Insight into the Origin of Pyrocatechol Inhibition on Oscillating Bray-Liebhafsky Reaction: Combined Experimental and Theoretical Study

Maksimović, Jelena P.; Tošović, Jelena; Pagnacco, Maja C.

doi:10.1246/bcsj.20190296

Cited by 8 publications

(11 citation statements)

References 55 publications

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“…Due to the presence of iodine in a + 5 oxidation state (iodate), as well as the reactive radical species (HO•, HOO•, IO 2 •), the Briggs–Rauscher oscillatory reaction is a highly oxidative medium [ 59 , 60 , 61 , 62 , 63 , 64 ]. Therefore, the addition of indigo carmine into the BR oscillatory reaction unambiguously leads to its oxidation.…”

Section: Resultsmentioning

confidence: 99%

“…Likely due to the high concentration of hydrogen peroxide (1.27 M), as well as the presence of iodide (I-) and manganese (Mn2+) ions in a BR system, the two remaining pathways (indigo carmine with hydrogen peroxide and indigo carmine with HO•, HOO•) are more likely to occur in a BR system. These ions strongly catalyze the decomposition of hydrogen peroxide through the production of HO• and HOO• radicals [ 59 , 60 , 61 ]. Therefore, the last two pathways may be considered to be only one ( Figure 5 b).…”

Section: Resultsmentioning

confidence: 99%

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Indigo Carmine in a Food Dye: Spectroscopic Characterization and Determining Its Micro-Concentration through the Clock Reaction

Pagnacco

Maksimović²,

Nikolić³

et al. 2022

Molecules

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Indigo carmine is a commonly used industrial blue dye. To determine its concentration in a commercially available food dye composed of a mixture of indigo carmine and D-glucose, this paper characterizes it through (ATR, KBr) FTIR micro-Raman as well as UV/Vis and clock: Briggs–Rauscher (BR) oscillatory reaction methods. The indigo carmine was detected in the bulk food dye only by applying micro-Raman spectroscopy, indicating a low percentage of the indigo carmine present. This research provides an improvement in the deviations from the experimental Raman spectrum as calculated by the B97D/cc-pVTZ level of theory one, resulting in a better geometrical optimization of the indigo carmine molecule compared to data within the literature. The analytical curves used to determine indigo carmine concentrations (and quantities) in an aqueous solution of food dye were applied by means of UV/Vis and BR methods. BR yielded significantly better analytical parameters: 100 times lower LOD and LOQ compared to commonly used UV/Vis. The remarkable sensitivity of the BR reaction towards indigo carmine suggests that not only does indigo carmine react in an oscillatory reaction but also its decomposition products, meaning that the multiple oxidation reactions have an important role in the BR’s indigo carmine mechanism. The novelty of this research is the investigation of indigo carmine using a clock BR reaction, opening new possibilities to determine indigo carmine in other complex samples (pharmaceutical, food, etc.).

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Indigo Carmine in a Food Dye: Spectroscopic Characterization and Determining Its Micro-Concentration through the Clock Reaction

Pagnacco

Maksimović²,

Nikolić³

et al. 2022

Molecules

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“…The observation of oscillatory dynamics with different techniques is particularly complicated, due to the usually narrow concentration range where oscillatory dynamics can be obtained and gas products that can affect measurements. , Therefore, finding any way to facilitate monitoring of the oscillatory reaction is always welcome. In this work, the optimization of experimental conditions for UV–Vis measurements of the Bray–Liebhafsky oscillatory reaction was done.…”

Section: Discussionmentioning

confidence: 99%

“…The time evolution of the Bray–Liebhafsky oscillatory reaction has so far been successfully monitored by potentiometric methods. − The spectroscopic method for monitoring the BL oscillatory reaction was first applied by Degn et al in 1967 at a reaction volume of 10 mL . The BL has also been later (in 1976) spectroscopically followed in the works of Noyes and Sharma, but there is no data about total reaction volume.…”

Section: Introductionmentioning

confidence: 99%

Problem and Solution of UV–Vis Time-Based Measurements of a Chemical System Involving Gas Product: Application to the Bray–Liebhafsky Oscillatory Reaction

2021

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Ultraviolet (UV)−visible (Vis) spectroscopy is widely used in all modern laboratories as a routine method of analysis. The monitoring of chemical reactions in an aqueous solution involving a gas product is a demanding task but particularly for oscillatory reactions which are obtainable in a narrow concentration range. In this work, the optimization of experimental conditions for UV−Vis measurements of the Bray− Liebhafsky (BL) oscillatory reaction producing oxygen was done by using an internal standard. After applying the method of the internal standard on iodine absorbance at 460 nm, the characteristic BL oscillatory parameters (and iodine changes) are clearly evident. The obtained results allow students to apply their existing knowledge and, through a simple experimental setup, understand the importance of the internal standard, but at the same time, they show how they can solve the problem of UV−Vis noise during the time-based measurements of reactions involving gas products in general.

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“…the rate of their formation [20,21]. There are at least two methods for complex oscillatory system study: i) the investigation of their chemical subsystems [22][23][24][25][26] and ii) the investigation of oscillatory system behavior under different perturbants [21,[27][28][29][30]. The BR reaction is sensitive to many organic molecules (for example, antioxidants).…”

Section: Introductionmentioning

confidence: 99%

A possible connection between phosphate tungsten bronzes properties and Briggs-Rauscher oscillatory reaction response

Maksimović

Tančić³

et al. 2021

Sci Sintering

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The calcium phosphate tungsten bronze (Ca-PWB) has been synthesized and characterized (TGA, DSC, XRPD, FTIR, SEM). The influence of solid insoluble materials Ca- PWB, as well as lithium doped (Li-PWB) and cation free phosphate tungsten (PWB) bronzes on the oscillatory Briggs-Rauscher (BR) reaction dynamics, is compared. The results show that doping with Li and Ca reduces sensitivity of the BR reaction towards bronzes addition. These findings suggest the usage of the BR reaction as an innovative method for testing of different properties of bronze material. The behavior of PWB in the BR reaction is significantly changed with divalent cation (Ca2+) doping. The reasons for the different bronzes behavior were found in their calculated unit cell volumes. Namely, the compressed Ca-PWB unit cell volume indicates the difficult availability of the active site for heterogeneous catalysis. Hence, the linear correlation (slope) of the BR oscillogram?s length (?osc) vs. mass of bronze in BR reaction might be considered as a new parameter for the evaluation of the bronzes catalytic activity.

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Insight into the Origin of Pyrocatechol Inhibition on Oscillating Bray-Liebhafsky Reaction: Combined Experimental and Theoretical Study

Cited by 8 publications

References 55 publications

Indigo Carmine in a Food Dye: Spectroscopic Characterization and Determining Its Micro-Concentration through the Clock Reaction

Indigo Carmine in a Food Dye: Spectroscopic Characterization and Determining Its Micro-Concentration through the Clock Reaction

Problem and Solution of UV–Vis Time-Based Measurements of a Chemical System Involving Gas Product: Application to the Bray–Liebhafsky Oscillatory Reaction

A possible connection between phosphate tungsten bronzes properties and Briggs-Rauscher oscillatory reaction response

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