A systematic study of collisions between surfactant-free organic drops in aqueous electrolyte solutions reveals the threshold at which continuum models provide a complete description of thin-film interactions. For collision velocities above 1 μm/s, continuum models of hydrodynamics and surface forces provide a complete description of the interaction, despite the absence of surfactant. This includes accurate prediction of coalescence at high salt concentration (500 mM). In electrolyte solutions at intermediate salt concentration (50 mM), drop–drop collisions at lower velocity (<1 μm) or extended time of forced drop–drop interaction exhibit a strong pull-off force of systematically varying magnitude. The observations have implications on the effects of ion-specificity and time-dependence in drop–drop interactions where kinetic stability is marginal.