A metodologia da espectroscopia no infravermelho próximo (NIRS Near Infrared Spectroscopy), recentemente empregada em várias áreas da ciência do solo associada à quimiometria, está sendo utilizada na quantificação de atributos químicos e físicos do solo. Esta técnica rápida, não destrutiva, reprodutiva e de baixo custo fundamenta-se na medida da intensidade de absorção de radiação eletromagnética na região do infravermelho próximo. De um modo geral, a NIRS tem se mostrado uma ferramenta válida para quantificar o teor de carbono (C) em amostras de solo. A importância da determinação do teor de C no solo reside no fato de representar a fixação do CO2 atmosférico na forma de matéria orgânica do solo (MOS), um compartimento chave do ciclo global deste elemento. O manejo sustentável dos agrossistemas deve assegurar a manutenção dos teores de carbono através da restituição de matéria orgânica ao solo. No caso da cultura de cana de açúcar, a substituição do sistema de colheita de manual com prévia queima da palhada (cana queimada) para mecanizada (cana crua) em que a palhada permanece sobre o solo, favorece o acúmulo e a diferenciação do teor de C no solo. O presente trabalho teve como objetivo comparar a metodologia NIRS, associada à quimiometria, com o método de referência tradicional da combustão a seco na quantificação do teor de C em amostras de solo provenientes do agroossistema cana-de-açúcar. Foram analisadas amostras de solo provenientes de três situações: cana queimada, cana crua e uma área nativa, totalizando 450 amostras, apresentando respectivamente teores médios de C de 18,30, 22,36 e 24,72 g kg-1. Modelos de calibração foram ajustados utilizando PLS nos dados espectrais, submetidos a 1ª derivada suavizados com Savitz Golay alisados com janela 15. As amostras foram aleatorizadas e divididas em 3 partes iguais, sendo 2/3 das 450 amostras para a calibração e validação cruzada e 1/3 para validação externa. Os parâmetros quimiométricos para a avaliação da qualidade do modelo escolhido foram: RMSEC, RMSECV, RMSEP, R2, BIAS, CV% e RPD. Os resultados de RMSEC> 1,93, RMSEP > 1,90, satisfatórios R2 0,94. Na área nativa obteve-se RMSEP 1,53 e R2 0,95, e na área de cana queimada RMSEP 1,90 e R2 0,50. Ao comparar as técnicas, de referência e NIRS, demonstrou que a técnica de referência tem SD 0,12 e CV% 0,65 e a técnica NIRS SD 0,18 e CV% 0,18, provando a eficiência do emprego da NIRS para a determinação de C no solo / The methodology of near infrared spectroscopy, recently used in several areas of soil science associated with chemometrics, has been used in the quantification of chemical and physical soil attributes. This rapid, nondestructive, reproductive and low cost technique is based on the measurement of the intensity of the electromagnetic radiation absorption in the near infrared region. In general, the NIRS has been proved as an effective tool to quantify the carbon (C) content in soil samples. The importance this determination is that it represents the fixation of atmospheric CO2 as soil organic matter (SOM), an important compartment of the global C cycle. The sustainable management of agro-systems must assure the maintenance of the carbon levels through the restoration of soil organic matter. In case of sugar cane crop, the replacement of the manual cutting system, preceded by residue burning (preharvest burning), by mechanized harvest (raw sugar cane) where the straw remains on the field, favors the accumulation and differentiation of the C content in the soil. This study aimed to compare the NIRS methodology, associated with chemometrics, to the traditional reference method of dry combustion quantifying the C content in soil samples from the sugar cane agro-system. Soil samples from three situations were analyzed: burnt sugar cane, raw sugar cane and a native area, totalizing 450 samples, with levels of respectively 18.30, 22.36 and 24.72 g C kg-1. Calibration models were adjusted using PLS in the spectral data, submitted to the first derivative and smoothing with Savitz Golay with window 15. Samples were randomized and divided into 3 parts: 2/3 of the 450 samples were designated to calibration and cross validation, and the odder 1/3 to external validation. The chemometrics parameters RMSEC, RMSECV, RMSEP, R2, BIAS, CV% and RPD were chosen to estimate the quality of the model. The results of RMSEC> 1.93, RMSEP> 1.90, and R2 0.94 were satisfactory. In the native area a range of RMSEP 1.53 and R2 0.95 was obtained, while in the area of burnt sugar cane it was R2 0.50 and RMSEP 1.90. Comparing the reference technique and NIRS, the first showed a SD 0.12 and CV 0.65%, while a SD 0.18 CV 0.81% was obtained for the second, proving the efficiency of the use of NIRS to determine C content in soil

One of the most important steps in the search for life on Mars is to determine if a specific sub-surface location it is "habitable", or that it provides the conditions and requirements to support life as we know it. In this thesis, I present a miniature, thermal-IR radiometer and reflectometer designed to determine temperature, the presence of water ice, and the discrimination of minerals, all necessary for a habitable environment. A dual use detector was selected for the thermal and five reflectance channels. The IR source is provided by five LEDs. These components were embedded in a thermally controlled aluminium block. Integrated electronics provided signal amplification and demodulation. This device will be suitable for drilling applications with less than 25 mm diameter boreholes and with limited available power (<5watts). Thermal testing was within a simulated borehole mounted in a thermal vacuum chamber. The results were compared to a theoretical model of the expected temperature. The maximum temperature error between predicted and measured was 0.21 K (∼0.08%). The total RMS error of all sources were calculated to be <3%. Reflectance testing in all five channels included a variety of minerals and a two point calibration method. The results were compared to the predicted reflectance values for the samples. The results of the reflectance channel testing demonstrated that the measured values matched the predicted values with a 2.5% measured error. The total RMS error was 6.1%. Detection and discrimination of water ice and hydrated minerals included a non-linear mixing model and/or testing. The model predicted that water ice mixed in a pyroxene mineral matrix can be detected and discriminated from 5% to 60% concentration by weight. Testing with a hydrated mineral mixed within a non-hydrated mineral matrix demonstrated that the measured result matched the predicted result from 5-45% concentration by weight.

La réaction de transestérification des huiles végétales avec de l'éthanol permet la production d’esters éthyliques dont les applications industrielles sont, à ce jour, essentiellement cosmétiques ou alimentaires. Pour ouvrir le champ des applications aux biocarburants (pour substituer les carburants actuels issus de ressources fossiles), il est apparu nécessaire de développer un procédé de transestérification plus performant pour être économiquement rentable. Selon le schéma réactionnel et les propriétés thermocinétiques du système, les limites des procédés batchs existants pourraient être franchies en utilisant des procédés continus. Le système étudié est complexe en raison des changements d’équilibres de phase notamment et de la présence simultanée de différents phénomènes (mélange, transferts de chaleur et de matière, réactions principales et compétitives) qui doivent être précisément contrôlés. Pour concevoir correctement un procédé continu et acquérir de nombreuses données, les microréacteurs apparaissent comme un outil approprié à cette transposition. Dans ce travail, nous avons transposé la réaction batch dans un dispositif microstructuré continu (tube PFA de diamètre interne 508 μm) induisant un meilleur contrôle des transferts de chaleur et de matière. L’étude de l’influence des conditions de fonctionnement (débits des réactifs, rapport molaire initial huile/éthanol, température…) a permis de trouver des paramètres réactionnels favorables qui permettent d’atteindre des conversions et rendements élevés. Dans ces conditions, nous avons montré qu’il est possible d’acquérir des données cinétiques dès les premières secondes de réaction, ce qui n’était pas réalisable en réacteur batch conventionnel. Pour acquérir ces données en batch et en microréacteurs, nous avons développé une méthode d’analyse en ligne par spectroscopie proche infrarouge en s’appuyant sur la chromatographie en phase gazeuse comme méthode de référence. Des modèles PLS ont alors été établis pour quantifier en ligne les teneurs en composés majoritaires lors de la réaction de transestérification de l’huile de tournesol hautement oléique avec l’éthanol. A partir de ces données, les phénomènes mis en jeu ont été modélisés et les constantes cinétiques ainsi que les coefficients de transfert de cette réaction ont été déterminés. Le modèle a ensuite été utilisé pour simuler des réactions avec d’autres conditions opératoires et il nous a permis de travailler sur la séparation des produits de la réaction. / Transesterification reaction of vegetable oil with ethanol leads to ethyl esters, used to date for applications principally in food and cosmetic industry. To open the application field to biofuels (to substitute current fuels resulting from fossil resources), process efficiency has to be developed to be economically profitable. According to the reaction scheme and thermokinetic properties, limits of current batch processes can be overcome by carrying out continuous processes. The studied system is complex due in particular to phase equilibrium changes as well as simultaneous presence of various phenomena (mixing, heat and mass transfers, principal and competitive reactions) which have to be precisely controlled. Therefore, microreactors appear as the appropriate tool for transposition to a continuous process and acquisition of numerous data. In this work, batch reaction was transposed to a micro-scaled continuous device (PFA tube of 508 μm internal diameter), inducing better heat and mass transfer. Study of the influence of the operational conditions (reactants flow, initial ethanol to oil molar ratio, temperature...) revealed the favourable reaction parameters necessary to reach high conversions and yields. In these conditions, we showed the possibility of acquiring kinetic data at the first seconds of the reaction, which was not feasible in a conventional batch process. To acquire data in batch and microreactors, an on-line analysis method by Near InfraRed (NIR) spectroscopy was developed by using gas chromatography as a reference method. PLS models were then set up to quantify the major compounds contents on-line during the transesterification reaction of high oleic sunflower oil with ethanol. These data were used to model occurring phenomena and to determine kinetic constants and transfer coefficients. The model was subsequently used to simulate reactions with other operational conditions and also to work on the separation of reaction products.

This Diploma Thesis deals with the production of butter and buttermilk. In the introduction it informs us about the technology of butter production, there are also the history, the composition and the using butter and its assortment explained. During the production of butter other product -- buttermilk is formed as its secondary product. The Thesis also describes the technology of buttermilk production and its composition. It also focuses on the positive influence of acid buttermilk in case of its regular consumption. The positive influence is mainly caused by the content of benefited lactic acid bacteria. The final part of literature summary comes nearer to the importance and the use of spectroscopy which is measured in the infrared radiation area. It also clarifies the importance close infrared spectroscopy and also concerns with some problems of chemometrics. The problems explain the using of the statistic method in the evaluation of results of the measurement in this work. In the practical part of the Thesis forty samples of fermented buttermilk taken from supermarket chains were compared and evaluated. We were analyzing their pH, titratable acidity, dry matter, fat and protein. After finishing measuring these samples via spectrometer Nicolet FT NIR (spectra in the range from 4000 to 10 000 cm-1) the results were assessed via TQ Analyst software and by using paired T-test to the middle value.

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Submitted by DIEGO ROSSI null (rossi_diego@ig.com.br) on 2016-02-16T18:58:22Z No. of bitstreams: 1 Dissertação D.Rossi - FINAL.pdf: 4611767 bytes, checksum: 71f830e143f447c9e962c2305462a623 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-02-17T16:11:21Z (GMT) No. of bitstreams: 1 rossi_d_me_bauru.pdf: 4611767 bytes, checksum: 71f830e143f447c9e962c2305462a623 (MD5) / Made available in DSpace on 2016-02-17T16:11:21Z (GMT). No. of bitstreams: 1 rossi_d_me_bauru.pdf: 4611767 bytes, checksum: 71f830e143f447c9e962c2305462a623 (MD5) Previous issue date: 2015-12-21 / Este trabalho tem por finalidade a deposição de filmes finos de carbono amorfo hidrogenado (a-C:H) e de filmes finos de carbono amorfo hidrogenado com silício (a-C:H:Si). Analisar a incorporação gradativa de cloro nos filmes, tornando-os clorados (a-C:H:Cl e a-C:H:Si:Cl). As técnicas utilizadas para a deposição dos filmes foram: (i) a deposição à vapor químico assistido por plasma (PECVD) e (ii) implantação iônica por imersão em plasma (PIIID). Os filmes foram produzidos a partir de misturas de vapores de propanol, CH3(CH2)2OH, vapores de tetrametilsilano, Si(CH3)4, vapores de clorofórmio, CHCl3, e argônio, Ar, respectivamente monômero 1, monômero 2, comonômero e gás plasmogênico. O aumento do clorofórmio na alimentação do reator acarretou em mudanças nas estruturas químicas do material depositado e também alterações nas suas características ópticas. Para averiguar as modificações nas propriedades ópticas dos filmes foram calculados o coeficiente de absorção, o índice de refração e o gap óptico com base em espectros de transmitância óptica na região do Ultravioleta, Visível e Infravermelho Próximo, (Uv/Vis/NIR). As modificações nas estruturas químicas dos filmes foram analisadas por espectroscopia de absorção no infravermelho por transformada de Fourier, FTIR, visando revelar os grupos químicos presentes nos filmes. Espectroscopia de fotoelétrons de raios X, (XPS), foi a técnica utilizada para desvendar a composição química elementar dos filmes e a 6concentração dos elementos presentes. As características de molhabilidade dos filmes foram medidas em um goniômetro, através da análise da interação da gota de um fluído com a superfície dos filmes. Espessuras medidas por perfilômetria foram comparadas a valores teóricos provenientes das constantes ópticas. Os resultados do XPS demonstraram a presença de cloro nos filmes, a concentração máxima obtida foi de ~ 8% at. Houve um aumento na taxa de deposição dos filmes em função do aumento da proporção de clorofórmio na entrada do reator. O ângulo de contato apresentou-se em torno de 75° para os filmes aC:H:Cl e em torno de 80° para os filmes a-C:H:Si:Cl. As análises ópticas Uv/Vis/NIR apresentaram índice de refração de ~1.5, calculadas por modelos computacionais iterativos, o gap de Tauc aumentou de 1,9 eV para 2,5 eV para filmes finos a-C:H clorados. / Thin hydrogenated amorphous carbon (a-C:H) and (a-C:H:Si) films were produced and the gradual incorporation of chlorine turn into a-C:H:Cl films and aC:H:Si:Cl films. The a-C:H:Cl and a-C:H:Si:Cl films were produced by plasma enhanced chemical vapor deposition (PECVD) from mixtures of vapor of propane, CH3(CH2)2OH, tetramethylsilane, Si(CH3)4, chloroform, CHCl3, and argon gas, Ar; respectively monomer 1, monomer 2, comonomer and argon gas. The increase of chloroform in the film composition resulted in changes in the chemical structure of the material and also changes in its optical characteristics. To investigate the changes in the optical properties of the films, the absorption coefficient, refractive index and band gap were calculated from optical transmittance spectra in the Ultraviolet, Visible and Near Infrared (Uv/Vis/NIR) regions. The modifications in chemical structures of the films were analyzed by Fourier transform infrared spectroscopy FTIR. X-ray photoelectron spectroscopy (XPS) was the technique used to measure the chemical composition of the films. The wettability characteristics were measured using a goniometer, through the analysis of the interaction of a fluid drop on the surface of the films. Film thicknesses were measured using perfilometry and compared with theoretical values derived from optical data. The XPS results showed chlorine in the film, and the maximum concentration was about 8% at. There was an increase in the deposition rate as 8chloroform proportion reactor inlet was added. The contact angle showed around 75° to a-C:H:Cl films and around 80° to a-C:H:Si:Cl films. The optical analyses Uv/Vis/NIR showed refractive index of ~1.5, calculated for interactive computer models. The Tauc band gap increased from 1,9 eV to 2,5 eV for a-C:H chlorinated films.

Organic solar cell (OSC) has been an active research field over the past decades, due to their intrinsic advantages, such as low consumption of materials and energy, the applicability on flexible substrates and the degradability of the organic components. Compared with the solution processing technology using polymers as electron donor materials, small molecule vacuum deposition is regarded as a promising fabrication method, avoiding the use of toxic aromatic solvents and guaranteeing constant batch-to-batch performance. Moreover, it is much easier to realize multi-junction tandem solar cells (TSCs) by thermal deposition, and the leading power conversion efficiency (PCE) of 13.2% was achieved using three different absorbers by vacuum deposition (“Heliatek sets new organic photovoltaic world record efficiency of 13.2%” 2016). In this dissertation, novel electron donor materials are synthesized based on the molecular skeleton of a famous chromophore, boron dipyrromethene (BODIPY), and chemical modifications are carried out to tune the intense absorption bands of these dyes to near infrared (NIR, λ>750,nm) region. Efficient small molecule NIR absorbers are highly required for TSCs, because they can construct a complementary absorption over the visible and NIR spectral region in cooperation with a wide bandgap material. Three β-fused aza-BODIPY molecules with heterocyclic substituents on α-positions are prepared using organolithium reagents and phthalonitrile as the starting materials. The organolithium reagents, namely N-methylpyrrole, N-methylindole and 2-trimethylsilylthiophene, are used instead of commonly used Grignard reagents. Moreover, three corresponding aza-BODIPY derivatives are obtained by replacing one fluorine atom in the BF_{2} moiety by a cyano group. UV-vis absorption spectra reveal that all these materials are strong NIR absorbers, and their abortion in solid state cover a wide range from 600 to 1000,nm. OSCs with these aza-BODIPY donors give a best PCE of 3.0%, which is a reasonable value for the NIR devices with the maximum and the onset of the EQE spectrum around 850 and 950,nm respectively. A series of furan-fused BODIPYs with a electron withdrawing CF_{3} group on the meso-C are synthesized, and the photophysical/electrochemical properties can be tuned easily by the electronic properties of the substituents on the peripheral aromatic rings. The most promising candidate gives a high PCE of 6.1% in a single junction OSC with a J_{sc} of 13.3,mA/cm^{2}, a V_{oc} of 0.73,V, and a FF of 62.7%. A serial connected TSC is fabricated using this BODIPY as the low bandgap donor and a “green” donor, and its EQE spectrum covers a wide range from 400 to 900,nm. The PCE reaches 9.9% with a J_{sc} of 9.9,mA/cm^{2}, a V_{oc} of 1.70,V, and a FF of 59.0%. Based on the general structure of furan-fused BODIPY, alkyl or fluorinated alkyl substituents with larger volume is introduced on either peripheral aromatic rings or the meso-C. The variations that caused by these substituents on the photophysical and electrochemical properties are negligible. The investigations on the OSCs demonstrate that the introduction of these alkyl chain substituents have positive influence on the PCE values, which benefit mainly from the increased photocurrent. However, there is no positive relationship between the device performance and the volume of the alkyl chain substituents. BODIPY molecules have been demonstrated as efficient and promising NIR electron donor materials for vacuum-deposited OSCs. Taking advantages of facile molecular modification, oustanding photophysical behaviors and tunable electrochemical properties, this series of dyes are also intereting for other semiconductor devices.

Cada vez mais, a indústria requer métodos em tempo real para o controle de qualidade da carne fresca, a fim de melhorar a eficiência produtiva, garantir homogeneidade dos produtos e atender expectativas do consumidor. No presente trabalho, a imagem hiperespectral foi empregada para avaliação da qualidade da carne de bovinos Nelore com ênfase para a maciez e características relacionadas, e, ainda, a construção de mapas de distribuição das características para observação da variabilidade dessas entre e dentro de amostras. Para investigar se o uso de diferentes grupos musculares aumenta a variabilidade dos valores de referência, promovendo melhora nos modelos de predição e classificação da maciez, foram utilizadas amostras do músculo Longissimus(94) e B. femoris (94) de bovinos Nelore. Para investigar se a seleção da região de interesse (ROI) na imagem no exato local onde foi coletado o cilindro para determinação da força de cisalhamento melhora os modelos de predição e classificação da maciez, foram utilizadas amostras do músculo Longissimus (50). Após a aquisição da imagem (1.000 - 2.500 nm), cada amostra foi avaliada seguindo metodologia tradicional para força de cisalhamento, matéria seca, proteína bruta, lipídios e comprimento de sarcômero. Os dados espectrais e espaciais foram analisados por técnicas quimiométricas e modelos PLSR e PLS-DA foram construídos. Em relação à abordagem com diferentes músculos, os dados foram modelados separadamente para evitar que fenômenos devidos às diferenças musculares fossem equivocadamente atribuídos às características investigadas. Ainda assim, amostras de Longissimus com maciez inaceitável foram classificadas com sensibilidade = 87% e amostras macias de B. femoris com sensibilidade = 90%, ambas na validação externa. Com relação à forma de seleção da ROI, os modelos de classificação utilizando ROI local apresentaram melhor desempenho do que os modelos com ROI de toda a amostra (sensibilidade na validação externa para a classe dura = 33% e 70%, respectivamente). Entretanto, o modelo mais geral tem desempenho melhor na construção de mapas de distribuição da maciez, com de 72% das imagens preditas corretamente classificadas. / Increasingly, industry requires real-time methods for quality control of fresh meat in order to improve production efficiency, ensure product homogeneity and meet consumer expectations. In the present work, the hyperspectral image was used to evaluate the quality of Nellore beef with emphasis on tenderness and characteristics related to it, and also the construction of distribution maps to observe the variability of these characteristics between and within samples. To investigate whether the use of different muscle groups increases the variability of the reference values, improving tenderness prediction and classification models, samples from Longissimus (94) and B. femoris (94) of Nellore cattle were used. To investigate whether the selection of the region of interest (ROI) in the image at the exact location where the shear force cores were collected improves tenderness prediction and classification models, samples from Longissimus muscle were used (50). After image acquisition (1,000 - 2,500 nm), each sample was evaluated following traditional methodology for shear force, dry matter, crude protein, lipids and sarcomere length. The spectral and spatial data were analyzed by chemometric techniques and PLSR and PLS-DA models were constructed. Regarding the approach with different muscles, the data were modeled separately to avoid that phenomena due to muscle differences were mistakenly attributed to the characteristics investigated. Nevertheless, samples from Longissimus with unacceptable tenderness were classified with sensitivity = 87% and tender samples from B. femoris with sensitivity = 90%, both in the external validation. Regarding the ROI selection, the classification models using local ROI presented better performance than the ROI models of the whole sample (external validation sensitivity for the tough class = 33% and 70%, respectively). However, the more general model had better performance in the tenderness distribution maps, with 72% of predicted images correctly classified.

A metodologia da espectroscopia no infravermelho próximo (NIRS Near Infrared Spectroscopy), recentemente empregada em várias áreas da ciência do solo associada à quimiometria, está sendo utilizada na quantificação de atributos químicos e físicos do solo. Esta técnica rápida, não destrutiva, reprodutiva e de baixo custo fundamenta-se na medida da intensidade de absorção de radiação eletromagnética na região do infravermelho próximo. De um modo geral, a NIRS tem se mostrado uma ferramenta válida para quantificar o teor de carbono (C) em amostras de solo. A importância da determinação do teor de C no solo reside no fato de representar a fixação do CO2 atmosférico na forma de matéria orgânica do solo (MOS), um compartimento chave do ciclo global deste elemento. O manejo sustentável dos agrossistemas deve assegurar a manutenção dos teores de carbono através da restituição de matéria orgânica ao solo. No caso da cultura de cana de açúcar, a substituição do sistema de colheita de manual com prévia queima da palhada (cana queimada) para mecanizada (cana crua) em que a palhada permanece sobre o solo, favorece o acúmulo e a diferenciação do teor de C no solo. O presente trabalho teve como objetivo comparar a metodologia NIRS, associada à quimiometria, com o método de referência tradicional da combustão a seco na quantificação do teor de C em amostras de solo provenientes do agroossistema cana-de-açúcar. Foram analisadas amostras de solo provenientes de três situações: cana queimada, cana crua e uma área nativa, totalizando 450 amostras, apresentando respectivamente teores médios de C de 18,30, 22,36 e 24,72 g kg-1. Modelos de calibração foram ajustados utilizando PLS nos dados espectrais, submetidos a 1ª derivada suavizados com Savitz Golay alisados com janela 15. As amostras foram aleatorizadas e divididas em 3 partes iguais, sendo 2/3 das 450 amostras para a calibração e validação cruzada e 1/3 para validação externa. Os parâmetros quimiométricos para a avaliação da qualidade do modelo escolhido foram: RMSEC, RMSECV, RMSEP, R2, BIAS, CV% e RPD. Os resultados de RMSEC> 1,93, RMSEP > 1,90, satisfatórios R2 0,94. Na área nativa obteve-se RMSEP 1,53 e R2 0,95, e na área de cana queimada RMSEP 1,90 e R2 0,50. Ao comparar as técnicas, de referência e NIRS, demonstrou que a técnica de referência tem SD 0,12 e CV% 0,65 e a técnica NIRS SD 0,18 e CV% 0,18, provando a eficiência do emprego da NIRS para a determinação de C no solo / The methodology of near infrared spectroscopy, recently used in several areas of soil science associated with chemometrics, has been used in the quantification of chemical and physical soil attributes. This rapid, nondestructive, reproductive and low cost technique is based on the measurement of the intensity of the electromagnetic radiation absorption in the near infrared region. In general, the NIRS has been proved as an effective tool to quantify the carbon (C) content in soil samples. The importance this determination is that it represents the fixation of atmospheric CO2 as soil organic matter (SOM), an important compartment of the global C cycle. The sustainable management of agro-systems must assure the maintenance of the carbon levels through the restoration of soil organic matter. In case of sugar cane crop, the replacement of the manual cutting system, preceded by residue burning (preharvest burning), by mechanized harvest (raw sugar cane) where the straw remains on the field, favors the accumulation and differentiation of the C content in the soil. This study aimed to compare the NIRS methodology, associated with chemometrics, to the traditional reference method of dry combustion quantifying the C content in soil samples from the sugar cane agro-system. Soil samples from three situations were analyzed: burnt sugar cane, raw sugar cane and a native area, totalizing 450 samples, with levels of respectively 18.30, 22.36 and 24.72 g C kg-1. Calibration models were adjusted using PLS in the spectral data, submitted to the first derivative and smoothing with Savitz Golay with window 15. Samples were randomized and divided into 3 parts: 2/3 of the 450 samples were designated to calibration and cross validation, and the odder 1/3 to external validation. The chemometrics parameters RMSEC, RMSECV, RMSEP, R2, BIAS, CV% and RPD were chosen to estimate the quality of the model. The results of RMSEC> 1.93, RMSEP> 1.90, and R2 0.94 were satisfactory. In the native area a range of RMSEP 1.53 and R2 0.95 was obtained, while in the area of burnt sugar cane it was R2 0.50 and RMSEP 1.90. Comparing the reference technique and NIRS, the first showed a SD 0.12 and CV 0.65%, while a SD 0.18 CV 0.81% was obtained for the second, proving the efficiency of the use of NIRS to determine C content in soil

Orientador: Jarbas José Rodrigues Rohwedder / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T12:58:01Z (GMT). No. of bitstreams: 1 Killner_MarioHenriqueMontazzolli_D.pdf: 3491134 bytes, checksum: 684c66e65646bff8d702f6275096bfa6 (MD5) Previous issue date: 2013 / Resumo: No presente trabalho foram desenvolvidos novos métodos analíticos empregando espectroscopia NIR e de RMN H, visando o monitoramento on-line da reação de transesterificação de óleos vegetais para a produção de biodiesel e determinação de parâmetros de qualidade de diesel combustível através da espectroscopia de RMN H. Empregando a espectroscopia NIR foi utilizada pela primeira vez a região espectral compreendida entre 5928 e 5959 cm para a determinação on-line, por meio de um modelo de regressão multivariada, das taxas de conversão dos triglicerídeos provenientes de óleo de soja em ésteres de ácidos graxos (biodiesel). O modelo desenvolvido foi avaliado no monitoramento de duas reações de transesterificação conduzidas a 20 ± 0,2 °C e 55 ± 0,2 °C que apresentaram erros médios de previsão para um conjunto de validação de 0,6 e 1,0% de conversão, respectivamente. De maneira similar foram desenvolvidos outros 3 métodos analíticos empregando um espectrômetro de RMN H de bancada de baixo campo para a determinação das taxas de conversão dos triglicerídeos provenientes do óleo de semente colza em ésteres metílicos de ácidos graxos. O primeiro método utiliza as áreas dos picos dos prótons metoxílicos dos ésteres de ácidos graxos e dos prótons etilênicos da cadeia de ácidos graxos para a determinação direta das taxas de conversão dos triglicerídeos. Um segundo método utiliza um modelo de regressão PLS para a determinação das taxas de conversão. Finalmente, o terceiro método emprega os desvios químicos dos prótons hidroxílicos do metanol e glicerol presentes na fase oleica para determinar as taxas de conversão dos triglicerídeos em ésteres. Outro importante resultado alcançado durante o desenvolvimento do trabalho foi o entendimento da partição das moléculas dos alcoóis (metanol e glicerol) entre as duas fases que constituem o meio reacional durante o processo de transesterificação. Este fato é importante para compreender melhor o mecanismo de reação de produção de biodiesel, uma vez que a taxa de reação depende da quantidade de metanol e catalisador dissolvidos inicialmente na fase oleica. A possibilidade de identificar os valores da partição dos alcoóis ao final da reação possibilita também o desenvolvimento de técnicas de separação que permitam otimizar a recuperação de biodiesel e metanol em uma planta de produção de biodiesel, refletindo diretamente na redução dos custos. Modelos de calibração PLS empregando espectros de RNM H de baixo campo também foram desenvolvidos para a determinação de diversos parâmetros de qualidade de diesel combustível B5, como: Massa Específica, Curva de Destilação para 10%, 50%, 85% e 90% de recuperação, Número de Cetano e Ponto de Fulgor. Os espectros foram adquiridos sem qualquer tipo de preparo de amostra ou utilização de padrão interno. Todos os modelos desenvolvidos apresentaram valores de RMSEP inferiores às reprodutibilidades das técnicas analíticas empregadas atualmente como referência pelas normas ASTM e ABNT NBR. A técnica de RMN H de baixo campo foi empregada também para a determinação do Teor de Biodiesel nas amostras de diesel combustível, apresentando um erro relativo médio de 2,5% em relação a técnica analítica de referência / Abstract: The present work reports on the development of new analytical methods, based on NIR and H NMR spectroscopy, aiming at on-line monitoring of the transesterification reaction of vegetable oils to produce biodiesel, and the determination of quality parameters of diesel fuel applying H NMR spectroscopy. The NIR spectral region between 5928 and 5959 cm-1 was used for the first time for on-line determination, employing a multivariate model, of the conversion ratio of triglycerides from the soybean oil into fatty acid methyl esters (biodiesel). The developed model was evaluated on the transesterification reaction monitoring of two new reactions carried out at 20 ± 0.2 °C and 55 ± 0.2 °C which showed RMSEP of 0.6 and 1.0 %, respectively. In a similar way 3 analytical methods were developed using a bench-size low-field NMR H spectrometer to determine the triglycerides (rapeseed oil) conversion ratios into fatty acid methyl esters. The first method applies the area of the methoxylic protons peak of fatty acid methyl esters and the ethylenic protons peak of fatty acid chain for direct determination of the triglycerides conversion ratios. A second method applies a PLS regression model to determine the conversion ratio. finally, a third method applies the hydroxylic protons chemical shift of methanol and glycerol present in the oleic phase to correlate the conversion ratio of triglycerides into esters. Another important result obtained during the development of this work was the comprehension of partitioning of alcohol molecules (methanol and glycerol) between the two phases that constitute the reactional medium during biodiesel production process. This fact is relevant to understand the reaction mechanism of the biodiesel production, because the reaction rate strongly depends on the methanol and catalyst amount initially dissolved in the oleic phase. Also, the possibility of identification of the alcohols partitioning values at the end of the reaction process helps in the development of new separation techniques to optimize the biodiesel and methanol recovering in a biodiesel producing plant, directly influencing the process costs. PLS regression models applying the low-field H NMR spectra were also developed for the determination of different quality parameters of diesel fuel (B5), such as: Specific Gravity, Distillation Curve (10%, 50%, 85% e 90% of recovering), Cetane Number and Flash Point. The spectra were acquired without adding any reference compound or sample pre-treatment. All regression models developed showed RMSEP values lower than the reproducibility of the analytical techniques used as reference by ASTM and ABNT NBR. The low-field H NMR technique were also used to determine the biodiesel content in diesel fuel samples, showing a mean relative error of 2.5% in comparison to the standard analytical technique / Doutorado / Quimica Analitica / Doutor em Quimica