Reverse pulse voltammetry in ec2 reactions. Electrochemistry of 1-alkyl-4-t-butylpyridinium ions

Dov Talmor, Joshua Hermolin, Emilia Kirowa-Eisner

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The applications of the reverse pulse method are extended in order to distinguish between different paths of electrodimerization. The method for determination of rate constants of the chemical reaction coupled with charge transfer (ec2) is further developed. Measurements of K′d vs. t p provide valuable information for the determination of rate constants. The reverse pulse method is applied in the study of the electrodimerization of 1-alkyl-4-t-butylpyridinium ions (1-alkyl=-CH3; -CH2CH3; -CH(CH 3)2) in acetonitrile. It is found that the electrodimerization mechanism is consistent with the sequence: Py+ + e = Py ⇋ 1 2 Py2. The formal potential Eo′ is measured directly for 1-CH(CH3)2, and indirectly for the other pyridium ions. All values are identical within experimental error (Eo′ = -1.835 V vs. Ag/Ag+). The values of kd and km are measured. With an increase in the size of the l-alkyl group, kd decreases and km increases. This is consistent with the expected "stabilization" of the radicals due to the increase of the l-alkyl group size which hinders the dimerization site (2- and 6-positions).

Original languageEnglish
Pages (from-to)81-95
Number of pages15
JournalJournal of Electroanalytical Chemistry
Issue number1
StatePublished - 8 Oct 1982


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