RESUMO
Copper(II) amine complexes supported on Amberlyst-15 cation resin were prepared and characterized by SEM, EDX and FTIR measurements. The kinetics of the heterogeneous oxidation of an organic dye, crystal violet, with H2O2 catalyzed by the supported catalysts was investigated in aqueous solution. The rate of reaction increases with increasing stability of the copper(II) amine complexes. The oxidation rate attained a first-order in the catalyst and the dye only at lower concentrations and second order in H2O2. A very fast formation of a peroxo-dye intermediate resulting from the interaction of H2O2 with the dye even in the presence of the catalyst was observed.
Assuntos
Anti-Infecciosos Locais/química , Corantes/química , Cobre/química , Violeta Genciana/química , Peróxido de Hidrogênio/química , Oxidantes/química , Catálise , Cátions , Cinética , Microscopia Eletrônica de Varredura , Oxirredução , Resinas Vegetais/química , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
The catalyzed kinetics of the oxidative mineralization of the cationic dye methylene blue, phenothiazonium, 3,7-bis(dimethylamino)-chloride, with hydrogen peroxide were studied both in buffered and unbuffered solutions. The supported alumina catalysts used were in the form of copper(II), cobalt(II), manganese(II), and nickel(II)-ions. Also, some copper(II)-complexes were used, e.g. copper(II)-ammine ([Cu(amm)4]2+), copper(II)-ethylenediamine ([Cu(en)2]2+) and copper(II)-monoethanolamine ([Cu(mea)2]2+). The reaction is first order with respect to methylene blue. On the other hand, the order with respect to hydrogen peroxide is concentration range dependent. This range depends strongly on the catalyst used. At lower [H2O2], the order was 1 which then decreases with increasing [H2O2] passing through 0 at the maximum rate and finally becomes negative. This phenomenon is parallel to the formation of a colored intermediate on the surface of the catalyst. This suggests that the intermediate has an inhibiting effect on the rate of color removal. Moreover, the rate of the reaction was found to be strongly dependent on the pH of the solution and its ionic strength. It increases with increasing both pH and the concentration of added potassium chloride. Also, the rate of reaction is inhibited in presence of sodium dodecylsulfate anionic surfactant. The repeated use of the different catalysts showed that their catalytic activities are almost unaffected. A reaction mechanism was proposed with the formation of free radicals as reactive intermediates.
