Kinetics and mechanism of the reduction of chromium(VI) by D-fructose

Silvia García, Laura Ciullo, María Silvina Olivera, Juan Carlos González, Sebastián Bellú, Antal Rockembauer, Lazlo Korecz, Luis F. Sala

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Abstract

The kinetics of the reduction of chromium(VI) to chromium(III) by d-fructose in HClO4 was studied at various concentrations of reactants and acidities. The redox reaction takes place through a complex multistep mechanism, which involves the formation of intermediate Cr IV and CrV species. CrIV reacts with d-fructose much faster than CrV and CrVI do, and cannot be directly detected. Superoxochromium(III), CrO22+, has been detected by UV spectroscopy, thus evidencing that CrII is an intermediary in these reactions and provides indirect evidence for the intermediary of CrIV reaction path. The complete rate law for the CrVI oxidation reaction is expressed by -d[CrVI]/dt = (a + b [d-Fru])[H+]2 [CrVI]T, where a = (1.66 ± 0.04) × 10 -4 M-2 s-1 and b = (1.79 ± 0.06) × 10-2 M-3 s-1. The EPR spectra show that five-coordinate oxo-CrV bischelates are formed in rapid pre-equilibria before the redox step: Cr(V) to Cr(III).

Original languageEnglish
Pages (from-to)1483-1490
Number of pages8
JournalPolyhedron
Volume25
Issue number6
DOIs
Publication statusPublished - Apr 17 2006

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Keywords

  • Cr(VI)
  • EPR pattern
  • Ketohexoses
  • Kinetics
  • Mechanism
  • Reduction

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

García, S., Ciullo, L., Olivera, M. S., González, J. C., Bellú, S., Rockembauer, A., Korecz, L., & Sala, L. F. (2006). Kinetics and mechanism of the reduction of chromium(VI) by D-fructose. Polyhedron, 25(6), 1483-1490. https://doi.org/10.1016/j.poly.2005.10.008