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Equation of state of charged colloidal suspensions and its dependence on the thermodynamic route
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View: Figures


Image of FIG. 1.
FIG. 1.

Effective pair potentials calculated using the MC simulations (squares), bare DLVO pair potential (dashed line), and DLVO with RJM effective parameters (solid line) for Z bare = 20, a = 10 Å, and λ B = 7.2 Å.

Image of FIG. 2.
FIG. 2.

Colloid-colloid pair correlation functions obtained using the MC simulations (Ref. 52) and the RJM-OZ approach, for (a) ρ s = 24.9 mM and (b) ρ s = 249 mM. In both cases, the bare charge is Z bare λ B /a = 21.6, and the volume fraction is η = 0.0084.

Image of FIG. 3.
FIG. 3.

Reduced osmotic compressibility as a function of the reservoir salt concentration ρ s for colloidal particles of radius a = 30 Å and bare charge Z = 1000. The colloidal volume fractions are: (a) η = 10−5, (b) η = 10−4, (c) η = 10−3, and (d) η = 10−2. We see a dramatic discrepancy between the predictions of the JEOS (solid lines) and the Kirkwood-Buff fluctuation theory (dashed lines), especially at intermediate salt concentrations and high volume fractions.

Image of FIG. 4.
FIG. 4.

Comparison between the osmotic pressure calculated using the JEOS, (solid line) and the explicit integration of Eq. (9) (dashed line), with the experimental results reported in Ref. 53. The reservoir salt concentration is ρ s = 8μM, while the Bjerrum length is λ B = 2.38 nm, the colloidal radius is a = 21.9 nm, and colloidal charges are: (a) Z = 34 and (b) Z = 40.

Image of FIG. 5.
FIG. 5.

Comparison between the osmotic compressibilities calculated using the JEOS Eq. (6) (solid lines); the JEOS with explicit ionic correlations Eqs. (6) and (17) (point lines); and the KB fluctuation theory, Eq. (9) (dashed lines). The radius of colloidal particles is a = 10 Å, the bare colloidal charge is Z = 1000, and the Bjerrum length is λ b = 7.2 Å. The volume fractions are: (a) η = 0.01 and (b) η = 0.05.


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Equation of state of charged colloidal suspensions and its dependence on the thermodynamic route