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Langmuir, Vol.30, No.44, 13121-13124, 2014
Second Virial Coefficient at the Critical Point in a Fluid of Colloidal Spheres Plus Depletants
VliegenthartLekkerkerker (VL) criterion B-2 = -6v(c) for second virial coefficient B-2 at the critical (colloidal) gasliquid point is considered for a mixture of spheres with volume v(c) plus depletants. For the onset of fluid-phase instability, the VL criterion holds for a wide range of shapes of direct attractive forces between hard-core spheres (Vliegenthart, G. A.; Lekkerkerker, H. N. W. J. Chem. Phys. 2000, 112, 5364). In the case of long-ranged attractions imposed indirectly via depletants, it is found that the VL relation fails. Instead, B-2/v(c) at the critical point depends strongly on the sphere/depletant size ratio. By making the hard spheres sticky, we find that B-2 moves gradually toward the VL criterion upon increasing the stickiness.