Oscillations of EPR Signals Accompanying Belousov–Zhabotinsky Reaction

Periodical transformation of ferroin to ferriin is accompanied by changes in magnetic properties of liquids during Belousov–Zhabotinsky (BZ) reaction malonic acid, sodium bromide, sodium bromate, ferroin, and sulfuric acid. Instead of the earlier studied oscillation of microwave conductivity accompanying an oscillating reaction, we propose a flash technique to interrupt the BZ reaction by rapid freezing. Rapid cooling of a solution during chemical oscillations results in a frozen system with a fixed concentration of paramagnetic centers Fe3+. EPR spectrum recorded at different stages of the interrupted reaction corresponds to the exact concentration of the ferroin and ferriin components. Following unfreezing unblocks the BZ reaction, and oscillations are still observed. A simulated spectrum allows one to distinguish two groups of Fe3+ ions of different symmetries. The obtained results are important to explain the earlier observed effect of inhomogeneous magnetic field on BZ reaction front velocity.

Sustained oscillations in interstellar chemistry models

Context. Nonlinear behavior in interstellar chemical models has been recognized for 25 years now. Different mechanisms account for the possibility of multiple fixed-points at steady-state, characterized by the ionization degree of the gas. Aims. Chemical oscillations are also a natural behavior of nonlinear chemical models. We study under which conditions spontaneous sustained chemical oscillations are possible, and what kind of bifurcations lead to, or quench, the occurrence of such oscillations. Methods. The well-known ordinary differential equations (ODE) integrator VODE was used to explore initial conditions and parameter space in a gas phase chemical model of a dark interstellar cloud. Results. We recall that the time evolution of the various chemical abundances under fixed temperature conditions depends on the density over cosmic ionization rate nH∕ζ ratio. We also report the occurrence of naturally sustained oscillations for a limited but well-defined range of control parameters. The period of oscillations is within the range of characteristic timescales of interstellar processes and could lead to spectacular resonances in time-dependent models. Reservoir species (C, CO, NH3, ...) oscillation amplitudes are generally less than a factor two. However, these amplitudes reach a factor ten to thousand for low abundance species, e.g. HCN, ND3, that may play a key role for diagnostic purposes. The mechanism responsible for oscillations is tightly linked to the chemistry of nitrogen, and requires long chains of reactions such as found in multi-deuteration processes.

Efficiency range of the Belousov–Zhabotinsky reaction to induce the self-organization of transient bonds in metallo-supramolecular polymeric systems

Although reaction parameters offer control over chemical oscillations in a transient metallo-supramolecular polymer gel network system, this does not result in a pronounced self-organization of metallo-supramolecular bonds.