TETRABUTYLAMMONIUM CATION EXPULSION VERSUS PERCHLORATE ELECTROLYTE ANION UPTAKE IN THE ELECTROCHEMICAL OXIDATION OF MICROCRYSTALS OF [(C4H9)(4)N][CR(CO)5I] MECHANICALLY ATTACHED TO A GOLD ELECTRODE - A VOLTAMMETRIC AND QUARTZ-CRYSTAL MICROBALANCE STUDY
Am. Bond et al., TETRABUTYLAMMONIUM CATION EXPULSION VERSUS PERCHLORATE ELECTROLYTE ANION UPTAKE IN THE ELECTROCHEMICAL OXIDATION OF MICROCRYSTALS OF [(C4H9)(4)N][CR(CO)5I] MECHANICALLY ATTACHED TO A GOLD ELECTRODE - A VOLTAMMETRIC AND QUARTZ-CRYSTAL MICROBALANCE STUDY, JOURNAL OF SOLID STATE ELECTROCHEMISTRY, 1(1), 1997, pp. 53-61
The electrochemistry of microcrystals of [(C4H9)(4)N][Cr(CO)(5)I] atta
ched to a gold electrode which is placed in aqueous (lithium or tetrab
utylammonium perchlorate) electrolyte media has been studied in detail
by chronoamperometric, voltammetric and electrochemical quartz crysta
l microbalance (ECQCM) techniques. Whilst chronoamperometric and volta
mmetric measurements show that the expected one-electron oxidation of
microcrystalline [Cr(CO)(5)I](-) solid to Cr(CO)(5)I occurs at the sol
id-electrode-solvent (electrolyte) interface, the ECQCM measurements r
eveal that charge neutralization does not occur exclusively via the ex
pected ejection of the tetrabutylammonium cation. Rather, uptake of Cl
O4- occurs under conditions where the solubility of sparingly soluble
[(C4H9)(4)N]ClO4 is exceeded. This is the first time that uptake of an
anion rather than loss of a cation has been detected in association w
ith an oxidation during electrochemical studies of microcrystals attac
hed to electrode surfaces. It is therefore now emerging that analogous
charge neutralization processes to those encounted in voltammetric st
udies 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 electrol
yte, an ion exchange process occurs leading to formation of Li[Cr(CO)(
5)I]. X H2O which then slowly dissolves in water at a rate that is str
ongly influenced by the electrolyte concentration, the relatively hydr
ophobic nature of the [(C4H9)(4)N](+) cation and the poor solubility o
f [(C4H9)(4)N]ClO4.