TL;DRAbstract
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 Cl2FeOOFeCl2. In the presence of excess lithium chloride, intermediates containing more chloride bound to iron become involved.
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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 Cl2FeOOFeCl2. In the presence of excess lithium chloride, intermediates containing more chloride bound to iron become involved.
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