Spontaneous Symmetry Breaking: The Case of Crazy Clock and Beyond

Abstract

In this work, we describe the crazy-clock phenomenon involving the state I (low iodide and iodine concentration) to state II (high iodide and iodine concentration with new iodine phase) transition after a Briggs–Rauscher (BR) oscillatory process. While the BR crazy-clock phenomenon is known, this is the first time that crazy-clock behavior is linked and explained with the symmetry-breaking phenomenon, highlighting the entire process in a novel way. The presented phenomenon has been thoroughly investigated by running more than 60 experiments, and evaluated by using statistical cluster K-means analysis. The mixing rate, as well as the magnetic bar shape and dimensions, have a strong influence on the transition appearance. Although the transition for both mixing and no-mixing conditions are taking place completely randomly, by using statistical cluster analysis we obtain different numbers of clusters (showing the time-domains where the transition is more likely to occur). In the case of stirring, clusters are more compact and separated, revealed new hidden details regarding the chemical dynamics of nonlinear processes. The significance of the presented results is beyond oscillatory reaction kinetics since the described example belongs to the small class of chemical systems that shows intrinsic randomness in their response and it might be considered as a real example of a classical liquid random number generator.

Stochastic Phase Transition Dynamics in Nonequilibrium System: Holographic Study

“…As previously published, 7,10,14 the State I → State II transition is essentially irreproducible in time (as its "crazy-clock" name indicates). Surprisingly, this crazy-clock behavior is preceded by a strongly reproducible oscillatory dynamics (at 25 °C, the oscillatory period lasts 240 s, with 33 oscillations), which happens before solid iodine formation, i.e., before the State I → State II transition.…”

“…Nonlinear systems are highly sensitive to the concentration of reactants, the geometries of the reaction vessel, mixing conditions, and external influences like light and temperature. ,− Up to now, the time evolution of nonlinear chemical systems has been successfully monitored by potentiometric methods. − However, the electrodes immersed in the solution could give rise to additional effects like catalytic effect, “dead volume” effect (i.e., when diffusion of chemical species is a controlling factor for the reaction), and a lot of other processes highly dependent on the nature of the working electrode. , Furthermore, the main reactant, hydrogen peroxide, could be decomposed on the platinum electrode, which is widely used in potentiometric measurements of oscillatory reactions. In addition, many details of a complex redox system are not fully understood .…”

“…18−21 However, the electrodes immersed in the solution could give rise to additional effects like catalytic effect, "dead volume" effect (i.e., when diffusion of chemical species is a controlling factor for the reaction), and a lot of other processes highly dependent on the nature of the working electrode. 10,19 Furthermore, the main reactant, hydrogen peroxide, could be decomposed on the platinum electrode, which is widely used in potentiometric measurements of oscillatory reactions. In addition, many details of a complex redox system are not fully understood.…”

“…Therefore, it is crucial to develop methods that offer new insight into the physics of oscillatory reactions, the pattern formations at the nanoscale, and their links with macroscopic behavior. In this article, we analyzed a nonequilibrium chemical system, an oscillatory Briggs–Rauscher (BR) reaction accompanied with phase transition, i.e., solid iodine formation. , Under the applied experimental conditions, after the BR oscillatory period, two states are observed: State I (low iodide and iodine concentration) and State II (high iodide and iodine concentration, with solid iodine formation). A sudden transition from State I to State II, so-called crazy-clock behavior , is accompanied by a liquid–solid iodine phase transition. ,, This process proved to be an ideal model for implementing a new holographic approach.…”

“…A sudden transition from State I to State II, so-called crazy-clock behavior, is accompanied by a liquid−solid iodine phase transition. 7,10,11 This process proved to be an ideal model for implementing a new holographic approach. In addition to holographic observations, potentiometric measurements are performed, as a comparison to assess the performance of our method.…”