Construction and evaluation of tetrafluoroborate selective electrodes

Summary The construction and evaluation of three types of tetrafluoroborate electrodes without internal reference solution is described. Sensors for electrodes of Type A and Type B use tetraoctylammonium tetrafluoroborate as carrier and 2-nitrophenyloctylether and dibutylphthalate, respectively, as solvent mediators. Electrodes of Type C use the 92-05-02 Orion commercial sensor based on a complex of tris(1,10-phenanthroline)-Ni(II) dissolved in p-nitrocymene. Membranes were applied on a conductive support consisting of a mixture of graphite with a non-conductive epoxy resin. The three types of electrodes showed a similar behaviour with linear responses within the concentration range 10^–5–10^–1 mol/l in tetrafluoroborate, with slopes of 58 mV per decade when the pH of the solutions was between 3 and 11.5. Electrodes of Type A showed the lowest short term hysteresis after treatment with interfering species and offered the best reproducibility and lifetime. Therefore, they were used in the determination of tetrafluoroborate ion in plating baths by means of the sample addition method, giving results with an average spike recovery of 100.5% and a mean coefficient of variation of 1.0%.