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Competitive binding of binary mixed counterions to the headgroups of adsorbed surfactant films has been investigated at solution surfaces by total reflection X-ray absorption fine structure (XAFS) spectroscopy. The obtained extended XAFS χ spectra for bromide counterions are linear combinations of the spectra of fully hydrated bromide ions (free Br) and partially dehydrated bromide ions bound to the headgroups of the surfactant ions (bound Br). From the fraction of bound Br in counterion mixed systems, two series of the relative strengths of counterion binding are proposed for the trimethylammonium (TA+) and 3-methylimidazolium (MIM+) headgroups: (a) TA–SO4 < TA–Cl < TA–Br < TA–BF4 and (b) MIM–Br < TA–Br < TA–BF4 < MIM–BF4. For the TA headgroup, matching the hydration of the headgroups and counterions gives series (a) according to Collins’ law, which states that the tendency of contact ion pair formation becomes larger when the absolute values of the hydration enthalpies of the ions match. For the MIM headgroup, the number of binding sites of hydrogen bonds between the MIM headgroup and counterion is essential, which leads to series (b) because of competition between the counterion and water for interaction with the MIM headgroup.

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