Electrochemistry of organic redox liquids at elevated pressures

Keith J. Stevenson, Henry S. White

Research output: Contribution to journalArticlepeer-review

19 Citations (Scopus)

Abstract

The effect of hydrostatic pressure on the 1-e reductions of acetophenone (AP) and nitrobenzene (NB) in the absence of an inert solvent is reported. Steady-state voltammetric responses for these redox systems are obtained at a 12.5 fim radius Pt microdisk in a three-electrode, high-pressure electrochemical cell. Reduction of 8.0 M AP and 9.1 M NB in solutions containing only a small quantity of supporting electrolyte (0.2 M [(;i-butyl)4N]PF6) yields well-defined sigmoidal-shaped voltammetric waves over the range of pressures investigated (P = 1 -1000 bar). Transport-limited currents for both AP and NB reduction are shown to decrease linearly with increasing pressure. Apparent (or integral) diffusion coefficients (Dapp) are computed from the voltammetric limiting currents for AP and NB reduction and compared to bulk solution molecular diffusivities (D) measured for a redox-active molecule (decamethylferrocene) added to the solutions at low concentration (~16 mM). The relative decreases in Dapp and D with increasing pressure are essentially identical in both NB and AP solutions for pressures up to 1000 bar. The results indicate that transport-limited currents for the reduction of these organic liquids are determined solely by diffusive processes.

Original languageEnglish
Pages (from-to)18818-18822
Number of pages5
JournalJournal of Physical Chemistry
Volume100
Issue number48
DOIs
Publication statusPublished - 1996
Externally publishedYes

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