Journal of Surfactants and Detergents

, Volume 18, Issue 4, pp 651–659 | Cite as

Salt-Induced Modulation of the Krafft Temperature and Critical Micelle Concentration of Benzyldimethylhexadecylammonium Chloride

  • Md. Nazrul Islam
  • Komol Kanta Sharker
  • Khokan Chandra Sarker
Original Article


In this work, the effect of some sodium salts on the Krafft temperature (T K) and critical micelle concentration (CMC) of benzyldimethylhexadecylammonium chloride (C16Cl) in aqueous solution has been studied. It was observed that the T K can be modulated to lower and higher values and the CMC can be depressed significantly upon the addition of the electrolytes. More chaotropic Br and I raise the T K with an increase of the concentration of the ions. On the other hand, less chaotropic NO3 initially lowers and then raises the T K. Kosmotropic F, SO4 2− and CO3 2− gradually lower the T K with increasing concentration of the electrolytes. The more chaotropic ions form contact ion pairs with the surfactant and decrease the solubility with a consequent increase in the T K. On the other hand, kosmotropic ions, being extensively hydrated in the bulk, remain separated from the surfactant by hydrated layers of water molecules. As a result, a significant electrostatic repulsion exists between the charged headgroups of the surfactant, resulting in a decrease in the T K. The CMC of the surfactant decreases significantly in the presence of these ions. The surface tension at the CMC (γCMC) also decreases in the presence of all the salts except for F. The electrostatic repulsion between the charged headgroups is significantly reduced because of screening of the surface charge of both micelles and adsorbed monolayers by the associated counterions, resulting in a decrease in both the CMC and γCMC.


Cationic surfactant Krafft temperature Critical micelle concentrations Hofmeister anions 



MNI is grateful for the financial assistance (CASR-243/67) approved by the Committee for Advanced Studies and Research (CASR), Bangladesh University of Engineering and Technology (BUET), for carrying out the present research.


  1. 1.
    Myers D (2004) Surfactant science and technology, 3rd edn. Wiley, New JerseyGoogle Scholar
  2. 2.
    Rosen MJ (2006) Surfactants and interfacial phenomena, 3rd edn. Wiley, New YorkGoogle Scholar
  3. 3.
    Schramm LL, Stasiuk EN, Marangoni DG (2003) Surfactants and their applications. Annu Rep Prog Chem Sect C 99:3–48CrossRefGoogle Scholar
  4. 4.
    Tsuji K, Mino J (1978) Krafft point depression of some zwitterionic surfactants by inorganic salts. J Phys Chem 82:1610–1614CrossRefGoogle Scholar
  5. 5.
    Chu Z, Feng YJ (2012) Empirical correlations between Krafft temperature and tail length for amidosulfobetaine surfactants in the presence of inorganic salt. Langmuir 28:1175–1181CrossRefGoogle Scholar
  6. 6.
    Carolina V-G, Bales BL (2003) Estimate of the ionization degree of ionic micelles based on Krafft temperature measurements. J Phys Chem B 107:5398–5403CrossRefGoogle Scholar
  7. 7.
    Shinoda K, Yamaguchi N, Carlsson A (1989) Physical meaning of the Krafft point: observation of melting phenomenon of hydrated solid surfactant at the Krafft point. J Phys Chem 93:7216–7218CrossRefGoogle Scholar
  8. 8.
    Bakshi MS, Sood R (2004) Cationic surfactant–poly(amido amine) dendrimer interactions studied by Krafft temperature measurements. Colloids Surf A 233:203–210CrossRefGoogle Scholar
  9. 9.
    Nakayama H, Shinoda K (1967) The effect of added salts on the solubilities and Krafft points of sodium dodecyl sulfate and potassium perfluoro-octanoate. Bull Chem Soc Jpn 40:1797–1799CrossRefGoogle Scholar
  10. 10.
    Shrestha RG, Carlos R-A, Aramaki K (2009) Worm-like micelles in mixed amino acid surfactant/nonionic surfactant aqueous systems and the effect of added electrolytes. J Oleo Sci 58(5):243–254CrossRefGoogle Scholar
  11. 11.
    Diamant H, Andelman D (1996) Kinetics of surfactant adsorption at fluid-fluid interfaces. J Phys Chem 100:13732–13742CrossRefGoogle Scholar
  12. 12.
    Iglauer S, Wu Y, Shuler P, Tang Y, Goddard WA (2010) New surfactant classes for enhanced oil recovery and their tertiary oil recovery potential. J Petrol Sci Eng 71:23–29CrossRefGoogle Scholar
  13. 13.
    Vijayan S, Ramachandran C, Shah DO (1981) Effect of salt and aging on surfactant formulation for enhanced oil recovery: a correlation of physical properties with microsctructure using spin-labels. J Am Oil Chem Soc 58:566–573CrossRefGoogle Scholar
  14. 14.
    Michele AD, Brinchi L, Profio PD, Germani R, Sawelli G, Onori G (2011) Effect of head group size, temperature and counterion specificity on cationic micelles. J Colloid Interf Sci 358:160–166CrossRefGoogle Scholar
  15. 15.
    Mata J, Varade D, Bahadur P (2005) Aggregation behavior of quaternary salt based cationic surfactants. Thermochim Acta 428:147–155CrossRefGoogle Scholar
  16. 16.
    Bojan S, Marija B-R (2009) Temperature and Salt-Induced micellization of dodecyltrimethylammonium chloride in aqueous solution: a thermodynamic study. J Colloid Interf Sci 338:216–221CrossRefGoogle Scholar
  17. 17.
    Sugihara G, Hisatomi M (1998) Roles of counterion binding in the micelle formation of ionic surfactants in water. J Jpn Oil Chem Soc 47:661–683CrossRefGoogle Scholar
  18. 18.
    Nakahara H, Shibata O, Moroi Y (2011) Examination of surface adsorption of cetyltrimethylammonium bromide and sodium dodecyl sulfate. J Phys Chem B 115:9077–9086CrossRefGoogle Scholar
  19. 19.
    Mesa CL, Ranieri GA, Terenzi M (1988) Studies on Krafft point solubility in surfactant solutions. Thermochim Acta 137:143–150CrossRefGoogle Scholar
  20. 20.
    Heckmann K, Schwarz R, Strnad J (1987) Determination of Krafft point and CMC of hexadecylpyridinium salts in electrolytes solutions. J Colloid Interf Sci 120:114–117CrossRefGoogle Scholar
  21. 21.
    Farias T, de Menorval LC, Zajacb J, Rivera A (2009) Solubilization of drugs by cationic surfactants micelles: conductivity and 1H NMR experiments. Coll Surf A 345:51–57CrossRefGoogle Scholar
  22. 22.
    Collins KD (2012) Why continuum electrostatics theories cannot explain biological structure, polyelectrolytes or ionic strength effects in ion–protein interactions. Biophys Chem 167:43–59CrossRefGoogle Scholar
  23. 23.
    Collins KD, Neilson GW, Enderby JE (2007) Ions in water: characterizing the forces that control chemical processes and biological structure. Biophys Chem 128:95–104CrossRefGoogle Scholar
  24. 24.
    Pegram LM, Record MTJ (2007) Hofmeister salt effects on surface tension arise from partitioning of anions and cations between bulk water and the air-water interface. J Phys Chem 111:5411–5417CrossRefGoogle Scholar
  25. 25.
    Jarvis NL, Schelman MA (1968) Surface potentials of aqueous electrolyte solutions. J Phys Chem 72:74–78CrossRefGoogle Scholar
  26. 26.
    Paluch M (2000) Electrical properties of free surface of water and aqueous solutions. Adv Colloid Interf Sci 84:27–45CrossRefGoogle Scholar
  27. 27.
    Goh MC, Hicks JM, Kemnitz K, Pinto GR, Bhattacharyya K, Eisenthal KB (1988) Absolute orientation of water molecules at the neat water surface. J Phys Chem 92:5074–5075CrossRefGoogle Scholar
  28. 28.
    Chaplin M (2009) Theory vs experiment: what is the surface charge of water? Water 1:1–28CrossRefGoogle Scholar
  29. 29.
    dos Santos AP, Dieh A, Levin Y (2010) Surface tensions, surface potentials, and the Hofmeister series of electrolyte solutions. Langmuir 13:10778–10783CrossRefGoogle Scholar
  30. 30.
    Zhang Y, Furyk S, Bergbreiter DE, Cremer PS (2005) Specific ion effects on the water solubility of macromolecules: PNIPAM and the Hofmeister series. J Am Chem Soc 127:14505–14510CrossRefGoogle Scholar
  31. 31.
    Heyda J, Lund M, Milan O, Slavicek P, Jungwirth P (2010) Reversal of Hofmeister ordering for pairing of NH4 + vs. alkylated ammonium cations with halide anions in water. J Phys Chem B 114:10843–10852CrossRefGoogle Scholar
  32. 32.
    Kozlov AG, Lohman TM (1998) Calorimetric studies of E. coli SSB protein-single-stranded DNA interactions. effects of monovalent salts on binding enthalpy. J Mol Biol 278:999–1014CrossRefGoogle Scholar
  33. 33.
    Lide David R (ed) (2005) CRC handbook of chemistry and physics. CRC Press, Boca RatonGoogle Scholar
  34. 34.
    Cheng J, Vecitis CD, Hoffmann MR, Colussi AJ (2006) Experimental anion affinities for the air/water interface. J Phys Chem B 110:25598–25602CrossRefGoogle Scholar
  35. 35.
    Cho Y, Zhang Y, Christensen T, Sagle LB, Chilkoti A, Cremer PS (2008) Effects of Hofmeister anions on the phase transition temperature of elastin-like polypeptides. J Phys Chem B 112:13765–13771CrossRefGoogle Scholar
  36. 36.
    Marcus Y (2009) Effect of Ions on the structure of water: structure making and breaking. Chem Rev 109:1346–1370CrossRefGoogle Scholar
  37. 37.
    Endom L, Hertz HG, Thul B, Zeidler MD (1967) A Microdynamic model of electrolyte solutions as derived from nuclear relaxation and self-diffusion data. Dtsch Bunsenges Phys Chem 71:1008–1031Google Scholar
  38. 38.
    Glasstone S (1947) Thermodynamics for Chemists, 3rd edn. Litton Educational Publishing Inc, New YorkGoogle Scholar
  39. 39.
    Islam MN, Sarker KC, Sharker KK (2015) Influence of some Hofmeister anions on the Krafft temperature and micelle formation of cetylpyridinium bromide in aqueous solution. J Surf Deterg 18:9–16CrossRefGoogle Scholar
  40. 40.
    Islam MN, Sarker KC, Akhtaruzzaman G (2014) Effect of electrolytes on the Krafft temperature of cetylpyridinium chloride in aqueous solution. J Surf Deterg 17:525–530CrossRefGoogle Scholar
  41. 41.
    Chen X, Sarah C, Flores SC, Lim S-M, Zhang Y, Yang T, Kherb J, Cremer PS (2010) Specific anion effects on water structure adjacent to protein monolayers. Langmuir 26:16447–16454CrossRefGoogle Scholar
  42. 42.
    Rembert KB, Paterova J, Heyda J, Hilty C, Jungwirth P, Cremer PS (2012) Molecular mechanisms of ion-specific effects on proteins. J Am Chem Soc 134:10039–10046CrossRefGoogle Scholar
  43. 43.
    Srinivasan V, Blankschtein D (2003) Effect of counterion binding on micellar solution behavior: 2. Prediction of micellar solution properties of ionic surfactant-electrolyte systems. Langmuir 19:9946–9961CrossRefGoogle Scholar
  44. 44.
    Lund M, Vacha R, Jungwirth P (2008) Specific ion binding to macromolecules: effects of hydrophobicity and ion pairing. Langmuir 24:3387–3391CrossRefGoogle Scholar
  45. 45.
    Nishikido N, Matauura R (1977) The effect of added inorganic salts on the micelle formation of micelle formation in aqueous solution. Bull Chem Soc Jpn 50:1690–1694CrossRefGoogle Scholar
  46. 46.
    Abezgauz L, Kuperkar K, Hassan PA, Ramon O, Bahadur P, Danino D (2010) Effect of Hofmeister anions on micellization and micellar growth of the surfactant cetylpyridinium chloride. J Colloid Interf Sci 342:83–92CrossRefGoogle Scholar
  47. 47.
    Salis A, Ninham BW (2014) Models and mechanisms of Hofmeister effects in electrolyte solutions, and colloid and protein systems revisited. Chem Soc Rev 43:7358–7377CrossRefGoogle Scholar
  48. 48.
    Aroti A, Leontidis E, Maltseva E, Brezesinski G (2004) Effects of Hofmeister anions on DPPC Langmuir monolayers at the air-water interface. J Phys Chem B 108:15238–15245CrossRefGoogle Scholar
  49. 49.
    Hossain MM, Islam MN, Okano T, Kato T (2002) Condensed structure formation in mixed monolayers of anionic surfactants and 2-hydroxyethyl laurate at the air–water interface. Colloids Surf A 205:249–260CrossRefGoogle Scholar
  50. 50.
    Marcus Y (1991) Thermodynamics of solvation of ions. Part 5. Gibbs free energy of hydration at 298.15 K. J Chem Soc Faraday Trans 87:2995–2999CrossRefGoogle Scholar

Copyright information

© AOCS 2015

Authors and Affiliations

  • Md. Nazrul Islam
    • 1
  • Komol Kanta Sharker
    • 1
  • Khokan Chandra Sarker
    • 1
  1. 1.Department of ChemistryBangladesh University of Engineering and TechnologyDhakaBangladesh

Personalised recommendations