Quantitative weaknesses of the Marcus-Hush theory of electrode kinetics revealed by Reverse Scan Square Wave Voltammetry: The reduction of 2-methyl-2-nitropropane at mercury microelectrodes

► Experimental comparison between Butler-Volmer and Marcus-Hush models is performed. ► The reduction of 2-methyl-2-nitropropane at mercury microelectrodes is considered. ► Reverse Scan Square Wave Voltammetry reveals significant differences between models. ► Butler-Volmer adequately fits experimental data with consistent kinetic parameters. ► Marcus-Hush does not enable satisfactory quantitative description of the redox system.