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Published 1968 | public
Book Section - Chapter

Oxidation of Iron(II) Chloride in Nonaqueous Solvents

Abstract

Autoxidation of iron(II) chloride in nonaqueous solvents is much faster than in water. The rate is first order in oxygen, and under controlled conditions, second order in iron(II). Various additives have powerful catalytic or inhibitory effects. The inhibition by iron(III) disappears in the presence of excess lithium chloride, so inhibition is attributed to competition between iron(II) and iron(III) for chloride ions. Induced autoxidation of benzoin to benzil has the same rate-limiting step as the autoxidation of iron(II) without cosubstrate. The data can be accommodated by a mechanism in which the rate-limiting step is production of iron(IV) by dissociation of a binuclear complex having the composition Cl_2FeOOFeCl_2. In the presence of excess lithium chloride, intermediates containing more chloride bound to iron become involved.

Additional Information

© 1968 American Chemical Society. Received October 20, 1967. Contribution No. 3357 from the Gates and Crellin Laboratories of Chemistry. This study was supported by a grant from the U.S. Public Health Service. We thank William C. Stwalley for his assistance in the runs for stoichiometric factor.

Additional details

Created:
August 19, 2023
Modified:
January 13, 2024