Journal of Solution Chemistry

, Volume 48, Issue 11–12, pp 1438–1460 | Cite as

The Theoretical Calculations and Experimental Measurements of Acid Dissociation Constants and Thermodynamic Properties of Betanin in Aqueous Solutions at Different Temperatures

  • Fatemeh ZabihiEmail author
  • Farhoush Kiani
  • Mojtaba Yaghobi
  • Seyed Ahmad Shahidi


In this study, we experimentally determined the protonation constants, enthalpy change (ΔHo), change in Gibbs energy (ΔGo), and entropy change (ΔSo) for the deprotonation process of betanin over the temperature range of 298.15 to 318.15 K and at an ionic strength of 0.1 mol·dm−3 (NaClO4) with a combination of spectrophotometric and potentiometric methods. In addition, we theoretically calculated the values of the acidic dissociation constants, the optimized structure, and the thermodynamic properties of betanin in aqueous solutions at various temperatures by ab initio and DFT methods. Density function theory (DFT) methods with the B3LYP/6-31 + G(d) level of theory were applied for calculating the acidic dissociation constants of betanin and also interactions among the solvent and solvated cation, anion, and neutral species of betanin. Thomasi’s method was used to analyze the formation of intermolecular hydrogen bonding between water molecules and various species of betanin. There is a good correlation between the theoretically calculated and experimentally determined values of pKa of betanin.


Acidic dissociation constant Thermodynamic properties Density function theory Ab initio calculations 



  1. 1.
    Zhang, D., Lanier, S.M., Downing, J.A., Avent, J.L., Lum, J., McHale, J.L.: Betalain pigments fot dye-sensitive solar cells. J. Photochem. Photobiol. A 195, 72–80 (2008)CrossRefGoogle Scholar
  2. 2.
    Sapers, G.M., Hornstein, G.S.: Varietal differences in properties and stability of red beet pigments. J. Food Sci. 44, 1245–1248 (1979)CrossRefGoogle Scholar
  3. 3.
    Hendry, G.A.R., Houghton, J.D.: Natural Food Colorants, 2nd edn. Blackie, University of Sheffield and University of Leeds, London (1996)CrossRefGoogle Scholar
  4. 4.
    Delgado-Vargas, F., Jiménez, A.R., Paredes-Lopez, O.: Natural pigments: carotenoids, anthocyanins, and betalins—Characteristics, biosynthesis, processing, and stability. Crit. Rev. Food Sci. Nutr. 40, 173–289 (2000)CrossRefGoogle Scholar
  5. 5.
    Ravichandran, K., Saw, N.M.M.T., Mohdaly, A.A.A., Gabr, A.M.M., Kastell, A., Riedel, H., Cai, Z., Knorr, D., Smetanska, I.: Impact of processing of red beet on betalain content and antioxidant activity. Food Res. Int. 50(2), 670–675 (2013)CrossRefGoogle Scholar
  6. 6.
    Roy, K., Gullapalli, S., Roy, U., Chakraborty, R.: The use of a natural colourant base on betalain in the manufacture of sweet products in India. Int. J. Food Sci. Technol. 39, 1087–1091 (2004)CrossRefGoogle Scholar
  7. 7.
    Saguy, I., Kopelman, I.J., Mizrahi, S.: Computer-aided determination of beet pigments. J. Food Sci. 43, 124–127 (1978)CrossRefGoogle Scholar
  8. 8.
    Gomes-Bombarelli, R., Gonzalez-Perez, M., Perez-Prior, M.T., Calle, E., Casado, J.: Computational study of esters and lactones. A case study of diketenese. J. Org. Chem 74, 4943–4948 (2009)CrossRefGoogle Scholar
  9. 9.
    Pehrsson, L., Ingman, F., Johansson, A.: Acid–base titrations by stepwise additions of equal volumes of titrant with special reference to automatic titrations Theory, discussion of the Gran functions, the Hofstee method and equivalence volumes. Talanta 23, 769–780 (1976)CrossRefGoogle Scholar
  10. 10.
    Gameiro, P., Reis, S., Lima, J.L.F.C., de Castro, B.: Calibration of pH glass electrodes by direct strong acid/strong base titrations under dilute conditions. Anal. Chim. Acta 405, 167–172 (2000)CrossRefGoogle Scholar
  11. 11.
    Ferrer, J.S., Couallier, E., Rakib, M., Durand, G.: Electrochemical determination of acidity level and dissociation of formic acid/water mixtures as solvent. Electrochim. Acta 52, 5773–5780 (2007)CrossRefGoogle Scholar
  12. 12.
    Gharib, F., Farajtabar, F., Farahani, A.M., Bahmani, F.: Solvent effects on protonation constants of tryptophan in some aqueous aliphatic alcohol solutions. J. Chem. Eng. Data 55, 327–332 (2010)CrossRefGoogle Scholar
  13. 13.
    Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Montgomery, J.A., Jr., Stratmann, R.E., Burant, J.C., Dapprich, S., Millam, J.M., Daniels, A.D., Kudin, K.N., Strain, M.C., Farkas, O., Tomasi, J., Barone, V., Cossi, M., Cammi, R., Mennucci, B., Pomelli, C., Adamo, C., Clifford, S., Ochterski, J., Petersson, G.A., Ayala, P.Y., Cui, Q., Morokuma, K., Salvador, P., Dannenberg, J.J., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Cioslowski, J., Ortiz, J.V., Baboul, A.G., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Gomperts, R., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M.W., Andres, J.L., Gonzalez, C., Head-Gordon, M., Replogle, E.S., Pople, J.A.: Gaussian 98. Gaussian, Inc., Pittsburgh, PA (1998)Google Scholar
  14. 14.
    Miertus, S., Tomasi, J.: approximate evaluations of the electrostatic free energy and internal energy changes in solution processes. Chem. Phys. 65, 239–245 (1982)CrossRefGoogle Scholar
  15. 15.
    Kiani, F., Yeganegi, S., Rostami, A.A., Sharifi, S.: ab initio study of restricted rotation in N-nitroso-azirine and N-Nitrosodiaziridine. Asian J. Chem. 21, 1210–1216 (2009)Google Scholar
  16. 16.
    Kiani, F., Rostami, A.A., Sharifi, S., Bahadori, A.: Calculation of acidic dissociation constants of glycylglycine in water at different temperatures using ab initio methods. J. Mol. Struct. 956, 20–25 (2010)CrossRefGoogle Scholar
  17. 17.
    Kiani, F., Rostami, A.A., Sharifi, S., Bahadori, A., Chaichi, M.J.: Determination of acidic dissociation constants of glycine, valine, phenylalanine, glycylvaline, and glycylphenylalanine in water using ab initio methods. J. Chem. Eng. Data 55, 2732–2740 (2010)CrossRefGoogle Scholar
  18. 18.
    Kiani, F., Izadi, H., Tahermansouri, H., Koohyar, F.: Determination of acidic dissociation constants of glutamine and isoleucine in water using ab initio methods. Türk Biyokimya Dergisi (Turkish J. Biochem.) 39, 503–515 (2014)Google Scholar
  19. 19.
    Kiani, F., Abbaszadeh, M., Pousti, M., Koohyar, F.: Ab initio and DFT studies on ionization of octopamine and 6-aminopenicillanic acid in aqueous solution. Indian J. Chem. 54A, 619–626 (2015)Google Scholar
  20. 20.
    Kiani, F., Abbaszadeh, M., Pousti, M., Koohyar, F.: Theoretically nanoscale study on ionization of muscimol nano drug in aqueous solution. Braz. J. Pharm. Sci. 51, 213–219 (2015)CrossRefGoogle Scholar
  21. 21.
    Kiani, F., Behzadi, H., Koohyar, F.: Thermodynamic study of asparagine and glycyl asparagine using computational methods. Braz. Arch. Biol. Technol. 58, 477–486 (2015)CrossRefGoogle Scholar
  22. 22.
    Kiani, F., Khanlarzadeh, B., Tahermansouri, H.: Ab initio and density functional theory study on ionization of betahistidine and cimetidine nano drug in aqueous solution. Farmacia 64, 339–347 (2016)Google Scholar
  23. 23.
    Chaires, J.B.: Calorimetry and thermodynamics in drug design. Annu. Rev. Biophys. 37, 135–151 (2008)CrossRefGoogle Scholar
  24. 24.
    Ruben, A.J., Kiso, Y., Freire, E.: Overcoming roadblocks in lead optimization: a thermodynamic perspective. Chem. Biol. Drug Des. 67, 2–4 (2006)CrossRefGoogle Scholar
  25. 25.
    Shukla, B.K., Yadava, U., Roychoudhury, M.: Theoretical explorations on the molecular structure and IR frequencies of 3-phenyl-1-tosyl-1H-pyrazolo [3,4-d] pyrimidin-4-amine in view of experimental results. J. Mol. Liq. 212, 325–330 (2015)CrossRefGoogle Scholar
  26. 26.
    Ogurlu, M.: Adsorption of a textile dye onto activated sepiolite. J. Microporous Mesoporous Mater. 119, 276–283 (2009)CrossRefGoogle Scholar
  27. 27.
    Arzu, Y.D.: A comparative study on determination of the equilibrium, kinetic and thermodynamic parameters of biosorption of copper(II) and lead(II) ions onto pretreated Aspergillusniger. J. Biochem. Eng. 28, 187–195 (2006)CrossRefGoogle Scholar
  28. 28.
    Pimentel, P.M., Melo, M.A.F., Melo, D.M.A., Assuncao, A.L.C., Henrique, D.M., Siva Jr., C.N., Gonzalez, G.: Kinetics and thermodynamics of Cu(II) adsorption on oil shale wastes. J. Fuel Process. Technol. 89, 62–67 (2008)CrossRefGoogle Scholar
  29. 29.
    Beck, M.T., Nagypal, I.: Chemistry of Complex Equilibria. Ellis Harwood, New York (1990)Google Scholar
  30. 30.
    Leggett, D.J.: Computation Methods for the Determination of Formation Constants. Plenum Press, New York (1985)CrossRefGoogle Scholar
  31. 31.
    Meloun, M., Javurek, M., Havel, J.: Multiparametric curve fitting. A structural classification of programs for analyzing multicomponent spectra and their use in equilibrium-model determination. Talanta 33, 513–524 (1986)CrossRefGoogle Scholar
  32. 32.
    Nilsson, T.: Studies into the pigments in beetroot (Beta vulgaris L. vulgaris var. rubra L.). Lantbrukshoegskolans Annaler 36, 179–219 (1970)Google Scholar
  33. 33.
    Tutone, M., Lauria, A., Almerico, A.: Theoretical determination of the pKa values of betalamic acid related to the free radical scavenger capacity comparison between empirical and quantum chemical methods. Interdiscip. Sci. Comput. Life Sci. (2015). CrossRefGoogle Scholar
  34. 34.
    Laitinen, H.A., Harris, W.E.: Chemical Analysis. McGraw-Hill, New York (1975)Google Scholar
  35. 35.
    Marcus, Y.: The properties of organic liquids that are relevant to their use as solvating solvents. Chem. Soc. Rev. 22, 409–416 (1993)CrossRefGoogle Scholar
  36. 36.
    Jeffrey, G.A.: An Introduction to Hydrogen Bonding. Oxford University Press, Oxford (1997)Google Scholar
  37. 37.
    Atkins, P.W.: Physical Chemistry, 6th edn. Oxford University Press, England (1998)Google Scholar
  38. 38.
    Ruff, F., Csizmadia, I.G.: Organic Reactions. Equilibria, Kinetics and Mechanism. Elsevier, London (1994)Google Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Fatemeh Zabihi
    • 1
    Email author
  • Farhoush Kiani
    • 2
  • Mojtaba Yaghobi
    • 1
  • Seyed Ahmad Shahidi
    • 3
  1. 1.Department of Physic, Faculty of Science, Ayatollah Amoli BranchIslamic Azad UniversityAmolIran
  2. 2.Department of Chemistry, Faculty of Science, Ayatollah Amoli BranchIslamic Azad UniversityAmolIran
  3. 3.Department of Food Science and Technology, College of Agriculture and Food Science, Ayatollah Amoli BranchIslamic Azad UniversityAmolIran

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