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For the purpose of this paper the following natural minerals: pyrite (FeS2), chalcopyrite (CuFeS2), galena (PbS), covellite (CuS) and chalcocite (Cu2S), were used as the indicator electrode for coulometric–potentiometric and potentiometric titrations of complex natural acid–base systems. These results were compared with those obtained by using of glass indicator electrode. The acidity of humic acid macromolecules was determined by combined coulometric–potentiometric method in alkaline solution which contained the sample of the substance that was being tested. Hydrogen ions generated by anode oxidation of hydrogen dissolved in palladium, while for the purpose of determining acidity of fulvic acids either in water and non-water environment (methanol, ethanol, acetone) tetraethylammonium hydroxide solution in methanol was used.
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