The oxidation of Cr(III) has been studied in NaCl solutions in the presence of two siderophore models, acetohydroxamic acid (Aha) and benzohydroxamic acid (Bha), the natural siderophore Desferal (DFOB) and the synthetic aminocarboxilate (ethylenedinitrilo)-tetra-acetic acid (EDTA) as a function of pH (8-9), ionic strength (0.01-2 M) and temperature (10-50 degrees C), at different Cr(III)-organic compound ratios. The addition of Aha and Bha caused the rates to increase at low ligand/Cr(III) ratios and decrease at high ratios. The variation of the pseudo first order rate constant (k(1)) as a function of the ligand concentration has been attributed to the formation of three Cr(III)-organo species (1:1, 1:2, 1:3), which can form in the presence of monohydroxamic acids. A kinetic model has been developed that gives a value of 600 (min(-1)) for the pseudo first order rate constant k(1CrAha)(2+) and values approaching zero for k(1CrAha2)(+) and k(1CrAha3). These kinetic results demonstrate that these monohydroxamic acids are able to bind with Cr(III) under experimental conditions that may occur in natural waters and can increase the oxidation rates of Cr(III) with H2O2 by a factor of 3.5 at an Aha/Cr(III) ratio of about 50-100. The monohydroxamic acids also affect the rates on aged products of Cr(III), suggesting that these ligands are able to affect the oxidation rates by releasing reactive Cr(III). DFOB and EDTA do not have a great effect on the oxidation of Cr(III) with H2O2. This is thought to be due to the much longer times they need to form complexes with Cr(III) compared to Aha and Bha. The rates for the formation of DFOB and EDTA complexes with Cr(III) are not competitive with the rates of the formation of aged Cr(III). After allowing Cr(III) and DFOB to react for 5 days to form the complex, reaction rates of Cr(III) with H2O2 appear to be lowered probably because of steric hindrance of the chelated Cr(III). (C) 2008 Elsevier Ltd. All rights reserved.
The effect of organic compounds in the oxidation kinetics of Cr(III) by H2O2 / Maurizio, Pettine; Francesca, Gennari; Campanella, Luigi; Frank J., Millero. - In: GEOCHIMICA ET COSMOCHIMICA ACTA. - ISSN 0016-7037. - 72:23(2008), pp. 5692-5707. [10.1016/j.gca.2008.09.009]
The effect of organic compounds in the oxidation kinetics of Cr(III) by H2O2
CAMPANELLA, Luigi;
2008
Abstract
The oxidation of Cr(III) has been studied in NaCl solutions in the presence of two siderophore models, acetohydroxamic acid (Aha) and benzohydroxamic acid (Bha), the natural siderophore Desferal (DFOB) and the synthetic aminocarboxilate (ethylenedinitrilo)-tetra-acetic acid (EDTA) as a function of pH (8-9), ionic strength (0.01-2 M) and temperature (10-50 degrees C), at different Cr(III)-organic compound ratios. The addition of Aha and Bha caused the rates to increase at low ligand/Cr(III) ratios and decrease at high ratios. The variation of the pseudo first order rate constant (k(1)) as a function of the ligand concentration has been attributed to the formation of three Cr(III)-organo species (1:1, 1:2, 1:3), which can form in the presence of monohydroxamic acids. A kinetic model has been developed that gives a value of 600 (min(-1)) for the pseudo first order rate constant k(1CrAha)(2+) and values approaching zero for k(1CrAha2)(+) and k(1CrAha3). These kinetic results demonstrate that these monohydroxamic acids are able to bind with Cr(III) under experimental conditions that may occur in natural waters and can increase the oxidation rates of Cr(III) with H2O2 by a factor of 3.5 at an Aha/Cr(III) ratio of about 50-100. The monohydroxamic acids also affect the rates on aged products of Cr(III), suggesting that these ligands are able to affect the oxidation rates by releasing reactive Cr(III). DFOB and EDTA do not have a great effect on the oxidation of Cr(III) with H2O2. This is thought to be due to the much longer times they need to form complexes with Cr(III) compared to Aha and Bha. The rates for the formation of DFOB and EDTA complexes with Cr(III) are not competitive with the rates of the formation of aged Cr(III). After allowing Cr(III) and DFOB to react for 5 days to form the complex, reaction rates of Cr(III) with H2O2 appear to be lowered probably because of steric hindrance of the chelated Cr(III). (C) 2008 Elsevier Ltd. All rights reserved.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
