Abstract

The electrochemistry of I −/I 3 − was studied in ionic liquids using a combination of cyclic voltammetry, chronoamperometry and scanning electrochemical microscopy (SECM). The electrolytes were 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C n C 1Im][Tf 2N], ionic liquids (where n = 2, 4 and 8) and I − was typically added at a concentration of approximately 11 mM. During cyclic voltammetry, two sets of peaks were observed in each ionic liquid due to oxidation and reduction of the I −/I 3 − redox couple and oxidation/reduction of the I 3 −/I 2 redox couple. The diffusion coefficients of I − and I 3 −, as determined using chronoamperometry, increased with increasing temperature and decreased with increasing ionic liquid viscosity. The effect of ionic liquid viscosity on ultramicroelectrode (UME) voltammetry was also determined using the I −/I 3 − redox couple. Steady-state behaviour was observed at 1.3 μm UMEs at slow voltammetric scan rates and steady-state SECM feedback approach curves were also obtained at a 1.3 μm Pt SECM tips, provided that the tip approach speed was sufficiently low.

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