Hofmeister effects in micromolar electrolyte solutions (Journal of Chemical Physics)

by S. Enami, H. Mishra, M. R. Hoffmann, A. J. Colussi
Year: 2012

Bibliography

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

Abstract

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

Keywords

Hofmeister series Specific ion effects