Studies of the Association of Dyes with Surfactants in Aqueous Solutions: Spectrophotometry and Computer Simulation


  • Serghey Shapovalov V.N. Karazin Kharkiv University
  • Vadim Ponomariov
  • Oryna Mosharenkova
  • Sophia Butenko



association, aqueous solutions, dyes, enthalpy of formation, spectroscopy, surfactants, semiempirical methods


The association of cationic dye (pinacyanol, PC) with anionic dyes (ethyleosin, EE, or rhodamine 200 C, R200C), and also the interaction “dye+surfactant” has been investigated in aqueous solutions by visible spectroscopy and computer simulation. Cetylpyridinium bromide (CPB), sodium dodecylsulfate (SDS) and triton X-100 (TX) were used as cationic, anionic and non-ionic surfactants respectively. The formation of “dye+surfactant” associates takes place at low dye concentrations (≥10‑6 M) and concentrations of surfactant, which are much smaller than the critical micelle concentrations (CMC). In contrast, similar concentrations (10‑6 – 10‑4 M) of small cations of tetramethylammonium or tetraethylammonium have no noticeable effect on the absorption spectra of the dye in the “dye+tetraalkylammonium salt” systems; it indicates the absence of formation of new compound between the dye and salt. The standard enthalpy of formation of “dye+dye” or “dye+surfactant” associates has been determined by AM1 and PM3 semiempirical methods. The computer simulation confirms that the formation of these associates is energetically beneficial.


Shapovalov SA. Processes of self-association of dyes in solutions. Riga: Academic Publishing of European Union, OmniScriptum Publishing group; 2018, pp. 1-122

Rashid S, Usman M, Shahzad T, Saeed M, Haq A, Ibrahim M, Siddiq M, Iram M. The Differential Spectroscopic Investigation of Partitioning of Reactive Dyes in Micellar Media of Cationic Surfactant, Cetyl Trimethylammonium Bromide (CTAB). Zeitschrift für Physikalische Chemie 2019;233(2):183-199.

Muhammad M, Nasiruddin Khan M. Oppositely charged dye surfactant interactions: Extent and selectivity of ion pair formation. Journal of Molecular Liquids 2018;266:591-596.

Olaseni SE, Osundiya MO, Oniya EO, Akeremale OA, Aboluwoye CO, Oyeneyin OE, Orunesajo A. Crystal Violet Partitioning in Anionic Surfactants Micellar Media: UV-Visible Spectroscopy Study. International Journal of Thermodynamics 2018;21(3):136-142.

Mall C, Solanki P. Spectrophotometric and conductometric studies of molecular interaction of brilliant cresyl blue with cationic, anionic and non-ionic surfactant in aqueous medium for application in photogalvanic cells for solar energy conversion and storage. Energy Reports 2018;4:23-30.

Ul Haq N, Usman M, Hussain A, Farooqi ZH, Saeed M, Hanif S, Irfan M, Siddiq M, Rana UA. Partitioning of reactive yellow 86 between aqueous and micellar media studied by differential absorption spectroscopy. Canadian Journal of Chemistry 2017;95(6):697-703.

Rub M, Azum N, Asiri A, Alfaifi S, Alharthi S. Interaction between antidepressant drug and anionic surfactant in low concentration range in aqueous/salt/urea solution: A conductometric and fluorometric study. Journal of Molecular Liquids 2017;227:1-14.

Wang W, Huang G, An C, Xin X, Zhang Y, Liu X. Transport behaviors of anionic azo dyes at interface between surfactant-modified flax shives and aqueous solution: Synchrotron infrared and adsorption studies. Applied Surface Science 2017;405:119-128.

Al-Omair N. Investigation of Interactions between Sodium Dodecyl Sulfate and Crystal Violet in Aqueous Solution. Asian Journal of Chemistry 2017;29(4):911-916.

Göktürk S, Keskin G, Talman R, Çakır N. Spectroscopic and conductometric studies on the interactions of thionine with anionic and nonionic surfactants. Coloration Technology 2017;133(5):362-368.

Wang N, Lin H, Zhu H. Study of the Association Behavior Between Bromophenol Blue and Octylphenol Polyoxyethylene Ether (10) in Aqueous Solution and the Solubilization of Bromophenol Blue by Micelles. Journal of Solution Chemistry 2016;45(12):1689-1700.

Ramadan M, Nabil G, Elmallah N, Shaker A. Spectral Studies for Interaction Between Methyl Orange Dye and Cationic Surfactants in Acetonitrile as co-solvent with Water. Asian Journal of Chemistry 2016;28(2):359-364.

Petcu A, Rogozea E, Lazar C, Olteanu N, Meghea A, Mihaly M. Specific interactions within micelle microenvironment in different charged dye/surfactant systems. Arabian Journal of Chemistry 2016;9(1):9-17.

Ghosh S, Mondal S, Das S, Biswas R. Spectroscopic investigation of interaction between crystal violet and various surfactants (cationic, anionic, nonionic and gemini) in aqueous solution. Fluid Phase Equilibria 2012;332:1-6.

Chernova RK, Kozlova LM, Shestopalova NB, Ryanova YuO. Test-methods determination organic substances in water environment. Izvestiya of Saratov University. Series: Chemistry, Biology, Ecology 2008; 2: 15-22

Kalenichenko KP. Opredelenie anionnyih poverhnostno-aktivnyih veschestv s pomoschyu indikatora v prirodnyih vodah. Journal of Water Chemistry and Technology 1987; 23(5): 107-110

Shapovalov S, Ponomariov V. Interaction of Dyes with Cationic Surfactants in Solutions: Determination of Critical Micelle Concentration. International Letters of Chemistry, Physics and Astronomy 2019;81:27-34.

Shapovalov SA, Ponomariov VK, inventors; V.N.Karazin KhNU, assignee. Method of spectrophotometric determination of the critical concentration of micelles of cationic surfactants in water. Ukraine patent 132448. 2019 Febr 2

Abdine H, Belal F, Zoman N. Simple spectrophotometric determination of cinnarizine in its dosage forms. Il Farmaco 2002;57(4):267-271.

Sabaté R, Estelrich J. Pinacyanol as effective probe of fibrillar β-amyloid peptide: Comparative study with Congo Red. Biopolymers 2003;72(6):455-463.

Patra N, Mandal B, Ghosh S. Spectroscopic Studies on the Interaction of Dye and Surface Active Ionic Liquid. Industrial & Engineering Chemistry Research 2017;56(36):10044-10052.

Dutta R, Ghosh S, Banerjee P, Kundu S, Sarkar N. Micelle-vesicle-micelle transition in aqueous solution of anionic surfactant and cationic imidazolium surfactants: Alteration of the location of different fluorophores. Journal of Colloid and Interface Science 2017;490:762-773.

Behera GB, Behera PK, Mishra BK. Self aggregation and behaviour in surfactants. Journal of Surface Science and Technology 2007; 23(1-2): 1-31

HyperChem 7 Release [Internet]. USA: Hypercube, Inc; © 2002. HyperChem getting started [about 2170 p.] Available from:

Astakhov SA, Baranov VI, Gribov LA. Theory and methods of computational vibronic spectroscopy. New York: Nova Science Publishers; 2008, 83 P.

Huang X, Yang J, Zhang W, Zhang Z, An Z. Determination of the Critical Micelle Concentration of Cationic Surfactants: An Undergraduate Experiment. Journal of Chemical Education 1999;76(1):93.

Hait S, Moulik S. Determination of critical micelle concentration (CMC) of nonionic surfactants by donor-acceptor interaction with lodine and correlation of CMC with hydrophile-lipophile balance and other parameters of the surfactants. Journal of Surfactants and Detergents 2001;4(3):303-309.

Obukhova E, Mchedlov-Petrossyan N, Vodolazkaya N, Patsenker L, Doroshenko A, Marynin A, Krasovitskii B. Absorption, fluorescence, and acid-base equilibria of rhodamines in micellar media of sodium dodecyl sulfate. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2017;170:138-144.

Motin M, Hafiz Mia M, Nasimul Islam A. Thermodynamic properties of Sodium Dodecyl Sulfate aqueous solutions with Methanol, Ethanol, n-Propanol and iso-Propanol at different temperatures. Journal of Saudi Chemical Society 2015;19(2):172-180.