| Summary: | Electrochemical oxidation of hydrogen sulfide gas (H2S) has been studied at a platinum microelectrode (10 μdiameter) in five room temperature ionic liquids (RTILs): [C4mim][OTt], [C4dmim][NTf 2], [C4mim][PF6], [C6mim][FAP], and [P14,6,6,6][FAP] (where [Cn, mim]+ = l-alkyl-3-methylimidazolium, [Cn,dmim]- = 1-alkyl2,3-dimethylimidazolium, [P14.6.6,6]- = tris(p-hexyl)-tetradecylphosphonium, [OTf]- = trifluoromethlysulfonate, [NTf2]- = bis(trifluoromethylsulfonyl)imide, [PF6]- = hexafluorophosphate, and [FAP]- = trifluorotris(pentafluoroethyl) phosphate). In four of the RTILs ([C4dmim][NTf2], [C 4mim][PF6], [C6mim][FAP], and [P 14,6,6,6][FAP]), no clear oxidative signal was observed. In [C 4mim][OTf], a chemically irreversible oxidation peak was observed on the oxidative sweep with no signal seen on the reverse scan. The oxidative signal showed an adsorptive stripping peak type followed by near steady-state limiting current behavior. Potential step chronoamperometry was carried out on the reductive wave, giving a diffusion coefficient and solubility of 1.6 x 10-10 m2 s-1 and 7 mM, respectively (at 25 °C). Using these data, we modeled the oxidation signal kinetically, assuming adsorption preceded oxidation and that adsorption was approximately Langmuirian. The oxidation step was described by an electrochemically fully irreversible Tafel law/Butler-Volmer formalism. Modeling indicated a substantial buildup of H2S in the double layer in excess of the coverage that would be expected for a monolayer of chemisorbed H2S, reflecting high solubility of the gas in [C4mim][OTf] and possible attractive interactions with the [OTf]- anions accumulated at the electrode at potentials positive of the potential of zero charge. Solute enrichment of the double layer in the solution adjacent to the electrode appears a novel feature of RTIL electrochemistry. © 2009 American Chemical Society.
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