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Transition Metal Chemistry

, Volume 19, Issue 6, pp 636–639 | Cite as

Osmium(VIII)-catalysed oxidation of chromium(III) by alkaline hexacyanoferrate(III)

  • Shivamurti C. Hiremath
  • Shivamurti A. Chimatadar
  • Javali R. Raju
Full Papers

Summary

Osmium(VIII) -catalysed hexacyanoferrate(III) oxidation of a freshly prepared solution of chromium(III) in aqueous alkali (pH > 12.5) at 25° C obeys the rate equation:
$$\begin{gathered} rate_c = - \frac{{d\left[ {Fe(CN)_6^{3 - } } \right]}}{{dt}} \hfill \\ = \frac{{kK_2 \left[ {Os^{VIII} } \right]_T \left[ {Cr^{III} } \right]_T \left[ {OH^ - } \right]_T }}{{1 + K_2 \left[ {OH^ - } \right]_T }} \hfill \\ \end{gathered}$$
wherek is the rate constant of slowest step andK2 is the equilibrium constant for:
$${\text{OsO}}_{\text{4}} {\text{(OH)}}_{\text{2}}^{{\text{2 - }}} {\text{ + OH}}^{\text{ - }} {\text{ }} \rightleftharpoons {\text{ OsO}}_{\text{5}} {\text{(OH) }}^{{\text{3 - }}} {\text{ + H}}_{\text{2}} {\text{O}}$$
Thek andK2 values are 833 (±50) dm3 mol−1 s−1 and 7.2 (±0.4) dm3 mol−1, respectively, at 25° C. The order of reaction with respect to Fe(CN) 6 3− is zero and the reaction rate increases with an increase in ionic strength. The active species are Cr(OH)4 and OsO5(OH)3−.

Keywords

Oxidation Physical Chemistry Chromium Inorganic Chemistry Catalysis 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Chapman & Hall 1994

Authors and Affiliations

  • Shivamurti C. Hiremath
    • 1
  • Shivamurti A. Chimatadar
    • 1
  • Javali R. Raju
    • 1
  1. 1.Department of ChemistryKarnatak UniversityDharwadndia

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