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Protonation of Patented Blue V in aqueous solutions: theoretical and experimental studies

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Abstract

The acid-base properties of the Patented Blue V dye were studied by spectrophotometry and tristimulus colourimetry. The mechanism of protonation of Patented Blue V has been investigated with semi-empirical and DFT methods. The quantum chemical calculations of total energy defined the most stable isomer for each protonated form in water solution. In addition to thermodynamic parameters, the condensed Fukui function and molecular electrostatic potential were successfully used as reactivity descriptors for the determination of the most favorable site for protonation. Moreover, for the explanation of the structure of the most deprotonated form of the dye in highly basic medium, the weak intramolecular interactions were investigated with the reduced density gradient function. The semi-empirical calculations of absorbance spectra explained the changing of the colour of the dye for the different protonated states. It has been shown that the dominant form of the Patented Blue V was the electro-neutral form, and the molar absorptivity (\(\upvarepsilon _{639}=1.06\times 10^{5}\,\hbox {dm}^{3}\cdot \hbox {mol}^{-1}\cdot \hbox {cm}^{-1})\) increases with the increase of the dielectric permittivity of the solvent. The replacement of polar solvents by less polar ones is causing a bathochromic shift of the absorption band of the dye, the value of which is correlated with the value of the Hansen parameter.

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SYNOPSIS The acid-base properties of the Patented blue V dye were studied by spectrophotometry and tristimulus colourimetry. The mechanism of protonation of Patented Blue V has been investigated with semi-empirical and DFT methods. The ionization constants of the dye functional groups were determined and the most probable protonation/deprotonation scheme was proposed.

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Acknowledgements

27 structures at different protonated states are shown with the difference in energy between the current form and the most stable form. Data for each state is available as Supplementary Information for this article at www.ias.ac.in/chemsci.

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Authors and Affiliations

  1. Department of Analytical Chemistry, Odessa I.I. Mechnikov National University, Dvoryanskaya 2, Odessa, 65082, Ukraine

    Kateryna Bevziuk, Alexander Chebotarev, Anastasiia Klochkova, Konstantin Pliuta & Denys Snigur

  2. Department of Organic Chemistry, Uzhhorod National University, Pidgirna 46, Uzhhorod, 88000, Ukraine

    Maksym Fizer

Authors
  1. Kateryna Bevziuk
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  2. Alexander Chebotarev
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  3. Maksym Fizer
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  4. Anastasiia Klochkova
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  5. Konstantin Pliuta
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  6. Denys Snigur
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Corresponding author

Correspondence to Denys Snigur.

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Bevziuk, K., Chebotarev, A., Fizer, M. et al. Protonation of Patented Blue V in aqueous solutions: theoretical and experimental studies. J Chem Sci 130, 12 (2018). https://doi.org/10.1007/s12039-017-1411-2

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  • DOI: https://doi.org/10.1007/s12039-017-1411-2

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