In recent years it has been shown that the concept of using partial molar excess Gibbs energy (G̅ex) to explain the behaviour of collectors in the recovery of minerals can be usefully applied to explain flotation performance. Fundamentally this is because hydrophobicity of a mineral particle on which a collector is adsorbed may be strongly related to the fact that the alkyl chain associated with the collector behaves in the same way as any hydrocarbon would in an aqueous medium. This hydrocarbon-water system represents a classical non-ideal mixture, and such mixtures are quantified thermodynamically by determining the activity coefficient of the hydrocarbon moiety of the collector and hence its G̅ex in the mixture. It has been shown that G̅ex is a more rigorous indicator of the contributions of various alkyl groups of a collector than HLB (Corin and O’Connor, 2014) and was also able to explain aspects of froth behaviour (Harris and O’Connor, 2017) and hydrophobicity (O’Connor, 2021). The present paper is aimed at extending the above concepts in two different ways. Firstly, a study is undertaken of a range of results previously reported in which various reagents containing different alkyl groups were analysed in terms of their effect on contact angle and their performance as flotation reagents in terms of recovery. These results sustain the previous observations that there is a robust positive relationship between hydrophobicity as indicated by flotation recovery and contact angle and G̅ex of the alkyl group associated with the collector. Secondly, on the basis of the observation that increases in G̅ex are indicative of increases in the hydrophobicity of the mineral particle-collector aggregate, a study was undertaken to examine the effect of ions typical of electrolytes in water as well as the effect of the presence of alcohols and of pH on G̅ex of the collector alkyl group. In the former two instances the absence of any correlation between G̅ex and recoveries supported the proposition of the respective authors of these studies that the major effect of these electrolytes and added alcohols may be on particle–bubble attachment rather than on the hydrophobicity of the mineral/collector in the aqueous system. On the other hand, the effect of pH on G̅ex correlated reasonably well with changes reported in the literature on the effect of pH on recovery and contact angle.