It is well known that the chemical environment determines the success of the flotation process, however its characterisation and control is difficult to achieve. This paper, as two parts, Part I and Part II, evaluates the use of various measurements and their interpretation to gain an understanding of the influence of varying parameters such as the type of milling media and copper sulphate addition on the flotation performance of sulphide minerals from a platinum group mineral (PGM) bearing Merensky ore. It shows the complexity of interpretation and the importance of analysing flotation performance holistically. Part I focuses on the pulp chemistry and mineral potential measurements have been used to show the differences in the response of the various mineral electrodes to different conditions. The final flotation recoveries of the sulphide minerals in the ore followed the same trend as the decrease in mineral potential due to collector addition viz. chalcopyrite > pentlandite > pyrrhotite. Type of milling media and copper sulphate addition slightly affected the mineral electrode potential and flotation recovery of chalcopyrite. Addition of copper sulphate increased the recovery of pentlandite and particularly pyrrhotite due to activation by copper (II) ions. The copper activation mechanism was likely to be in the form of initial adsorption of copper hydroxide followed by reduction to Cu+ at the surface. However, the changes in flotation performance of the different minerals in the ore could not be completely described by the electrochemical changes, demonstrating the limitations of these measurements. Part II addresses the effect of froth stability as demonstrated by the variations in the mass and water recovery data resulting from the different milling conditions and addition of copper sulphate which emphasised the importance of considering the froth phase in the evaluation of flotation data. (c) 2005 Elsevier B.V. All rights reserved.