Search results for "Electrochemical kinetics"
showing 5 items of 5 documents
Grand canonical rate theory for electrochemical and electrocatalytic systems I: General formulation and proton-coupled electron transfer reactions
2020
A generally valid rate theory at fixed potentials is developed to treat electrochemical and electrocatalytic potential-dependent electron, proton, and proton-coupled electron reactions. Both classical and quantum reactions in adiabatic and non-adiabatic limits are treated. The applicability and new information obtained from the theory is demonstrated for the gold catalyzed acidic Volmer reaction.
Convective mass transfer to partially recessed and porous electrodes
2003
Abstract The diffusional problem of a rotating porous electrode has been analysed based on the mass transfer equations for a partially blocked electrode. It is shown that the porous geometry leads to a dependence of the current on rotation rate identical to that corresponding to a coupled diffusion-activated electron transfer mechanism. The apparent rate constant, however, is related only to the geometry of the porous surface. It is shown that the characteristic diffusional length corresponds to the pore dimension modified by a term including the transition from linear to spherical diffusional geometry at the pore entrance. The theory is compared with experimental results for the reduction …
Polymer dynamics in thin p-type conducting films investigated by ac-electrogravimetry. Kinetics aspects on anion exclusion, free solvent transfer, an…
2015
A new transfer model is proposed to explain ac-electrogravimetry response of p-doped films. This model takes into account the exclusion effect occurring as a result of the anion transfer. The insertion/expulsion of anions inside a film involves simultaneously the expulsion/insertion of free solvent molecules. The number of solvent molecules excluded depends on the volume of anion transferred. Solvent transfer stimulated by the conformational changes of films constitutes the remaining electrogravimetric response when the exclusion process cannot explain by itself this response. Consequently, the kinetics of this free solvent transfer can be directly related to the kinetics of conformational …
Rate Theory for Electrocatalytic Systems: Fixed Potential Formulation for General, Electron Transfer, and Proton-Coupled Electron Transfer Reactions
2019
Atomistic modeling of electrocatalytic reactions is most naturally conducted within the grand canonical ensemble (GCE) which enables fixed chemical potential calculations. While GCE has been widely adopted for modeling electrochemical and electrocatalytic thermodynamics, the electrochemical reaction rate theory within GCE is lacking. Molecular and condensed phase rate theories are formulated within microcanonical and canonical ensembles, respectively, but electrocatalytic systems described within the GCE require extension of the conventionally used rate theories for computation reaction rates at fixed electrode potentials. In this work, rate theories from (micro) canonical ensemble are gene…
Spatiotemporal colorimetry to reveal electrochemical kinetics of poly(o-toluidine) films along ITO surface
2018
Abstract Sheet resistance of transparent conducting electrodes can affect dramatically the electrochromic response of surface confined active species in any electrochromic device. The generated gradient of effective potential on the electrode surface has a direct impact on the electrochemical kinetics of these species. In this work, the electrochromic poly (o-toluidine) (POT) film, a derivative polyaniline, was deposited along a narrow, long transparent indium tin oxide (ITO) supporting electrode with a sheet resistivity of 30 Ω cm−1. This configuration was used as a model to simulate a surface electrical conduction from the external metallic contact to the opposite extreme of ITO with an i…