A new model is developed to quantify the surface tension of ionic surfactants from surface affinity and ionization equilibrium. The model successfully predicts two important molecular structure-surface activity factors: the length of single-branch homologues and the nature of counterions. The modeling results also clarify the underlying mechanisms of the two processes. Changing the counterion only affects the ionization, not the affinity. On the other hand, increasing carbon length dramatically increases the affinity while having a small effect on ionization. The modeling framework consistently resolves structure-activity observations, some of which have been reported since the 19th century. The model can be extended for surfactants with more than one ionic state and surfactant/electrolyte mixtures.
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