RESUMO

The sonochemical (850 kHz) Cr(VI) reduction (0.30 mM, pH 2) in the presence of citric acid (Cit, 2 mM) was analyzed under different working atmospheres: reactor open to air without sparging (ROAWS), and Ar, O2, air and N2 sparging. Hydrogen peroxide formation in pure water at pH 2 and KI dosimetry were also measured. Zero-order kinetics was observed in all cases. A complete Cr(VI) reduction after 180 min insonation was obtained with the ROAWS and under Ar, while a lower Cr(VI) reduction efficiency was achieved under the other conditions. The Cr(VI) reduction and H2O2 formation rates followed the order ROAWS â‰… Ar > air â‰… O2 ≫ N2, while for KI dosimetry the order was ROAWS â‰« O2 â‰… air > Ar â‰« N2. This indicates that H2O2 formation rate is a better measure of the system reactivity for Cr(VI) reduction. For air, O2 and N2, once the sparging was stopped, Cr(VI) reduction rate increased up to approximately the same value obtained for the ROAWS, suggesting that the sparging decreased the generation of reactive species and, thus, the Cr(VI) reduction rate. Nitrate production was measured at low concentrations (micromolar range) in the ROAWS, air and N2 systems. Formic and acetic acids were detected as Cit degradation products. Reaction mechanisms were proposed. It can be concluded that the best condition for Cr(VI) removal is with the ROAWS because of a higher Cr(VI) reduction rate, no atmosphere control is required, and it is a less expensive system.

Assuntos

Cromo/química , Ácido Cítrico/química , Gases , Peróxido de Hidrogênio , Concentração de Íons de Hidrogênio , Cinética , Oxirredução

RESUMO

The sonochemical (850 kHz) reduction of Cr(VI) (0.3 mM, pH 2, reactor open to air) was analyzed in the presence of different additives. The effects on Cr(VI) reduction efficiency of added formic acid (FA, 10 mM), citric acid (Cit, 2 mM), ethylenediaminetetraacetic acid (EDTA, 1 mM), methanol (MeOH, 0.1 M), ethanol (EtOH, 0.1 M), 2-propanol (2-PrOH, 0.1 M), tert-butanol (t-BuOH, 0.1 M), phenol (PhOH, 2 mM) and sodium lauryl sulfate (SLS, 1 mM) have been evaluated in comparison with the system in the absence of additives. Complete Cr(VI) reduction was obtained only when using EDTA (at 120 min) and Cit (at 180 min). Cr(III) complexes with these compounds or with their degradation products were detected as final products. For EDTA, Cit, t-BuOH, FA and SLS, the Cr(VI) decay could be adjusted to a zero-order kinetics; in the cases of MeOH, EtOH and 2-PrOH, there was a deviation from the zero-order kinetics. The Cr(VI) conversion increased in the order SLS (very low) < no additive ≅ MeOH ≅ EtOH ≅ 2-PrOH < FA < t-BuOH < PhOH < Cit < EDTA. The role of EDTA and Cit in stabilizing intermediate Cr(V) peroxo compounds and enhancing their direct transformation into different Cr(III) species is considered a major factor in the acceleration of Cr(VI) reduction processes. Mechanistic pathways are proposed.