Persistent ion pairing in aqueous hydrochloric acid

For strong acids, like hydrochloric acid, the complete dissociation into an excess proton and conjugated base as well as the formation of independent solvated charged fragments is assumed. The existence of chloride-hydronium (Cl^-···H₃O⁺) contact ion pairs even in moderate concentration hydrochloric acid (2.5 m) demonstrates that the counterions do not behave merely as spectators. Through comparison of recent extended X-ray absorption fine structure (EXAFS) measurements to state-of-the-art density functional theory (DFT) simulations, we are able to obtain a unique view into the molecular structure of medium-to-high concentrated electrolytes. Here we report that the Cl ^-···H₃O⁺ contact ion pair structure persists throughout the entire concentration range studied and that these structures differ significantly from moieties studied in microsolvated hydrochloric acid gas phase clusters. Characterizing distinct populations of these ion pairs gives rise to a novel molecular level description of how to view the reaction network for acid dissociation and how it relates to our picture of acid-base equilibria.