Micellar rate effects on the kinetics of nitrophenol violet anion reaction with HO– ion: Comparing Piszkiewicz's, Berezin's, and Pseudophase Ion-Exchange models

Laguta, Anna N.; El'tsov, S. V.; Mchedlov‐Petrossyan, Nikolay O.

doi:10.1016/j.molliq.2018.12.012

Cited by 16 publications

(17 citation statements)

References 37 publications

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“…This phenomenon is caused by the association of the HOions with the cationic head groups of the surfactant. 19 This effect was earlier observed in CTAB micelles for the nucleophilic attachment of the HOion to the dianion R 2of dye 6 19 and for alkaline hydrolysis of diacetylflorescein. 20…”

Section: Surfactant Effect: 45-dinitrosulfonefluorescein In the Aqueous Ctab/naoh Systemmentioning

confidence: 55%

“…Such effect should be ascribed to the lower effective polarity in the pseudophase, in view of Scatchard's equation. 19 (1) However, the so-called diverting effect may also contribute to the total result. This phenomenon is caused by the association of the HOions with the cationic head groups of the surfactant.…”

Section: Surfactant Effect: 45-dinitrosulfonefluorescein In the Aqueous Ctab/naoh Systemmentioning

confidence: 99%

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4,5‐Dinitrosulfonefluorescein and related dyes: Kinetics of reversible rupture of the pyran ring and their interaction with lysozyme

Kriklya

Gromovoy

Mchedlov‐Petrossyan

2021

Coloration Technology

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The rupture of the pyran ring of fluorescein and rhodamine dyes is well documented. [1][2][3][4][5] For the mother compound fluorescein (1), the process occurs in extremely alkaline media. According to Orndorff et al, 3 in cold 33% aqueous potassium hydroxide (KOH) first the absorption band at 496 nm is only observed, whereas a new band with λ max = 583 nm (2) appears only after 5-10 weeks (Scheme 1). (It should be taken into account that, according to Lewis, these λ max values are 10-20 nm overestimated. 6 ) However, in hot aqueous KOH of the same concentration the last-named band appears immediately.Accordingly, the intensity of the first band decreases, but over time the solution is discoloured owing to formation of carbinol 3. 3 The latter is a result of nucleophilic attack of the hydroxide (HO -) on the nodal carbon atom. Even earlier, Meyer and Fischer observed the spectrum of the "violet fluorescein" after boiling fluorescein with sodium hydroxide (NaOH). 2 Analogous reactions were described for rhodamine dyes; further research is summarised in the corresponding review. 1 For eosin, the opening of the heterocycle occurs at markedly lower alkali concentration. 4 Contrary to halogen derivatives of triphenylmethine and hydroxyxanthene dyes, the nitro derivatives are largely ignored. However, as early as 1900-1902 it was already known that in alkaline solutions, 2,7-dibromo-4,5-dinitrofluorescein and 4,5-dinitrofluorescein gradually turned from yellow to deep blue, and the last dye becomes colourless after action of hot alkali over time. 7,8 El'tsov et al 9 proved the results for the last-named dye spectroscopically. In a 0.1 mol/L sodium hydrogen carbonate (NaHCO 3 ) aqueous solution, the initial dye exists in the form of a double-charged anion (λ max = 482 nm), while at pH > 11 the pyran cycle opens; λ max = 580 nm. The

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Section: Surfactant Effect: 45-dinitrosulfonefluorescein In the Aqueous Ctab/naoh Systemmentioning

confidence: 55%

Section: Surfactant Effect: 45-dinitrosulfonefluorescein In the Aqueous Ctab/naoh Systemmentioning

confidence: 99%

4,5‐Dinitrosulfonefluorescein and related dyes: Kinetics of reversible rupture of the pyran ring and their interaction with lysozyme

Kriklya

Gromovoy

Mchedlov‐Petrossyan

2021

Coloration Technology

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“…It should be noted that this approach is quite applied [14,15]. Its validity is to some extent confirmed based on particle size data obtained by the dynamic light scattering, where it was found that at the presence of the triphenylmethine dye the micelle formation occurs earlier than in a dye-free system [1,2].…”

Section: The Results Of Quantitative Analysis According To Berezin's Model and Their Discussionmentioning

confidence: 74%

“…Where for reliable calculations of the partition coefficient of HOion by electrostatic approach it is necessary to take into account the change in the local concentration of the HOions due to a compression of the double electric layer upon addition of reacting ions to the system. Moreover, Berezin's model, like the pseudophase ion-exchange model, does not take into account the "diverting" effect of cationic head-groups owing to their electrostatic attraction of the HOions [1][2][3].…”

Section: Discussionmentioning

confidence: 99%

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Quantitative analysis of micellar effect on the reaction rate of cationic triphenylmethine dyes with water according to Berezin’s model

2020

Chemical Series

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Several approaches quantitatively describe the effect of surfactant micellar solution on the reaction rate. The most used among them are Piszkiewicz’s, Berezin’s, and Pseudophase Ion-Exchange (PIE) models. The last-named was developed by Bunton and Romsted. Piszkiewicz’s model is based on representations of the micellization according to the mass action law with the formation of a catalytic micelle, which consists of some surfactant molecules and a substrate. In our previously paper, this model was used to explain the kinetic micellar effect on the reaction of cationic triphenylmethine dyes with water once again showed the main disadvantages of this approach. Berezin’s model is based on another model of micelle formation viz. the pseudophase model, and the binding of reagents by micelles is considered as the distribution of a substance between two phases. In this work, we aim to consider the applicability of Berezin’s approach for the interaction of malachite green and brilliant green cations with water molecule as a nucleophile in aqueous systems of nonionic, anionic, cationic, and zwitterionic surfactants. On the whole, Berezin's model performed well when applied to the description of the micellar effect on the reaction of similar dye with the hydroxide ion. However, it was revealed that this model does not take into account the change in the local concentration of the HO– ions due to a compression of the double electric layer upon addition of reacting ions to the system, as well as the constant of association of the HO– ions with cationic head groups of surfactant. In this case, when water is used as a nucleophile, the question of the degree of nucleophile binding can be solved differently. The PIE model is also based on a pseudophase model of micellization, but a substrate binding by micelles is considered as an association in a stoichiometric ratio of 1:1, and a nucleophile concentration is expressed in a local concentration based on the neutralization degree of micelles. Given the latter, its approach cannot be applied to the kinetic micellar influence on the reaction of cationic triphenylmethine dyes with water.

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Cationic Surfactant-Based Catalysis on the Oxidation of Glutamic Acid by Bis-(2-pyridinealdoximato)dioxomolydate(IV) Complex

et al. 2023

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Micellar rate effects on the kinetics of nitrophenol violet anion reaction with HO– ion: Comparing Piszkiewicz's, Berezin's, and Pseudophase Ion-Exchange models

Cited by 16 publications

References 37 publications

4,5‐Dinitrosulfonefluorescein and related dyes: Kinetics of reversible rupture of the pyran ring and their interaction with lysozyme

4,5‐Dinitrosulfonefluorescein and related dyes: Kinetics of reversible rupture of the pyran ring and their interaction with lysozyme

Quantitative analysis of micellar effect on the reaction rate of cationic triphenylmethine dyes with water according to Berezin’s model

Cationic Surfactant-Based Catalysis on the Oxidation of Glutamic Acid by Bis-(2-pyridinealdoximato)dioxomolydate(IV) Complex

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