Abstract
The potentialities of electrochemical and combined methods for the determination of thermodynamic characteristics and kinetic parameters of intermediates are analyzed. The electrochemical methods include polarography, versions of voltammetry, and chronopotentiometry. The combined methods combine nonelectrochemical (or indirect) generation of intermediates with electrochemical methods of their subsequent investigation: photomodulation voltammetry, method of polarography of pulsed-radiolysis products, method of indirect electrolysis, electrochemiluminescence, and a group of laser photoemission methods. Theoretical foundations and basic advantages and disadvantages of the laser photoemission methods (the measurement of photocurrents in potentiostatic conditions—method of time resolved voltammograms obtained under chopped illumination and the measurement of the kinetics of variations in the potential of an electrode after illuminating it by a pulsed laser—in coulostatic conditions) are described in detail. The potentialities of the laser photoemission methods for the determination of thermodynamic (standard potentials E 0 of redox pairs R⋅/R-, standard adsorption free energies) and kinetic (values of rate constants W 0 at an equilibrium potential, bulk lifetime of radicals R⋅and products of their reduction R-) characteristics of intermediates are demonstrated by studying a trifluoromethyl radical.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: 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.
