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

Keywords: Berezin's model, malachite green, brilliant green, micellar rate effect, surfactant

Abstract

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.

Downloads

Download data is not yet available.

References

Laguta A. N., Eltsov S. V., Mchedlov-Petrossyan N. O. Micellar rate effects on the kinetics of nitrophenol violet anion reaction with HO– ion: Comparing Piszkiewicz's, Berezin's, and Pseudophase Ion-Exchange models. J. Mol. Liq. 2019, 277, 70–77, https://doi.org/10.1016/j.molliq.2018.12.012.

Laguta A. N., Eltsov S. V., Mchedlov-Petrossyan N. O. Kinetics of alkaline fading of methyl violet in micellar solutions of surfactants: Comparing Piszkiewicz's, Berezin's, and pseudophase ion-exchange models. Int. J. Chem. Kin. 2019, 51 (2), 83–94, https://doi.org/10.1002/kin.21231.

Laguta A. N., Eltsov S. V., Mchedlov-Petrossyan N. O. Quantitative analysis of micellar effect on the reaction rate of alkaline fading of phenolphthalein. Kharkiv University Bulletin. Chemical Se-ries, 2018, 30 (53), 18–26, https://doi.org/10.26565/2220-637X-2018-30-02.

Martinek K., Yatsimirski A. K., Osipov A. P., Berezin I. V. Micellar effects on kinetics and equilibrium of synthesis and hydrolysis of benzylideneaniline: A general kinetic conception of micellar catalysis. Tetrahedron 1973, 29 (7), 963–969, https://doi.org/10.1016/0040-4020(73)80046-8.

Zakharova L., Valeeva F., Zakharov A., Ibragimova A., Kudryavtseva L., Harlampidi H. Micellization and catalytic activity of the cetyltrimethylammonium bromide–Brij 97–water mixed micellar system. J. Coll. Interface Sci. 2003, 263 (2), 597–605, https://doi.org/10.1016/S0021-9797(03)00343-6.

Almgren M., Rydholm R. Influence of counterion binding on micellar reaction rates. Reaction between p-nitrophenyl acetate and hydroxide ion in aqueous cetyltrimethylammonium bromide. J. Phys. Chem. 1979, 83 (3), 360–364, https://doi.org/10.1021/j100466a013.

Laguta A. N., Eltsov S.V. Micellar effects in kinetics of interaction of malachite green and brilliant green with water. Kharkiv University Bulletin. Chemical Series, 2017, 28 (51), 96–103 [Rus], https://doi.org/10.26565/2220-637X-2017-28-14.

Martinek K., Yatsimirski A. K., Levashov A. V., Berezin I. V. The kinetic theory and the mechanisms of micellar effects on chemical reactions. In Micellization, Solubilization, and Microemulsions, Mittal, K. L., Ed. Springer: Boston, 1977; Vol. 2, pp 489–508, https://doi.org/10.1007/978-1-4613-4157-4_1.

Berezin I. V., Martinek K., Yatsimirskii A. K. Physicochemical foundations of micellar catalysis. Russ. Chem. Rev. 1973, 42 (10), 1729–1756, https://doi.org/10.1070/RC1973v042n10ABEH002744.

Farafonov V. S. Localization and hydration of organic dyes in surfactant micelles by molecular dynamics simulations. The thesis for a candidate degree in chemistry: speciality 02.00.04 – physi-cal chemistry. V. N. Karazin Kharkiv National University, 2018 [Ukr].

Berthod A., Garcia-Alvarez-Coque C. Micellar liquid chromatography. CRC Press: New York, 2000; p 603.

Sesta B. Physicochemical properties of decyldimethylammonium propanesulfonate and its homologous compounds in aqueous medium. J. Phys. Chem. 1989, 93 (22), 7677–7680, https://doi.org/10.1021/j100359a029.

Mittal K. L., Lindman B. Surfactants in solution. Plenum Press: New York, 1984; Vol. 2.

Bunton C. A., Moffatt J. R. Ionic competition in micellar reactions: a quantitative treatment. J. Phys. Chem. 1986, 90 (4), 538–541, https://doi.org/10.1021/j100276a006.

Bunton C. A., Robinson L. B. Micellar effects upon the reaction of P-nitrophenyl diphenyl phosphate with hydroxide and fluoride ions. J. Org. Chem. 1969, 34 (4), 773–780, https://doi.org/10.1021/jo01256a002.

Cigén R., Bengtsson C. Studies on a furane analogue of malachite green. Protolytic equilibria and reaction rate constants of furane green in aqueous solutions. Acta Chem. Scand. 1963, 17 (7), 2091–2100.

Cigén R. Studies on derivatives of malachite green. Protolytic equilibria and reaction rate constants of m-hydroxy and m-methoxy malachite green. Acta Chem. Scand. 1961, 15, 1892–1904.

Horobin R. W. A numerical approach to understanding fixative action: being a re‐analysis of the fixation of lipids by the dye‐glutaraldehyde system. Journal of Microscopy 1989, 154 (1), 93–96.

Hansch C., Leo A., Hoekman D. Exploring QSAR. Hydrophobic, electronic, and steric constants. American Chemical Society: Washington, 1995; p 348.

Rashid F., Horobin R. W. Interaction of molecular probes with living cells and tissues. Part 2. Histochemistry 1990, 94 (3), 303–308, https://doi.org/10.1007/BF00266632.

Amis E. S. Rates mechanisms and solvent. J. Anal. Chem. 1955, 27 (11), 1672–1678, https://doi.org/10.1021/ac60107a001.

Amis E. S. Solvent effects on reaction rates and mechanisms. Academic Press: New York, 1966; p 328.

Reichardt C., Welton T. Solvents and solvent effects in organic chemistry. John Wiley & Sons: New York, 2011; p 692.

Laguta A. M. Kinetics of reactions of triphenylmethane dyes with nucleophiles in organized solu-tions. The thesis for a candidate degree in chemistry: speciality 02.00.04 – physical chemistry. V. N. Karazin Kharkiv National University, 2019 [Ukr].

Kruse H., Mrazikova K., d'Ascenzo L., Sponer J., Auffinger P. Short but Weak: The Z‐DNA Lone‐Pair π Conundrum Challenges Standard Carbon Van der Waals Radii. Angewandte Chemie International Edition 2020, 59 (38), 16553–16560, https://doi.org/10.1002/anie.202004201.

Atkins P., De Paula J. Atkins’ Physical Chemistry. OUP: Oxford, 2014; p. 1053.

Mchedlov-Petrossyan N. O., Vodolazkaya N. A., Kamneva N. N. Acid-base equilibrium in aqueous micellar solutions of surfactants. In Micelles: Structural biochemistry, formation and functions and usage, Nova Publishers: New York, 2013; pp 1–71.

Iwunze M. O. The determination of the effective dielectric constant of micelles and microemulsions. Physics and Chemistry of Liquids 2005, 43 (2), 195–203, https://doi.org/ 10.1080/00319100500038686.

Published
2020-12-29
Cited
How to Cite
Laguta, A. (2020). Quantitative analysis of micellar effect on the reaction rate of cationic triphenylmethine dyes with water according to Berezin’s model. Kharkiv University Bulletin. Chemical Series, (35), 37-44. https://doi.org/10.26565/2220-637X-2020-35-03