RESUMO
FTIR spectroscopy and multivariate analysis were used in the chemical study of the terroirs of Coffea canephora. Conilon coffees from Espírito Santo and Amazon robusta from Matas of Rondônia, were separated by PCA, with lipids and caffeine being the markers responsible for the separation. Coffees from Bahia, Minas Gerais, and São Paulo did not exhibit separation, indicating that the botanical variety had a greater effect on the terroir than geographic origin. Thus, the genetic factor was investigated considering the conilon and robusta botanical varieties. This last group was composed of hybrid robusta and apoatã. The DD-SIMCA favored the identification of the genetic predominance of the samples. PLS-DA had a high classification performance regarding the conilon, hybrid robusta, and apoatã genetic nature. Lipids, caffeine, chlorogenic acids, quinic acid, trigonelline, proteins, amino acids, and carbohydrates were identified as chemical markers that discriminated the genetic groups.
Assuntos
Coffea , Coffea/genética , Coffea/química , Cafeína/análise , Brasil , Café/química , LipídeosRESUMO
In this paper, a 400â¯ppm aqueous solution of guar gum polysaccharide was submitted to a turbulent flow regime in order to monitor molecular degradation and drag reduction. Guar gum samples were isolated and analyzed by spectroscopic, thermoanalytical and viscosimetric techniques. The drag reduction promoted by guar gum is compromised as the polysaccharide undergoes degradation. Viscosimetric analysis of guar gum showed a reduction in viscous molecular mass. Mid-infrared spectra and hydrogen nuclear magnetic resonance suggest that mechanical degradation promotes hydrolysis of the glycosidic bond α (1â¯ââ¯6) releasing (d)-galactose owing to the appearance of the carbonyl functional group. Thermal analysis revealed the reduction of the polysaccharide's thermal stability by reduction of the polymer chain. A comprehensive analysis of these combined parameters affords a foundation for the development of more efficient biopolymers in the context of improved drag reduction.
Assuntos
Fenômenos Químicos , Galactanos/química , Mananas/química , Gomas Vegetais/química , Análise Espectral , Termogravimetria , Biopolímeros/química , Hidrólise , Estrutura Molecular , Peso Molecular , ViscosidadeRESUMO
Guar gum is used in low concentrations as a drag reducing agent in turbulent flows to significantly accelerate flow in oil pipelines, oil well operations and aqueous systems. Drag reduction also promotes a decrease in energy demand in pumping systems. However, the polymers undergo mechanical degradation and lose the ability to promote drag reduction over time. In this paper, the drag reduction, the power required by the pumps and the degradation of the guar gum were evaluated during a turbulent flow of an aqueous solution containing the biopolymer. The results indicate the mechanism of degradation of guar gum by the hydrolysis of the bond α (1â¯ââ¯6), liberating the galactose, which justice to the loss of efficiency throughout the process. An understanding of this mechanism should allow for the development of more mechanically resistant polymers and the increase of drag reduction capacity over time.
Assuntos
Galactanos/química , Mananas/química , Fenômenos Mecânicos , Gomas Vegetais/química , Espectroscopia de Infravermelho com Transformada de Fourier , Indústria de Petróleo e GásRESUMO
A procedure for the direct GFAAS determination of Ni in petroleum samples using a solid sampling strategy is proposed. Palladium was used as conventional modifier. Central composite design multivariate optimization defined the optimum temperature program and the Pd mass, allowing calibration using aqueous analytical solution. The limit of detection (LOD) at the optimized conditions was 0.23 ng of Ni, for typical sample masses between of 0.10 and 0.60 mg. Linearity at least up to 11 ng of Ni and a characteristic mass of 45 pg were observed, defining a dynamic range between 0.52 and 110 microg g(-1). Typical coefficients of variation (n = 10) in the analysis of oil reference materials were 7%. Method validation was performed both by the analysis of oil certified reference materials and by comparison with an independent method (ASTM 5863-B). No statistically significant difference was observed between obtained and expected values. The total determination cycle lasted 5 min, equivalent to a sample throughput of 6 h(-1) for duplicate determinations.
RESUMO
A procedure for the determination of As in diesel, gasoline and naphtha at microg L(-1) levels by GFAAS is proposed. Sample stabilization was achieved by the formation of three component solutions prepared by mixing appropriate volumes of the samples propan-1-ol and nitric acid aqueous solution. This mixture resulted in a one-phase medium, which was indefinitely stable. No changes in the analyte signals were observed over several days in spiked samples, proving long-term stabilization ability. The use of conventional (Pd) and permanent (Ir) modification was investigated and the former was preferred. Central composite design multivariate optimization defined the optimum microemulsion composition as well as the temperature program. In this way, calibration using aqueous analytical solutions was possible, since the same sensitivity was observed in the investigated microemulsion media and in 0.2% v/v HNO(3). Coefficients of correlation larger than 0.999 and an As characteristic mass of 22 pg were observed. Recoveries (n=4) obtained from spiked samples were 98+/-4, 99+/-3 and 103+/-5%, and the limits of detection in the original samples were 1.8, 1.2 and 1.5 microg L(-1) for diesel, gasoline and naphtha, respectively. Validation was performed by the analysis of a set of commercial samples by independent comparative procedures. No significant difference (Student's t-test, p<0.05) was observed between comparative and proposed procedure results. The total determination cycle lasted 4 min for diesel and 3 min for gasoline and naphtha, equivalent to a sample throughput of 7 h(-1) for diesel and 10 h(-1) for gasoline and naphtha.