Catalytic effect of supported metal ion complexes on the induced oxidative degradation of pyrocatechol violet by hydrogen peroxide.

Kinetics of the oxidative degradation of pyrocatechol violet dye (PCV) [2-[(3,4-dihydroxyphenyl)(3-hydroxy-4-oxocyclohexa-2,5-dien-1-ylidene) methyl]-benzenesulfonic acid] by H(2)O(2) catalyzed by supported transition metal complexes have been studied. The reaction was followed by conventional UV-vis spectrophotometer at lambda(max)=440 nm in a buffer solution at pH 5.1. The supports used were silica gel and cation exchange resins (Dowex-50W, 2 and 8% DVB), while the complexes were [Cu(amm)(4)](2+), [Cu(en)(2)](2+), [Cu(ma)(4)](2+), [Co(amm)(6)](2+), and [Ni(amm)(6)](2+) (amm=ammonia, en=ethylenediamine, and ma=methylamine). The reaction exhibited first-order kinetics with respect to [PCV] and [H(2)O(2)]. The reactivity of the catalysts is correlated with the redox potential of the metal ions, the type of support, and the amount of supported complexes. The rate of the reaction increases with increasing pH and the addition of NaCl. Addition of SDS and CTAB showed inhibiting effects. The reaction is enthalpy-controlled as confirmed from the isokinetic relationship. A reaction mechanism involved the generation of free radicals as an oxidant has been proposed.