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Kinetics and mechanism of periodate oxidation of ternary orotatochromium(iii) complexes bearing oxalate or malonate co-ligands

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Abstract

Oxidation kinetics of complexes [CrIII(OR)(HOX)(H2O)3]+ and [CrIII(OR)(HM)(H2O)3]+ (OR is orotic acid, HOX is oxalic acid, HM is malonic acid) by periodate in aqueous acidic medium was studied using spectrophotometric measurements in the pH range 3.34–4.63 at different temperatures. The reaction is first order in concentrations of both the IO4 − ion and complex. For both complexes, the oxidation rate increases with the pH increase. The experimental rate law is consistent with a mechanism in which the deprotonated ([CrIII(OR)(OX)(H2O)2]) and protonated ([CrIII(OR)(HM)(H2O)3]+) species are significantly more reactive. Apparently, electron transfer proceeds through an inner sphere mechanism via coordination of the IO4 − ion to chromium(iii). Thermodynamic activation parameters were calculated using the transition state theory equations.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah, 21589, Saudi Arabia

    I. M. I. Ismail, H. A. Ewais & Sh. A. K. Elroby

  2. The Center of Excellence in Environmental Studies, King Abdulaziz University, P.O. Box 80216, Jeddah, 21589, Saudi Arabia

    I. M. I. Ismail

  3. Chemistry Department, Faculty of Science, Beni-Suef University, Beni-Suef City, Egypt

    H. A. Ewais & Sh. A. K. Elroby

Authors
  1. I. M. I. Ismail
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  2. H. A. Ewais
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  3. Sh. A. K. Elroby
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Correspondence to H. A. Ewais.

Additional information

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0591–0598, March, 2014.

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Ismail, I.M.I., Ewais, H.A. & Elroby, S.A.K. Kinetics and mechanism of periodate oxidation of ternary orotatochromium(iii) complexes bearing oxalate or malonate co-ligands. Russ Chem Bull 63, 591–598 (2014). https://doi.org/10.1007/s11172-014-0478-x

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  • DOI: https://doi.org/10.1007/s11172-014-0478-x

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