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Phase diagrams of charged colloids from thermodynamic integration

A-P Hynninen1 and A Z Panagiotopoulos2

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We present full phase diagrams (including solid phases) of spherical charged colloids, using Monte Carlo sampling and thermodynamic integration of the Helmholtz free energy. Colloids and their co- and counterions are described by the primitive model for ionic systems that consists of hard-spheres with central point charges, while the solvent is taken into account solely through its dielectric constant. Two systems are considered: (i) a size-asymmetric system of oppositely charged spheres with size ratios q = 0.3 and 0.5 and (ii) a charge- and size-asymmetric system with colloid charge Q = 10 and counterions of charge −1 in the presence of monovalent added salt. In system (i), for both size ratios, the stable solid phase is equivalent to the NaCl crystal where the oppositely charged spheres take the lattice positions of Na and Cl ions. In system (ii), the phase diagram consists of gas–liquid and fluid–solid coexistence regions. We show that added salt stabilizes the fluid phase and shrinks the fluid–solid coexistence region, in agreement with experimental and theoretical results.


PACS

82.70.Dd Colloids

65.20.-w Thermal properties of liquids

82.70.Kj Emulsions and suspensions

77.22.Ch Permittivity (dielectric function)

Subjects

Soft matter, liquids and polymers

Condensed matter: electrical, magnetic and optical

Chemical physics and physical chemistry

Dates

Issue 46 (18 November 2009)

Received 9 June 2009, in final form 17 September 2009

Published 26 October 2009



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