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Oxidation of Iron(II) Chloride in Nonaqueous Solvents

Hammond, George S. and Wu, Chin-Hua S. (1968) Oxidation of Iron(II) Chloride in Nonaqueous Solvents. In: Oxidation of Organic Compounds. Advances in Chemistry Series. No.77. American Chemical Society , Washington, DC, pp. 186-207.

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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.

Item Type:Book Section
Alternate Title:Oxidation of Iron(2) Chloride in Nonaqueous Solvents
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.
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U.S. Public Health Service (USPHS)UNSPECIFIED
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Other Numbering System NameOther Numbering System ID
Caltech Gates and Crellin Laboratories of Chemistry3357
Series Name:Advances in Chemistry Series
Issue or Number:77
Record Number:CaltechAUTHORS:20150303-090350407
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:55453
Deposited By: Tony Diaz
Deposited On:03 Mar 2015 23:17
Last Modified:03 Oct 2019 08:05

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