The limit of applicability of the monomer-enhanced mechanism as dominant mechanism ruling the initiation process of the polymerization of acrylamide (AM) initiated with potassium persulfate (K2S2O8) has been determined The kinetics and mechanisms for radical generation were studied in solution at very low monomer and initiator concentrations The transition of the initiation mechanism from dominant monomer-enhanced dissociation to dominant thermal decomposition of persulfate was observed Both mechanisms contribute equally to radical generation at [AM] / [K2S2O8] approximate to 4 5 Thermal decomposition dominates at lower [AM] or higher [K2S2O8] and opposite variations promote the monomer-enhanced dissociation This work also includes quantification of the rate coefficients, efficiencies and activation energies of the mentioned mechanisms, and the kinetics of AM polymerization when photochemically initiated with phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide