Square‐Wave Voltammetry of Cathodic Stripping Reactions. Diagnostic Criteria, Redox Kinetic Measurements, and Analytical Applications

Abstract

A comparative study of different types of cathodic stripping reactions under conditions of square-wave voltammetry is presented. Cathodic stripping processes involving reactions of second order as well as reactions coupled by adsorption of the reacting ligand are analyzed The inherent parameters, controlling the overall voltammetric behavior of each cathodic stripping electrode reaction are derived. The criteria for qualitative distinguishing of each mechanism are established as well as a methodology for redox kinetic measurements is proposed. The influence of the parameters of the excitation signal on the properties of the voltammetric response is analyzed in order to find optimal conditions for analytical application. The theoretical results are illustrated by the experiments with a series of uracil derivatives.

Diagnostics of Anodic Stripping Mechanisms under Square-Wave Voltammetry Conditions Using Bismuth Film Substrates

“…31 In agreement with previous findings, the position of the quasireversible maximum depends on particular value of k s , revealing that it can be exploited for estimation of the latter kinetic parameter (k s ) in a simple procedure elaborated in detail in previous studies. 30,31 In the reversible kinetic region, the real net peak current depends linearly on the square-root of the frequency, while the net peak potential shifts linearly with log( f) toward more positive potentials. Alongside to the frequency, the SW amplitude is the second powerful instrumental tool to study the electrode reaction for the purpose of the electrode kinetic measurements, as well as optimization of the response for analytical application.…”

The Influence of Rhodium(+3) onVoltammetry of Selenium(+4) in Perchloric Acid

“…Additionally, such a product should be reducible within the accessible potential range. Mathematical models [15,16] take into account accumulation and stripping of HgX, HgX 2 and Hg 2 X 2 compounds. For the cases, which include deposition of Me a X b after production of X in the electrode process and (possible) reduction of the initially present metal ions to a lower oxidation state, theory does not exist.…”

Redox Properties of Mixed Lutetium/Yttrium Nitride Clusterfullerenes: Endohedral LuxY3−xN@C80(I) (x=0–3) Compounds

“…This pattern can mirror the contribution of adsorption phenomena to the re-oxidation. [22,23] The process of the first reduction step is similar for all four NCFs, and the standard reduction potential of the first step corresponds to the LUMO (lowest unoccupied molecular orbital) energy. As demonstrated in Table 1, the LUMO seems to be nearly unchanged by the composition of the encaged nitride cluster.…”