Abstract
The theory of differential linear sweep voltabsorptometry (DLSVA) and differential cyclic voltabsorptometry (DCVA) in long-path-length spectroelectrochemistry is presented for irreversible (Eir), quasi-reversible (Eqr) and ErCi′ mechanisms under conditions of semi-infinite diffusion. It is concluded that this method may be suitable for estimating electrochemical parameters because it is more sensitive than the approach using an optically transparent electrode. All the theoretical results re experimentally verified. The standard heterogeneous rate constant k s and the transfer coefficient α of two electrochemical quasi-reversible systems (methylene blue in 1.0 M HCl and indigo carmine in 0.1 M HCl) were estimated using the simplex method and good fits between theory and experiment were obtained. A system comprising K 4Fe(CN) 6 + ascorbic acid in 0.5 M HNO 3 + 0.5 M glycine buffer was utilized to test the theory for the ErCi′ mechanism. The rate constant of the pseudo-first-order catalytic reaction was also estimated by simplex fitting. The estimated results are in agreement with experimental values.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.