ABSTRACT In drying processes and in the storage of agricultural products, the study of thermodynamic properties is indispensable in the search for solutions to issues of stability and optimization of the conditions of agro-industrial processes. The aim of this work was to determine hygroscopic equilibrium isotherms and study the thermodynamic properties of white bean grains submitted to different equilibrium temperatures and relative humidity levels. Phaseolus vulgaris L. grains were used, with an initial water content of 0.142 (dry basis), temperature variations ranging between 18 and 50 °C, and relative humidity between 19% and 78%. Fifteen mathematical models were tested to determine the hygroscopic equilibrium isotherms, and the Sigma model was the one that best suited the experimental data. The thermodynamic properties of the beans were determined from Sigma-Copace model. The integral isosteric heat of desorption and the differential entropy increased with the reduction of the water content, and the phenomenon of water desorption of white bean grains was a non-spontaneous process controlled by enthalpy.

ABSTRACT Knowledge regarding the static pressure drop in granular layers is of fundamental importance in the development of efficient drying and aeration projects of agricultural products. Thus, the objective of this study was to evaluate the effects of impurity contents on the static pressure drop in different bed depth of castor bean grains, as well as modify the mathematical models per the obtained experimental data and select the model that best represents this phenomenon. First, impurities in castor bean grains of the Guarani variety were eliminated and 6% of the moisture content (dry basis) was retained. The coarse impurity contents were obtained with 2%, 4%, and 6% of mass addition. The pressure drop in different bed depth of clean and impure castor bean grains were determined using an experimental determination equipment of pressure drop in bed depth with an airflow rate ranging 0.2 - 1.0 m3 s−1 m−2. The pressure drop linearly increases with an increase in the depth of the grain layer, and the increase in the airflow rate leads to an increased pressure drop in the castor bean grains layer. The impurity contents increase causes a reduction in pressure drop. The models that best represent castor beans grains pressure drop experimental data, without and with impurities, are Hukill & Ives (1955) and Nimkar & Chattopadhyay (2002), respectively.

ABSTRACT Knowledge on sorption isotherms is important for predicting drying and storage processes of a product. A sorption isotherm can be generated from two processes: desorption and adsorption. The lag between these two curves is called hysteresis. Static method was used to obtain the equilibrium moisture content of paddy rice grains, in different temperature (10, 20, 30, 40 and 50 ± 1°C) and relative humidity (between 11 and 76% ± 2%) conditions. Equilibrium moisture content data were correlated with eight mathematical models and. The Chung Pfost model had the best fit to the experimental data. Desorption and adsorption isotherms, represented by the Chung Pfost model, showed a sigmoidal shape, characteristic of type II curve. Equilibrium moisture content values obtained by desorption were higher than those obtained by adsorption, evidencing the hysteresis phenomenon.

ABSTRACT The present research aimed to study the water sorption behavior of quinoa seeds analyzing the hysteresis phenomenon and determining thermodynamic properties. Static gravimetric technique was used to obtain the equilibrium moisture content of quinoa seeds in different temperature conditions (15, 25, 35 e 50 °C) and relative humidity (between 11 and 96%). Equilibrium moisture content data were adjusted by eight mathematical models and the Modified Halsey model was the best one to describe the water sorption phenomena of quinoa seeds. Hygroscopic equilibrium moisture content of quinoa seeds is directly proportional to the water activity and decreases with increasing temperature. The hysteresis phenomena were observed throughout the range of water activity, showing more evident at low temperatures. Integral isosteric heat and differential entropy decreased with the increase of equilibrium moisture content. Gibbs free energy decreased with the increase of temperature and equilibrium moisture content. Compensation enthalpy-entropy theory was confirmed and the sorption mechanism is controlled by enthalpy.

ABSTRACT The quality of sesame (Sesamum indicum L.) seeds is directly influenced by their physical characteristics, which are seldom studied notwithstanding their extreme importance in the entire production chain. Therefore, the objective of this study was to quantify the physical properties of two types of sesame seeds, collected at three points in the plant with different maturation levels, measured with digital caliper, and to evaluate the feasibility of using a digital image to determine their physical characteristics. The seeds were initially evaluated for water content and mass of 1000 seeds, and later with the data of the characteristic dimensions A (length), B (width), and C (thickness), obtained by a caliper and digital images, we determined their sphericity, circularity, projected area, and geometric diameter. We observed that water content did not affect the physical properties of the cream (CNPA G4) and black sesame cultivars. In addition, seeds of the black cultivar presented higher results than the seeds of the cream cultivar for the mass of 1000 seeds (2.7 ± 0.08 g), sphericity (58.8 ± 0.47%), projected area (4.03 ± 0.12 mm2), and geometric diameter (1.65 ± 0.03 mm). Seed batches harvested after 70% maturation had the highest mass of 1000 seeds (2.7 ± 0.12 g). The results of the physical analyses of sesame seeds performed with caliper and digital image are equivalent, which shows that digital images can be used as tools to obtain the physical properties of seeds.

ABSTRACT This study aimed to determine the thermodynamic properties of sorption processes (desorption and adsorption) of rice in the husk, cv. Urucuia. A static-gravimetric method was used to reach equilibrium moisture content at different temperatures (10, 20, 30, 40, and 50 °C ± 1°C) and relative humidity levels (10, 30, 50, 70, and 90 % ± 2%). A decrease in moisture content led to an increment of the integral isosteric heat of sorption, indicating a higher demand for energy to remove moisture from the product. Differential entropy of sorption decreased along with a moisture content increment, with higher values for desorption. This indicates a higher mobility of water molecules during desorption if compared to adsorption. Gibbs free energy decreased with increasing temperature in both processes, with positive values for desorption (endothermic process), and negative for adsorption (exothermic process). The enthalpy-entropy compensation theory is valid for both sorption phenomena (desorption and adsorption) of rice in the husk, being both processes enthalpy controlled.

ABSTRACT The control of the temperature of the storage air have the ability to improve a better preservation of some types of agricultural products. However, the most effective temperature for storage as well as the duration of storage varies between products. Therefore, special attention should be concentrated on the storage temperature and its effects on the integrity and longevity of the produce. The objective of the present study was to evaluate the effects of storage temperature and storage period on the quality of castor beans. Castor seeds with a water content of approximately 6.1% (w.b.) were stored for 180 days at temperatures of 15, 25 and 35 °C. The quality of the seeds was evaluated every 45 days throughout the study period by measuring dry matter loss, electrical conductivity, color, and the free fatty acid and peroxide content of the crude oil extracted. Our results indicated that: a) higher storage temperature negatively affect the quality of the seeds and the extracted oil; b) the negative effect of temperature increase with longer storage period; c) the storage temperature of 15 °C least affect the quality of castor bean and the extracted oil.

RESUMO Objetivou-se determinar as propriedades termodinâmicas de grãos de feijão danificados. Foram utilizados grãos com teor de água inicial de 53,85% (b.s.); parte dos grãos foi utilizada para se obter as isotermas de dessorção, enquanto que a outra foi submetida a secagem até o teor de água de 5,26% (b.s.), para que a mesma fosse submetida ao processo de adsorção. Para a indução da danificação foi utilizado um Stein Breakage Tester. Para obter o teor de água de equilíbrio, os grãos foram colocados em câmara climática cujas temperaturas foram de 20, 30, 40 e 50 ± 1 ºC combinadas com umidades relativas de 30, 40, 50, 70 e 90 ± 3%. Na dessorção, os grãos danificados apresentaram menor entalpia diferencial quando comparados com a testemunha enquanto o inverso foi observado na adsorção. A danificação mecânica provocou a formação de um número maior de sítios disponíveis de sorção, resultando em maiores valores de entropia diferencial na adsorção e menores valores na dessorção quando comparados com a testemunha. A danificação mecânica não teve efeito sobre a energia livre de Gibbs.

ABSTRACT This study aims to determine the thermodynamic properties of damaged beans. Grains with initial moisture content of 53.85% (d.b.) were used. A part of the grains was used to obtain the desorption isotherms, while another part was subjected to drying until a moisture content of 5.26% (d.b.) was achieved; therefore, it was subjected to the adsorption process. To induce damage, a Stein breakage tester was used. To obtain the equilibrium moisture content, grains were placed in a climatic chamber whose temperatures were 20, 30, 40, and 50 ± 1 °C combined with a relative humidity of 30, 40, 50, 70, and 90 ± 3%. Although in the desorption process, damaged grains had a lower differential enthalpy compared with the control, the reverse behavior was observed in the adsorption process. Mechanical damage caused the formation of a greater number of available adsorption sites, resulting in higher differential entropy values in adsorption and lower values in desorption compared with the control. The mechanical damage had no effect on the Gibbs free energy.

RESUMO Objetivou-se, neste trabalho, modelar a cinética de sorção de água de grãos de feijão danificado. Foram utilizados grãos com teor de água inicial de 53,85% base seca (bs). Parte dos grãos foi utilizada para se obter as isotermas de dessorção enquanto outra foi submetida à secagem até o teor de água de 5,26% (bs), para que a mesma fosse submetida à adsorção. Para a indução da danificação foi utilizado um Stein Breakage Tester. Visando obter o teor de água de equilíbrio, os grãos foram colocados em câmara climática cujas temperaturas foram de 20, 30, 40 e 50 ± 1 ºC combinadas com umidades relativas de 30, 40, 50, 70 e 90 ± 3%. O modelo de GAB ajustou-se bem aos dados experimentais de equilíbrio higroscópico de grãos danificados e testemunha. Com o aumento de temperatura os valores do teor de água da monocamada diminuíram para processos de adsorção e dessorção variando entre 9,84 a 5,10% b.s. O menor teor de água da monocamada nos grãos danificados indica que é necessário menor teor de água para garantir sua conservação.

ABSTRACT The objective of this study was to model the water sorption kinetics of damaged beans. Grains with initial moisture content of 53.85%, dry basis (d.b.), were used. One portion of the grains was used to obtain desorption isotherms, while the other was subjected to drying until the moisture content of 5.26% (d.b.), so that it was subjected to the adsorption. For the induction of damage, a Stein Breakage Tester was used. To obtain the equilibrium moisture content, grains were placed in a climatic chamber at 20, 30, 40 and 50 ± 1 °C combined with relative humidity of 30, 40, 50, 70 and 90 ± 3%. The GAB model fitted well to the equilibrium moisture experimental data of damaged grains and control. With increasing temperature, the monolayer moisture contents decreased in adsorption and desorption processes, ranging from 9.84 to 5.10% d.b. The lower moisture content in the monolayer in damaged grains indicates that lower moisture content is necessary to ensure their conservation.

RESUMO Sementes de Lactuca sativa são altamente sensíveis às condições edafoclimáticas; portanto, faz-se necessário armazená-las de forma segura e racional, a fim de manter suas características qualitativas e quantitativas. Estudos sobre a higroscopicidade têm a finalidade de amenizar possíveis alterações nos produtos agrícolas em determinadas condições climáticas. Dito isto, objetivou-se, neste trabalho, determinar o modelo matemático mais adequado para predizer as isotermas de dessorção de sementes de Lactuca sativa. O equilíbrio higroscópico foi alcançado por meio do método estático-gravimétrico, nas temperaturas de 10, 20, 30, 40 e 50 °C e atividade de água entre 0,11 e 0,96. Seis modelos matemáticos foram ajustados aos dados experimentais do teor de água de equilíbrio das sementes de Lactuca sativa. O modelo mais adequado foi escolhido considerando-se o coeficiente de determinação (R2), magnitude do erro médio relativo (MRE), desvio padrão da estimativa (SE) e análise de distribuição de resíduos. O modelo de Oswin Modificado foi o que melhor representou a higroscopicidade de sementes de Lactuca sativa, apresentando valores de 8,02% e 0,55 de MRE e SE, respectivamente, e distribuição aleatória dos resíduos. As curvas isotérmicas de sementes de Lactuca sativa estimadas pelo modelo Oswin Modificado apresentaram formato sigmoidal, característica de curva do tipo II.

ABSTRACT Lactuca sativa seeds are highly sensitive to climate conditions; thus, they should be stored securely to maintain their qualitative and quantitative characteristics. Studies on hygroscopicity aim to decrease possible changes in agricultural products under specific environmental conditions. Accordingly, this study aims to develop an appropriate mathematical model to represent the desorption isotherms of Lactuca sativa seeds. The hygroscopic equilibrium was achieved using a static-gravimetric method at temperatures of 10, 20, 30, 40 and 50 °C and water activity in the range 0.11-0.96. Six mathematical models were fitted to the experimental data of the equilibrium moisture content of Lactuca sativa seeds. The best model was chosen based on the determination coefficient (R2), magnitude of mean relative error (MRE), standard deviation of the estimate (SDE), and analysis of residue distribution. The modified Oswin model best represented the hygroscopicity of the Lactuca sativa seeds, with values of 8.02% and 0.55 for the MRE and SDE, respectively; moreover, the residual values were randomly distributed. The shape of the isotherms of the Lactuca sativa seeds estimated using the modified Oswin model is sigmoidal, which is characteristic of a type II curve.

RESUMO Este trabalho teve como objetivo avaliar o efeito da danificação mecânica na histerese de grãos de feijão, em diferentes condições de temperatura e umidade relativa. Foram utilizados grãos de feijão (Phaseolus vulgaris L.) colhidos manualmente com teor de água de 35% (b.u.). Parte desse produto foi submetido à danificação mecânica induzida (via Stein Breakage Tester) e a secagem controlada (amostra danificada e testemunha), para os processos de dessorção e adsorção. As isotermas de adsorção e dessorção da água foram analisadas para diferentes condições de temperatura: 20, 30, 40 e 50 oC e umidade relativa: 0,3; 0,4; 0,5; 0,7 e 0,9 (decimal). Os dados de teor de água de equilíbrio foram correlacionados com seis modelos matemáticos; o modelo Oswin Modificado foi o que melhor se ajustou aos dados experimentais. Uma vez visualizadas as isotermas supracitadas foi possível verificar o fenômeno da histerese das amostras danificadas e testemunha, fenômeno este mais pronunciado na amostra testemunha.

ABSTRACT This study aimed to evaluate the effect of mechanical damage on the hysteresis of beans with induced mechanical damage under different conditions of temperature and relative humidity. Beans (Phaseolus vulgaris L.) harvested manually with 35% water content (w.b.) were used. Part of this product was subjected to induced mechanical damage by Stein Breakage Tester and controlled drying (damaged and control sample), for sorption processes. The sorption isotherms of water were analyzed for different temperature conditions: 20, 30, 40 and 50 oC; and relative humidity: 0.3; 0.4; 0.5; 0.7 and 0.9 (decimal). Equilibrium moisture content data were correlated with six mathematical models, and the Modified Oswin model was the one that best fitted to the experimental data. According to the above mentioned isotherms, it was possible to observe the phenomenon of hysteresis of damaged and control samples, and this phenomenon was more pronounced in control ones.

RESUMO O conhecimento da sorção de água pelos produtos agrícolas é extremamente importante para a tomada de decisões durante os procedimentos pós-colheita; visando aperfeiçoar este conhecimento as propriedades termodinâmicas relativas à sorção de água fornecem dados úteis. Propriedades termodinâmicas de grãos de mamona relacionadas à sorção, foram determinadas. A técnica de gravimetria estática em diferentes temperaturas (25, 35, 45 e 55 ± 1 °C) foi usada e soluções salinas saturadas na faixa de 37-87% ± 2% foram utilizadas para criar o requerido ambiente controlado de umidade relativa. Entalpia diferencial, entropia diferencial e energia livre de Gibbs foram calculadas e decresceram com o aumento dos valores de teor de água de equilíbrio.

ABSTRACT Knowledge on the water sorption within agricultural products is extremely important for decision making during post-harvest procedures. In order to improve this knowledge, thermodynamic properties regarding water sorption provide useful data. Thermodynamic properties of castor beans, related to sorption, were determined. Static gravimetric technique under different conditions of temperature (25, 35, 45 and 55 ± 1 °C) was used. Saturated salt solutions in the range of 37-87% ± 2% were utilized to create the required controlled humidity environment. After the sorption procedure, differential enthalpy, differential entropy and Gibbs free energy of this process were calculated and decreased with increased values of equilibrium moisture content.

RESUMO As isotermas de sorção são de grande importância em procedimentos pós-colheita de produtos agrícolas, em especial para predizer os processos de secagem e armazenamento os quais auxiliam a estabelecer o teor de água final no produto em determinada condição ambiental. A histerese é um fenômeno que ocorre em virtude da diferença entre as curvas de adsorção e dessorção que auxilia a avaliação de deteriorações químicas e microbiológicas indicando a estabilidade de produtos armazenados. Isotermas de sorção de grãos de mamona foram determinadas e a histerese analisada. Utilizou-se a técnica de gravimetria estática em diferentes temperaturas (25, 35, 45 e 55 ± 1 °C). Soluções salinas saturadas na faixa de 37-87% ± 2% foram utilizadas para criar o requerido ambiente controlado de umidade relativa. Os dados de teor de água de equilíbrio foram correlacionados com diferentes modelos matemáticos e o modelo de Halsey Modificado apresentou bom ajuste aos dados, de acordo com procedimentos estatísticos. Histerese entre as isotermas de adsorção e dessorção está presente na faixa de 0,2-0,9 de atividade de água independentemente da temperatura; este fenômeno decresce com o aumento da temperatura.

ABSTRACT Sorption isotherms are of great importance in post-harvest procedures, especially for predicting drying and storage, which help to establish the final moisture content of the product under certain environmental condition. Hysteresis is a phenomenon that occurs due to the difference between adsorption and desorption curves, which aids the evaluation of chemical and microbiological deteriorations, indicating the stability of stored products. Moisture sorption isotherms of castor beans were determined and hysteresis was analyzed. Static gravimetric technique at different temperatures (25, 35, 45 and 55 ± 1 °C) was used. Saturated salt solutions in the range of 37-87% ± 2% were utilized to create the required controlled relative humidity environment. Equilibrium moisture content data were correlated by different mathematical models and the Modified Halsey model presented good adjustment for the data, according to statistical procedures. Hysteresis between adsorption and desorption isotherms is present over the range of 0.2-0.9 of water activity, regardless of the temperature. This phenomenon decreases with temperature increase.

RESUMO A jabuticaba é um fruto nativo do Brasil e além de conter muitas qualidades nutricionais também possui bom campo para a utilização em subprodutos como farinhas para bolos e biscoitos, suco, licor, geleia e outros. Objetivou-se modelar a cinética de secagem e determinar as propriedades termodinâmicas de casca de jabuticaba em diferentes temperaturas do ar de secagem. Foram utilizadas jabuticabas maduras, colhidas e separadas da polpa manualmente, da espécie Myrciaria jaboticaba. A secagem foi realizada em estufa de circulação forçada de ar com velocidade de 5,6 m s-1 nas temperaturas de 40; 50; 60 e 70 °C. Seis modelos matemáticos usualmente utilizados para a representação do processo de secagem de produtos agrícolas foram ajustados aos dados experimentais. A relação do tipo Arrhenius foi utilizada para representar a constante de secagem em função da temperatura. O modelo de Midilli foi o que melhor se ajustou aos dados experimentais da secagem. A constante de secagem aumentou com o incremento da temperatura de secagem e proporcionou energia de ativação de 37,29 kJ mol-1. A entalpia e a energia livre de Gibbs diminuíram com o aumento da temperatura de secagem; já a entropia diminuiu e foi negativa.

ABSTRACT Jabuticaba is a fruit native of Brazil and, besides containing many nutritional qualities, it also has a good field for use in products such as flour for cakes and biscuits, juice, liqueur, jelly and others. This study aimed to model the drying kinetics and determine the thermodynamic properties of jabuticaba peel at different drying air temperatures. Ripe fruits of jabuticaba (Myrciaria jaboticaba) were collected and pulped manually. Drying was carried out in a forced-air circulation oven with a flow of 5.6 m s-1 at temperatures of 40, 50, 60 and 70 °C. Six mathematical models commonly used to represent the drying process of agricultural products were fitted to the experimental data. The Arrhenius model was used to represent the drying constant as a function of temperature. The Midilli model showed the best fit to the experimental data of drying. The drying constant increased with the increment in drying temperature and promoted an activation energy of 37.29 kJ mol-1. Enthalpy and Gibbs free energy decreased with the increase in drying temperature, while entropy decreased and was negative.

RESUMO Objetivou-se, com este trabalho, avaliar a influência dos níveis de torrefação e moagem sobre o teor de água e ângulo de repouso de café, durante o armazenamento. Foram utilizados grãos de café cru (Coffea canephora e Coffea arabica), descascados e secos e torrados em dois níveis: média clara (SCAA#65) e moderadamente escura (SCAA#45). Os grãos foram então moídos em três granulometrias: fina (0,59 mm), média (0,84 mm) e grossa (1,19 mm) além do lote de café inteiro. Realizada a moagem as amostras foram armazenadas em duas temperaturas (10 e 30 ºC) e analisadas em cinco tempos distintos (0, 30, 60, 120 e 180 dias). A torrefação a nível moderadamente escuro proporcionou menores valores de teor de água. Obtiveram-se, com amostras mais finas, maiores valores de ângulo de repouso. Conclui-se que a granulometria, o nível de torrefação e o tempo de armazenamento afetaram significativamente o teor de água e o ângulo de repouso do café.

ABSTRACT The present study evaluates the influence of the level of roasting and the grind size on the moisture content and repose angle of coffee during storage. Raw coffee beans (Coffea canephora and Coffea arabica), hulled and dried, were roasted to two different levels: medium light (SCAA#65) and moderately dark (SCAA#45). The beans were then ground into three different grind sizes: fine (0.59 mm), medium (0.84 mm) and coarse (1.19 mm). An additional coffee lot was kept whole. Following grinding, samples were stored at two different temperatures (10 and 30 ºC) and analyzed after five different storage durations (0, 30, 60, 120 and 180 days). The moderately dark roast was found to have a lower moisture content. Finely ground samples had higher angles of repose. It is concluded that the grind size, level of roasting and duration of storage significantly affect the moisture content and angle of repose of coffee.