Temperature-dependent benzoic acid elimination mechanisms in pyrolysis of (-)-cocaine

The thermal elimination of benzoic acid from (-)-cocaine is shown to be temperature-dependent. In the temperature range of 200-500 °C only a trans-elimination is observed leading to methylecgonidine. Above ca. 500 °C a second mechanism, the cis-elimination, comes up yielding a novel alkaloid methylisoecgonidine which has been characterized by means of mass spectrometry. At 600 °C the cis-elimination predominates. The trans-elimination is postulated a two-step process consisting of a 1,7- and a 1,5-hydrogen shift. The chemistry of cocaine base smoking is explained using the theory of chemical activation.

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.

Characterization of phosphate structures in biochar from swine bones

The objective of this work was to develop an alternative methodology to study and characterize the phosphate crystalline properties, directly associated with solubility and plant availability, in biochar from swine bones. Some phosphate symmetry properties of pyrolyzed swine bones were established, using solid state nuclear magnetic resonance spectroscopy, principal component analysis, and multivariate curve resolution analysis, on four pyrolyzed samples at different carbonization intensities. Increasing carbonization parameters (temperature or residence time) generates diverse phosphate structures, increasing their symmetry and decreasing the crossed polarizability of the pair ¹H-31P, producing phosphates with, probably, lower solubility than the ones produced at lower carbonization intensity. Additionally, a new methodology is being developed to study and characterize phosphate crystalline properties directly associated with phosphate solubility and availability to plants.

Biochar and soil nitrous oxide emissions

The objective of this work was to evaluate the effect of biochar application on soil nitrous oxide emissions. The experiment was carried out in pots under greenhouse conditions. Four levels of ground commercial charcoal of 2 mm (biochar) were evaluated in a sandy Albaqualf (90% of sand): 0, 3, 6, and 9 Mg ha-1. All treatments received 100 kg ha-1 of N as urea. A cubic effect of biochar levels was observed on the N2O emissions. Biochar doses above 5 Mg ha-1 started to mitigate the emissions in the evaluated soil. However, lower doses promote the emissions.

Determinação de fósforo em aços por espectrometria de absorção atômica no forno de grafite

A method for the determination of phosphorus in steel samples by graphite furnace atomic absorption spectrometry, using the Zeeman effect background correction and the STPF conditions is proposed. The effect of iron (III) on the phosphorus signal was studied. It was verified, through the pyrolysis temperature curves, that iron (III) is an efficient chemical modifier, thermically stabilizing phosphorus up to 1400ºC. The phosphorus signal increases with the iron (III) concentration, but in the range, which corresponds to the usual concentrations of iron in the sample solutions, the increase is small. Phosphorus was determined in three standard reference materials, after its dissolution in a mixture of hydrochloric and perchloric acids in a PTFE bomb. The agreement with the certified concentration values was excellent. Iron (III) was added to the reference analytical solutions prepared in the blank of the dissolution, while the sample solutions were measured directly, since they already contained the modifier. The detection limit (k = 2) was 0.0042% of phosphorus in the steel sample.

Determinação direta de selênio em água de coco e em leite de coco utilizando espectrometria de absorção atômica com atomização eletrotérmica em forno de grafite

Selenium is both essential and toxic to man and animals, depending on the concentration and the ingested form. Most fruits and vegetables are poor sources of selenium, but coconut can be a good selenium source. Samples were suspended (1 + 4 v/v) in a mixture of tertiary amines soluble in water (10% v/v CFA-C). This simple sample treatment avoided contamination and decreased the analysis time. The standard additions method was adopted for quantification. The action of the autosampler was improved by the presence of the amines mixture in the suspension. A Varian model AA-800 atomic absorption spectrometer equipped with a graphite furnace and a GTA 100 autosampler was used for selenium determination in coconut water and coconut milk. Background correction was performed by means of the Zeeman effect. Pyrolytically coated graphite tubes were employed. Using Pd as chemical modifier, the pyrolysis and the atomization temperatures were set at 1400 and 2200ºC, respectively. For six samples, the selenium concentration in coconut water varied from 6.5 to 21.0 mug L-1 and in coconut milk from 24.2 to 25.1 mug L-1. The accuracy of the proposed method was evaluated by an addition-recovery experiment and all recovered values are in the 99.5-102.3% range. The main advantage of the proposed method is that it can be directly applied without sample decomposition.

Emprego de planejamento fatorial para a otimização das temperaturas de pirólise e atomização de Al, Cd, Mo e Pb por ETAAS

This work describes a factorial design for the optimization of pyrolysis and atomization temperatures in ETAAS. As examples, Cd and Pb were determined using lower pyrolysis and atomization temperatures and Al and Mo with higher pyrolysis and atomization temperatures. Good results were obtained for Cd employing Rh (m o = 1.4 pg) as a permanent modifier with pyrolysis and atomization temperatures of 640 and 1500 °C, respectively. For Zr, W or Zr+W, the Cd pyrolysis and atomization temperatures were 500 and 1500 °C, respectively, with m o = 1.4 pg using Zr or W and 1.5 pg using Zr+W. The best results for Pb were those using Rh, Zr, W and Zr+Rh, obtaining characteristic masses of 42, 37, 34 and 36 pg, respectively. Pyrolysis and atomization temperatures of 910 and 1850 °C, respectively, were achieved for this metal. For Al, the best results were obtained when Zr or Zr+W were used. Mo was also tested as a possible permanent modifier for Al, but the results were not satisfactory. The results obtained for Mo without modifier were similar to those with conventional modifiers (Mg or Pd+Mg) and the results obtained using permanent chemical modifiers were not satisfactory. In all situations, the experiments were performed faster than those using the univariate procedure.

Influência da geometria da plataforma na determinação de chumbo em zidovudina (AZT) por ET AAS

The aim of this work was to compare the performances of the L'vov and integrated platforms in order to overcome the interferences found on lead determination in zidovudine by ET AAS. Pyrolysis and atomization temperatures found with integrated platform were 700 and 1400°C, respectively. The characteristic masses were 12.7 ± 1.2 pg with integrated platform and 11.1 ± 1.3 pg with grooved platform. The ratio between the slopes of zidovudine and aqueous curves shows a decrease in the interferences when the L'vov platform is used (bAZT/b aq = 0.97 ± 0.10) and the detection limit found was 0.03 µg.g-1. That ratio was 0.85 ± 0.07 with the integrated platform.

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.

Caracterização dos produtos líquidos e do carvão da pirólise de serragem de eucalipto

This study proposes the low temperature pyrolysis as an alternative conversion process for residual biomass and for obtaining gaseous, liquid and solid chemical feedstocks. Using a bench electrical pyrolysis oven, four product fractions from eucalyptus sawdust were obtained: a gaseous one, two liquid (aqueous and oily), and a solid residue (char). These products were characterized by different analytical methods. The liquid fractions showed themselves as potential sources for input chemicals. The residual char revealed appreciable adsorption capability. The process demonstrated good efficiency, generating at least two fractions of great industrial interest: bio oil and char.

Determinação simultânea de As, Cd e Pb em amostras de água purificada para hemodiálise por espectrometria de absorção atômica com forno de grafite, após otimização multivariada baseada no uso de planejamento experimental

This paper reports the development of a methodology for simultaneously determining As, Cd and Pb, employing GF AAS with polarized Zeeman-effect background correction. In order to make the procedure applicable, the influence of pyrolysis and atomization temperatures and the amount of chemical modifiers were studied. Factorial and central composite designs were used to optimize these variables. Precision and accuracy of the method were investigated using Natural Water Reference material, Nist SRM 1640. Results are in agreement with certified values at the 95% confidence limit when the Student t-test is used. This methodology was used for quality control of purified water for hemodialysis.

Preparação de carvão ativado em baixas temperaturas de carbonização a partir de rejeitos de café: utilização de FeCl3 como agente ativante

Ferric chloride as a new activating agent was used to obtain activated carbons from agroindustrial waste. This material was prepared at three temperatures of pyrolysis, 200, 280 and 400 ºC. The carbonaceous materials obtained after the activation processes showed high specific surface areas (BET), with values higher than 900 m² g-1. The materials showed different behaviors in the adsorption of methylene blue dye and reactive red textile dye in water solutions. An important fact in the use of FeCl3 as an activating agent is that the activation temperature is at 280 ºC, well below of those commonly employed in chemical or physical activations described in the literature.

A pirólise como técnica analítica

In this paper historical aspects of analytical pyrolysis, the equipment used, the fundamentals and the mechanisms of pyrolysis of different polymeric materials are discussed. The latest work on analytical pyrolysis applied to various types of synthetic and natural samples is reviewed. Current applications of this technique that are discussed include identification of microorganisms, analysis of trace compounds by forensic laboratories, investigation of food and agricultural products, study of the chemical composition of wood, authentication and conservation of artworks, and the study of environmental and geochemical samples.

Determination of Cd and Pb in fuel ethanol by filter furnace electrothermal atomic absorption spectrometry

A method was developed for quantification of Cd and Pb in ethanol fuel by filter furnace atomic absorption spectrometry. Filter furnace was used to eliminate the need for chemical modification, to stabilize volatile analytes and to allow the application of short pyrolysis step. The determinations in samples were carried out against calibration solutions prepared in ethanol. Recovery tests were made in seven commercial ethanol fuel samples with values between 90 and 120%. Limits of detection were 0.1 µg L-1 for Cd and 0.3 µg L-1 for Pb. Certified water samples (APS 1071, APS 1033, NIST 1643d, NIST 1640) were also used to evaluate accuracy and recoveries from 86.8% to115% were obtained.

Determinação da relação siringila/guaiacila da lignina em madeiras de eucalipto por pirólise acoplada à cromatografia gasosa e espectrometria de massas (PI CG/EM)

The use of analytical pyrolysis combined with gas chromatography/mass spectrometry (Py-GC/MS) to determine the syringyl/guaiacyl ratio (S/G) in lignins from Eucalyptus spp woods was investigated. Sample of E. grandis and "E. urograndis" wood, with and without extractives, were subjected to pyrolysis from 300 ºC to 600 ºC. The products that results from pyrolysis were identified by mass spectrometry and the S/G ratio was determined based on the areas of the peaks corresponding to the guaiacyl and syringyl derivatives. The best S/G estimation is achieved when pyrolysis is carried out at 550 ºC. Extractives and carbohydrate present in the woods do not interfere with the results.