ECE and disproportionation: Part VI. General resolution. Application to potential step chronoamperometry

摘要: Abstract The competition between homogeneous and heterogeneous electron transfers in ECE-DISP mechanisms: A+eB BC C+eD B+C→A+D is analyzed the context of potential step chronoamperometry. Starting from expressions apparent number electrons for limiting situation, ECE, DISP1, DISP2, transition two these “pure” mechanisms systematically investigated. general system then large values kinetic parameters, i.e., particular case a stationary state arising mutual compensation diffusion chemical reaction (“pure kinetic” conditions). This provides an estimation range parameters where numerical analysis actually necessary together with tests accuracy computation procedures. In this framework most involving no assumption about magnitude thermodynamic leads to three-dimensional zone diagram which allows predict effects intrinsic (equilibrium rate constants) operational (time, concentration) on displacement one situation other. On bases, practical effectiveness single-step techniques discriminating discussed. It shown that discrimination DISP2 either ECE DISP1 can be easily carried out terms concentration or time dependence current response. much more difficult requires high experimental effective.