Periodic Motion in the Chaotic Phase of an Unstirred Ferroin-Catalyzed Belousov Zhabotinsky Reaction.

The Belousov Zhabotinsky reaction, a self-organized oscillatory color-changing reaction, can show complex behavior when left unstirred in a cuvette environment. The most intriguing behavior is the transition from periodicity to chaos and back to periodicity as the system evolves in time. It was shown that this happens thanks due to the decoupling of reaction, diffusion and convection. We have recently discovered that, as the so-called chaotic transient takes place, periodic bulk motions in form of convective cells are created in the reaction solution. In this work we investigated this phenomenon experimentally by changing cuvette size and reaction volume, in order to allow different types of convection patterns to appear. So far, we have observed single and double convection cells in the system. There are indications that the convection patterns are connected to the duration of the chaotic phase. A simplified mathematical model confirms the form and dynamics of the observed convection cells and explains the connection between chemical chaos and hydrodynamical order.

Hofmeister Effect in Self-Organized Chemical Systems.

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.