Dynamic behavior of the pH-regulated oscillations has been studied for the hydrogen peroxide oxidation of thiosulfate ions in the presence of trace amounts of copper(II) ions in a semibatch reactor. A solution of 0.08 M Na(2)S(2)O(3) and 0.112 M NaOH was flowed at 0.160 mL/min into 300 mL of solution containing the H(2)O(2) and Cu(2+) in a vessel. There exists a critical value of the H(2)O(2) or Cu(2+) concentrations below which the system does not oscillate. The oscillations appear due to an infinite period bifurcation at low initial concentrations of the H(2)O(2). The initial concentration of Cu(2+) may be considered as a bifurcation parameter in this case. Increase of the initial hydrogen peroxide concentration causes the pH-regulated oscillations through a nondegenerate supercritical Hopf bifurcation. The classification of bifurcations is based on the analysis of the behavior of oscillation amplitude and period at different initial concentrations of the H(2)O(2) and Cu(2+). Our results show a possibility to distinguish different scenarios for the appearance of transient oscillations in semibatch experiments. (c) 1996 American Institute of Physics.
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http://dx.doi.org/10.1063/1.166188 | DOI Listing |
Angew Chem Int Ed Engl
February 2020
Department of Chemical and Biological Engineering, University of Sheffield, Mappin Street, Sheffield, S1 3JD, UK.
Highly ordered superstructures composed of inorganic nanoparticles appear in natural and synthetic systems, however the mechanisms of non-equilibrium self-organization that may be involved are still poorly understood. Herein, we performed a kinetic investigation of the precipitation of calcium phosphate using a process widely found in microorganisms: the hydrolysis of urea by enzyme urease. With high initial ratio of calcium ion to phosphate, periodic precipitation was obtained accompanied by pH oscillations in a well-stirred, closed reactor.
View Article and Find Full Text PDFAcc Chem Res
March 2015
‡Department of Chemistry and Volen Center for Complex Systems, MS 015, Brandeis University, Waltham, Massachusetts 02453, United States.
The hydrogen ion is arguably the most ubiquitous and important species in chemistry. It also plays a key role in nearly every biological process. In this Account, we discuss systems whose behavior is governed by oscillations in the concentration of hydrogen ion.
View Article and Find Full Text PDFChaos
September 1996
L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Prospect Nauki 31, Kiev 252028, UkraineDepartment of Chemistry and Biochemistry, University of Southern Mississippi, Hattiesburg, Mississippi 39406-5043.
Dynamic behavior of the pH-regulated oscillations has been studied for the hydrogen peroxide oxidation of thiosulfate ions in the presence of trace amounts of copper(II) ions in a semibatch reactor. A solution of 0.08 M Na(2)S(2)O(3) and 0.
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