On the fluid-fluid phase separation in charged-stabilized colloidal suspensions

Details On the fluid-fluid phase separation in charged-stabilized colloidal suspensions On the fluid-fluid phase separation in charged-stabilized colloidal suspensions

2004-01-12

arxiv.org/abs/cond-mat/0401175v1

J. Phys: Condens. Matt 15, S3523 (2003)

Physics

Condensed Matter

Soft Condensed Matter

Scientific paper

10.1088/0953-8984/15/48/012

We develop a thermodynamic description of particles held at a fixed surface potential. This system is of particular interest in view of the continuing controversy over the possibility of a fluid-fluid phase separation in aqueous colloidal suspensions with monovalent counterions. The condition of fixed surface potential allows in a natural way to account for the colloidal charge renormalization. In a first approach, we assess the importance of the so called ``volume terms'', and find that in the absence of salt, charge renormalization is sufficient to stabilize suspension against a fluid-fluid phase separation. Presence of salt, on the other hand, is found to lead to an instability. A very strong dependence on the approximations used, however, puts the reality of this phase transition in a serious doubt. To further understand the nature of the instability we next study a Jellium-like approximation, which does not lead to a phase separation and produces a relatively accurate analytical equation of state for a deionized suspensions of highly charged colloidal spheres. A critical analysis of various theories of strongly asymmetric electrolytes is presented to asses their reliability as compared to the Monte Carlo simulations.

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