Analytical solutions for the study of homogeneous first-order chemical kinetics via UV–vis spectroelectrochemistry

Analytical solutions are reported for the identification and study of homogeneous chemical reactions via UV–vis spectroelectrochemistry. Expressions are presented for the concentration profiles and the absorbance response of any the species of the CEC mechanism when applying a potential-pulse pertur...

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Bibliographic Details
Published in:Journal of electroanalytical chemistry (Lausanne, Switzerland) Switzerland), 2018-06, Vol.819, p.202-213
Main Authors: Molina, A., Laborda, E., Gómez-Gil, J.M., Martínez-Ortiz, F., Compton, R.G.
Format: Article
Language:English
Subjects:
Absorbance
Analytical chemistry
Analytical theory
Chemical reactions
Concentration profiles
Constant potential chronoamperometry
Electrodes
Organic chemistry
Reaction kinetics
Reaction mechanism
UV–vis spectroelectrochemistry
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Summary:Analytical solutions are reported for the identification and study of homogeneous chemical reactions via UV–vis spectroelectrochemistry. Expressions are presented for the concentration profiles and the absorbance response of any the species of the CEC mechanism when applying a potential-pulse perturbation under semi-infinite linear diffusion conditions. With this theory it is possible to relate easily the absorbance transient to the physicochemical dynamics of the redox system. In particular, the influence of the chemical reactions involving the oxidized and/or the reduced species will be investigated both in the normal and parallel beam configurations. Expressions for the reaction schemes CE, EC and E can be deduced as particular cases. The EC solutions are applied to the study of facilitated ion transfers across liquid|liquid interfaces where the likely different diffusivity of the ion in the two phases has been considered. •Analytical expressions are deduced for the CEC mechanism spectroelectrochemistry.•Normal and parallel-beam configurations are considered upon applying a potential pulse.•The E, CE, EC and ion transfer mechanisms are studied as particular cases.•Solutions relate the absorbance transient with the system physicochemical dynamics.
ISSN:1572-6657
1873-2569
DOI:10.1016/j.jelechem.2017.10.031