Skip to main content
SpringerLink
Log in

Studies of the Micellization of Cationic–Anionic Surfactant Systems in Water and Methanol–Water Mixed Solvents

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Measurements of the conductance of binary mixtures of cetyltrimethylammonium bromide and sodium dodecylsulfate in pure water and in methanol–water mixed solvent media containing 0.10, 0.20, and 0.30 volume fractions of methanol at 308.15, 318.15, and 323.15 K are reported. The concentration of sodium dodecylsulfate varied from 0.001 to 0.04 mol·L−1 in the presence of ~5.0 × 10−4 mol·L−1 cetyltrimethylammonium bromide. The results showed a sharp increase in the conductance with increasing concentrations of the surfactant mixture. The conductance is found to increase with increasing temperature over the entire concentration range in pure water and in a given mixed solvent medium but is found to decrease with increasing methanol content in the solvent. Estimation of the pre-cmc (S 1) and post-cmc (S 2) slopes for the CTAB–SDS system, to calculate the critical micelle concentration, provides important insight regarding the solution behavior of the mixed surfactants. The critical micelle concentration (cmc) and degree of micellar dissociation (α) of sodium dodecylsulfate in the presence of cetyltrimethylammonium bromide increase in the methanol–water mixed solvent medium. Additionally, the values of cmc and α increase with increasing temperature. The thermodynamic functions for the micellization were calculated at various conditions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Tadros, T.F.: Applied Surfactants: Principles and Applications. Wiley, New York (2005)

    Book  Google Scholar 

  2. Holmberg, K., Jönsson, B., Kronberg, B., Lindman, B.: Surfactants and Polymers in Aqueous Solution, 2nd edn. Wiley, Chichester (2003)

    Google Scholar 

  3. Lucassen-Reyolds, E.H., Lucassen, J., Giles, D.: Surface and bulk properties of mixed anionic/cationic surfactant systems. J. Colloid Interface Sci. 81, 150–157 (1981)

    Article  Google Scholar 

  4. Cui, Z.G., Canselier, J.P.: Interfacial and aggregation properties of some anionic/cationic surfactant binary systems II. Mixed micelle formation and surface tension reduction effectiveness. Colloid Polym. Sci. 279, 259–267 (2001)

    Article  CAS  Google Scholar 

  5. Wang, C., Lucy, C.A.: Mixed cationic/anionic surfactants for semipermanent wall coatings in capillary electrophoresis. Electrophoresis 25, 825–832 (2004)

    Article  CAS  Google Scholar 

  6. Kume, G., Gallotti, M., Nunes, G.: Review on anionic/cationic surfactant mixtures. J. Surfact. Deterg. 11, 1–11 (2008)

    Article  CAS  Google Scholar 

  7. Filipović-Vinceković, N., Bujan, M., Dragčević, Đ., Nekić, N.: Phase behavior in mixtures of cationic and anionic surfactants in aqueous solutions. Colloid Polym. Sci. 273, 182–188 (1995)

    Article  Google Scholar 

  8. Segota, S., Tezak, D.: Spontaneous formation of vesicles. Adv. Colloid Interface Sci. 121, 51–75 (2006)

    Article  CAS  Google Scholar 

  9. Safran, S.A., Pincus, P., Andelman, D.: Theory of spontaneous vesicle formation in surfactant mixtures. Science 248, 354–356 (1990)

    Article  CAS  Google Scholar 

  10. Panda, A.K., Possmayer, F., Petersen, N.O., Nag, K., Moulik, S.P.: Physico-chemical studies on mixed oppositely charged surfactants: their uses in the preparation of surfactant ion selective membrane and monolayer behavior at the air water interface. Colloid Surf A: Physicochem. Eng. Aspects 264, 106–113 (2005)

    Article  CAS  Google Scholar 

  11. Herrington, K.L., Kaler, E.W., Miller, D.D., Zasadzinski, J.A., Chiruvolu, S.: Phase behavior of aqueous mixtures of dodecyltrimethylammonium bromide (DTAB) and sodiumdodecyl sulfate (SDS). J. Phys. Chem. 97, 13792–13802 (1993)

    Article  CAS  Google Scholar 

  12. Hines, J.D.: Theoretical aspects of micellisation in surfactant mixtures. Curr. Opin. Colloid Interface Sci. 6, 350–356 (2001)

    Article  CAS  Google Scholar 

  13. Ogino, K., Abe, M. (eds.): Mixed Surfactant Systems, Surfactant Science Series, vol. 46, pp. 317. Marcel Dekker, New York (1993)

  14. Kronberg, B.: Surfactant mixtures. Curr. Opin. Colloid Interface Sci. 2, 456–463 (1997)

    Article  CAS  Google Scholar 

  15. Desai, T.R., Dixit, S.G.: Interaction and viscous properties of aqueous solutions of mixed cationic and nonionic surfactants. J. Colloid Interface Sci. 177, 471–477 (1996)

    Article  CAS  Google Scholar 

  16. Shiloach, A., Blankschtein, D.: Predicting micellar solution properties of binary surfactant mixtures. Langmuir 14, 1618–1636 (1998)

    Article  CAS  Google Scholar 

  17. Guo, H., Liu, Z., Yang, S., Sun, C.: The feasibility of enhanced soil washing of p-nitrochlorobenzene (pNCB) with SDBS/Tween80 mixed surfactants. J. Haz. Mater. 170, 1236–1241 (2009)

    Article  CAS  Google Scholar 

  18. Devinsky, P.M., Lacko, F.I.: Critical micelle concentration, ionization degree and micellisation energy of cationic dimeric (gemini) surfactants in aqueous solution and in mixed micelles with anionic surfactant. Acta Facult. Pharm. Univ. Comenianae 50, 119–131 (2003)

    Google Scholar 

  19. Zana, R., Levy, H., Dganino, D., Talmon, Y., Kwetkat, K.: Mixed micellization of cetyltrimethylammonium bromide and an anionic dimeric (gemini) surfactant in aqueous solution. Langmuir 13, 402–408 (1997)

    Article  CAS  Google Scholar 

  20. Schulz, P.C., Minardi, R.M., Vuano, B.: Dodecyltrimethylammonium bromide–disodium dodecanephosphate mixed micelles. Colloid Polym. Sci. 277, 837–845 (1999)

    Article  CAS  Google Scholar 

  21. Patist, A., Chhabra, V., Pagidipati, R., Shah, R., Shah, D.O.: Effect of chain length compatibility on micellar stability in sodium dodecylsulphate/alkyltrimethylammonium bromide solutions. Langmuir 13, 432–434 (1997)

    Article  CAS  Google Scholar 

  22. Kato, T., Takeuchi, H., Seimiya, T.: Concentration dependence of micellar size and composition in mixed anionic/cationic surfactant solutions studied by light scattering and pulsed-gradient FT–NMR spectroscopy. J. Phys. Chem. 96, 6839–6843 (1992)

    Article  CAS  Google Scholar 

  23. Xiao, J.X., Bao, Y.X.: An unusual variation of surface tension with concentration of mixed cationic–anionic surfactants. Chin. J. Chem. 19, 73–75 (2001)

    Article  CAS  Google Scholar 

  24. Rodriguez, J., Clavero, E., Laria, D.: Computer simulations of catanionic surfactants adsorbed at air/water interfaces. J. Phys. Chem. B 109, 24427–24433 (2005)

    Article  CAS  Google Scholar 

  25. Sohrabi, B., Gharibi, H., Tajik, B., Javadian, S., Hashemianzadeh, M.: Molecular interactions of cationic and anionic surfactants in mixed monolayers and aggregates. J. Phys. Chem. B 112, 14869–14876 (2008)

    Article  CAS  Google Scholar 

  26. Mukerjee, P., Mysels, K.J.: Critical Micelle Concentration of Aqueous Surfactant Systems. National Bureau of Standards, Washington DC (1970)

    Google Scholar 

  27. Khan, A.M., Shah, S.S.: Determination of critical micelle concentration of sodium dodecylsulphate and effect of low concentration pyrene on its cmc using origin software. J. Chem. Soc. Pak. 30, 186–191 (2008)

    CAS  Google Scholar 

  28. Cifuentes, A., Bernal, J.L., Deiz-Masa, J.C.: Determination of critical micelle concentration values using capillary electrophoresis instrumentation. Anal. Chem. 69, 4271–4274 (1997)

    Article  CAS  Google Scholar 

  29. Tang, Y., Du, B.Y., Yang, J., Zhang, Y.M.: Temperature effects on surface activity and application in oxidation of toluene derivatives of CTAB–SDS with KMnO4. J. Chem. Sci. 118, 281–285 (2006)

    Article  CAS  Google Scholar 

  30. Jenkins, S.I.: Novel Aqueous Two-Phase Systems: Characterization and Applications in Chemical Separation. Ph.D. dissertation, North Carolina State University (2012)

  31. Huang, J.B., Zhu, B.Y., Zhao, G.X., Zhang, Z.Y.: Vesicle formation of a 1:1 catanionic surfactant mixture in ethanol solution. Langmuir 13, 5759–5761 (1997)

    Article  CAS  Google Scholar 

  32. Zana, R., Michels, B.: On the formation of vesicles by mixtures of anionic and cationic surfactants in ethanol. Langmuir 14, 6599–6602 (1998)

    Article  CAS  Google Scholar 

  33. Huang, J.-B., Zhu, B.-Y., Mao, M., He, P., Wang, J., He, X.: Vesicle formation of 1:1 cationic and anionic surfactant mixtures in nonaqueous polar solvents. Colloid Polym. Sci. 277, 354–360 (1999)

    Article  CAS  Google Scholar 

  34. Tomasic, V., Stefanic, I., Filipovic-Vincekovic, N.: Adsorption, association and precipitation in hexadecyltrimethylammonium bromide/sodium dodecylsulphate mixtures. Colloid Polym. Sci. 277, 153–163 (1999)

    Article  CAS  Google Scholar 

  35. Bhattarai, A., Chatterjee, S.K., Niraula, T.P.: Effects of concentration, temperature and solvent composition on density and apparent molar volume of the binary mixtures of cationic–anionic surfactants in methanol–water mixed solvent media. SpringerPlus 2, 280 (2013)

    Article  Google Scholar 

  36. Apelblat, A.: Representation of electrical conductances for polyvalent electrolytes by the Quint–Viallard conductivity equation. Part 4. Symmetrical 2:2, 3:3 and unsymmetrical 2:1, 3:1 and 1:3 type electrolytes in pure organic solvents. J. Solution Chem. 40, 1234–1257 (2011)

    Article  CAS  Google Scholar 

  37. Bhattarai, A., Nandi, P., Das, B.: The effects of concentration, relative permittivity and temperature on the transport properties of sodium polystyrenesulphonate in methanol–water mixed solvent media. J. Polym. Res. 13, 475–482 (2006)

    Article  CAS  Google Scholar 

  38. Bhattarai, A., Chatterjee, S.K., Deo, T.K., Niraula, T.P.: Effects of concentration, temperature, and solvent composition on the partial molar volumes of sodium lauryl sulfate in methanol (1) + water (2) mixed solvent media. J. Chem. Eng. Data 56, 3400–3405 (2011)

    Article  CAS  Google Scholar 

  39. Chatterjee, A., Das, B.: Electrical conductances of tetrabutylammonium bromide, sodium tetraphenylborate, and sodium bromide in methanol (1) + water (2) mixtures at (298.15, 308.15, and 318.15) K. J. Chem. Eng. Data 51, 1352–1355 (2006)

    Article  CAS  Google Scholar 

  40. Albright, P.S., Gasting, L.J.: Dielectric constants of methanol–water system from 5 to 55°. J. Am. Chem. Soc. 68, 1061–1063 (1946)

    Article  CAS  Google Scholar 

  41. Yilmaz, H., Guler, S.: Excess properties of methanol–water binary system at various temperatures. Il Nuovo Cimento D 20, 1853–1861 (1998)

    Article  Google Scholar 

  42. Chakraborty, T., Chakraborty, I., Ghosh, S.: Sodium carboxymethylcellulose–CTAB interaction: a detailed thermodynamic study of polymer–surfactant interaction with opposite charges. Langmuir 22, 9905–9913 (2006)

    Article  CAS  Google Scholar 

  43. Lin, S.Y., Lin, Y.Y., Chen, E.M., Hsu, C.T., Kwan, C.C.: A study of the equilibrium surface tension and the critical micelle concentration of mixed surfactant solutions. Langmuir 15, 4370–4376 (1999)

    Article  CAS  Google Scholar 

  44. Umlong, I.M., Ismail, K.: Micellization behaviour of sodium dodecylsulphate in different electrolyte media. Colloids and Surfaces A: Physicochem. Eng. Aspects 299, 8–14 (2007)

    Article  CAS  Google Scholar 

  45. Lind Jr, J.E., Zwolenik, J.J., Fuoss, R.M.: Calibration of conductance cells at 25 °C with aqueous solutions of potassium chloride. J. Am. Chem. Soc. 81, 1557–1559 (1957)

    Article  Google Scholar 

  46. Das, B., Hazra, D.K.: Studies on the viscosities, conductance and adiabatic compressibilities of some tetraalkylammonium perchlorates in 2-methoxyethanol. Bull. Chem. Soc. Jpn. 65, 3470–3476 (1992)

    Article  CAS  Google Scholar 

  47. Das, B., Hazra, D.K.: Conductometric, viscometric, and spectroscopic investigations on the solvation phenomena of alkali-metal ions and ion pairs in 2-methoxyethanol. J. Phys. Chem. 99, 269–273 (1995)

    Article  CAS  Google Scholar 

  48. Zana, R.: Ionization of cationic micelles: effect of the detergent structure. J. Colloid Interface Sci. 78, 330–337 (1980)

    Article  CAS  Google Scholar 

  49. Aslanzadeh, S., Yousefi, A.: The effect on ethanol on nanostructures of mixed cationic and anionic surfactants. J. Surfactant Deterg. 17, 709–716 (2014)

    Article  CAS  Google Scholar 

  50. del Rio, J.M., Prieto, G., Sarmiento, F., Mosquera, V.: Thermodynamics of micellization of N-octyltrimethylammonium bromide in different media. Langmuir 11, 1511–1514 (1995)

    Article  Google Scholar 

  51. Attwood, D., Florence, A.T.: Surfactant Systems: Their Chemistry, Pharmacy and Biology. Chapman and Hall, London (1983)

    Book  Google Scholar 

  52. Khan, A., Marques, E.: Catanionic Surfactants in Specialists Surfactants. Blackie Academic and Professional, pp. 37–76. Chapman and Hall, London (1997)

    Google Scholar 

  53. Chen, L., Xiao, J.-X., Ruan, K., Ma, J.: Homogeneous solutions of equimolar mixed cationic–anionic surfactants. Langmuir 18, 7250–7252 (2002)

    Article  CAS  Google Scholar 

  54. Bakshi, M.S.: Mixed micelles of cationic surfactants in aqueous polyethylene glycol 1000. J. Dispers. Sci. Technol. 20, 1715–1735 (1999)

    Article  CAS  Google Scholar 

  55. Bakshi, M.S.: Cetylpyridinium chloride + tetradecyltrimethylammonium bromide mixed micelles in polyethylene glycol 1000 + water mixtures. J. Macromol. Sci. Pure Appl. Chem. A 36, 879–892 (1999)

    Article  Google Scholar 

  56. Javadian, S., Gharibi, H., Sohrabi, B., Bijanzadeh, H., Safarpour, M.A., Behjatmanesh, A.: Determination of the physico-chemical parameters and aggregation number of surfactant in micelles in binary alcohol–water mixtures. J. Mol. Liq. 137, 74–79 (2008)

    Article  CAS  Google Scholar 

  57. Varade, D., Joshi, T., Aswal, V.K., Goyal, P.S., Hassand, P.A., Bahadur, P.: Effect of salt on the micelles of cetylpyiridinium chloride. Colloid Surf. A: Physicochem. Eng. Aspects 259, 95–101 (2005)

    Article  CAS  Google Scholar 

  58. Dubey, N.: A conductometric study of interaction between sodium dodecyl sulfate and 1-propanol, 1-butanol 1-pentanol and 1-hexanol at different temperatures. J. Surface Sci. Technol. 24, 139–148 (2008)

    CAS  Google Scholar 

  59. Hiemenz, P.C., Rajagopalan, R.: Principles of Colloid and Surface Chemistry, pp. 335–404. Dekker, New York (1997)

    Google Scholar 

  60. Norvaisas, P., Petrauskas, V., Matulis, D.: Thermodynamics of cationic and anionic surfactant interaction. J. Phys. Chem. B 116, 2138–2144 (2012)

    Article  CAS  Google Scholar 

  61. Rub, M.A., Asiri, A.M., Naqvi, A.Z., Rahman, M.M., Khan, S.B., Din, K.: Mixed micellization between amphiphilic drug promethazine hydrochloride and cationic surfactant(conventional as well as gemini). J. Mol. Liq. 177, 19–25 (2013)

    Article  CAS  Google Scholar 

  62. Talhout, R., Engberts, J.: Self-Assembly in mixtures of sodium alkyl sulfates and alkyltrimethylammonuium bromides: aggregation behavior and catalytic properties. Langmuir 13, 5001–5006 (1997)

    Article  CAS  Google Scholar 

  63. Li, W., Han, Y.C., Zhang, J.L., Wang, L.X., Song, J.: Thermodynamic modeling of CTAB aggregation in water–ethanol mixed solvents. Colloid J. 68, 304–310 (2006)

    Article  CAS  Google Scholar 

  64. Moulik, S.P., Haque, M.E., Jana, P.K., Das, A.R.: Micellar properties of cationic surfactants in pure and mixed states. J. Phys. Chem. 100, 701–708 (1996)

    Article  CAS  Google Scholar 

  65. Mitra, D., Chakraborty, I., Bhattacharya, S.C., Moulik, S.P.: Interfacial and solution properties of tetraalkylammonium bromides and their sodiumdodecyl sulfate interacted products: a detailed physicochemical study. Langmuir 23, 3049–3061 (2007)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by a Research Grant for the fiscal year 2012/2013 of Nepal Academy of Science and Technology (NAST), Khumaltar, Lalitpur, Nepal under Research Grant Program. This work was also supported by the grant from University Grants Commission, Nepal for some chemicals. The author is grateful to Professor Bijan Das, presently in the Department of Chemistry, Presidency University, Kolkata, India for valuable suggestions and discussions. The author sincerely thanks the Head of the Department of Chemistry, Mahendra Morang Adarsh Multiple Campus, Tribhuvan University, Biratnagar, Nepal for providing the available research facilities to conduct this work.

Author information

Authors and Affiliations

  1. Department of Chemistry, M.M.A.M.C., Tribhuvan University, Biratnagar, Nepal

    Ajaya Bhattarai

Authors
  1. Ajaya Bhattarai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ajaya Bhattarai.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 14 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Bhattarai, A. Studies of the Micellization of Cationic–Anionic Surfactant Systems in Water and Methanol–Water Mixed Solvents. J Solution Chem 44, 2090–2105 (2015). https://doi.org/10.1007/s10953-015-0391-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-015-0391-4

Keywords

Search

Navigation