Colloidal particles are ubiquitous in natural and engineered environments. Processes like filtration, deposition, aggregation, transport of colloidal particles and associated chemical species, phase behavior of colloidal suspensions, and organization of large biomolecules such as DNA are governed by colloidal interactions. Traditionally, these interactions have been described by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. In the DLVO theory, colloidal particles are modeled as uniformly charged surfaces embedded in solutions containing non-interacting ions that lack size. Although the DLVO theory can be applied to cases within certain restrictions, many deviations between experimental observations and theoretical predictions have been reported in the literature. For example, it has been reported that deposition and remobilization of colloidal particles takes place at conditions predicted as unfavorable by the DLVO theory. The effects of lifting the DLVO theory assumption of continuous charge is examined via a combination of molecular modeling and atomic force microscopy in this work. The formation of the EDL, interactions of approaching EDLs, and development of surface charge in solutions containing symmetric and asymmetric electrolytes are investigated. Phenomena such as size exclusion effects, like-charge attraction, and surface charge heterogeneities, not predicted by the DLVO theory, were detected by just considering the discrete nature of surface charge and charge distribution within the EDL. The occurrence of these phenomena provides a plausible explanation for the deviations between theory and experiments reported in the literature.