Chlorite-based oscillators

IIIL) Orban, M., De Kepper, P., Epstein, I. R. Systematic Design of Chemical Oscillators, 1982-1 Part 77. An Iodine-free Chlorite-based Oscillator. The Chlorite-Thiosulfate Reaction in a Continuous Flow Stirred Tank Reactor. J. Phys. Chem., 86, 431-433... 

The chlorite-iodide reaction is clearly the minimal oscillator of the subfamily of chlorite-iodide xidant oscillating reactions, and, since iodate and iodine appear to be produced in all of them, it can be considered to be the progenitor of a still larger family that includes the chlorite-iodate-reductant and cWorite-iodine-reductant groups listed in Table 4.1. Clearly, the chlorite-iodide reaction cannot be minimal for the entire family of chlorite-based oscillators since many of them contain no iodine species. It is not at all obvious that a minimal oscillator for the entire chlorite family exists. 

Other mixed-mode oscillations of this type have been seen in the Bray reaction (Chopin-Dumas, 1978) and several chlorite-based oscillators (Orban and Epstein, 1982 Alamgir and Epstein, 1985a, 1985b). In Figure 8.9, we present a phase diagram that shows the progression of 1" oscillations in the chlorite-thiosulfate system. 

A chlorite-thiosulfate system showed oscillations in a CSTR, and is the first chlorite-based oscillator involving no iodine-containing species. ... 

The recently discovered chlorine(III) (chlorite-based) oscillators show a wide range of dynamical phenomena in "batch" and "flow."... 

Evidence for XCIO Intermediates in Chlorite-Based Oscillators... 

Synthesis of Chemical Oscillations 79 Table 4.1 Chlorite-Based Chemical Oscillators in a CSTR... 

By studying appropriately perturbed autocatalytic reactions in a flow reactor (cSTR), we have produced a family of some 20 new oscillators containing chlorite ion. In addition, several new bromate oscillators (e.g., BrOs -Mn -Br " and BrOs - ), which are simpler in composition and mechanism than the classic Belous ov-Zhabotinskii system, have been discovered. Mechanistic considerations have given rise to a tentative classification of oxyhalogen based oscillators which shows the linkage and differences between the various classes. 

The chlorite-iodate-arsenite oscillator was the first oscillating reaction discovered which is based upon chlorite chemistry. The BZ reaction and its relatives are bromate oscillators, while the BL and Briggs-Rauscher oscillators are iodate systems. The initial chlorite oscillator was rapidly followed by a large family of related systems58"60, which are summarized in Table 8. We note that while most of these systems contain an iodine species (I-, I2, IOf) as well as the chlorite, at least two iodine-free chlorite oscillators exist. 

While the early oscillators were based upon bromate or iodate chemistry, the largest group of new oscillators contains a third oxyhalogen ion, chlorite. Table 1 lists the known chlorite oscillators, all of which were discovered in a stirred tank reactor (CSTR). 

A major step toward understanding the bromate oscillators was the formulation by Noyes ([ 32]) of a mechanistically based classification scheme for the known (batch) bromate oscillators. Since that time, a variety of additional oxyhalogen (bromate, chlorite, iodide) systems have been shown to oscillate in the... 

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