Search results for "Belousov–Zhabotinsky"
showing 10 items of 19 documents
Mechanistic Investigations of the BZ Reaction with Oxalic Acid Substrate. I. The Oscillatory Parameter Region and Rate Constants Measured for the Rea…
2004
This paper is the first part of a study reinvestigating the mechanism of the Belousov-Zhabotinsky (BZ) reaction of oxalic acid, which is the simplest organic substrate for a BZ oscillator. New experiments are performed to find the oscillatory region in 1 M sulfuric acid at 20 °C. The removal rate of the end product bromine by an inert gas stream is a critical parameter here: oscillations can be observed only in a window of that parameter. The “rate constant” for the physical removal of bromine is measured as a function of the gas flow rate and reactor volume; furthermore, the rate constants of three component reactions important in this system are also determined. These are oxygen atom tran…
Isotopic Effect on the Kinetics of the Belousov-Zhabotinsky Reaction
2007
In this work we present results about the deuterium isotope effect on the global kinetics of a Belousov-Zhabotinsky reaction in batch conditions. A nonlinear dependence of the Induction Period upon the percentage of deuterated reactants was found. The isotopic effect on the bromination reaction of malonic acid was evaluated.
Role of the reagents consumption in the chaotic dynamics of the Belousov-Zhabotitinsky oscillator in closed unstirred reactors
2010
Chemical oscillations generated by the Belousov–Zhabotinsky reaction in batch unstirred reactors, show a characteristic chaotic transient in their dynamical regime, which is generally found between two periodic regions. Chemical chaos starts and finishes by following a direct and an inverse Ruelle–Takens–Newhouse scenario, respectively. In previous works we showed, both experimentally and theoretically, that the complex oscillations are generated by the coupling among the nonlinear kinetics and the transport phenomena, the latter due to concentration and density gradients. In particular, convection was found to play a fundamental role. In this paper, we develop a reaction–diffusion–convecti…
The effect of N-tetradecyl-N,N-dimethylamine oxide micelles on the kinetics of the electron transfer reaction of Ce(IV) with substituted malonic acids
2009
Abstract The kinetics of the oxidation of malonic acid and (its substituted compounds, methyl-, ethyl-, butyl- and benzyl-malonic acid) by ceric ions has been studied at 20.0 °C in the absence and the presence of the surfactant N-tetradecyl-N,N-dimethylamine oxide (C 14 DMAO). The addition of increasing amounts of C 14 DMAO influences the rate of the redox process to an extent that significantly depends on the hydrophobicity of the reducing species. The reactivity data together with the estimated binding constants and the standard transfer free energies of the malonic acids from water to the micelles suggest that the malonic acid is confined to the aqueous pseudo-phase while for the other s…
Chaotic dynamics in an unstirred ferroin catalyzed Belousov–Zhabotinsky reaction
2009
Abstract The Belousov–Zhabotinsky (BZ) reaction is the best known example of far from equilibrium self-organizing chemical reaction. Among the many dynamical behaviors that this reaction can exhibit, spatio-temporal chaos attracted particular interest, both for the ferroin and cerium catalyzed systems. In recent years transient chaos was found in the cerium catalyzed BZ reaction, when conducted in batch and unstirred reactors. It was established that the chaotic oscillations, originated by the coupling among chemical kinetics and transport phenomena, appeared and disappeared following a Ruelle–Takens–Newhouse scenario. In this Letter, we show results about the ferroin catalyzed system condu…
Deuterium isotope effect on the induction period of the cerium catalyzed Belousov-Zhabotinsky reaction
2009
Abstract In this work we present results about the deuterium isotopic effect on the global kinetics of a cerium catalyzed Belousov–Zhabotinsky reaction. A nonlinear dependence of the induction period upon the percentage of deuterated reactants was found in batch conditions. In order to understand this result, we investigated two reaction pathways responsible for the length of the induction period, namely: (a) the reaction between the enolic form of the malonic acid with molecular bromine and (b) the oxidation of malonic acid by the Ce(IV) ion. In both cases we obtained a linear dependence of the kinetic constants on the percentage of deuterated reactants. Nevertheless, by inserting the expe…
New Features in the dynamics of a ferroin-catalyzed Belousov-Zhabotinsky reaction induced by a zwitterionic surfactant
2008
Abstract Interactions between reaction–diffusion systems and aggregated host environments are a subject of widespread interest. In this work, the behavior of the Belousov–Zhabotinsky reaction was investigated in a micellar environment formed by the zwitterionic surfactant N-tetradecyl-N,N-dimethylamine oxide (C14DMAO). The appearance of an induction period with a threshold-like dependence upon the surfactant concentration, was detected at [C14DMAO] = 5.0 × 10−3 mol dm−3. These new features were explained in terms of the segregation ability typical of the amphiphilic self-assembling systems. Numerical simulations were also performed to confirm the proposed mechanism.
Efficiency range of the Belousov-Zhabotinsky reaction to induce the self-organization of transient bonds in metallo-supramolecular polymeric systems.
2020
The periodic change of the oxidation state of the metal catalyst in the oscillating Belousov-Zhabotinsky (BZ) reaction has been reported to establish a periodic organization of metallo-supramolecular bonds in polymeric systems, which results in autonomous viscosity oscillations. To appraise the possible extent of quantitative control on the viscosity oscillation features, we assess how the kinetics of the BZ reaction affects the periodic self-organization of the metal-ligand coordination, and vice versa. Our model system includes mono-, bis-, and tetra-functional polyethyleneglycol (PEG) precursors end grafted with terpyridine ligands that are complexed with ruthenium ions, which oscillate …
Spatio-temporal perturbation of the dynamics of the ferroin catalyzed Belousov-Zhabotinsky reaction in a batch reactor caused by sodium dodecyl sulfa…
2008
The effects of the anionic surfactant sodium dodecyl sulfate (SDS) on the spatio-temporal and temporal dynamics of the ferroin-catalyzed Belousov-Zhabotinsky (BZ) reaction have been studied over a wide surfactant concentration range. For the first time, investigations were performed also for unstirred systems. The presence of SDS in the reaction mixture influences the oscillatory parameters to an extent that significantly depends on the surfactant concentration. The trend of the wave speed v upon the increasing amount of SDS was found to have a maximum at [SDS] = 0.075 mol dm (-3) ( v = 0.071 mm s (-1)), after which the speed decreased to 0.043 mm s (-1) at [SDS] = 0.5 mol dm (-3), which is…
Chemical self-organization in self-assembling biomimetic systems
2009
Abstract Far-from-equillibrium oscillating chemical reactions are among the simplest systems showing complex behaviors and emergent properties. This class of reactions is often employed to mimic and understand the mechanisms of a great variety of biological processes. In this context, pattern formation due to the coupling between reaction and transport phenomena represent an active and promising research area. In this paper, we present results coming from experiments where we tried to blend the structural properties of self-assembled matrixes (sodium dodecyl sulphate micelles and phospholipid bilayers) together with the evolutive peculiarities of the Belousov–Zhabotinsky reaction. A series …