Abstract

The phase-boundary potential between the moderately hydrophobic ionic liquid and a low ionic strength aqueous solution is demonstrated to be stable and constant with the standard deviation of 0.4 mV down to 20 μmol kg −1 HBr, LiBr, and KBr solutions, for three ionic liquids that consist of either N -methyl- N -octylpyrrolidinium, N -heptyl- N -methylpyrrolidinium, or N -hexyl- N -methylpyrrolidinium and a common anion species, bis(pentafluoroethanesulfonyl)amide. This stability is promising for accurate measurements of pH of low ionic strength samples and reliable estimates of single ion activities in general. The phase-boundary potential deviates from the value determined by the partition of the ionic liquid in further dilute aqueous solutions. The magnitude of the deviation ranges from 3 to 11 mV at 5 μmol kg −1 MBr (M is H + , Li + , or K + ). The solubility of these ionic liquids in water is 0.2 mmol dm −3 at most at 25 °C, which is another advantage of ionic liquid salt bridge in electroanalytical chemistry.

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