The processes by which a metal–oxygen bond dissociates in aqueous complexes are discussed and the reactions related to more complicated pathways of mineral dissolution. The dissolution of oxide minerals, and in fact many other classes of surface reactions, can be viewed as a ligand-exchange reaction because the bridging oxygens that link the metal to the mineral are progressively replaced by non-bridging functional groups. These ligand-exchange reactions are accelerated by protonations, hydroxylations and ligand substitutions that modify the lability of surface oxygens, but always at specific sites. Molecular information is important because reactions at some sites retard rates while reaction at other sites enhance them. Virtually all of the important variables that affect these reaction rates are local.