Screening analysis of biodiesel feedstock using UV-vis, NIR and synchronous fluorescence spectrometries and the successive projections algorithm

This paper investigates the use of UV-vis, near infrared (NIR) and synchronous fluorescence (SF) spectrometries coupled with multivariate classification methods to discriminate biodiesel samples with respect to the base oil employed in their production. More specifically, the present work extends previous studies by investigating the discrimination of corn-based biodiesel from two other biodiesel types (sunflower and soybean). Two classification methods are compared, namely full-spectrum SIMCA (soft independent modelling of class analogies) and SPA-LDA (linear discriminant analysis with variables selected by the successive projections algorithm). Regardless of the spectrometric technique employed, full-spectrum SIMCA did not provide an appropriate discrimination of the three biodiesel types. In contrast, all samples were correctly classified on the basis of a reduced number of wavelengths selected by SPA-LDA. It can be concluded that UV-vis, NIR and SF spectrometries can be successfully employed to discriminate corn-based biodiesel from the two other biodiesel types, but wavelength selection by SPA-LDA is key to the proper separation of the classes.Fil: Insausti, Matías. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Gomes, Adriano A.. Universidade Federal da Paraíba; BrasilFil: Cruz, Fernanda V.. Universidade Federal da Paraíba; BrasilFil: Pistonesi, Marcelo Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Ugulino de Araújo, Mário C.. Universidade Federal Da Paraíba; BrasilFil: Galvão, Roberto K.H.. Universidade Federal da Paraíba; BrasilFil: Pereira, Claudete F.. Universidade Federal da Paraíba; BrasilFil: Fernández Band, Beatriz Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

Steam reforming on transition-metal carbides from density-functional theory

A screening study of the steam reforming reaction (CH_4 + H_2O -> CO + 3H_2) on early transition-metal carbides (TMC's) is performed by means of density-functional theory calculations. The set of considered surfaces includes the alpha-Mo_2C(100) surfaces, the low-index (111) and (100) surfaces of TiC, VC, and delta-MoC, and the oxygenated alpha-Mo_2C(100) and TMC(111) surfaces. It is found that carbides provide a wide spectrum of reactivities towards the steam reforming reaction, from too reactive via suitable to too inert. The reactivity is discussed in terms of the electronic structure of the clean surfaces. Two surfaces, the delta-MoC(100) and the oxygen passivated alpha-Mo_2C(100) surfaces, are identified as promising steam reforming catalysts. These findings suggest that carbides provide a playground for reactivity tuning, comparable to the one for pure metals.Comment: 6 pages, 4 figure

CO on Pd(100)/SiO2: a computational study of the effect of CaO on the energetics of adsorption

The semiempirical atom superposition and electron delocalisation molecular orbital (ASED-MO) theory was used to study the CO/Pd-Ca-SiO2 interaction. Addition of a single CaO molecule to simulate a different interaction with both the metal and the CO molecule was also considered. Ca was added as a sublayer between the SiO2 and the metallic cluster. A simple diatomic CaO molecule was positioned on the Pd21 surface. The energetics of CO adsorption was studied in both cases. In our adsorption scheme, CO was considered to be perpendicular to the surface. The results indicate that in general adsorption on twofold sites seems to be more favourable. The Ca sublayer stabilises CO adsorption by less than 0.1 eV for twofold short bridge adsorption site. Fourfold site is de-stabilised by 0.6 eV and is 2 eV less favourable than the twofold sites. The effect of Ca and CaO on the adsorption is of small magnitude. © 2000 Published by Elsevier Science B.V. All rights reserved.status: publishe

Automatized flow-batch method for fluorescent determination of free glycerol in biodiesel samples using on-line extraction

An automatic method, based on flow-batch (FB), for determining glycerol in biodiesel was developed. The FB systems draw upon the useful features of flow, batch and multi-commutation approaches. The standards and samples preparation, as well as, derivatization and analysis were fully automated. For that purpose, a homemade chamber was built. The proposed method is based on liquid-liquid extraction of glycerol and simultaneous oxidation with periodate, generating formaldehyde that reacts with acetylacetone. A fluorescent product of 3,5-diacetyl-1,4-dihydrolutidine was obtained. The fluorescence signal was recorded at λex = 417 nm and λem = 514 nm. A linear response was observed from 0.10 to 5.00 mg L-1 glycerol, variation coefficient 1.5%, sampling rate 14 h-1 and detection limit 0.036 mg L-1 glycerol. The procedure was successfully applied to the analysis of biodiesel samples, and the results agreed with the reference method (ASTM D6584-07) at 95% confidence level.Fil: Lima, Marcelo B.. Universidade Federal da Paraíba; BrasilFil: Insausti, Matías. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Domini, Claudia Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Pistonesi, Marcelo Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Ugulino de Araújo, Mário C.. Universidade Federal da Paraíba; BrasilFil: Fernández Band, Beatriz Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

Using a simple digital camera and SPA-LDA modeling to screen teas

Classification or screening analysis of natural unprocessed teas using simple digital images and a variable selection algorithm is described. The proposed methodology uses color histograms generated on free downloadable software ImageJ 1.44p as a source of analytical information. Two chemometric methods were compared for classification of the resulting images, namely Soft Independent Modeling of Class Analogy (SIMCA), and Linear Discriminant Analysis (LDA) with variable selection by the Successive Projections Algorithm (SPA). The results were evaluated in terms of errors found in a sample set separate from the modeling process. The choice of more informative photometric color attributes (red-green-blue (RGB), hue (H), saturation (S), brightness (B), and grayscale) for screening the tea samples was made during the color modeling because SIMCA failed to give good results. Therefore the data treatment used SPA-LDA, which correctly classified all samples according to their geographical regions, whether from Brazilian, Argentinian or foreign soils.Fil: Diniz, Paulo H. G. D.. Universidade Federal da Paraíba; BrasilFil: Dantas, Hebertty V.. Universidade Federal da Paraíba; BrasilFil: Melo, Karla D. T.. Universidade Federal da Paraíba; BrasilFil: Barbosa, Mayara F.. Universidade Federal da Paraíba; BrasilFil: Harding, David P.. Universidade Federal da Paraíba; BrasilFil: Nascimento, Elaine C. L.. Universidade Federal da Paraíba; BrasilFil: Pistonesi, Marcelo Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Fernández Band, Beatriz Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Araújo, Mário C. U.. Universidade Federal da Paraíba; Brasi