Applied Chemical Engineering

Ion-specific effects on equilibrium adsorption layers of ionic surfactants

Stoyan I. Karakashev

Department of Physical Chemistry, Sofia University, Sofia 1164, Bulgaria.

DOI: https://doi.org/10.24294/ace.v3i2.603

Keywords: Ionic Surfactants, Ion Specific Effects, Effect of Hofmeister

---

Abstract

This review article reports the effect of the counter-ions on the ionic surfactant adsorption layer and its relation to the stability of foams and emulsions. The adsorption theory of Davies about the ionic surfactant monolayer was revisited and it is shown how to account for the type of the counter-ions. The experimental validation of this theory on thin liquid films was shown as well, thus explaining the effect of Hofmeister. However, their effect on foams and emulsions is more complex. Furthermore, it is shown how the counter-ions affect in complex way the stability of foams and emulsions via the surfactant adsorption layer in the light of the newest theory. To elucidate the nature of this effect, further investigation is called for.

---

References

[1] Lewith S. The behaviour of the proteins in the blood serum in the presence of salts. Archiv Fuer Experimentelle Pathologie und Pharmakologie 1887; XXIX: 1–16.

[2] Hofmeister F. About regularities in the protein precipitating effects of salts and the relation of these effects with the physiological behaviour of salts. Archiv Fuer Experimentelle Pathologie und Pharmakologie 1887; XXIV: 247–60.

[3] Hofmeister F. About the water withdrawing effect of the salts. Archiv Fuer Experimentelle Pathologie und Pharmakologie 1888; XXV: 1–30.

[4] Limbeck Rv. About the diuretic effect of salts. Archiv Fuer Experimentelle Pathologie und Pharma-kologie 1888; XXV: 69–86.

[5] Hofmeister F. Investigations about the swelling process. Archiv Fuer Experimentelle Pathologie und Pharmakologie 1890; XVII: 395–413.

[6] Hofmeister F. The contribution of dissolved components to swelling processes. Archiv Fuer Experimentelle Pathologie und Pharmakologie 1991; XXVIII: 210–38.

[7] Muenzer E. The general effect of salts. Archiv Fuer experimentelle Pathologie und Pharmakologie 1898; XLI: 74–96.

[8] Kunz W. Specific ion effects in colloidal and biological systems. Current Opinion in Colloid & Interface Science 2010; 15: 34–9.

[9] Kunz W, Lo Nostro P, Ninham BW. The present state of affairs with Hofmeister effects. Current Opinion in Colloid & Interface Science 2004; 9: 1–18.

[10] Ninham BW, Yaminsky V. Ion binding and ion specificity: The Hofmeister effect and Onsager and Lifshitz theories. Langmuir 1997; 13: 2097–108.

[11] Bostrom M, Williams DRM, Ninham BW. Specific ion effects: Why DLVO theory fails for biology and colloid systems. Physical Review Letters 2001; 87.

[12] Bostroem M, Williams DRM, Ninham BW. Surface tension of electrolytes: Specific ion effects ex-plained by dispersion forces. Langmuir 2001; 17: 4475–8.

[13] Bostrom M, Kunz W, Ninham BW. Hofmeister effects in surface tension of aqueous electrolyte solu-tion. Langmuir 2005; 21: 2619–23.

[14] Moreira LA, Bostrom M, Ninham BW, et al. Hofmeister effects: Why protein charge, pH titration and protein precipitation depend on the choice of background salt solution. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2006; 282: 457–63.

[15] Bostroem M, Ninham BW. Contributions from dispersion and born self-free energies to the solvation energies of salt solutions. The Journal of Physical Chemistry B 2004; 108: 12593–5.

[16] Tavares FW, Bratko D, Blanch HW, et al. Ion-specific effects in the colloid-colloid or protein-protein potential of mean force: Role of salt-macroion van der Waals interactions. The Journal of Physical Chemistry B 2004; 108: 9228–35.

[17] Warszynski P, Lunkenheimer K, Czichocki G. Effect of counterions on the adsorption of ionic surfactants at fluid-fluid interfaces. Langmuir 2002; 18: 2506–14.

[18] Para G, Jarek E, Warszynski P. The Hofmeister series effect in adsorption of cationic surfactants - theoretical description and experimental results. Advances in Colloid and Interface Science 2006; 122: 39–55.

[19] Para G, Jarek E, Warszynski P. The surface tension of aqueous solutions of cetyltrimethylammonium cationic surfactants in presence of bromide and chloride counterions. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2005; 261: 65–73.

[20] Li HH, Imai Y, Yamanaka M, et al. Specific counter-ion effect on the adsorbed film of cationic surfactant mixtures at the air/water interface. Journal of Colloid and Interface Science 2011; 359: 189–93.

[21] Shimamoto K, Onohara A, Takumi H, W et al. Miscibility and distribution of counter-ions of imidazolium ionic liquid mixtures at the air/water surface. Langmuir 2009; 25: 9954–9.

[22] Hayami Y, Ichikawa H, Someya A, et al. Thermodynamic study on the adsorption and micelle formation of long chain alkyltrimethylammonium chlorides. Colloid and Polymer Science 1998; 276: 595–600.

[23] Davies JT. Adsorption of long-chain ions I. Proceedings of the Royal Society of London. Series A 1958; 245: 417–28.

[24] Davies JT, Rideal EK. Interfacial Phenomena, 2nd ed. New York: Academic Press; 1963.

[25] Borwankar RP, Wasan DT. Equilibrium and dynamics of adsorption of surfactants at fluid-fluid interfaces. Chemical Engineering Science 1988; 43: 1323–37.

[26] Ivanov IB, Marinova KG, Danov KD, et al. Role of the counter-ions on the adsorption of ionic surfactants. Advances in Colloid and Interface Science 2007; 134-135: 105–24.

[27] Ivanov IB, Ananthapadmanabhan KP, Lips A. Adsorption and structure of the adsorbed layer of ionic surfactants. Advances in Colloid and Interface Science 2006; 123-126: 189–212.

[28] Slavchov RI, Karakashev SI, Ivanov IB. Ionic surfactants and ion-specific effects: Adsorption, micel-lization, thin liquid films. In: Romsted LS (editor). Surfactant science and technology: Retrospects and prospects. New York: Taylor & Francis Group; 2014. p. 593.

[29] Ivanov IB, Slavchov RI, Basheva ES, et al. Hofmeister effect on micellization, thin films and emulsion stability. Advances in Colloid and Inter-face Science 2011; 168: 93–104.

[30] Robinson RA, Stokes RH. Electrolyte Solutions. 2nd ed. London: Butterworths Scientific Publications; 1959. p. 560.

[31] Lucassen-Reynders EH. Surface equation of state for ionized surfactants. The Journal of Physical Chemistry 1966; 70: 1777–85.

[32] Davies JT. Study of foam stabilizers using a new (\“viscous-traction\”) surface viscometer. Proceedings of the Second International Congress of Sur-face Activity 1957: 220–4.

[33] Lu JR, Marrocco A, Su T, et al. Adsorption of dodecyl sulfate surfactants with monovalent metal counter-ions at the air-water interface studied by neutron reflection and surface tension. Journal of Colloid and Interface Science 1993; 158: 303–16.

[34] Israelachvili JN. Intermolecular and surface forces. New York: Academic Press; 1985.

[35] Jones G, Ray WA. The surface tension of solutions of electrolytes as a function of the concentration. III. Sodium chloride. Journal of the American Chemical Society 1941; 63: 3262–3.

[36] Collins KD. Charge density-dependent strength of hydration and biological structure. Biophysical Journal 1997; 72: 65–76.

[37] Marcus Y. Effect of ions on the structure of water: Structure making and breaking. Chemical Reviews 2009; 109: 1346–70.

[38] Marcus Y. Ion properties. New York: Marcel Dekker; 1997.

[39] Marcus Y. Thermodynamics of ion hydration and its interpretation in terms of a common model. Pure and Applied Chemistry 1987; 59: 1093–101.

[40] Kunz W, Belloni L, Bernard O, et al. Osmotic coefficients and surface tensions of aqueous electrolyte solutions: Role of dispersion forces. The Journal of Physical Chemistry B 2004; 108: 2398–404.

[41] Nikolskij BP. Handbook of the Chemist (In Russian). Moscow: Khimia; 1966.

[42] Dietrich B, Kintzinger JP, Lehn JM, et al. Stability, molecular-dynamics in solution, and X-Ray structure of the ammonium cryptate [NH4+⸦ 2.2.2]PF6–. Journal of Physical Chemistry 1987; 91: 6600–6.

[43] Lide DR. CRC Handbook of chemistry and physics. 83rd ed. New York, London: CRC Press; 2002. p. 2664.

[44] Sett S, Karakashev SI, Smoukov SK, et al. Ion-specific effects in foams. Advances in Colloid and Interface Science 2015; 225: 98–113.

[45] Churaev NV, Derjagiun BV, Muller VM. Surface Forces. New York: Springer; 1987. p. 440.

[46] Ivanov IB, Hadjiiski A, Denkov ND, et al. Energy of adhesion of human T cells to adsorption layers of monoclonal antibodies measured by a film trapping technique. Biophysical Journal 1998; 75: 545–56.

[47] Hadjiiski A, Dimova R, Denkov ND, et al. Film trapping technique - Precise method for three-phase contact angle determination of solid and fluid particles of micrometer size. Langmuir 1996; 12: 6665–75.

[48] Hadjiiski A, Tcholakova S, Ivanov IB, et al. Gentle film trapping technique with application to drop entry measurements. Langmuir 2002; 18: 127–38.

[49] Tcholakova S, Denkov ND, Ivanov IB, et al. Coalescence in beta-lactoglobulin-stabilized emulsions: Effects of protein adsorption and drop size. Langmuir 2002; 18: 8960–71.

[50] Karakashev SI, Georgiev P, Balashev K. Foam production — ratio between foaminess and rate of foam decay. Journal of Colloid and Interface Science 2012; 379: 144–7.