The basic condition necessary for flotation is hydrophobicity of the surface of the mineral to be floated. For sulphides, this condition usually requires treatment with a collector solution. The conditions for this treatment have until recently usually been chosen by the trial and error principle which has indeed been working relatively well under favourable conditions; ie for simple homogeneous ores. However, the present tendency to increasing use of complex and often relatively lean ores sets increasing requirements for the control of the flotation process. This development is the reason for the present rapid development of process control methods in flotation. In addition to the already well-established practices of pH and reagent feed controls, the importance of measuring and controlling the electrochemical potential of the ore particles to be floated is recognised in the case of sufficiently conductive minerals. In fact, the electrochemical potential seems to be the basic quantity determining the flotation behaviour of such relatively well-conducting minerals as sulphides. Since the hydrophobicity of the mineral and, hence, its flotation properties are ultimately determined by the composition and structure of its surface, information on these under different process conditions is important for design and operation of efficient flotation processes. The basic requirement set for the methods used for obtaining this information is high surface sensitivity of the method. The recent rapid development of surface characterisation has produced several methods which fulfil this requirement. Their application to the problem of characterising surfaces of mineral samples in contact with collector solution is, however, often complicated. The main reason for this is the vacuum environment necessary for the measurement. In the case of flotation experiments this means that in most of these methods the measurement cannot be made in situ, but the sample must be extracted from the liquid and subsequently evacuated in the vacuum chamber of the instrument.
It is essential to carry out these steps so as to avoid to the extent possible changes in the sample surface. For the purpose of establishing whether this has been accomplished it is important to compare the results of methods operating in vacuum with some available in situ method. An optimal choice of methods seems therefore to be a combination of the available powerful vacuum methods with in situ measurements. The most usual combination seems to be X-ray photoelectron spectroscopy (XPS or ESCA), Fourier transform infrared spectroscopy (FTIR) and electrochemical measurements. This choice combines the unique possibilities for direct elemental and chemical characterisation offered by XPS (Cecile, 1985) with the in situ capability of FTIR and electrochemistry. In the XPS measurements, it is essential to apply a special sample handling technique to avoid loss or damage of some sensitive species of the collector-based layer on the mineral surface. In the following will be given some examples of the application of the XPS technique in combination with electrochemical methods of sample treatment to studies of the layer formed on sulphide substrates in ethyl xanthate (EX).