Imaging Ion Pairs Forming Structural Arrangements in Interfacial Regions.

A technique to image ion pairs in solution is reported. We investigated structural and dynamic properties of ion-pair distributions deposited on highly oriented pyrolytic graphite (HOPG) surfaces in electrolyte solutions. Atomic force microscopy images of HOPG immersed in NaCl and KCl solutions display regular arrangements on top of the hexagonal carbon rings forming the HOPG atomic structure. These arrangements are the result of the low value of the aqueous interfacial dielectric constant (εr ≈ 3-11). The measured ion-pair radius is a function of the salt present in the solution; for KCl, the ion-pair radius is equal or smaller than 0.42 nm; for NaCl, the ion-pair radius is 0.36 nm. A comparison of these values with their crystalline lattice dimensions indicates that both KCl and NaCl ion pairs in solution at the HOPG/solution interfacial region exist as tight contact ion pairs in quasistationary distributions. The NaCl ion-pair distribution forms an aligned arrangement, and the KCl distribution is formed by intercalated pairs.