Journal of Surfactants and Detergents

, Volume 17, Issue 2, pp 231–242 | Cite as

The Effect of NaCl on the Krafft Temperature and Related Behavior of Cetyltrimethylammonium Bromide in Aqueous Solution

  • Jagadish Chandra Roy
  • Md. Nazrul Islam
  • Gazi Aktaruzzaman
Original Article


This paper presents the effect of NaCl on the Krafft temperature (T K), surface adsorption and bulk micellization of cetyltrimethylammonium bromide (CTAB) in aqueous solution. The critical micelle concentration (CMC) of CTAB in the presence of NaCl increased and then decreased with increasing temperature. Thus, the CMC–temperature data can be represented by a bell-shaped curve. The micellar dissociation (fraction of counterion binding) and energetic parameters (free energy, enthalpy and entropy changes) of both adsorption and micellization were calculated. The processes were found to be both enthalpy and entropy controlled and appeared to be more and more enthalpy driven with increasing temperature. An enthalpy–entropy compensation rule was observed for both adsorption and micelle formation. The T K of the surfactant decreased significantly in the presence of NaCl, which is a sharp contrast to the usual behavior of the effect of electrolytes on the T K of classical ionic surfactants. The surface excess concentrations decreased with increasing temperature. However, the values were much higher in the presence of NaCl compared to the corresponding values in pure water. The solubilization behavior of a water-insoluble dye, Sudan red B (SRB), in the micellar system was studied by the UV–visible spectrophotometric technique. The molar solubilization ratio in the presence of NaCl was found to be about three times higher than that in pure water, indicating that the solubilization of SRB in the CTAB micelles significantly increases in the presence of NaCl.


Krafft temperature Micelle Formation Adsorption Surface excess concentration 



The authors thank the members of the Board of Post-graduate Studies (BPGS) of the Department of Chemistry, BUET for helpful discussion during the preparation of the research project. The financial assistance (CASR-229/31) approved by the Committee for Advanced Studies and Research (CASR), BUET for carrying out the present work is highly appreciated.


  1. 1.
    Rosen MJ (2004) Surfactants and interfacial phenomena, 3rd edn. Wiley, New YorkCrossRefGoogle Scholar
  2. 2.
    Marin P-R, Prieto G, Rega C, Varela LM, Sarmiento F, Mosquera V (1998) Comparative study of the determination of the critical micelle concentration by conductivity and dielectric constant measurements. Langmuir 14:4422−4226Google Scholar
  3. 3.
    Moulik SP, Haque ME, Jana PK, Das AR (1996) Micellar properties of cationic surfactants in pure and mixed states. J Phys Chem 100:701−708Google Scholar
  4. 4.
    Chakraborty T, Ghosh S, Moulik SP (2005) Micellization and related behavior of binary and ternary surfactant mixtures in aqueous medium: cetyl pyridinium chloride (CPC), cetyl trimethyl ammonium bromide (CTAB), and polyoxyethylene (10) cetyl ether (Brij-56) derived system. J Phys Chem B 109:14813–14823CrossRefGoogle Scholar
  5. 5.
    Bohmer MR, Koopal LK, Lyklema J (1991) Micellization of ionic surfactants. Calculations based on a self-consistent field lattice model. J Phys Chem 95:9569–9578CrossRefGoogle Scholar
  6. 6.
    Metha SK, Bhasin KK, Chauhan R, Dham S (2005) Effect of temperature on critical micelle concentration and thermodynamic behavior of dodecyldimethylethylammonium bromide and dodecyltrimethylammonium chloride in aqueous media. Colloids Surf A 255:153–157CrossRefGoogle Scholar
  7. 7.
    Aguiar J, Molina-B JA, Peula-G JM, Ruiz CC (2002) Thermodynamics and micellar properties of tetradecyltrimethylammonium bromide in formamide–water mixtures. J Colloid Interf Sci 255:382–390CrossRefGoogle Scholar
  8. 8.
    Polepu R, Gharibi H, Bloor DM, Wyn-Jones W (1993) Electrochemical studies associated with the micellization of cationic surfactants in aqueous mixtures of ethylene glycol and glycerol. Langmuir 9:110–112CrossRefGoogle Scholar
  9. 9.
    Callaghan A, Doyle R, Alexander E, Palepu R (1993) Thermodynamic properties of micellization and adsorption and electrochemical studies of hexadecylpyridinium bromide in binary mixtures of 1,2-ethanediol with water. Langmuir 9:3422–3426CrossRefGoogle Scholar
  10. 10.
    Ropers MH, Czichocki G, Brezesinski G (2003) Counterion effect on the thermodynamics of micellization of alkyl sulphates. J Phys Chem B 107:5281–5288CrossRefGoogle 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.
    Choucair A, Eisenberg A (2003) Interfacial solubilization of model amphiphilic molecules in block copolymer micelles. J Am Chem Soc 125:11993–12000CrossRefGoogle Scholar
  13. 13.
    Francis MF, Piredda M, Winnik FM (2003) Solubilization of poorly water soluble drugs in micelles of hydrophobically modified hydroxypropylcellulose copolymers. J Controlled Release 93:59–68CrossRefGoogle Scholar
  14. 14.
    Liu C, Desai KGH, Liu C (2004) Solubility of valdecoxib in the presence of ethanol and sodium lauryl sulfate at 298.15, 303.15, and 308.15 K. J Chem Eng Data 49:1847–1850CrossRefGoogle Scholar
  15. 15.
    Paria S, Yuet PK (2006) Solubilization of naphthalene by pure and mixed surfactants. Ind Eng Chem Res 45:3552–3558CrossRefGoogle Scholar
  16. 16.
    Lee J, Moroi Y (2004) Solubilization of n-alkylbenzenes in aggregates of sodium dodecyl sulfate and a cationic polymer of high charge density (II). Langmuir 20:6116–6119CrossRefGoogle Scholar
  17. 17.
    Nayyar SP, Sabatini DA, Harwell JH (1994) Surfactant adsolubilization and modified admicellar sorption of nonpolar, polar, and ionizable organic contaminants. Environ Sci Technol 28:1874–1881CrossRefGoogle Scholar
  18. 18.
    Paria S, Yuet PK (2009) Solubilization of naphthalene in the presence of plant−synthetic mixed surfactant systems. J Phys Chem 113:474–481CrossRefGoogle Scholar
  19. 19.
    Chu Z, Feng Y (2012) Empirical correlations between Krafft temperature and tail length for amidosulfobetaine surfactants in the presence of inorganic salt. Langmuir 28:1175–1181CrossRefGoogle Scholar
  20. 20.
    Tsuji K, Mino J (1978) Krafft point depression of some zwitterionic surfactants by inorganic salts. J Phys Chem 82:1610–1614CrossRefGoogle Scholar
  21. 21.
    Mesa CL, Ranieri GA, Terenzi M (1988) Studies on Krafft point solubility in surfactant solutions. Thermochim Acta 137:143–150CrossRefGoogle Scholar
  22. 22.
    Heckmann K, Schwarz R, Strnad J (1987) Determination of Krafft point and CMC of hexadecylpyridinium bromide in electrolytes solutions. J Colloid Interface Sci 120:114–117CrossRefGoogle Scholar
  23. 23.
    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
  24. 24.
    Davey TW, Ducker WA, Hayman AR, Simpon J (1998) Krafft temperature depression in quaternary ammonium bromide surfactants. Langmuir 14:3210–3213CrossRefGoogle Scholar
  25. 25.
    Islam MN, Kato T (2003) Thermodynamic study on surface adsorption and micelle formation of poly(ethylene glycol) mono-n-tetradecyl ethers. Langmuir 19:7201–7205CrossRefGoogle Scholar
  26. 26.
    Islam MN, Kato T (2003) Temperature dependence of the surface phase behavior and micelle formation of some nonionic surfactants. J Phys Chem B 107:965–971CrossRefGoogle Scholar
  27. 27.
    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
  28. 28.
    Heyda J, Lund M, Oncak M, 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 114:10843–10852Google Scholar
  29. 29.
    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
  30. 30.
    Pegram LM, Record MT (2008) Thermodynamic origin of hofmeister ion effects. J Phys Chem 112:9428–9436Google Scholar
  31. 31.
    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
  32. 32.
    Glasstone S (1947) Thermodynamics for chemists, 3rd edn. Litton Educational Pub Inc, NYGoogle Scholar
  33. 33.
    Williams F, Woodberry NT, Dixon JK (1957) Purification and surface tension properties of alkyl sodium sulfosuccinates. J Colloid Sci 12:452–459CrossRefGoogle Scholar
  34. 34.
    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 Interface Sci 358:160–166CrossRefGoogle Scholar
  35. 35.
    Mata J, Varade D, Bahadur P (2005) Aggregation behavior of quaternary salt based cationic surfactants. Thermochim Acta 428:147–155CrossRefGoogle Scholar
  36. 36.
    Mukerjee P, Mysels K, Kapauan J (1967) Counterion specificity in the formation of ionic micelles—size, hydration, and hydrophobic bonding effects. J Phys Chem 71:4166–4175CrossRefGoogle Scholar
  37. 37.
    Bojan S, Marija B-R (2009) Temperature and salt-induced micellization of dodecyltrimethylammonium chloride in aqueous solution: a thermodynamic study. J Colloid Interface Sci 338:216–221CrossRefGoogle Scholar
  38. 38.
    Lu JR, Li ZX, Thomas RK, Staples EJ, Thompson L, Tucker I, Penfold J (1994) Neutron reflection from a layer of monododecyl octaethylene glycol adsorbed at the air-liquid interface: the structure of the layer and the effects of temperature. J Phys Chem 98:6559–6567CrossRefGoogle Scholar
  39. 39.
    Ritacco H, Langevin D, Diamant H, Andelman D (2011) Dynamic surface tension of aqueous solutions of ionic surfactants: role of electrostatics. Langmuir 27:1009–1014CrossRefGoogle Scholar
  40. 40.
    Dahanayake M, Cohen AW, Rosen MJ (1982) Relationship of structure to properties of surfactants. 13. Surface and thermodynamic properties of some oxyethylenated sulfates and sulfonates. J Phys Chem 90:2413–2418CrossRefGoogle Scholar
  41. 41.
    Fisicaro E, Biemmi M, Compari C, Duce E, Peroni M (2007) Thermodynamics of aqueous solutions of dodecyldimethylethylammonium bromide. J Colloid Interface Sci 305:301–307CrossRefGoogle Scholar
  42. 42.
    Mankowich AM (1966) The energetics of surfactant adsorption at the air-water interface. J Am Oil Chem Soc 42:615–619CrossRefGoogle Scholar
  43. 43.
    Lumry R, Rajender S (1970) Enthalpy–entropy compensation phenomena in water solutions of proteins and small molecules: a ubiquitous properly of water. Biopolymers 9:1125–1227CrossRefGoogle Scholar
  44. 44.
    Sugihara G, Hisatomi M (1999) Enthalpy–entropy compensation phenomenon observed for different surfactants in aqueous solution. J Colloid Interface Sci 219:31–36CrossRefGoogle Scholar
  45. 45.
    Kabir-ud-Din K, Koya AP, Khan ZA (2010) Conductometric studies of micellization of gemini surfactant pentamethylene-1,5-bis(tetradecyl dimethylammonium bromide) in water and water–organic solvent mixed media. J Colloid Interface Sci 342:340–347CrossRefGoogle Scholar
  46. 46.
    Awan MA, Shah SS (1997) Hydrophobic interaction of amphiphilic hemicyanine dyes with cationic and anionic surfactants. Colloids Surf A 122:97–101CrossRefGoogle Scholar
  47. 47.
    Sabate R, Gallardo M, Maza ADL, Estelrich JA (2001) Spectroscopy study of the interaction of pinacyanol with n-dodecyltrimethylammonium bromide micelles. Langmuir 17:6433–6437CrossRefGoogle Scholar
  48. 48.
    Fujio K, Mitsui T, Kurumizawa H, Tanaka Y, Uzu Y (2004) Solubilization of a water-insoluble dye in aqueous NaBr solution of alkylpyridinium bromides and its relation with micellar size and shape. Colloid Polym Sci 282:223−229Google Scholar
  49. 49.
    Kuiper JM, Buwalda RT, Hulst R, Engberts JBFN (2001) Novel pyridinium surfactants with unsaturated alkyl chains: aggregation behavior and interactions with methyl orange in aqueous solution. Langmuir 17:5216–5224CrossRefGoogle Scholar
  50. 50.
    Harendra S, Vipulanandan C (2011) Effects of surfactants on solubilization of perchloroethylene (PCE) and trichloroethylene (TCE). Ind Eng Chem Res 50:5831–5837CrossRefGoogle Scholar
  51. 51.
    Schott H (1967) Solubilization of a water-insoluble dye II. J Phys Chem 71:3611–3617CrossRefGoogle Scholar

Copyright information

© AOCS 2013

Authors and Affiliations

  • Jagadish Chandra Roy
    • 1
  • Md. Nazrul Islam
    • 1
  • Gazi Aktaruzzaman
    • 1
  1. 1.Department of ChemistryBangladesh University of Engineering and TechnologyDhakaBangladesh

Personalised recommendations