An Electrochemical and Infrared Study of Chloranil in n-Butylpyridinium Chloride: Aluminum Chloride Ionic Liquid.

Abstract

The electrochemical behavior of tetrachlorobenzoquinone (chloranil, Q) has been studied in the aluminum chloride-n-butylpyridinium chloride (BuPyC) ionic liquid system. The reduction of chloranil proceeds in a two-electron step, giving rise to the dianion. Both the electrochemistry and infra-red spectroscopy appear to indicate that, depending on the acidity of the system, chloranil is complexed by AC3, initially on the carbonyl oxygen, and on the ring chlorines. The second carbonyl appears to remain uncomplexed. Large shifts in the reduction potential for chloranil are observed as the solvent acidity (mole ratio of AC3 to BuPyc) is varied, indicating the extensive degree of interaction of the solute with the solvent. Cyclic voltammetry indicates the presence of one or as many as three species, depending on the acidity, which are concluded to be in rather slow equilibrium. Nernst plots of the potential of an indicator electrode as a function of the Q/Q= ratio indicate potentiometric reversibility; at a fixed Q/Q= ratio, the potential variation as a function of melt acidity indicates a gain of three AC3 molecules per Q= relative to Q, suggesting that it is complexed by 6 AC3 molecules in the acid system. (Author)

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Document Details

Document Type
Technical Report
Publication Date
Jun 01, 1982
Accession Number
ADA115882

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  • Graham Cheek
  • R. A. Osteryoung

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  • University at Buffalo

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