Hofmeister effects in micromolar electrolyte solutions
S. Enami, H. Mishra, M. R. Hoffmann, A. J. Colussi, Journal of Chemical Physics (2012) 136, 154707; DOI: 10.1063/1.4704752
Ions induce both specific (Hofmeister) and non-specific (Coulomb) effects at aqueous interfaces. More than a century after their discovery, the origin of specific ion effects (SIE) still eludes explanation because the causal electrostatic and non-electrostatic interactions are neither local nor separable. Since direct Coulomb effects essentially vanish below ∼ 10 μ M (i.e., at > 50 nm average ion separations in water), we decided to investigate whether SIE operate at, hitherto unexplored, lower concentrations. Herein, we report the detection of SIE above ∼ 0.1 μ M in experiments where relative iodide/bromide populations, χ = I− /Br− , were determined on the surface of aqueous (NaI + NaBr) jets by online electrospray mass spectrometry in the presence of variable XCl (X = H, Na, K, Cs, NH4 , and N(C4 H9 )4 ) and NaY (Y = OH, Cl, NO3 , and ClO4 ) concentrations. We found that (1) all tested electrolytes begin to affect χ below ∼ 1 μ M and (2) I− and Br− are preferentially suppressed by co-ions closely matching their interfacial affinities. We infer that these phenomena, by falling outside the reach of even the longest ranged electrostatic interactions, are dynamical in nature