An Application of Chemical Oscillation: Distinguishing Two Isomers Between Cyclohexane-1, 3-dione and 1, 4-cyclohexanedione
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Published on 2016 by
Graphical abstract: Highlights: A novel Briggs–Rauscher (BR) oscillating system could be used for distinguishing two isomers. This Briggs–Rauscher oscillating system involves a macrocyclic complex as catalyst. Cyclohexane-1, 3-dione (1, 3-CHD) and 1, 4-cyclohexanedione (1, 4-CHD) were distinguished. Two isomers were distinguished by their different perturbation effects on BR system. 1, 3-CHD involves radical oxidization while 1, 4-CHD involves idiodation and elimination. Abstract: In the analytical field, previous applications of chemical oscillation focused on quantitative analysis. We report in this paper a novel qualitative method electrochemically distinguishing two positional isomers by utilizing their perturbation effects on a catalyzed Briggs–Rauscher (BR) oscillation. The catalyst in the system is a macrocyclic nickel (II) complex NiL(ClO4 )2, where the ligand L in the complex is 5, 7, 7, 12, 14, 14-hexemethyl-1, 4, 8, 11-tetraazacyclotetradeca-4, 11-diene. The experimental results indicated that addition of cyclohexane-1, 3-dione (1, 3-CHD) or 1, 4-cyclohexanedione (1, 4-CHD) could affect the profiles of potentiometric oscillations, but their changes in the profiles are greatly different. When 1, 3-CHD was injected into the oscillating system, there was an initial spiking of the oscillations, accompanying by quenching of oscillations before the regeneration of oscillations. While 1, 4-CHD was injected into the dynamic mixture, the oscillatory system responded to the perturbation with only slight decrease followed by a sharp increase in the potential, before it resumed to its normal oscillation state. The perturbation of 1, 3-CHD involves inhibition time, whereas the perturbation of 1, 4-CHD does not. Hence these two positional isomers could be distinguished by using their different perturbation effects on a BR dynamic system in the range of 9.0 × 10 −4 to 8.0 × 10 −3 M. Our assumption is that, perturbation of 1, 3-CHD on the oscillating system involves a radical oxidization process to produce carboxylic acid, whereas perturbation of 1, 4-CHD assumes idiodation and elimination steps to form 1, 4-benzoquinone. Such different perturbation mechanisms are responsible for the difference in potentiometric oscillation profiles change. This hypothesis was confirmed by products analysis by FTIR and UV spectra.
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