A comparative study of several transition metals in Fenton-like reaction systems at circum-neutral pH

The N,N'-(5-nitro-1,3-phenylene)bisglutaramide hydroxylation assay for spectrophotometric determination of the rate of oxidising species generation in Fenton-like systems was used to obtain comparative data for Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), and Zn(II). The pH range of interest was 5.5-9.5 and was controlled by addition of an appropriate phosphate buffer. The temperature of the reaction mixture was controlled in the range 25-80 o C. The rates of production of oxidising species at pH 7 decrease in the following order: Cu(II) > Cr(III) > Co(II) > Fe(III) > Mn(II) > Ni(II), while Cd(II) and Zn(II) did not exhibit any catalytic activity and Ni(II) only led to a significant production of oxidising species at pH > 7.5. In mixtures of Cu(II) and Fe(III) the rate of oxidising species production may be considered as the sum of contributions of individual metals. This was not the case of a mixture containing additional small amounts of Zn(II), Co(II) and Mn(II). The later two had strong pro-oxidative effects, the addition of Zn(II) had an anti-oxidative effect. Apparent activation energies for oxidising species generation are in the range 75-110 kJ mol -1 , and decrease in the following order: Cu(II) > Ni(II) > Mn(II) > Fe(III) > Co(II).

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