Effects of the dipolar double layer on elemental electrode processes

Material type: 文書・図像類

Author: Aoki, Koichi Jeremiahほか

Publisher: Royal Society of Chemistry

Publication date: 2018-01-29

Material Format: Digital

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Note (General)：: Determination of heterogeneous rate constants of redox reactions or charge transfer resistances always involves ambiguities due to participation in do...

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Material Type: 文書・図像類
Title: Effects of the dipolar double layer on elemental electrode processes
Author/Editor: Aoki, Koichi Jeremiah
Chen, Jingyuan
Author Heading: Aoki, Koichi Jeremiah
Chen, Jingyuan
Publication, Distribution, etc.: Royal Society of Chemistry
Publication Date: 2018-01-29
Publication Date (W3CDTF): 2018-01-29
Periodical title: Faraday Discussions
Pages: 1-9
ISSN (Periodical Title): ISSN : 1364-5498
Text Language Code: eng
Target Audience: 一般
Note (General): Determination of heterogeneous rate constants of redox reactions or charge transfer resistances always involves ambiguities due to participation in double layer (DL) capacitances and solution resistances. The rate constants determined by the steady-state voltammograms at ultra-microelectrodes are inconsistent with time-dependent voltammograms, implying participation of the DL impedance. We examine controlling factors of DLs through the frequency-dependence of the capacitance on the basis of the definition of the current and the capacitance. The capacitance is obeyed by the power law of the frequency. It is controlled by orientation of limited amount of solvent dipoles, independent of salts. Redox species, of which dipoles are oriented oppositely to the solvent dipoles, decrease the DL capacitance and make the value negative at high concentration of the specie. The decrease in the capacitance increases the real impedance, as predicted from the phase angle, yielding an extra resistance. This may be a ghost charge transfer resistance. However, there are a number of actually well-defined charge transfer resistances, which are observed as transferring rates through films on electrodes.
Access Restrictions: 限定公開
Related Material (DOI): 10.1039/C7FD00212B
Data Provider (Database): 国立情報学研究所 : 学術機関リポジトリデータベース（IRDB）（機関リポジトリ）
https://irdb.nii.ac.jp
Original Data Provider (Database): 福井大学 : 福井大学学術機関リポジトリ