Thermodynamics of micellization of multiheaded single-chain cationic surfactants

Bhattacharya, Santanu ; Haldar, Jayanta (2004) Thermodynamics of micellization of multiheaded single-chain cationic surfactants Langmuir, 20 (19). pp. 7940-7947. ISSN 0743-7463

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Official URL: http://pubs.acs.org/doi/abs/10.1021/la0495433

Related URL: http://dx.doi.org/10.1021/la0495433

Abstract

The energetics of micelle formation of three single-chain cationic surfactants bearing single (h = 1), double (h = 2), and triple (h = 3) trimethylammonium [+N(CH3)3] headgroups have been investigated by microcalorimetry. The results were compared with the microcalorimetric data obtained from well-known cationic surfactant, cetyl trimethylammonium bromide (CTAB), bearing a single chain and single headgroup. The critical micellar concentrations (cmc's) and the degrees of counterion dissociation (α) of micelles of these surfactants were also determined by conductometry. The cmc and the α values increased with the increase in the number of headgroups of the surfactant. The relationship between the cmc of the surfactant in solution and its free energy of micellization (ΔGm) was derived for each surfactant. Exothermic enthalpies of micellization (ΔHm) and positive entropies of micellization (ΔSm) were observed for all the surfactants. Negative ΔHm values increased from CTAB to h = 1 to h = 2 and decreased for h = 3 whereas ΔSm values decreased with increase in the number of headgroups. The ΔGm values progressively became less negative with the increase in the number of headgroups. This implies that micelle formation becomes progressively less favorable as more headgroups are incorporated in the surfactant. From the steady-state fluorescence measurements using pyrene as a probe, the micropolarities sensed by the probe inside various micelles were determined. These studies suggest that the micelles are more hydrated with multiheaded surfactants and the micropolarity of micelles increases with the increase in the number of headgroups.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:21010
Deposited On:20 Nov 2010 09:23
Last Modified:20 Nov 2010 09:23

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