL lyophilized hydroethanolic (1:1) root crude extract of P. umbellata standardized for 4-nerolidylcatechol (7.09%). The activity of the enzymes was compared with that of untreated gel. At 48 h after injury, the activity of all MMPs was increased compared with untreated eyes. When the gels were incubated with P. umbellata extract the activity of MMP-2, pro-MMP-2 and MMP-9 decreased in a dose-dependent manner. MMP-9 activity decreased by approximately 50% after incubation with 50 µg/mL and was completely abolished at 100 and 250 µg/mL of the extract. After incubation with 50 µg/mL the activity of pro-MMP-2 and MMP-2 also decreased by 50%. The activity of pro-MMP-2 was almost completely abolished after incubation with 250 µg/mL of the extract. For MMP-2 the incubation with 100 or 250 µg/mL of the extract of P. umbellata promoted a 10-fold decrease in activity. In conclusion, P. umbellata root crude extract can be useful as an alternative therapy to control MMP activity after corneal injury.

Carbon dioxide efflux in a rhodic hapludox as affected by tillage systems in southern Brazil

Agricultural soils can act as a source or sink of atmospheric C, according to the soil management. This long-term experiment (22 years) was evaluated during 30 days in autumn, to quantify the effect of tillage systems (conventional tillage-CT and no-till-NT) on the soil CO2-C flux in a Rhodic Hapludox in Rio Grande do Sul State, Southern Brazil. A closed-dynamic system (Flux Chamber 6400-09, Licor) and a static system (alkali absorption) were used to measure soil CO2-C flux immediately after soybean harvest. Soil temperature and soil moisture were measured simultaneously with CO2-C flux, by Licor-6400 soil temperature probe and manual TDR, respectively. During the entire month, a CO2-C emission of less than 30 % of the C input through soybean crop residues was estimated. In the mean of a 30 day period, the CO2-C flux in NT soil was similar to CT, independent of the chamber type used for measurements. Differences in tillage systems with dynamic chamber were verified only in short term (daily evaluation), where NT had higher CO2-C flux than CT at the beginning of the evaluation period and lower flux at the end. The dynamic chamber was more efficient than the static chamber in capturing variations in CO2-C flux as a function of abiotic factors. In this chamber, the soil temperature and the water-filled pore space (WFPS), in the NT soil, explained 83 and 62 % of CO2-C flux, respectively. The Q10 factor, which evaluates CO2-C flux dependence on soil temperature, was estimated as 3.93, suggesting a high sensitivity of the biological activity to changes in soil temperature during fall season. The CO2-C flux measured in a closed dynamic chamber was correlated with the static alkali adsorption chamber only in the NT system, although the values were underestimated in comparison to the other, particularly in the case of high flux values. At low soil temperature and WFPS conditions, soil tillage caused a limited increase in soil CO2-C flux.

An improved method for measuring soil microbial activity by gas phase flow injection analysis

The rate of carbon dioxide production is commonly used as a measure of microbial activity in the soil. The traditional method of CO2 determination involves trapping CO2 in an alkali solution and then determining CO2 concentration indirectly by titration of the remaining alkali in the solution. This method is still commonly employed in laboratories throughout the world due to its relative simplicity and the fact that it does not require expensive, specific equipment. However, there are several drawbacks: the method is time-consuming, requires large amounts of chemicals and the consistency of results depends on the operator's skills. With this in mind, an improved method was developed to analyze CO2 captured in alkali traps, which is cheap and relatively simple, with a substantially shorter sample handling time and reproducibility equivalent to the traditional titration method. A comparison of the concentration values determined by gas phase flow injection analysis (GPFIA) and titration showed no significant difference (p > 0.05), but GPFIA has the advantage that only a tenth of the sample volume of the titration method is required. The GPFIA system does not require the purchase of new, costly equipment but the device was constructed from items commonly found in laboratories, with suggestions for alternative configurations for other detection units. Furthermore, GPFIA for CO2 analysis can be equally applied to samples obtained from either the headspace of microcosms or from a sampling chamber that allows CO2 to be released from alkali trapping solutions. The optimised GPFIA method was applied to analyse CO2 released from degrading hydrocarbons from a site contaminated by diesel spillage.

Soil CO2 flux: a method comparison of closed static chambers in a sugarcane field

A large variety of techniques have been used to measure soil CO2 released from the soil surface, and much of the variability observed between locations must be attributed to the different methods used by the investigators. Therefore, a minimum protocol of measurement procedures should be established. The objectives of this study were (a) to compare different absorption areas, concentrations and volumes of the alkali trapping solution used in closed static chambers (CSC), and (b) to compare both, the optimized alkali trapping solution and the soda-lime trapping using CSC to measure soil respiration in sugarcane areas. Three CO2 absorption areas were evaluated (7; 15 and 20 % of the soil emission area or chamber); two volumes of NaOH (40 and 80 mL) at three concentrations (0.1, 0.25 and 0.5 mol L-1). Three different types of alkaline traps were tested: (a), 80 mL of 0.5 mol L-1 NaOH in glass containers, absorption area 15 % (V0.5); (b) 40 mL of 2 mol L-1 NaOH retained in a sponge, absorption area 80 % (S2) and (c) 40 g soda lime, absorption area 15 % (SL). NaOH concentrations of 0.5 mol L-1 or lower underestimated the soil CO2-C flux or CO2 flux. The lower limit of the alkali trap absorption area should be a minimum of 20 % of the area covered by the chamber. The 2 mol L-1 NaOH solution trap (S2) was the most efficient (highest accuracy and highest CO2 fluxes) in measuring soil respiration.

CHARACTERIZATION OF BULK SOIL HUMIN AND ITS ALKALINE-SOLUBLE AND ALKALINE-INSOLUBLE FRACTIONS

Humic substances are the major components of soil organic matter. Among the three humic substance components (humic acid, fulvic acid, and humin), humin is the most insoluble in aqueous solution at any pH value and, in turn, the least understood. Humin has poor solubility mainly because it is tightly bonded to inorganic soil colloids. By breaking the linkage between humin and inorganic soil colloids using inorganic or organic solvents, bulk humin can be partially soluble in alkali, enabling a better understanding of the structure and properties of humin. However, the structural relationship between bulk humin and its alkaline-soluble (AS) and alkaline-insoluble (AIS) fractions is still unknown. In this study, we isolated bulk humin from two soils of Northeast China by exhaustive extraction (25 to 28 times) with 0.1 mol L-1 NaOH + 0.1 mol L-1 Na4P2O7, followed by the traditional treatment with 10 % HF-HCl. The isolated bulk humin was then fractionated into AS-humin and AIS-humin by exhaustive extraction (12 to 15 times) with 0.1 mol L-1 NaOH. Elemental analysis and solid-state 13C cross-polarization magic angle spinning nuclear magnetic resonance (13C CPMAS NMR) spectroscopy were used to characterize and compare the chemical structures of bulk humin and its corresponding fractions. The results showed that, regardless of soil types, bulk humin was the most aliphatic and most hydrophobic, AS-humin was the least aliphatic, and AIS-humin was the least alkylated among the three humic components. The results showed that bulk humin and its corresponding AS-humin and AIS-humin fractions are structurally differed from one another, implying that the functions of these humic components in the soil environment differed.

Contaminação por mercúrio no Brasil: fontes industriais vs garimpo de ouro

This paper reviews the history of Hg contamination in Brazil by characterizing and quantifying two major sources of Hg emissions to the environment: industrial sources and gold mining. Industry was responsible for nearly 100% of total Hg emissions from the late 1940's to the early 1970's, when efficient control policies were enforced, leading to a decrease in emissions. Gold mining, on the other hand was nearly insignificant as a Hg source up to the late 1970's, but presently is responsible for over 80% of total emissions. Presently, over 115 tons of Hg are released into the atmosphere in Brazil annually. Nearly 78 tons come from gold mining operations, 12 tons come from chlor-alkali industry and 25 tons come from all other industrial uses. Inputs to soils and waters however, are still unknown, due to lack of detailed data base. However, emissions from diffuse sources rather than well studied classical industrial sources are probably responsible for the major inputs of mercury to these compartments.

Estimativa da entalpia de decomposição (deltaD Hmº) de adutos por termogravimetria

An empirical equation: deltaD HmO = t i/2.2(2-n) is obtained and tested for 102 adducts (mainly adducts with zinc group halides). In the equation, t i is the Kelvin temperature of the beginning of the thermal decomposition of the adduct, (obtained by thermogravimetry), and n is the number of ligands. For 1/3 of the tested adducts the difference between experimental and calculated values was less than 5%. For about 1/3 of the adducts that difference exceeds 15%.

Estimativa da entalpia reticular de adutos (DM Hm o ) utilizando-se formas modificadas da equação de Kapustinskii

In this work are presented two modified forms of Kapustinskii equation that could be used to estimate the values of the lattice enthalphies for adducts: DM Hm o=(-n.z+ .z- .10(2)/D).(1-d*/D) .K and DM Hm o=(-n.z+ .z-.10(2)/d).(1-d*/d).K.d. Two new parameters related with steric effects and donor power of the ligands, J anddare introduced. The proposed equations were tested for 49 adducts (mainly from the zinc group halides). The difference between experimental (calorimetric) and calculated values (using the proposed equations) values are less than 5% for 41 of the tested adducts.

Síntese e caracterização de compostos organometálicos de estanho (IV)

Organotin(IV) derivatives containing bulky R groups have been synthesized and characterized. It is discussed how their syntheses depend on the reaction conditions, such as stoichiometry of starting materials, bulkiness of the organo group attached to the Sn centre as well as temperature in which the reaction is carried out. Finally the molecular structure of Sn2Ph6, determined by X-ray diffraction is reviewed.

Estimating the value of the metal-ligand bond dissociation enthalpy<D> (M-L) for adducts using empirical equations supported by TG data

In this work is presented and tested (for 106 adducts, mainly of the zinc group halides) two empirical equations supported in TG data to estimate the value of the metal-ligand bond dissociation enthalpy for adducts: <D> (M-O) = t i / g if t i < 420 K and <D> (M-O) = (t i / g ) - 7,75 . 10-2 . t i if t i > 420 K. In this empirical equations, t i is the thermodynamic temperature of the beginning of the thermal decomposition of the adduct, as determined by thermogravimetry, andg is a constant factor that is function of the metal halide considered and of the number of ligands, but is not dependant of the ligand itself. To half of the tested adducts the difference between experimental and calculated values was less than 5%. To about 80% of the tested adducts, the difference between the experimental (calorimetric) and the calculated (using the proposed equations) values are less than 15%.

Termoquímica na Unicamp: depoimento sobre uma jornada de 25 anos

This article describes the progress of a group of investigation on thermochemistry, which started in 1972. A homemade calorimeter was employed to provide quantitative support to the information on interative effect between lanthanide cations and halides or pseudohalides, in non-aqueous solvents, previously derived from conductometric titrations. However, the features of this instrument were not able to detect the thermal effects. Therefore, the great input to the group came from the acquisition of an LKB commercial apparatus, by the University in 1975. Considering the historical development of the coordination chemistry in Brazil, which was previously dedicated to strutural features of adducts, without focusing the energetic envolved in any coordinationcompound. Since starting the thermochemistry study, numerous masters and doctoral thesis covering more than a hundred adducts and a reasonable number of chelates, were presented systematizing data in order to understand the behavior of this kind of coordination compounds (C. Airoldi and A. P. Chagas, Coord. Chem. Rev. 1992, 119, 29). This knowledge enabled an extension of the study to include some heterogeneous systems formed by natural or synthetic materials like immobilized silica gel, lamellar phosphate, phosphonate or sulphate compounds, clays, polysaccharides, chrysotile, soils, etc. Many students are now engaged as staff members in Universities, Research Instituitions or other private institutions, developing many activities. Due to a multiplying effect on the formation of researchers, the group is now reaching the fourth generation.

Decomposição térmica do bicarbonato de sódio: do processo Solvay ao diagrama tipo Ellingham

A didactic experiment based on the thermal decomposition of sodium bicarbonate using a reagent found in the marketplace is proposed. The reaction products are identified by qualitative tests and stoichiometric calculations. The thermal stability of carbonates and the influence of lattice energies are discussed, emphasizing periodic trends in the alkali and alkaline earth families. The industrial importance of the reaction is also explored.