Dynamics of Ion Pairing in Dilute Aqueous HCl Solutions by Spectroscopic Measurements of Hydroxyl Radical Conversion...

The rate of formation of dichloride anions (Cl₂^•-) in dilute aqueous solutions of HCl (2-100 mmol·kg^-1) was measured by the technique of pulse radiolysis over the temperature range of 288-373 K. The obtained Arrhenius dependence shows a concentration averaged activation energy of 7.3 ± 1.8 kJ·mol^-1, being half of that expected from the mechanism assuming the ^•OHCl^- intermediate and supporting the ionic equilibrium-based mechanism, i.e., the formation of Cl₂^•- in the reaction of ^•OH with a hydronium-chloride (Cl^-·H₃O⁺) contact ion pair. Assuming diffusion-controlled encounter of the hydronium and chloride ions and including the effect of the ionic atmosphere, we showed that the reciprocal of τ, the lifetime of (Cl^-·H₃O⁺), follows an Arrhenius dependence with an activation energy of 23 ± 4 kJ·mol^-1, independent of the acid concentration. This result indicates that the contact pair is stabilized by hydrogen bonding interaction of the solvent molecules. We also found that at a fixed temperature, τ is noticeably increased in less-concentrated solutions (m_HCl < 0.01 m). Since this concentration effect is particularly pronounced at near ambient temperatures, the increasing pair lifetime may result from the solvent cage effect enhanced by the presence of large supramolecular structures (patches) formed by continuously connected four-bonded water molecules.