The Chlorate-Iodine-Nitrous Acid Clock Reaction

Sant'Anna, Rafaela T. P.; Faria, Roberto B.

doi:10.1371/journal.pone.0109899

Cited by 7 publications

(10 citation statements)

References 11 publications

(22 reference statements)

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“…Simpler spectrophotometric methods for chlorate detection are, in theory, amenable for field use. These methods are generally based on bleaching the color of a dye species [6,[11][12][13][14] or the catalyzed generation of colored triiodide anion [15][16][17][18] in the presence of chlorate. The color change may be visible to the naked eye or with the aid of very simple instrumentation, permitting development of a lightweight system that requires little or no power to operate.…”

Section: Introductionmentioning

confidence: 99%

Statistical evaluation of an electrochemical probe for the detection of chlorate

Trammell

Shriver‐Lake

Dressick

2017

Sensors and Actuators B: Chemical

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We describe the use and characterization of a multilayer film, prepared via layer-by-layer deposition of cationic para-rosaniline acetate dye (i.e., PR) and the vanadium-containing Keggintype polyoxometalate anion, [PMo 11 VO 40 ] 5 (i.e., PVMo 11 ), on indium tin oxide (ITO) as an electrode for determination of chlorate. A linear cyclic voltammetry (CV) current response was observed for the 0 M  [ClO 3  ]  1000 M range with a detection limit of ~220 M ClO 3  (S/N > 3) in a pH = 2.5 solution of 100 mM sodium acetate. Electrode response was insensitive to interference by oxygen and nitrogen-based explosives like TNT, a prerequisite for use in the field. A Taguchi L16 array was used to investigate the performance of the electrode as functions of number of PVMo 11 /PR bilayers (L; 3-6 bilayers), solution pH (H; pH ~1.32 -2.85), solution [ClO 3  ] (C; 250 -1000 M), CV scan rate (S; 50-200 mVs 1 ), and film age (A; 1-8 weeks). Maximum current response was obtained for a 1 week old 5 bilayer film immersed in a pH 2.85 0.10 M NaCl (aq) solution containing 1000 M ClO 3  . However, current response fell as films aged, requiring aging of films for approximately 8 weeks prior to use to obtain reproducible analyses. A two-level full factorial design using films aged 8 weeks identified the variables S, L, H, and C and variable interactions LS and HS as statistically significant contributors to the film current response and provided a model describing film performance.

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Section: Introductionmentioning

confidence: 99%

Statistical evaluation of an electrochemical probe for the detection of chlorate

Trammell

Shriver‐Lake

Dressick

2017

Sensors and Actuators B: Chemical

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“…During our study of chlorate–iodine–nitrous acid clock reaction, we noticed that the chlorate–nitrous acid reaction, which was previously studied by Lowe and Brown and by Emeish, produces chlorine dioxide, together with nitrate. This was the first time that chlorine dioxide was observed to be formed by the reaction between chlorate and nitrous acid, suggesting that this reaction deserves to be reinvestigated.…”

Section: Introductionmentioning

confidence: 75%

Kinetics and Mechanism of the Chlorate–Nitrous Acid Reaction

Sant'Anna

Faria

2017

Inorg. Chem.

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The chlorate-nitrous acid reaction was investigated in acid media, using a high concentration of reagents. It was followed via ultraviolet-visible light (UV-vis) spectroscopy and presented a complex behavior. The order of reagents, and the products formed by this reaction, are dependent on the concentration of reagents. For the high concentration set we used, the reaction has shown a first-order behavior for H and HNO, and an order equal to 0.79 for chlorate. In this case, chlorine dioxide is formed. Moreover, chlorine dioxide starts to form only after all HNO has been consumed. This is the first time chlorine dioxide was observed to be formed by this reaction. Reduction of the concentration of reagents decreases the order of HNO to 0.91 and no chlorine dioxide is formed. An isosbestic point was found at 312 nm, which indicates a 1:1 ratio between nitrate ion and nitrous acid species. A model, with 14 independent species and 12 reactions is presented, which is able to simulate the experimental behavior for the low and high concentrations sets of reagents and it is a significant improvement in the understanding of the complex nitrogen and chlorine aqueous chemistry.

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“…As the starting point for the discovery of this oscillating reaction was the chlorate–iodine–nitrous acid clock reaction, it is reasonable to consider that the mechanism for the chlorate–nitrous acid–iodine–iodide oscillation reaction is based on the same reactions. In this mechanism, the reaction between chlorate and nitrous acid produces chlorite, which is immediately converted to HClO 2 . This species starts a sequence of reactions with iodide, HOI, and HIO 2 that includes an autocatalytic sequence on HOI and HOCl (reaction , which is the sum of reactions , , and ), which should be responsible for the nonlinear dynamics shown by this oscillating reaction. …”

Section: Resultsmentioning

confidence: 99%

“…It is also the first oscillating reaction to use nitrous acid as a reactant. It was a planned discovery, inspired by the discovery of the chlorate–nitrous acid–iodine clock reaction . Considering that this clock reaction presents the autocatalysis necessary to produce oscillations, we managed the experiments to find the conditions that should favor emergence of the oscillating behavior.…”

Section: Introductionmentioning

confidence: 99%

“…It was a planned discovery, inspired by the discovery of the chlorate−nitrous acid−iodine clock reaction. 28 Considering that this clock reaction presents the autocatalysis necessary to produce oscillations, we managed the experiments to find the conditions that should favor emergence of the oscillating behavior. First, we set up a continuous stirred tank reactor (CSTR), but oscillations were observed only when iodide was included as a reactant.…”

Section: Introductionmentioning

confidence: 99%

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The Chlorate–Nitrous Acid–Iodine–Iodide Oscillating Reaction

2021

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This work presents a new oscillating reaction based on chlorate and observed in a CSTR at room temperature. This can be the first member of a new family of oscillating reactions. In addition, it is also the first oscillating reaction to use nitrous acid as a reactant. Four different behaviors were observed: simple oscillations, mixed mode oscillations, bursts, and quasiperiodicity. The period of oscillations is very short, which is around 1 s. Together with the fact that it also shows fast bursts, it opens the possibility that it can be used to simulate fast biological events, like the neuron's communications signals.

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The Chlorate-Iodine-Nitrous Acid Clock Reaction

Cited by 7 publications

References 11 publications

Statistical evaluation of an electrochemical probe for the detection of chlorate

Statistical evaluation of an electrochemical probe for the detection of chlorate

Kinetics and Mechanism of the Chlorate–Nitrous Acid Reaction

The Chlorate–Nitrous Acid–Iodine–Iodide Oscillating Reaction

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