Understanding the fundamental principles governing the reactions at surfaces has always been the goal of theoretical surface science. The atomistic simulation techniques have been used to calculate the surface structures and the stability of quartz and wollastonite, and their adsorption behaviour in the presence of molecular and dissociative water, and the two widely used collector head group molecules of methanoic acid and methylamine. The dissolution behaviour of wollastonite has also been modelled. The calculated surface energy, hydration energy and reaction energy values have been examined and discussed in the light of flotation literature. These studies have given an insight into the interactions at atomic level, which indicate that modelling techniques should be capable of predicting the adsorption behaviour and to design the selective collector molecules, which is of central importance to the mineral processing technique of flotation.