Virial expansion for charged colloids and electrolytes |
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Authors: | AG Moreira RR Netz |
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Institution: | Max-Planck-Institut für Kolloid- und Grenzfl?chenforschung, 14424 Potsdam, Germany, DE
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Abstract: | Using a field-theoretic approach, we derive the first few coefficients of the exact low-density (“virial”) expansion of a
binary mixture of positively and negatively charged hard spheres (two-component hard-core plasma, TCPHC). Our calculations
are nonperturbative with respect to the diameters d+ and d- and charge valences q+ and q- of positive and negative ions. Consequently, our closed-form expressions for the coefficients of the free energy and activity
can be used to treat dilute salt solutions, where typically d
+∼d
- and q
+∼q
-, as well as colloidal suspensions, where the difference in size and valence between macroions and counterions can be very
large. We show how to map the TCPHC on a one-component hard-core plasma (OCPHC) in the colloidal limit of large size and valence
ratio, in which case the counterions effectively form a neutralizing background. A sizable discrepancy with the standard OCPHC
with uniform, rigid background is detected, which can be traced back to the fact that the counterions cannot penetrate the
colloids. For the case of electrolyte solutions, we show how to obtain the cationic and anionic radii as independent parameters
from experimental data for the activity coefficient.
Received 6 September 2001 / Received in final form 20 May 2002 Published online 24 September 2002 |
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Keywords: | PACS 82 70 -y Disperse systems complex fluids – 52 25 -b Plasma properties – 61 20 Qg Structure of associated liquids: electrolytes molten salts etc |
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