Electrochemical characterization of tenoxicam using a bare carbon paste electrode under stagnant and forced convection conditions

Highlights: ► Tenoxicam electrochemical oxidation was studied from aqueous solution with a CPE. ► Both stagnant and forced convection conditions were considered. ► We found tenoxicam electrochemical oxidation is a mass transfer-controlled process. ► An EC mechanism was found where the electrodic and chemical kinetics are fast. ► It was found that in this case n = 2 and E1/2 = 0.770 V. ► Calculated D was 4.09 × 10−6 cm2 s−1 which compares with theoretically estimated. - Abstract: From potentiostatic current transients and voltammetry studies, carried out under both stagnant and forced convection conditions, the tenoxicam electrochemical behavior on a bare carbon paste rotating disk electrode was assessed in an aqueous solution (pH = 0.403). It was found that tenoxicam's electrochemical oxidation is a mass transfer-controlled process where a current peak is clearly formed at around 0.74 V when the potential scan was varied in the positive direction. However, when the potential was switched to the negative direction, up to the initial potential value, no reduction peak was formed. Tenoxicam's electrochemical oxidation follows an EC mechanism where the electrodic and chemical kinetics are fast. From sample-current voltammetry both the number of electrons, n, that tenoxicam losses during its electro-oxidation and its half-wave potential, E1/2, were determined to be 2 and 0.770 V vs. Ag/AgCl, respectively. Moreover, from differential pulse voltammetry plots it was confirmed that effectively in this case n = 2. Considering 2 electrons and both the Randles-Sevcik and Cotrell equations, the tenoxicam's diffusion coefficient, D, was determined to be (3.745 ± 0.077) × 10−6 and (4.116 ± 0.086) × 10−6 cm2 s−1, respectively. From linear sweep voltammetry plots recorded under forced convection conditions, it was found that Levich's equation describes adequately the limiting current recorded as a function of the electrode rotation rate, from where the D value was also found to be (4.396 ± 0.058) × 10−6 cm2 s−1. Therefore, the average D value was (4.09 ± 0.33) × 10−6 cm2 s−1. Furthermore, from the radius of the tenoxicam molecule, previously optimized at M052X/6-31 + G(d,p) level of theory, and using the Stokes–Einstein approach, D was also estimated to be 4.54 × 10−6 cm2 s−1 which is similar to the experimentally estimated values, under both stagnant and forced convection hydrodynamic conditions.