Hofmeister Effect in Self-Organized Chemical Systems

Abstract

We studied the effect of spectator ions in the prototype of far-from-equilibrium self-organized chemical systems, the Belousov–Zhabotinsky (BZ) reaction. In particular, we investigated the specific ion effect of alkali metal cations, connoted for their kosmotropic and chaotropic properties. By means of combined experimental and numerical approaches, we could show a neat and robust evidence for the Hofmeister effect in this system. Spectator cations induce a marked increment of the induction period that preludes regular oscillations and decrease the oscillation amplitude following the sequence Li+ < Na+ ≪ K+ ∼ Cs+. These ions affect the system kinetics by interfering in the interaction between the oxidized form of the catalyst and the organic substrate, responsible for resetting the BZ system to pre-autocatalytic (reduced) conditions. The specific ion effect on these key reactive steps is systematically characterized and correlated with different parameters which describe the interaction of the cations with the solvent.