The equilibrium constant for the extraction of thiocyanic acid by methylisobutyl ketone at constant ionic strength, depends on the nature of alkaline cations present in the aqueous phase. The phenomenon could be explained by the existence of ion pairs for which the association constantKpis derivable. However the extraction of chlorpromazinium thiocyanate by the same solvent and the formation of the monothiocyanate complex of zirconium in aqueous phase are both independent of the nature of the electrolyte. The observed variations for the extraction of thiocyanic acid which exist also for the extraction of hydrochloric and perchloric acids by methylisobutyl ketone, result from the variation of species activities with a change in the identity of the cations.