Microemulsions as macroelectrolytes

• Published in: The Journal of chemical physics 1995-07, Vol.103 (4), p.1655-1668
• Main Authors: Halle, Bertil, Björling, Mikael
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/1.469738

Water-in-oil microemulsions, composed of discrete aqueous droplets dispersed in a continuous oil medium, constitute a special class of electrolyte solutions. Such macroelectrolytes are analogous to conventional electrolyte solutions in most respects, with the notable difference that, in a microemulsion, the ionic (droplet) charge is not fixed but depends on the droplet interactions. Describing the microemulsion as a primitive-model electrolyte mixture with ions of variable charge and evaluating the statistical mechanics within the mean-spherical approximation (MSA), we construct a self-consistent theory of charge fluctuations and droplet interactions in ionic microemulsions. The droplet charge distribution is calculated as a function of the size, shape, polydispersity, and volume fraction of the droplets. We argue that the net droplet charges can have a decisive influence on microemulsion structure, especially at the higher volume fractions where clustering and spinodal decomposition are observed. At lower volume fractions, where the MSA treatment should be quantitatively accurate, the Coulomb interaction between charged droplets has no effect on the structure factor deduced from scattering data.