Lamellar miscibility gap in a binary catanionic surfactant-water system

• Type: Article in International Scientific Journal
• Date: 2007

Authors

Bruno F B Silva (Author) FCUP; Eduardo F Marques (Author) FCUP; Ulf Olsson (Author) Other

Journal

Title: Journal of Physical Chemistry B

Vol. 111

Pages: 13520-13526

ISSN: 1520-6106

Publisher: American Chemical Society

Indexing

ISI Web of Knowledge - 27 Citations

Scopus - 27 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

Other information

Authenticus ID: P-004-5SV

DOI: 10.1021/jp076321f

Abstract (EN): The coexistence of two lamellar liquid-crystalline phases in equilibrium for binary surfactant-water systems is a rare and still puzzling phenomenon. In the few binary systems where it has been demonstrated experimentally, the surfactant is invariably ionic and the miscibility gap is thought to stem from a subtle balance between attractive and repulsive interbilayer forces. In this paper, we report for the first time a miscibility gap for a catanionic lamellar phase formed by the surfactant hexadecyltrimethylammonium octylsulfonate (TASo) in water. Synchrotron small-angle X-ray scattering, polarizing light microscopy, and H-2 NMR unequivocally show the coexistence of a dilute (or swollen) lamellar phase, L-alpha', and a concentrated (or collapsed) lamellar phase, L alpha ''. Furthermore, linear swelling is observed for each of the phases, with the immiscibility region occurring for 15-54 wt % surfactant. In the dilute region, the swollen lamellar phase is in equilibrium with an isotropic micellar region. Vesicles can be observed in this two-phase region as a dispersion of L alpha' in the solution phase. A theoretical cell model based on combined DLVO and short-range repulsive potentials is presented in order to provide physical insight into the miscibility gap. The surfactant TASo is net uncharged, but it undergoes partial dissociation owing to the higher aqueous solubility of the short octylsulfonate chain. Thus, a residual positive charge in the bilayer is originated and, consequently, an electrostatic repulsive force, whose magnitude is dependent on surfactant concentration. For physically reasonable values of the solubility of the octyl chain, assumed to be constant with surfactant volume fraction, a fairly good agreement is observed between the experimental miscibility gap and the theoretical one.

Language: English

Type (Professor's evaluation): Scientific