Kinetics of radical dimerization. Simple evaluation of rate constant from convolution voltammetry and faradaic phase angle data

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F19%3A00511919" target="_blank" >RIV/61388955:_____/19:00511919 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/19:00502103

Výsledek na webu

<a href="http://hdl.handle.net/11104/0302153" target="_blank" >http://hdl.handle.net/11104/0302153</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.electacta.2019.01.119" target="_blank" >10.1016/j.electacta.2019.01.119</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Kinetics of radical dimerization. Simple evaluation of rate constant from convolution voltammetry and faradaic phase angle data

Popis výsledku v původním jazyce

Search for possible ways of the binary information storage evoked an interest in the mechanism of the electrochemical monomer/dimer switching. Thus, determination of the rate of radical-to-dimer conversion became an issue. Mathematical formulation describing the electrochemical generation of a radical followed by a bimolecular chemical reaction contains a quadratic term, in which case the inverse Laplace transformation does not exist. Until now, kinetic data were obtained by using finite difference simulations. We report an alternative and simpler evaluation method, which uses the frequency dependence of the faradaic impedance. Determination of the required surface concentration uses convoluted voltammogram recorded at the same bulk concentration as the impedance data. Functional dependence of the faradaic phase angle on frequency (cot phi vs. omega(1/2)) shows a maximum at lower frequencies containing information on the dimerization kinetics and a linear asymptote at the highest frequency range yields the electron transfer rate. This new procedure was applied to four different known redox systems, all involving radical dimerization process. (C) 2019 Elsevier Ltd. All rights reserved.

Název v anglickém jazyce

Kinetics of radical dimerization. Simple evaluation of rate constant from convolution voltammetry and faradaic phase angle data

Popis výsledku anglicky

Search for possible ways of the binary information storage evoked an interest in the mechanism of the electrochemical monomer/dimer switching. Thus, determination of the rate of radical-to-dimer conversion became an issue. Mathematical formulation describing the electrochemical generation of a radical followed by a bimolecular chemical reaction contains a quadratic term, in which case the inverse Laplace transformation does not exist. Until now, kinetic data were obtained by using finite difference simulations. We report an alternative and simpler evaluation method, which uses the frequency dependence of the faradaic impedance. Determination of the required surface concentration uses convoluted voltammogram recorded at the same bulk concentration as the impedance data. Functional dependence of the faradaic phase angle on frequency (cot phi vs. omega(1/2)) shows a maximum at lower frequencies containing information on the dimerization kinetics and a linear asymptote at the highest frequency range yields the electron transfer rate. This new procedure was applied to four different known redox systems, all involving radical dimerization process. (C) 2019 Elsevier Ltd. All rights reserved.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

<a href="/cs/project/GA18-04682S" target="_blank" >GA18-04682S: Studium mechanismu transportu elektronů v jednotlivých molekulách pomocí vodivostních a termoelektrických měření.</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Electrochimica acta

ISSN

0013-4686

e-ISSN

—

Svazek periodika

300

Číslo periodika v rámci svazku

MAR 2019

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

6

Strana od-do

284-289

Kód UT WoS článku

000458488200034

EID výsledku v databázi Scopus

2-s2.0-85060957140