Phase behavior of weakly polydisperse sticky hard spheres: perturbation theory for the Percus-Yevick solution.
We study the effects of size polydispersity on the gas-liquid phase behavior of mixtures of sticky hard spheres. To achieve this, the system of coupled quadratic equations for the contact values of the partial cavity functions of the Percus-Yevick solution [R. J. Baxter, J. Chem. Phys. 49, 2770 (1968)] is solved within a perturbation expansion in the polydispersity, i.e., the normalized width of the size distribution. This allows us to make predictions for various thermodynamic quantities which can be tested against numerical simulations and experiments. In particular, we determine the leading order effects of size polydispersity on the cloud curve delimiting the region of two-phase coexistence and on the associated shadow curve; we also study the extent of size fractionation between the coexisting phases. Different choices for the size dependence of the adhesion strengths are examined carefully; the Asakura-Oosawa model [J. Chem. Phys. 22, 1255 (1954)] of a mixture of polydisperse colloids and small polymers is studied as a specific example.
Fantoni
Riccardo
R
Istituto Nazionale per la Fisica della Materia and Dipartimento di Chimica Fisica, Università Ca' Foscari di Venezia, Santa Marta DD 2137, I-30123 Venezia, Italy. rfantoni@unive.it
Gazzillo
Domenico
D
Giacometti
Achille
A
Sollich
Peter
P