2 research outputs found
A simulational and theoretical study of the spherical electrical double layer for a size-asymmetric electrolyte: the case of big coions
Monte Carlo simulations of a spherical macroion, surrounded by a
size-asymmetric electrolyte in the primitive model, were performed. We
considered 1:1 and 2:2 salts with a size ratio of 2 (i.e., with coions twice
the size of counterions), for several surface charge densities of the
macrosphere. The radial distribution functions, electrostatic potential at the
Helmholtz surfaces, and integrated charge are reported. We compare these
simulational data with original results obtained from the Ornstein-Zernike
integral equation, supplemented by the hypernetted chain/hypernetted chain
(HNC/HNC) and hypernetted chain/mean spherical approximation (HNC/MSA)
closures, and with the corresponding calculations using the modified
Gouy-Chapman and unequal-radius modified Gouy-Chapman theories. The HNC/HNC and
HNC/MSA integral equations formalisms show good concordance with Monte Carlo
"experiments", whereas the notable limitations of point-ion approaches are
evidenced. Most importantly, the simulations confirm our previous theoretical
predictions of the non-dominance of the counterions in the size-asymmetric
spherical electrical double layer [J. Chem. Phys. 123, 034703 (2005)], the
appearance of anomalous curvatures at the outer Helmholtz plane and the
enhancement of charge reversal and screening at high colloidal surface charge
densities due to the ionic size asymmetry.Comment: 11 pages, 7 figure
The electrical double layer for a fully asymmetric electrolyte around a spherical colloid: an integral equation study
The hypernetted chain/mean spherical approximation (HNC/MSA) integral
equation is obtained and solved numerically for a totally asymmetric primitive
model electrolyte around a spherical macroparticle. The ensuing radial
distribution functions show a very good agreement when compared to our Monte
Carlo and molecular dynamics simulations for spherical geometry and with
respect to previous anisotropic reference HNC calculations in the planar limit.
We report an analysis of the potential vs charge relationship, radial
distribution functions, mean electrostatic potential and cumulative reduced
charge for representative cases of 1:1 and 2:2 salts with a size asymmetry
ratio of 2. Our results are collated with those of the Modified Gouy-Chapman
(MGC) and unequal radius Modified Gouy-Chapman (URMGC) theories and with those
of HNC/MSA in the restricted primitive model (RPM) to assess the importance of
size asymmetry effects. One of the most striking characteristics found is
that,\textit{contrary to the general belief}, away from the point of zero
charge the properties of an asymmetric electrical double layer (EDL) are not
those corresponding to a symmetric electrolyte with the size and charge of the
counterion, i.e. \textit{counterions do not always dominate}. This behavior
suggests the existence of a new phenomenology in the EDL that genuinely belongs
to a more realistic size-asymmetric model where steric correlations are taken
into account consistently. Such novel features can not be described by
traditional mean field theories like MGC, URMGC or even by enhanced formalisms,
like HNC/MSA, if they are based on the RPM.Comment: 29 pages, 13 figure