Abstract
The polarography of methanesulphonic, trifluoromethanesulphonic, and fluorosulphonic acids has been studied with methylene chloride as solvent and 0.1 mol dm −3 tetra-n-butylammonium tetrafluoroborate as base electrolyte. The single wave found for CH 3SO 3H was identified as due to reduction of HA. The other two acids gave the same wave and also another with less negative E 1/2 which is due to reduction of H 2A +. All waves are irreversible; the sequence of the E 1/2(H 2A +) follows that of the strength of the acids. For all three acids the total current depends rectilinearly on [HA] 0, so that this feature can be used analytically. From the slopes of the limiting current vs. [HA] 0 plots the equilibrium constant K of the binary ionogenic reaction 2 HA⇌A −+H 2A + can be calculated as 7.2×10 −3 for CF 3SO 3H and 9.8×10 −2 for FSO 3H.
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