927 resultados para Chitosan. Adsorption kinetics. Kinetic Model. Adsorption Isotherm.Tetracycline. Sodium Cromoglycate
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Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.
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The role of computer modeling has grown recently to integrate itself as an inseparable tool to experimental studies for the optimization of automotive engines and the development of future fuels. Traditionally, computer models rely on simplified global reaction steps to simulate the combustion and pollutant formation inside the internal combustion engine. With the current interest in advanced combustion modes and injection strategies, this approach depends on arbitrary adjustment of model parameters that could reduce credibility of the predictions. The purpose of this study is to enhance the combustion model of KIVA, a computational fluid dynamics code, by coupling its fluid mechanics solution with detailed kinetic reactions solved by the chemistry solver, CHEMKIN. As a result, an engine-friendly reaction mechanism for n-heptane was selected to simulate diesel oxidation. Each cell in the computational domain is considered as a perfectly-stirred reactor which undergoes adiabatic constant- volume combustion. The model was applied to an ideally-prepared homogeneous- charge compression-ignition combustion (HCCI) and direct injection (DI) diesel combustion. Ignition and combustion results show that the code successfully simulates the premixed HCCI scenario when compared to traditional combustion models. Direct injection cases, on the other hand, do not offer a reliable prediction mainly due to the lack of turbulent-mixing model, inherent in the perfectly-stirred reactor formulation. In addition, the model is sensitive to intake conditions and experimental uncertainties which require implementation of enhanced predictive tools. It is recommended that future improvements consider turbulent-mixing effects as well as optimization techniques to accurately simulate actual in-cylinder process with reduced computational cost. Furthermore, the model requires the extension of existing fuel oxidation mechanisms to include pollutant formation kinetics for emission control studies.
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Titanium dioxide (TiO2) nanoparticles with different sizes and crystalloid structures produced by the thermal method and doped with silver iodide (AgI), nitrogen (N), sulphur (S) and carbon (C) were applied as adsorbents. The adsorption of Methyl Violet (MV), Methylene Blue (MB), Methyl Orange (MO) and Orange II on the surface of these particles was studied. The photocatalytic activity of some particles for the destruction of MV and Orange II was evaluated under sunlight and visible light. The equilibrium adsorption data were fitted to the Langmuir, Freundlich, Langmuir-Freundlich and Temkin isotherms. The equilibrium data show that TiO2 particles with larger sizes and doped with AgI, N, S and C have the highest adsorption capacity for the dyes. The kinetic data followed the pseudo-first order and pseudo-second order models, while desorption data fitted the zero order, first order and second order models. The highest adsorption rate constant was observed for the TiO2 with the highest anatase phase percentage. Factors such as anatase crystalloid structure, particle size and doping with AgI affect the photocatalytic activity significantly. Increasing the rutile phase percentage also decreases the tendency to desorption for N-TiO2 and S-TiO2. Adsorption was not found to be important in the photocatalytic decomposition of MV in an investigation with differently sized AgI-TiO2 nanoparticles. Nevertheless C-TiO2 was found to have higher adsorption activity onto Orange II, as the adsorption role of carbon approached synchronicity with the oxidation role.
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Os estudos de adsorção de corantes alimentícios de soluções aquosas geralmente estão voltados para a remoção de um corante específico, porém, as misturas binárias são mais realistas para simular efluentes industriais. A adsorção de corantes com quitosana é considerada uma tecnologia alternativa eco amigável, e quando a estrutura da quitosana é modificada quimicamente, resulta em um adsorvente mais adequado. A reticulação da quitosana com cianoguanidina apresenta vantagens, como melhoria na estabilidade em soluções ácidas e diminuição do custo do adsorvente. Nesta pesquisa, o objetivo do trabalho foi modificar a quitosana com cianoguanidina para remoção de corantes alimentícios em sistema aquoso binário. A fim de verificar o comportamento dos adsorventes na operação de adsorção, foram preparadas amostras de quitosana com diferentes graus de desacetilação (75%, 85% e 95%), e após, foram realizadas modificações destas amostras com cianoguanidina. Os adsorventes foram caracterizados e aplicados para a adsorção de azul indigotina e amarelo tatrazina em sistema aquoso binário e em sistema simples. O efeito do pH e do grau de desacetilação foram verificados para a remoção dos corantes por quitosana com e sem modificação em sistema simples e binário. Curvas de equilíbrio foram obtidas em diferentes temperaturas e o modelo estendido de Langmuir foi ajustado aos dados experimentais. O comportamento cinético foi avaliado através dos modelos pseudo-primeira ordem, pseudo-segunda ordem e Avrami. Os parâmetros termodinâmicos foram determinados e estudos de dessorção do adsorvente foram realizados. O pH mais adequado foi 3, e o melhor grau de desacetilação foi 95% para ambos os sistemas aquosos e adsorbatos. As capacidades de adsorção da quitosana sem e com modificação não apresentaram diferença significativa. O modelo de Langmuir estendido apresentou ajuste adequado às curvas de equilíbrio e as máximas capacidades de adsorção foram 595,3 e 680,0 mg g-1, obtidas à 25ºC, para o os corantes azul indigotina e amarelo tatrazina, respectivamente. O modelo de Avrami foi o que melhor se ajustou aos dados cinéticos de adsorção. A dessorção do adsorvente foi possível por dois ciclos, mantendo sua capacidade de adsorção em 209,7 mg g-1 no primeiro ciclo e 200,2 mg g-1 no segundo ciclo. A quitosana modificada com cianoguanidina apresentou-se como um adsorvente promissor para a remoção de corantes alimentícios em sistema binário.
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O objetivo no presente estudo foi investigar a operação de secagem da microalga Spirulina platensis em camada delgada através da modelagem matemática e otimização da operação, avaliando as características do produto final através de análises físico-químicas. Foram analisados os dados da umidade de equilíbrio para a isoterma de adsorção a 10, 20 e 30°C e de dessorção a 40, 50 e 60°C, através dos modelos de GAB e BET. O calor isostérico foi determinado pela aplicação da equação de Clausius-Clapeyron. O modelo de GAB apresentou melhor ajuste aos dados experimentais. Os valores da área superficial calculados pelos modelos de GAB e BET foram próximos. O calor isostérico e a entropia diferencial da isoterma de dessorção apresentaram comportamento similar. A teoria da compensação entalpia-entropia foi aplicada nas isotermas, indicando que são controladas pela entalpia. A cinética de secagem foi analisada na faixa de temperatura de 50-70°C, através dos modelos de Lewis, Henderson e Pabis, Henderson, Page e Overhults. O modelo de Henderson e Pabis foi escolhido por apresentar maior significado físico para estimar o valor de difusividade efetiva (Def), sendo os valores encontrados na faixa de 5,54 - 6,60×10-11 m 2 /s, para as temperaturas de 50 e 60°C, respectivamente, e de 1,58×10-10 m2 /s para a temperatura de 70°C. A energia de ativação apresentou um valor de 47,9 kJ/mol. A secagem alterou a cor quando comparada ao material in natura. A secagem foi otimizada na faixa de espessuras e temperaturas do ar de secagem de 3-7 mm e de 50-70ºC, respectivamente, através da metodologia de superfície de resposta para ácido tiobarbitúrico (TBA) e perda de ficocianina no produto final. A melhor condição de secagem foi a 55°C e a 3,7 mm, apresentando uma perda de ficocianina de aproximadamente 37% e valor de TBA de 1,5 mgMDA/kgamostra. Nesta condição de secagem, a composição de ácidos graxos da microalga Spirulina não apresentou diferença significativa (P > 0,05) em relação a microalga in natura.
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Na indústria têxtil grandes volumes de efluentes são gerados, os quais são caracterizados por serem coloridos e poluentes , devido à presença de corantes em sua composição. Com a necessidade de descontaminação, diferentes métodos são utilizados no tratamento, sendo um deles, a biossorção. Este consiste na remoção das substâncias tóxicas recorrendo a biossorventes obtidos a partir de resíduos agrícolas e sub-produtos de processos industriais. O objetivo principal deste trabalho foi estudar a remoção do corante Preto Reafix Super 2R em soluções aquosas por meio de biossorção com bagaço de malte. Baseando-se sobretudo no estudo da cinética e equilíbrio entre o biossorvente e o corante. Numa primeira fase foi estudada a influência dos parâmetros operacionais, como a influência do diâmetro médio das partículas do biossorvente, o pH da solução e a velocidade de agitação da solução. Sendo as condições ótimas de biossorção definidas a pH 2, velocidade de agitação de 150 rpm e biomassa sem peneiramento. Posteriormente, ajustaram-se os modelos cinéticos de Pseudo-primeira ordem, Pseudo-segunda ordem e de Difusão intrapartícula aos resultados experimentais obtidos pela cinética de adsorção avaliando também a influência da temperatura no tempo de contato para se alcançar o equilibrio. O modelo de Pseudo-segunda ordem conduziu ao melhor ajuste, com um coeficiente de correlação (R2) de apróximadamente 1. A partir dos testes de equilíbrio realizados com diferentes concentrações de corante, foram ajustadas as isotermas de Langmuir, Freundlich, Tempkin aos resultados experimentais tendo-se obtido parâmetros bastante significativos para o modelo Langmuir, cuja capacidade máxima de remoção (qmax) obtida foi de 40,16 mg.g-1. A análise dos parâmetros termodinâmicos permitiram avaliar que o processo de adsorção ocorre espontaneamente, sendo endotérmico e que ao longo do processo aumenta a aleatoriedade na interface sólido/solução, devido à desorganização do processo em virtude das interações que ocorrem.
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In this paper agricultural waste; Canarium schweinfurthii was explored for the sequestering of Fe and Pb ions from wastewater solution after carbonization and chemical treatment at 400oC. Optimum time of 30 and 150 min with percentage removal of 95 and 98% at optimum pH of 2 and 6 was obtained for Fe and Pb ions. Kinetics model followed pseudofirst order as sum of absolute error (EABS) between Qe and Qc greater than that of pseudo second order. Parameters evaluated from isothermal equation (Freundlich and Langmuir) showed that KL and QO for Fe > Pb and R2 for Langmuir> Freundlich. The study reveals the suitability of the adsorbent for sequestering of Fe and Pb ions from industrial wastewater.
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The destructive impact of improper disposal of heavy metals in the environment increases as a direct result of population explosion, urbanization and industrial expansion and technological developments. Argil are potential materials for adsorption of inorganic and the pelletization of it is required for use in adsorptive columns of fixed bed. The low cost and the possibility of regeneration makes these materials attractive for use in the purification process, capable of removing inorganic compounds in contaminated aquatic environments. In this work was made pellets of a mixture of dolomite and montmorillonite by wet agglomeration, in different percentages. The removal of Pb (II) was investigated through experimental studies, and was modeled by kinetic models and isotherms of adsorption. The materials were characterized using the techniques of XRD, TG / DTA, FT-IR, and surface area by BET method. The results showed the adsorption efficiency of the contaminant by the composite material studied in synthetic solution. The study found that the adsorption follows the Langmuir model, and the kinetics of adsorption follows the model of pseudosecond order
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Activated carbon was prepared from date pits via chemical activation with H3PO4. The effects of activating agent concentration and activation temperature on the yield and surface area were studied. The optimal activated carbon was prepared at 450 °C using 55 % H3PO4. The prepared activated carbon was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric-differential thermal analysis, and Brunauer, Emmett, and Teller (BET) surface area. The prepared date pit-based activated carbon (DAC) was used for the removal of bromate (BrO3 −). The concentration of BrO3 − was determined by ultra-performance liquid chromatography-mass tandem spectrometry (UPLC-MS/MS). The experimental equilibrium data for BrO3 − adsorption onto DAC was well fitted to the Langmuir isotherm model and showed maximum monolayer adsorption capacity of 25.64 mg g−1. The adsorption kinetics of BrO3 − adsorption was very well represented by the pseudo-first-order equation. The analytical application of DAC for the analysis of real water samples was studied with very promising results.
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An integrated analysis of naproxen adsorption on bone char in batch and packed-bed column conditions has been performed. Kinetic, thermodynamic and breakthrough parameters have been calculated using adsorption models and artificial neural networks. Results show that naproxen removal using bone char in batch conditions is a feasible and effective process, which could involve electrostatic and non-electrostatic interactions depending mainly on pH conditions. However, the application of packed-bed column for naproxen adsorption on bone char is not effective for the treatment of diluted solutions due to the low degree of adsorbent utilization (below 4%) at tested operating conditions. The proposed mechanism for naproxen removal using bone char could include a complexation process via phosphate and naproxen, hydrogen bonding and the possibility of hydrophobic interactions via π–π electron. This study highlights the relevance of performing an integrated analysis of adsorbent effectiveness in batch and dynamic conditions to establish the best process configuration for the removal of emerging water pollutants such as pharmaceuticals.
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The mesoporous SBA-15 silica with uniform hexagonal pore, narrow pore size distribution and tuneable pore diameter was organofunctionalized with glutaraldehyde-bridged silylating agent. The precursor and its derivative silicas were ibuprofen-loaded for controlled delivery in simulated biological fluids. The synthesized silicas were characterized by elemental analysis, infrared spectroscopy, (13)C and (29)Si solid state NMR spectroscopy, nitrogen adsorption, X-ray diffractometry, thermogravimetry and scanning electron microscopy. Surface functionalization with amine containing bridged hydrophobic structure resulted in significantly decreased surface area from 802.4 to 63.0 m(2) g(-1) and pore diameter 8.0-6.0 nm, which ultimately increased the drug-loading capacity from 18.0% up to 28.3% and a very slow release rate of ibuprofen over the period of 72.5h. The in vitro drug release demonstrated that SBA-15 presented the fastest release from 25% to 27% and SBA-15GA gave near 10% of drug release in all fluids during 72.5 h. The Korsmeyer-Peppas model better fits the release data with the Fickian diffusion mechanism and zero order kinetics for synthesized mesoporous silicas. Both pore sizes and hydrophobicity influenced the rate of the release process, indicating that the chemically modified silica can be suggested to design formulation of slow and constant release over a defined period, to avoid repeated administration.
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The adsorption capacity of alpha-chitosan and its modified form with succinic anhydride was compared with the traditional adsorbent active carbon by using the dye methylene blue, employed in the textile industry. The isotherms for both biopolymers were classified as SSA systems in the Giles model, more specifically in L class and subgroup 3. The dye concentration in the supernatant in the adsorption assay was determined through electronic spectroscopy. By calorimetric titration thermodynamic data of the interaction between methyene blue and the chemically modified chitosan at the solid/liquid interface were obtained. The enthalpy of the dye/chitosan interaction gave 2.47 ± 0.02 kJ mol-1 with an equilibrium constant of 7350 ± 10 and for the carbon/dye interaction this constant gave 5951 ± 8. The spontaneity of these adsorptions are reflected by the free Gibbs energies of -22.1 ± 0.4 and -21.5 ± 0.2 kJ mol-1, respectively, found for these systems. This new adsorbent derived from a natural polysaccharide is as efficient as activated carbon. However 97% of the bonded dye can be eluted by sodium chloride solution, while this same operation elutes only 42% from carbon. Chitosan is efficient in dye removal with the additional advantage of being cheap, non-toxic, biocompatible and biodegradable.
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A commercial corrosion inhibitor used in petroleum production was characterized by means of infrared spectroscopy and energy dispersive spectroscopy (EDS). Predicting the adsorption behavior of corrosion inhibitor onto steel, sandstone and esmectite is the key to improve working conditions. In this study, the adsorption kinetics of inhibitor formulations in HCl 15% or in Mud Acid (HCl 13,5% and ammonium bifluoride) onto steel, sandstone and esmectite was determined by means of spectrophotometry. Kinetic parameters indicated that adsorption of inhibitor in the presence of bifluoride was favored. Moreover, the adsorption constant rate was the largest when the substrate was esmectite.
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Lipase from Burkholderia cepacia immobilized on superparamagnetic nanoparticles using adsorption and chemisorption methodologies was efficiently applied as recyclable biocatalyst in the enzymatic kinetic resolution of (RS)-1-(phenyl)ethanols via transesterification reactions. (R)-Esters and the remaining (S)-alcohols were obtained with excellent enantiomeric excess (> 99%), which corresponds to a perfect process of enzymatic kinetic resolution (conversion 50%, E > 200). The transesterification reactions catalysed with B. cepacia lipase immobilized by the glutaraldehyde method showed the best results in terms of reusability, preserving the enzyme activity (conversion 50%, E > 200) for at least 8 successive cycles.