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Issue 24, 2003
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Reinvestigation of the kinetics of reduction of bromite by hexacyanoferrate(ii) in slightly basic solution

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Abstract

The reaction BrO2 + 4 Fe(CN)64− + 2 H2O → Br + 4 Fe(CN)63− + 4 OH has been studied by spectrophotometry at 30, 40 and 50 °C and both with equivalent amounts of reactants and with an excess of bromite. It follows the kinetic expression with kobs = 8.2 M−2 s−1 at 25 °C, ΔH = 66 kJ mol−1 and ΔS = −121.7 J K−1 mol−1. The proposed mechanism is a two-stage process, the first, rate-determining stage being reduction of bromite to hypobromous acid, the second further reduction to bromide. Either stage consists of two bimolecular reactions. The major contribution to the energy barriers comes from electrostatic repulsion between negative ions.

Graphical abstract: Reinvestigation of the kinetics of reduction of bromite by hexacyanoferrate(ii) in slightly basic solution

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Article information


Submitted
28 Jul 2003
Accepted
13 Oct 2003
First published
23 Oct 2003

Dalton Trans., 2003, 4651-4653
Article type
Paper

Reinvestigation of the kinetics of reduction of bromite by hexacyanoferrate(II) in slightly basic solution

H. E. Lundager Madsen, Dalton Trans., 2003, 4651
DOI: 10.1039/B308878B

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