Biblioteca Digital

Brazil is considered one of the largest producers and consumers of tropical fruits. Green coconut (Cocos nucifera L.) stands out not only for its production and consumption, but also for the high amount of waste produced by coconut water industry and in natura consumption. Therefore, there is a need for utilization of this by-product. This study aims to study the adsorption isotherms of green coconut pulp and determine its isosteric heat of sorption. The adsorption isotherms at temperatures of 30, 40, 50, 60, and 70 °C were analyzed, and they exhibit type III behavior, typical of sugar rich foods. The experimental results of equilibrium moisture content were correlated by models present in the literature. The Guggenheim, Anderson and De Boer (GAB) model proved particularly good overall agreement with the experimental data. The heat of sorption determined from the adsorption isotherms increased with the decrease in moisture content. The heat of sorption is considered as indicative of intermolecular attractive forces between the sorption sites and water vapor, which is an important factor to predict the shelf life of dried products.; O Brasil é considerado um dos maiores produtores e consumidores de frutas tropicais. O coco verde (Cocos nucifera L.) se destaca tanto em termos de produção e consumo quanto em quantidade de resíduos gerada por indústrias de água de coco e pelo consumo in natura. Portanto...

The objective of this research was the preparation of a silsesquioxane functionalized with eight chloropropyl chains (T8-PrCl) and of a new derivative functionalized with a pendant linear chain (2-amino-1,3,4-thiadiazole - ATD; T8-Pr-ATD). The two nanostructured materials were characterized by 13C and 29Si NMR, FTIR and elemental analysis. The new nanostructured material, octakis[3-(2-amino-1,3,4-thiadiazole)propyl] octasilsesquioxane (T8-Pr-ATD), was tested as a ligand for transition-metal ions with a special attention to adsorption isotherms. The adsorption was performed using a batchwise process and the organofunctionalized surface showed the ability to adsorb the metal ions Cu (II), Co (II), and Ni (II) from water and ethanol. The adsorption isotherms were fitted by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) model. The kinetics of adsorption of metals were performed using three models such as pseudo-first order, pseudo-second order and Elovich. The Langmuir and Elovich models were the most appropriate to describe the adsorption and kinetic data, respectively. Furthermore, the T8-Pr-ATD was successfully applied to the analysis of environmental samples (river and sea water). Subsequently, a new nanomaterial was prepared by functionalization of the T8-Pr-ATD with a Mo (II) organometallic complex (T8-Pr-ATD-Mo). Only a few works in the literature have reported this type of substitution...

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES); Pós-graduação em Agronomia (Ciência do Solo) - FCAV; A informação sobre a adsorção de selênio (Se) em solos da região tropical é restrita e existem poucos parâmetros numéricos disponíveis para a definição de estratégias de remediação de áreas contaminadas. Os objetivos deste trabalho foram: avaliar a retenção de Se por amostras superficiais (0-0,2 m) de 30 solos representativos do Estado de São Paulo, pela quantificação de parâmetros de adsorção (Kd, Koc, Adsmáx, KL, Kf e n); gerar modelos de regressão e correlacionar os atributos químicos e físicos dos solos com os parâmetros de adsorção. Os experimentos de adsorção de Se foram conduzidos de acordo com o método “batch”. Isotermas de adsorção foram construídas a partir dos resultados experimentais e comparadas com as isotermas ajustadas pelos modelos de Langmuir e de Freundlich. A adsorção de Se foi representada por isotermas tipo L (exponencial) e tipo C (linear) e a equação de Langmuir ajustou melhor os resultados de adsorção de Se do que a isoterma de Freundlich. Os valores médios dos parâmetros de adsorção foram: Kd = 133 L kg-1, Koc = 2927 L kg-1, Adsmáx = 976 mg kg-1...

Activated carbons are one of the most promising techniques for the removal of organic and inorganic compounds from waters. In this work three activated carbons were produced using as precursor primary paper mill sludge. Chemical activation was performed using three different activation agents, KOH, NaOH and ZnCl2, and the same pyrolysis conditions were applied. The characterization of the obtained materials was made by means of total organic carbon analysis (TOC), Fourier infrared spectroscopy with attenuated total reflectance (FTIR-ATR), proximate and ultimate analysis, scanning electron microscopy (SEM), Hg porosimetry, BET isotherms and point of zero charge (PZC) determination. Adsorption studies were made, beginning with adsorption kinetic and then adsorption equilibrium (isotherms of adsorption), all performed in batch experiments. Generally, the carbons presented an equilibrium time of around six hours. Equilibrium studies allowed test the adsorption capacity of the produced carbons for fluoxetine-HCl. These two studies were also performed to the primary sludge pyrolysed under the same conditions without activation and also to a commercial activated carbon as reference. Among the produced materials, the carbon activated with ZnCl2 has the higher BET surface area and percentage of carbon. The maximum adsorption capacity (mg g-1) was of 96.2 ± 1.0 for PBFG4; 120.4 ± 2.5 for PS800-10; 191.6 ± 4.8 for PS800-10KOH; 136.6 ± 9.6 for PS800-10NaOH; and 28.4 ± 0.3 for PS800-10ZnCl2. The isotherms obtained point for different mechanism of adsorption between the carbons...

The adsorption of phenol and 4-nitrophenol from aqueous solutions by carbon blacks was studied. Particular attention was paid to the characterisation of the surface chemistry and ionisation of the carbon blacks by use of a simple carbon surface ionisation model, as well as the use of a normalised form of the Freundlich equation for the analysis of the adsorption isotherms. The results indicated that the solutes interact directly with the graphene layers and that the adsorption is sensitive to the π-electron density. Phenol has a weaker interaction and is more sensitive to the system conditions. In particular, it is more sensitive to oligomerisation under certain conditions. Comparison of the results with those previously reported for activated carbons with similar points of zero charge prepared from cork confirms the existence of a significant micropore-narrowing effect in the adsorption of organic solutes by activated carbons and which can lead to up to a doubling of the value of the Freundlich exponent, nF.

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica; This work aims to develop a LabVIEW interface for monitoring, controlling and automate the simultaneous experimental determination of one adsorption isotherm of gas in two distinct solid adsorbents. The magnetic suspension balance has two samples and this way it’s possible to determinate, simultaneously, the equilibrium adsorption for two different adsorbents. The developed software allows the registration of weight values and the control of the state of the balance, which has three main positions (ZP, MP1 and MP2). To determine a isotherm point is necessary for the system to reach the equilibrium. The software records the different values of ZP, MP1 and MP2, calculating the adsorbed mass values for each of the adsorbents. When the average of the adsorbed masses remain constant, the pressure value is changed and is possible to proceed with the determination of a new point isotherm. The software was developed in LabVIEW utilizing a software previously developed for a balance with only one sample. The old software was built using just one interface, which made the process of changing routines and new programming interfaces complicated. It was developed a sketch of a new software...

Brazil is considered one of the largest producers and consumers of tropical fruits. Green coconut (Cocos nucifera L.) stands out not only for its production and consumption, but also for the high amount of waste produced by coconut water industry and in natura consumption. Therefore, there is a need for utilization of this by-product. This study aims to study the adsorption isotherms of green coconut pulp and determine its isosteric heat of sorption. The adsorption isotherms at temperatures of 30, 40, 50, 60, and 70 °C were analyzed, and they exhibit type III behavior, typical of sugar rich foods. The experimental results of equilibrium moisture content were correlated by models present in the literature. The Guggenheim, Anderson and De Boer (GAB) model proved particularly good overall agreement with the experimental data. The heat of sorption determined from the adsorption isotherms increased with the decrease in moisture content. The heat of sorption is considered as indicative of intermolecular attractive forces between the sorption sites and water vapor, which is an important factor to predict the shelf life of dried products.

This work describes the preparation and characterization of a cellulose acetate fiber coated with Al2O3, resulting in the organic-inorganic hybrid Cella/Al2O3. Furthermore, it was modified by attaching organofunctional groups, by reaction with the precursor reagents (RO)3Si(CH2)3L (L = -NH2, NH(CH2)2NH2, NH(CH2)2NH(CH2) 2NH2 and NC3H3N), resulting in Cella/Al2O3/Si(CH2 )3NH2 (1), Cella/Al2O3/Si(CH2 )3NH(CH2)2NH2 (2), Cella/Al2O3/Si(CH 2)3NH(CH2)2 NH(CH2)2NH2 (3) and Cella/Al2O3/Si(CH2 )3NC3H3N (imidazole) (4). The amount of attached organofunctional groups were (in mmol per gram of the material): 1 = 1.90, 2 = 1.89, 3 = 1.66 and 4 = 1.35. The adsorption isotherms from ethanol solutions of FeCl3, CuCl2 and ZnCl2 by Cella/Al2O3/Si(CH2 )3L were obtained at 298 K. The results obtained in flow experiments showed a retention and recovery of ca. 100% of the metal ions by Cella/Al2O3/Si(CH2 )3L packed in a column, for a solution containing either one or mixture of the ions.

The adsorption of cetyltrimethylammonium (CTA) bromide and cetylpyridinium (CP) chloride on Na+-rich montmorillonite (MMT) was studied. An ad hoc isotachophoretic (ITP) method was developed for the simultaneous and rapid determination of the cationic surfactants (CSs) adsorbed. In order to decrease the detection limits, ITP was on-line coupled with capillary zone electrophoresis. Adsorption data were analysed by their fitting with adsorption isotherms. The adsorption of CP is well described by the Langmuir isotherm. It indicates the monolayer arrangement of CP on the MMT surface. In case of the CTA data, the best fitting Langmuir-Freundlich model with the power constant r<1 was found. It can be explained by the CTA interactions because of its intercalation into the MMT interlayer space.

Chitosan is a natural polymer that has been employed in dye adsorption. In this work, adsorption and thermodynamic data for the interaction of FD&C Red n° 40 food dye with chitosan in aqueous solutions were investigated. The equilibrium adsorption isotherms were determined by the batch method, from 298 to 338 K. Adsorption data were adjusted to five isotherm models: Langmuir, Freundlich, Redlich-Peterson, Temkin and Dubinin-Radushkevich, in order to determine which presented the best adjustment to the experimental data. Error analysis showed that the Langmuir isotherm model was the most appropriate for fitting the experimental data, with a maximum monolayer adsorption of 3065.8 µmol g-1 at 308 K. Negative enthalpy (-112.7 kJ mol-1), entropy (-0.338 kJ mol-1 K-1) and Gibbs free energy (-15.6 to 1.0 kJ mol-1) values demonstrated that the adsorption process is exothermic, spontaneous, favorable, and that randomness of the system decreases during the adsorption process.

The aim of this work was to study the drying curves and equilibrium isotherms of extruded fish feed. The drying curves were determined at air temperatures of 50, 60, 70 and 80°C and airflow velocities of 1.5, 2.5 and 3.5 m/s). The equilibrium isotherms of relative humidity of air were obtained between 10 and 80% at 30, 40, 50, and 70°C. The experimental data were fitted for non-linear regression by using Statistica® to the models reported in the literature. The results showed that the drying curves and the equilibrium isotherms were significantly influenced by variations of the air temperature in a similar way to solid materials as described in the literature. The statistical results for models of Page and Peleg showed that the fitting of the experimental drying curve and isotherm data were satisfactory.

Dipalmitoylphosphatidylcholine (DPPC) vesicles acquire negative surface charge on adsorption of negatively charged pentachlorophenolate (PCP-), and lipophilic ions tetraphenylborate (TPhB-), and dipicrylamine (DPA-). We have obtained (a) zeta-potential isotherms from the measurements of electrophoretic mobility of DPPC vesicles as a function of concentration of the adsorbing ions at different temperatures (25-42 degrees C), and (b) studied the effect of PCP- on gel-to-fluid phase transition by measuring the temperature dependence of zeta-potential at different PCP- concentrations. The zeta-potential isotherms of PCP- at 25, 32, and 34 degrees C correspond to adsorption to membrane in its gel phase. At 42 degrees C the zeta-potential isotherm corresponds to membrane in its fluid phase. These isotherms are well described by a Langmuir-Stern-Grahame adsorption model proposed by McLaughlin and Harary (1977. Biochemistry. 15:1941-1948). The zeta-potential isotherm at 37 degrees C does not follow the single-phase adsorption model. We have also observed anomalous adsorption isotherms for lipophilic ions TPhB- and DPA- at temperatures as low as 25 degrees C. These isotherms demonstrate a gel-to-fluid phase transition driven by ion adsorption to DPPC membrane during which the membrane changes from weakly to a strongly adsorbing state. The anomalous isotherm of PCP- and the temperature dependence of zeta-potential can be described by a two-phase model based on the combination of (a) Langmuir-Stern-Grahame model for each phase...

Chitosan is a natural polymer that has been employed in dye adsorption. In this work, adsorption and thermodynamic data for the interaction of FD&C Red n° 40 food dye with chitosan in aqueous solutions were investigated. The equilibrium adsorption isotherms were determined by the batch method, from 298 to 338 K. Adsorption data were adjusted to five isotherm models: Langmuir, Freundlich, Redlich-Peterson, Temkin and Dubinin-Radushkevich, in order to determine which presented the best adjustment to the experimental data. Error analysis showed that the Langmuir isotherm model was the most appropriate for fitting the experimental data, with a maximum monolayer adsorption of 3065.8 μmol g-1 at 308 K. Negative enthalpy (-112.7 kJ mol-1), entropy (-0.338 kJ mol-1 K-1) and Gibbs free energy (-15.6 to 1.0 kJ mol-1) values demonstrated that the adsorption process is exothermic, spontaneous, favorable, and that randomness of the system decreases during the adsorption process.

The adsorption of 3,5-dimethyltetrahydro-1,3,5-thiadiazine-2-thione (dazomet) on bentonite and clinoptilolite has been studied at four temperatures (288, 293, 298 and 303 K) and two different solutions (water and water-ethyl alcohol mixture, 50% v/v). The adsorption rates at low concentrations of dazomet were found to fit the first-order kinetic equation. For each system at constant concentration, the rate constants increased with increasing temperature in aqueous solution, but these constants decreased with increasing temperature for 50% (v/v) water-ethyl alcohol mixture solution. By using the Arrhenius equation, the activation energies for each system were calculated. Thermodynamic parameters were evaluated according to Eyring's equation. The values of enthalpy of activation, deltaH*, are lower than TdeltaS*. The results indicated that the adsorption process was entropy-controlled for each system. Adsorption isotherms were determined at 288 and 303 K. These isotherms were fitted to Freundlich equation for aqueous solution at 15 °C, but adsorption from the two different solutions at 30 °C were modeled according to the Langmuir and BET isotherms.

Solid mixtures for refreshment are already totally integrated to the Brazilian consumers' daily routine, because of their quick preparation method, yield and reasonable price - quite lower if compared to 'ready-to-drink' products or products for prompt consumption, what makes them economically more accessible to low-income populations. Within such a context, the aim of this work was to evaluate the physicochemical and mineral composition, as well as the hygroscopic behavior of four different brands of solid mixture for mango refreshment. The BET, GAB, Oswim and Henderson mathematical models were built through the adjustment of experimental data to the isotherms of adsorption. Results from the physiochemical evaluation showed that the solid mixtures for refreshments are considerable sources of ascorbic acid and reductor sugar; and regarding mineral compounds, they are significant sources of calcium, sodium and potassium. It was also verified that the solid mixtures for refreshments of the four studied brands are considered highly hygroscopic.

8 pages, 8 figures.-- Printed version published Dec 2007.; The adsorption properties of CO2, N2 and CH4 in all-silica zeolites were studied using molecular simulations. Adsorption isotherms for single components in MFI were both measured and computed showing good agreement. In addition simulations in other all silica structures were performed for a wide range of pressures and temperatures and for single components as well as binary and ternary mixtures with varying bulk compositions. The adsorption selectivity was analyzed for mixtures with bulk composition of 50:50 CO2/CH4, 50:50 CO2/N2, 10:90 CO2/N2 and 5:90:5 CO2/N2/CH4 in MFI, MOR, ISV, ITE, CHA and DDR showing high selectivity of adsorption of CO2 over N2 and CH4 that varies with the type of crystal and with the mixture bulk composition.; This work is supported by the Spanish “Ministerio de Educación y Ciencia” (CTQ2007-63229/BQU), by the National Science Foundation (CTS-0507013), and by the resources, technical expertise and assistance provided by BSC-CNS. E. García-Pérez wishes to thank the MEC for a predoctoral fellowship. RK acknowledges the grant of a TOP subsidy from the Netherlands Foundation for Fundamental Research (NWO-CW) for intensification of reactors and NWO/NCF for provision of high performance computing resources. JBP thanks ITQ-CSIC for kindly supplying the silicalite.; Peer reviewed

The work described in this thesis focuses on the effects that adsorption processes on catalytic surfaces pose in controlling key steps that can affect and control reaction pathways. To that, the development of Nuclear Magnetic Resonance (NMR) relaxometry methods and the comparison with traditional catalytic was performed with a series of C5 and C6 unsaturated hydrocarbons on two different alumina supports, ?- and ?-Al2O3. The developed techniques were applied in the study of liquid phase selective hydrogenation of citral on 5% Pt/SiO2. Infrared (IR) spectroscopy, volumetric adsorption isotherms, dynamic isotherms via a Tapered Element Oscillating Microbalance (TEOM), temperature programmed desorption (TPD) as well as 13C T1 NMR and 1H 2D T1-T2 relaxometry methods were employed. Energies of adsorption as a function of coverage were obtained via adsorption isotherms and the particular surface adsorbate interactions were described with IR spectroscopy. For example, 1-pentyne showed the strongest interaction with the alumina (94 kJ mol-1) while 1-pentene presented a weaker interaction (46 kJ mol-1) on ?-Al2O3. Desorption energies obtained from TPD ranged 85 ? 130 kJ mol-1, irrespective of the adsorbate. Reactivity of the aluminas was captured with TPD...

Adsorption isotherms of carbon tetrachloride at temperatures between 273 and 323 K have been determined on the pure silica form of MCM-41 of pore diameter ca. 3.4 nm. All isotherms were of Type V, the isotherms at 273, 288 and 303 K showing hysteresis loops, whereas the isotherm at 323 K was completely reversible. Despite the questionable validity of the Kelvin equation when applied to narrow mesopores, changes in the relative pressure positions of capillary condensation and evaporation as a function of the temperature appear to be well described. Neutron diffraction measurements at 200 and 273 K show significant changes in the physical properties of the adsorbed CCl4 in the MCM-41 from those of bulk adsorbate. The results also suggest a highly heterogeneous surface and appear to show some flexibility in the pore walls upon pore filling. The conditions required for first order reversible capillary condensation are discussed.

The adsorption of gemini surfactants of the form alkanediyl-α,ω-bis (dodecyldimethylammonium bromide) to a silica substrate is investigated using optical reflectometry (OR) and atomic force microscopy (AFM). The adsorption isotherms and kinetics of adso

Moisture adsorption isotherms for yellow pitahaya fruits were studied at 15, 25, and 35 °C using the gravimetric method for a 0.111-0.901 water activity range. Experimental values were adjusted by using the GAB, BET, Henderson, Smith, Caurie, and Peleg models. The isosteric heat of adsorption (Qst) was determined using the Clausius-Clapeyron equation. The results showed that yellow pitahaya fruits exhibit type III adsorption isotherms and that the equilibrium moisture content (EMC) is temperature-dependent. For the same water activity value, the EMC decreased when temperature increased. The GAB model presented the best fitto the experimental values. The Qst dropped from 57.154 to 45.79 kJ/mol when the EMC increased from 0.05 to 0.40 g water/g dry matter, respectively. These results are important for establishing the best storage conditions for dehydrated pitahaya fruits as well as for shelf-life prediction and the design of packaging materials.