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Tetrabutylammonium cation expulsion versus perchlorate electrolyte anion uptake in the electrochemical oxidation of microcrystals of [(C4H9)4N][Cr(CO)5I] mechanically attached to a gold electrode: a voltammetric and quartz crystal microbalance study


Citation

Bond, Alan M. and Colton, Ray and Mahon, Peter J. and Tan, Wee Tee (1997) Tetrabutylammonium cation expulsion versus perchlorate electrolyte anion uptake in the electrochemical oxidation of microcrystals of [(C4H9)4N][Cr(CO)5I] mechanically attached to a gold electrode: a voltammetric and quartz crystal microbalance study. Journal of Solid State Electrochemistry, 1 (1). pp. 53-61. ISSN 1432-8488

Abstract / Synopsis

The electrochemistry of microcrystals of [(C4H9)4N][Cr(CO)5I] attached to a gold electrode which is placed in aqueous (lithium or tetrabutylammonium perchlorate) electrolyte media has been studied in detail by chronoamperometric, voltammetric and electrochemical quartz crystal microbalance (ECQCM) techniques. Whilst chronoamperometric and voltammetric measurements show that the expected one-electron oxidation of microcrystalline [Cr(CO)5I]− solid to Cr(CO)5I occurs at the solid-electrode-solvent (electrolyte) interface, the ECQCM measurements reveal that charge neutralization does not occur exclusively via the expected ejection of the tetrabutylammonium cation. Rather, uptake of ClO4 − occurs under conditions where the solubility of sparingly soluble [(C4H9)4N]ClO4 is exceeded. This is the first time that uptake of an anion rather than loss of a cation has been detected in association with an oxidation during electrochemical studies of microcrystals attached to electrode surfaces. It is therefore now emerging that analogous charge neutralization processes to those encounted in voltammetric studies on conducting polymers are available in voltammetric studies of microcrystals attached to electrodes which are placed in contact with solvent (electrolyte) media. In the presence of LiClO4 as the electrolyte, an ion exchange process occurs leading to formation of Li[Cr(CO)5I] . X H2O which then slowly dissolves in water at a rate that is strongly influenced by the electrolyte concentration, the relatively hydrophobic nature of the [(C4H9)4N]+ cation and the poor solubility of [(C4H9)4N]ClO4.


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Additional Metadata

Item Type: Article
Divisions: Universiti Pertanian Malaysia
DOI Number: https://doi.org/10.1007/s100080050022
Publisher: Springer
Keywords: Electrochemical quartz crystal microbalance (ECQCM); Iodopentacarbonyl chromium(0) [Cr(Co)5I]-; Ion transfer; Voltammetry mechanically attached solid
Depositing User: Nurul Ainie Mokhtar
Date Deposited: 17 May 2016 15:43
Last Modified: 17 May 2016 15:43
Altmetrics: http://www.altmetric.com/details.php?domain=psasir.upm.edu.my&doi=10.1007/s100080050022
URI: http://psasir.upm.edu.my/id/eprint/35817
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