Decomposição térmica de complexos de Zn e Cd com isomaleonitriladitiolato (imnt)

Thermal decomposition of [Bu4N]2[Zn(imnt)2] and [M(NH3)2(imnt)] complexes with M = Zn and Cd, and imnt = (bis 1,1-dicyanoethylene-2,2 dithiolate) in inert atmosphere was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). Pyrolysis studies at different temperatures, 300, 400, 500, and 600 ºC, in N2 atmosphere were performed and the products were characterized by X-ray diffraction (XRD), infrared and Raman spectroscopy, and scanning electron microscopy (SEM). The products were identified as sulfide sub-micron particles, along with amorphous carbon. Particle sizes estimated by SEM were ca. 50 nm for the cationic complexes and 500 nm for the neutral complexes.

Estimativa do fluxo de amônia na interface ar-mar na Baía de Guanabara: estudo preliminar

In the begining of April 2004, concentrations of NHx (NH3 + NH4+) were measured in surface waters of the Guanabara Bay. Concentrations varied from 2 to 143 mmol L-1. Ammonia exchange at the air-sea interface was quantified using a numerical model. No measurement of NH3 concentration in air (c air) was performed. Thus, calculations of NH3 flux were based on the assumptions of c air = 1 and 5 µg m-3. Fluxes were predominantly from the water to the atmosphere and varied from -20 to almost 3500 µg N m-2 h-1.

The Role of Surfactant Properties of Extractants in Hydrometallurgical LiquidLiquid Extraction Processes

The amphiphilic nature of metal extractants causes the formation of micelles and other microscopic aggregates when in contact with water and an organic diluent. These phenomena and their effects on metal extraction were studied using carboxylic acid (Versatic 10) and organophosphorus acid (Cyanex 272) based extractants. Special emphasis was laid on the study of phase behaviour in a pre neutralisation stage when the extractant is transformed to a sodium or ammonium salt form. The pre neutralised extractants were used to extract nickel and to separate cobalt and nickel. Phase diagrams corresponding to the pre neutralisation stage in a metal extraction process were determined. The maximal solubilisation of the components in the system water(NH3)/extractant/isooctane takes place when the molar ratio between the ammonia salt form and the free form of the extractant is 0.5 for the carboxylic acid and 1 for the organophosphorus acid extractant. These values correspond to the complex stoichiometry of NH4A•HA and NIi4A, respectively. When such a solution is contacted with water a microemulsion is formed. If the aqueous phase contains also metal ions (e.g. Ni²+), complexation will take place on the microscopic interface of the micellar aggregates. Experimental evidence showing that the initial stage of nickel extraction with pre neutralised Versatic 10 is a fast pseudohomogeneous reaction was obtained. About 90% of the metal were extracted in the first 15 s after the initial contact. For nickel extraction with pre neutralised Versatic 10 it was found that the highest metal loading and the lowest residual ammonia and water contents in the organic phase are achieved when the feeds are balanced so that the stoichiometry is 2NH4+(org) = Nit2+(aq). In the case of Co/Ni separation using pre neutralised Cyanex 272 the highest separation is achieved when the Co/extractant molar ratio in the feeds is 1 : 4 and at the same time the optimal degree of neutralisation of the Cyanex 272 is about 50%. The adsorption of the extractants on solid surfaces may cause accumulation of solid fine particles at the interface between the aqueous and organic phases in metal extraction processes. Copper extraction processes are known to suffer of this problem. Experiments were carried out using model silica and mica particles. It was found that high copper loading, aromacity of the diluent, modification agents and the presence of aqueous phase decrease the adsorption of the hydroxyoxime on silica surfaces.

Decomposição térmica de espumas de poliuretano para fabricação de vitrocerâmica celular de Li2O-ZrO2-SiO2-Al2O3 (LZSA)

Characterization of the thermal decomposition of polyurethane (PUR) foams was performed by Fourier-transformed infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). Three main weight loss paths were observed by TGA, the residue being lower than 3 wt.% for 3 different PUR foams analyzed. FT-IR spectra indicated CO2, CO, NH3 and isocyanides as main decomposition products. PUR foams of different cell sizes were immersed in a slurry of the parent glass ceramic of composition Li2O-ZrO2-SiO2-Al 2O3 (LZSA) and submitted to heat treatment. The LZSA cellular glass ceramics obtained after sintering and crystallization resembled the original morphology of the PUR foams.

Aporte atmosférico de amônio, nitrato e sulfato em área de floresta ombrófila densa montana na Serra dos Órgãos, RJ

Wet and dry (dust) deposition was measured in the Serra dos Órgãos National Park. VWM pH was 5.3. Non-sea-salt (nss) SO4(2-) comprised 97% of total SO4(2-). The molar ratio [2(nss-SO4(2-)) + NO3-]/[NH4+ + H+] was 1.1, suggesting that pH is predominantly controlled by H2SO4, HNO3, and NH3. Wet deposition of NH4+, NO3-, and nss-SO4(2-) was respectively 0.59, 0.25, and 0.30 kmol ha-1 yr-1. Assuming that dry deposition of N can comprise 30-50% of its total (dry + wet) deposition, the latter is estimated to be 1.2-1.7 kmol ha-1 yr-1 (17-24 kg N ha-1 yr-1).

Selective hydrogenation of furfural on Ir/TiO2 catalysts

Titania-supported Ir catalysts were used in the hydrogenation of furfural. Reactions were carried out in a stirred batch type reactor at 0.62MPa and 363K using a 0.10M solution of furfural in a 1:1 mixture n-heptane -ethanol as solvent. Catalysts containing 2 wt% of Ir were reduced in H2 flow at different temperatures in the range 473-773K. The catalysts were characterized by H2 chemisorption, TEM, TPR, TPD of NH3 and XPS. Conversion of furfural is higher at lower reduction temperatures, but leads to byproducts whereas reduction at higher temperatures shows selectivity to furfuryl alcohol close to 100%.

Abordagem teórico-experimental da teoria do campo cristalino na disciplina de síntese inorgânica

We describe herein the synthesis and characterization of the complexes KNiF3, [Ni(en)3]I2, [Ni(en)3]Cl2, [Ni(acac)2(H2O)2], [Ni(en)2(H2O)2]Cl2 and [Ni(NH3)6](BF4)2 (en = ethylenediamine, acac- = acetylacetonate) performed in the inorganic synthesis major course at the Chemistry Institute of UFRGS (Universidade Federal do Rio Grande do Sul). The compounds were characterized by infrared and electronic spectroscopy and the electrolytic conductivity was measured. The parameters 10Dq and B were obtained from the electronic spectra and the nefelauxetic and spectrochemical series were determined. The obtained spectrochemical series was F- < acac- < NH3 < en and the nefeulaxetic series was en < NH3 < acac- < F-.

A brief introduction to molecular orbital theory of simple polyatomic molecules for undergraduate chemistry students

A simple, four-step method for better introducing undergraduate students to the fundamentals of molecular orbital (MO) theory of the polyatomic molecules H2O, NH3, BH3 and SiH4 using group theory is reported. These molecules serve to illustrate the concept of ligand group orbitals (LGOs) and subsequent construction of MO energy diagrams on the basis of molecular symmetry requirements.

Isolamento do tungstênio da volframita da mina de Igarapé Manteiga (Rondônia - Brasil) por lixiviação ácida

We report results of the efficiency of tungsten extraction from wolframite concentrate (containing 61.5 wt % WO3) from the Igarapé Manteiga mine (state of Rondônia, Brazil) through acid leaching with strong mineral acids at 100 ºC and 400 rpm for 2-4 h. HCl yielded insoluble matter containing the highest WO3 content (90 wt %). This solid was dissolved in concentrated NH3(aq) at 25 ºC and the insoluble matter filtrated. The filtrate was slowly evaporated. 70 wt % of the tungsten present in the starting concentrate material was recovered as ammonium paratungstate (APT).

ACIDITY OF MODIFIED MORDENITES SYNTHESIZED FROM RICE HUSK SILICA AND CATALYTIC TRANSFORMATION OF METHYLBUTYNOL

Mordenite (MOR) was synthesized using rice husk silica and modified by base (B), acid (A) or acid-base (AB) and converted to H-form. The modification did not destroy the MOR structure but increased surface area and generated mesopores. Lewis acidity of the parent and modified MOR samples investigated by aluminum NMR and NH3-TPD showed a decrease in the following order: HMOR > BMOR > ABMOR > AMOR. For the catalytic transformation of methylbutynol, ABMOR provided the highest conversion and selectivity of products from acid sites.

SIMULTANEOUS DETERMINATION OF PROTOCATECHUIC ALDEHYDE AND PROTOCATECHUIC ACID USING THE LOCALIZED SURFACE PLASMON RESONANCE PEAK OF SILVER NANOPARTICLES AND CHEMOMETRIC METHODS

A simple and sensitive spectrophotometric method is proposed for the simultaneous determination of protocatechuic acid and protocatechuic aldehyde. The method is based on the difference in the kinetic rates of the reactions of analytes with [Ag(NH3)2]+ in the presence of polyvinylpyrrolidone to produce silver nanoparticles. The data obtained were processed by chemometric methods using principal component analysis artificial neural network and partial least squares. Excellent linearity was obtained in the concentration ranges of 1.23-58.56 µg mL-1 and 0.08-30.39 µg mL-1 for PAC and PAH, respectively. The limits of detection for PAC and PAH were 0.039 and 0.025 µg mL-1, respectively.

USE OF A LOW-COST TEMPLATE-FREE ZSM-5 FOR ATMOSPHERIC PETROLEUM RESIDUE PYROLYSIS

To understand the physicochemical properties and catalytic activity during the pyrolysis of atmospheric petroleum residue, a template-free ZSM-5 zeolite was synthesized using a direct method without additional seeds or an organic structure director and compared with conventionally synthesized ZSM-5. The crystallinities of the two zeolites were evaluated by XRD and FTIR and were quite similar; however, structural analyses using SEM and argon physisorption revealed that the zeolites diverged in particle diameter and in the external surface area of the micropores. The synthesis procedure without a template incorporated additional aluminum into the crystalline network, according to ICP-AES and TPD NH3 experiments. The catalytic pyrolysis performed over the template-free ZSM-5 generated results comparable to those for pyrolysis performed over the conventional ZSM-5 according to its hydrocarbon distribution. The selectivity to aromatics compounds was exactly the same for both ZSM-5 zeolites, and these values stand out compared to thermal pyrolysis. The template-free ZSM-5 produced 20% of light hydrocarbons (C4-C6), where such compounds are olefins and paraffins of great interest to the petrochemical industry. Therefore, template-free ZSM-5 is promising for industrial use due to its lowered synthesis time, low-cost and significant distribution to light hydrocarbons.

Dinâmica da série nitrogenada nas águas da bacia hidrográfica Apodi/Mossoró - RN - Brasil

A bacia hidrográfica Apodi/Mossoró é um dos mais importantes recursos hídricos do Rio Grande do Norte. Estudos recentes mostraram que os compostos nitrogenados destacam-se entre os principais contaminantes deste corpo aquático, mostrando a necessidade de relacioná-los com outras propriedades físico-químicas que influenciam na dinâmica das suas formas. Deste modo, este trabalho tem por objetivo correlacionar as concentrações de NO3-, NO2- e NH3 com os valores de pH, T, Eh e OD nas águas desta bacia. Os resultados indicam o predomínio de um meio fortemente oxidante, destacando o NO3- como a principal forma de nitrogênio presente, mesmo nos locais onde foram observadas reduções significativas de Eh e OD. Este trabalho busca contribuir para o desenvolvimento de medidas de controle e manejo das fontes poluidoras e o melhor gerenciamento deste recurso hídrico.

Determinação de amônia no ar utilizando um sensor piezelétrico de quartzo

Neste estudo, procurou-se desenvolver e avaliar filmes para a captação e quantificação de vapores de amônia no ar, através de um sensor piezelétrico de quartzo. Muitas substâncias e suas misturas, em diferentes proporções, foram investigadas como possíveis filmes captores. Em etapas seguintes, verificaram-se alguns parâmetros importantes como o efeito da vazão do poluente, da temperatura de trabalho e da massa da película, otimizando-se as condições experimentais para a montagem do método. Concluiu-se que o filme mais promissor, sob as condições ajustadas, seria uma mistura 2:1 (v/v) de solução comercial (A) de ácido glicólico (70 % m/m) em água, adicionada a tetrakis(hidroxietil)etilenodiamina - THEED (3:4 v/v), com uma solução saturada (B) de ácido tânico em acetona. Estudos de repetibilidade, do tempo de contacto (poluente-sensor) e de alguns possíveis interferentes completaram os trabalhos. As curvas analíticas resultantes mostraram faixas lineares na região de trabalho (2,0 a 11 ppm v ou 1,4 a 7,7 mg/m³ de NH3), para quatro diferentes tempos de exposição (0,5; 1; 2 e 3 min), com coeficientes de correlação (r) variando entre 0,9994 e 0,9980, e respectivas sensibilidades de 13,5 a 42,0 Hz / ppm v.

Qualidade do ar, ambiente térmico e desempenho de suínos criados em creches com dimensões diferentes

Em uma suinocultura, a fase de creche é considerada crítica, na qual o animal fica exposto às condições ambientais do recinto onde está alojado, sem a proteção da matriz e inserido em um meio social coletivo e desconhecido. Essa fase requer ambiente térmico mais aquecido e, por isso, em período de inverno, os abrigos são mantidos mais fechados, o que pode ser agravante em termos de renovação do ar. Este trabalho teve como objetivo avaliar duas creches de dimensões diferentes, em período de inverno, levando-se em consideração o ambiente térmico, a qualidade do ar e o desempenho dos animais alojados nessas instalações. Foram utilizadas duas creches com dimensões diferentes (I e II), ambas sem nenhum tipo de aquecimento. Foram feitas medições de concentrações instantâneas de NH3 (ppm), CO (ppm) e CO2 (ppm). Dados relativos ao conforto térmico ambiente (temperatura e umidade) foram coletados continuamente. Concluiu-se que a concentração dos gases CO2 e NH3, mensurados em ambas as creches, não atingiram níveis que possam causar danos à saúde dos animais; não houve concentração mensurável do gás monóxido de carbono em nenhuma das mesmas; o ambiente térmico nas creches, no período estudado, esteve em condições consideradas confortáveis.