The adsorption mechanisms of various thiol collectors can be subdivided into four classes: chemisorption, EC-mechanism, catalytic oxidation and metathetical substitution. The chemisorption mechanism occurs at potentials below the thermodynamic potentials for the metal-thiol compound formation and is reversible. The EC-mechanism occurs when the mineral is sufficiently oxidised to liberate metal ions to form metal-xanthates; therefore, it is observed with more easily oxidisable minerals and/or with collectors having large pK values. Thionocarbamates adsorb on sulphide minerals via the EC-mechanism due to their large pK values. Although the adsorption occurs at very low potentials as compared to xanthates, it is irreversible with large overpotentials. On the other hand, the adsorption of modified thiophosphates and thiophosphinates occurs near the thermodynamic potentials because of the low pK values. The metathetical substitution is believed to occur only when a mineral is highly oxidised. These classifications are useful for studying the effects of electrochemical potentials and the molecular structure on the collector adsorption Mechanisms.