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The potentiometric titration method can be used for quantitative determination of germanium sulfide and germanium mercaptide evolved during the sol–gel processing of GeS2 from germanium ethoxide and H2S. The titrations were performed in 2-propanol or in a 50–50 vol.% mixture of 2-propanol and toluene. The ion selective Ag/Ag2S electrode was used for equivalence point detection.