The interactions of O-isopropyl-N-ethylthionocarbamate (IPETC) and O-isobutyl-N-ethoxycarbonylthionocarbamate (IBECTC) with Cu₂S, CuFeS₂ and FeS₂ have been characterized using thermodynamic calculations, electrochemistry, microflotation tests, contact angle measurements, FTIR, and UV spectroscopy. Pearson’s theory of hard and soft acids and bases (HSAB) has also been applied to these flotation systems, through the use of Drago’s acid-base concept and flow microcalorimetry. The results of the thermodynamic calculations and electrochemical measurements suggest that IPETC and IBECTC adsorption on copper and chalcocite are dependent on potential. This has been verified by contact angle and in-situ spectroelectrochemical measurements. Microflotation tests with these thionocarbamates show that the floatability of Cu₂S and CuFeS₂ is dependent on pH. The floatability of FeS₂ only becomes significant at acidic conditions and high collector additions. Spectroscopic measurements also show that thionocarbamate adsorption is dependent on pH and is most favored on Cu₂S followed by CuFeS₂ and FeS₂. FTIR results indicate that IPETC is adsorbed on Cu°, Cu₂S, and CuFeS₂ through a coordination of the sulfur atom with the surface Cu. IBECTC adsorption on these substrates involves the coordination of Cu with both sulfur and oxygen atoms to form a six-membered chelate ring. Adsorption of these collectors cannot remove or prevent the formation of sulfoxy oxidation products on the FeS₂ surface, unlike the case with the xanthate-pyrite system. This may explain the improved selectivity of IPETC and IBECTC over xanthates. Infrared reflection-absorption spectroscopic studies show that KEX is preferentially adsorbed on Cu° over IPETC and IBECTC. Between IPETC and IBECTC, the latter is more favorably adsorbed than the former. Kinetic studies using UV spectroscopy show that the rate of thionocarbamate adsorption is highest on Cu₂S followed by CuFeS₂ and FeS₂. IBECTC adsorption on each sulfide mineral is relatively faster than IPETC, indicating the higher collecting power of IBECTC. The HSAB concept suggests that the interaction of thionocarbamates (soft bases) with sulfide minerals that are classified as soft acids should be favored. The C/E ratios of Cu₂S and FeS₂ were determined to be 0.86 and 0.52, respectively. This indicates that FeS₂ is a harder acid than Cu₂S, thus providing an explanation for the observed selectivity of both IPETC and IBECTC against FeS₂. / Ph. D.