The kinetics and mechanism of the oxidation of DL ethionine and thiourea by potassium ferrate

• Published in: Transition metal chemistry (Weinheim) 2004-03, Vol.29 (2), p.149-158
• Main Authors: Read, John F., MacCormick, K. Julia, McBain, Adina M.
• Format: Article
• Language: English
• Subjects: Kinetics
• ISSN: 0340-4285; 1572-901X
• DOI: 10.1023/B:TMCH.0000019412.93362.a8

The kinetics of the reaction between ethionine and thiourea were investigated under pseudo and non-pseudo-first-order conditions. Ethionine was oxidized to the sulfoxide within 500 s and thiourea was oxidized to urea within 10 s. Above a pH of ca. 8.5 the reaction was first-order in the concentration of the organosulfur compound, the hydrogen ions and the ferrate ions, whereas, below this pH, the kinetics were independent of the hydrogen ion concentration. A possible mechanism for both compounds is initial protonation of the ferrate ion followed by the two electron rate-determining step of addition of oxygen to the organosulfur compound. The kinetic parameters for ethionine compare favorably with those for similar compounds, whereas thiourea tends to be more active. The rate constant for the rate-determining step is 4.1 × 10^sup 2^ M^sup -1^ s^sup -1^ for ethionine and 4.1 × 10^sup 3^ M^sup -1^ s^sup -1^ for thiourea.[PUBLICATION ABSTRACT]