The effect of aliphatic alcohols on the rates of electrochemical electron tunneling across monolayers of n-alkanethiols and n-alkaneselenols  self-assembled on an expandable hanging mercury drop electrode (HMDE) is described. The electron transfer between the solution dissolved redox species and mercury electrode across the monolayer occurs via super-exchange through-bond tunneling (ET).  Gradual additions of aliphatic alcohols to the solution result in a decrease of the ET rate, by a maximum of 7-fold, dependent upon the alcohol concentration, but independent of the thickness of the n-alkanethiol monolayer (SAM) and the alcohol's chain length. The mechanism involving competitive adsorption of the alcohol on the SAM surface is proposed to interpret the kinetic data.

Electron tunneling through monolayers self-assembled on a hanging mercury drop electrode in the presence of aliphatic alcohols

240th National Meeting (2010)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.