Abstract
Kinetic and thermodynamic parameters for ferrate(VI) oxidation of phenol have been measured in isotopic solvents, H2O and D2O, using ambient and high-pressure stopped-flow UV−visible spectroscopy. An increase (fast stage) and then a decrease (slow stage) in absorbance at 400 nm are observed when potassium ferrate (K2FeO4) and aqueous phenol solutions are mixed rapidly. This suggests that small amounts of unstable intermediate 4,4‘-biphenoquinone are produced during this redox process. An electron paramagnetic resonance signal for the reaction mixture of ferrate and phenol trapped by spin-trap α-(4-pyridyl-1-oxide)-N-tert-butylnitrone indicates a radical reaction pathway. Gas chromatographic/mass spectrometric measurements show p-benzoquinone is a major organic product, and the red ferric thiocyanate complex formed from addition of potassium thiocyanate to the spent reaction solution indicates that Fe(VI) is reduced to Fe(III). Activation enthalpy, entropy, and volume changes have been determined. There is...
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