Spatiotemporal behavior induced by differential diffusion in Landolt systems

J Phys Chem A. 2014 Nov 13;118(45):10699-705. doi: 10.1021/jp508836p. Epub 2014 Oct 31.

Abstract

The spatiotemporal dynamics of Landolt type reactions, for instance reactions between sulfite ions and strong oxidants, performed in a medium fed by the diffusion from a boundary is investigated numerically by using a simple general reaction scheme. In these conditions, the model can generate various spatiotemporal phenomena, e.g., spatial bistability, simple and complex oscillations, birhythmicity, and chaos, even though in a spatially homogeneous open reactor only steady-state bistability can develop. The model consists of two reactions, a protonation equilibrium of the reductant and an oxidation step that is autoactivated by hydrogen ions. The rich dynamics is the result of two factors: (i) long-range activation, through the rapidly diffusing hydrogen ions, (ii) the presence of two parallel autocatalytic pathways. Long range activation provides the necessary negative feedback, whereas the dual nature of the autocatalysis leads to the appearance of two different oscillatory modes. The presence of a second-order term in the rate law of the autocatalytic reaction is linked to a large amplitude oscillations that affect the system as a whole, whereas the third-order one gives rise to localized front oscillations. The complex phenomena, like mixed mode and chaotic oscillations are observed at the meeting of these different oscillatory modes.