The homologous series of saturated fatty acids investigated in this study generally show a steady gradation of properties with chain length. The solution pKa values were assumed constant at 4.9, however reported pKa values could be lower or higher. Hematite flotation response and surface pressure for aqueous solutions of these fatty acids were measured as a function of pH. For the shorter chain fatty acids, the undissociated acid was shown to be the predominant surface active species with flotation, supplemented by the physical adsorption of acid anions as the chain length increased. The reduced solubility of the longer fatty acid carbon chains made these reagents ineffective as flotation agents. The maximum flotation response of hematite using tetradecanoic acid corresponded with the precipitation edge of the reagent. The results show that the values of surface pressure of the surfactants are not always a good indication of their effectiveness as flotation collectors.