We explore via simulation, the cyclic voltammetry of the following mechanism involving a reversible electrode process coupled with a follow up reaction in which the product (B) of the electrode reaction reacts chemically with the reactant, A, to form a species C:2A−2e−⇄BB+A⇌kbkfC Such a mechanism is shown, under certain critical combinations of rate constant and reactant concentration to give rise to two voltammetric peaks despite the assumption of a single redox couple (A/B). This results from the formation of C during the first peak whilst the second peak, seen at more oxidizing potentials, reflects the dissociation of C releasing A. A mechanism of the type investigated may hold during the oxidation of bromide(Br−, A) in solution to form bromine(Br2, B) and tribromide (Br3−,C). Simulations are used to explore the conditions for which two peaks are expected in the bromide oxidation system in aqueous solution and for which the two following limiting cases operate3Br−−2e−⇄Br3− and2Br−−2e−⇄Br2 We report experimental data for the bromide oxidation in aqueous solution. These are interpreted via simulations using independent literature values for the rate and equilibrium constants for tribromide formation.