Sulphur potential measurements with a two-phase sulphideoxide electrolyte

The open circuit potentials of the galvanic cell,Pt (or Au)¦(Ar + H2S + H2)′∥CaS + ZrO2(CaO)∥ (Ar + H2S+ H2)″£t (or Au) has been measured in the temperature range 1000 to 1660 K and PH2S:PH2 ratios from 1.73×10−5 to 2.65×10−1. The solid electrolyte consists of a dispersion of calcium sulphide in a matrix of calcia-stabilized zirconia. The surface of the electrolyte is coated with a thin layer of calcium sulphide to prevent the formation of water vapour by reaction of hydrogen sulphide with calcium oxide or zirconia present in the electrolyte. The use of a ‘point electrode’ with a catalytically active tip was necessary to obtain steady emfs. At low temperatures and high sulphur potentials the emfs agreed with the Nernst equation. Deviations were observed at high temperatures and low sulphur potentials, probably due to the onset of significant electronic conduction in the oxide matrix of the electrolyte. The values of oxygen and sulphur potentials at which the electronic conductivity is equal to ionic conductivity in the two-phase electrolyte have been evaluated from the emf response of the cell. The sulphide-oxide electrolyte is unsuitable for sulphur potential measurements in atmospheres with high oxygen potentials, where oxidation of calcium sulphide may be expected.