Abstract
Isonicotinic amide was studied by dc and DP polarography and linear sweep cyclic voltammetry in a strong acid medium (pH < 3). Tafel slopes and reaction orders were obtained at potentials corresponding to the foot of the polarographic wave. In a very strong acidic medium the process occurs through the formation of a protonated gem-hydroxylamine which is transformed into the aldehyde via a substitution by water, which is the rate-determining step. For 0 < pH < 3, the gem-hydroxylamine formed after two reversible electron transfers can eliminate an ammonia molecule in two ways: (a) proton-catalysed substitution by water followed by the formation of a hydrated aldehyde; and (b) non-catalysed elimination to form the free aldehyde. The limiting current of the wave is partially controlled by these concurrent chemical reactions and. consequently, the process appears as ECE.
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