Anal. Chem.
1997, 69, 361-363
Effect of Electrical Double-Layer Overlap on the
Electroosmotic Flow in Packed-Capillary Columns
Qian-Hong Wan*
Laboratory for Analytical Chemistry, University of Amsterdam, Nieuwe Achtergracht 166,
1018 WV Amsterdam, The Netherlands
A plug electroosmotic velocity profile is generally assumed
to be characteristic of capillary electrochromatography.
However, this ideal plug flow may be illusive in some
experiments with packed-capillary columns due to overlap
of electrical double layers in flow channels. We report
here a theoretical analysis of the double-layer overlap
effects in packed-capillary columns, which is based on
Rice and Whitehead’s theory of electroosmotic flow com-
bined with a capillary tube model for porous packing. The
results show that the electroosmotic velocity under the
influence of double-layer overlap depends strongly on the
operating parameters, which increases with the column
porosity, the particle diameter, and the electrolyte con-
centration.
In recent years, capillary electrochromatography (CEC) has
come to be appreciated as a promising separation method.1-7 In
this method, neutral solutes are carried through an open-tubular3
or packed-capillary column1,2 by electroosmotic flow and separated
by partitioning between the mobile and stationary phases. Owing
to the plug nature of this electrically induced flow, CEC offers
the potential to attain column efficiency much higher than that
possible with parabolic pressure-induced flow. Despite enormous
efforts devoted to the improvement of column preparation,1,2,4,6,7
CEC with packed columns is shown to be only marginally superior
to pressure-driven system in terms of plate height, and the
expected very narrow solute peaks have not been seen on a
routine basis. In our study of key factors which limit the
performance of CEC, we found electrical double-layer overlap
effects to be of particular interest, as they might contribute to
excessive peak dispersion in packed-column CEC.
The electrical double-layer overlap may occur when the size
of the flow channel is not significantly greater in magnitude than
the electrical double-layer thickness.8 This double-layer overlap
has detrimental effects in CEC not only because it causes a
reduction in the electroosmotic velocity, but also because it
induces a peak dispersion due to a transition of the velocity profile
from flat to parabolic. Although the double-layer overlap effects
* Present address: Department of Chemistry, Dalhousie University, Halifax,
Nova Scotia, Canada B3H 4J3. Email: wang@is.dal.ca.
(1) Jorgenson, J. W.; Lukacs, K. D. J. Chromatogr. 1981, 218, 209-216.
(2) Knox, J. H.; Grant, I. H. Chromatographia 1987, 24, 135-143.
(3) Bruin, G. J. M.; Tock, P. P. H.; Kraak, J. C.; Poppe, H. J. Chromatogr. 1990,
517, 557-572.
(4) Knox, J. H.; Grant, I. H. Chromatographia 1991, 32, 317-328.
(5) Yamamoto, Y.; Baumann, J.; Erni, F. J. Chromatogr. 1992, 593, 313-319.
(6) Yan, C.; Dadoo, R.; Zhao, H.; Zare, R. N.; Rakestraw, D. J. Anal. Chem. 1995,
67, 2026-2029.
(7) Liao, J.-L.; Chen. N.; Ericson, C.; Hjerten, S. Anal. Chem. 1996, 68, 3468-
3472.
(8) Rice, C. L.; Whitehead, R. J. Phys. Chem. 1965, 69, 4017-4024.
S0003-2700(96)00478-7 CCC: $14.00 © 1997 American Chemical Society
on electroosmotic flow in a cylindrical capillary tube were
discussed by Rice and Whitehead8 30 years ago, detailed studies
in the context of CEC have been limited.2,9 In this work, we
investigate the double-layer overlap effects in a packed column,
using a theoretical model in which the porous packing structure
is viewed as a bundle of capillaries of the size determined by the
local packing density so that the electroosmotic flow in the packed
column can be described by Rice and Whitehead’s theory.
Relative velocity, which is defined as the ratio of the electroosmotic
velocity with to that without the double-layer overlap effects, is
used to show the variation of electroosmotic flow with packing
density, particle size, and electrolyte concentration.
RESULTS AND DISCUSSION
The expression for the electroosmotic velocity in a cylindrical
flow channel has been derived by Rice and Whitehead8 as
[ ]
0rζE I0(κr)
u(r) ) 1- (1)
η I0(κa)
where 0, r, ζ, κ, E, η, r, and a represent respectively the
permittivity of a vacuum, the relative permittivity of the medium,
the zeta potential of the flow channel, the reciprocal of the
electrical double-layer thickness, the applied electric field strength,
the viscosity of the medium, the distance from the channel center,
and the radius of the flow channel. The cross-sectional average
velocity is then given by
u)
0rζE
η [
1-
2I1(κa)
κaI0(κa) ] (2)
In eqs 1 and 2, I0 and I1 are respectively the zero-order and first-
order modified Bessel functions of the first kind.
Asymptotic expansions show that the functions in brackets
approach unity for large values of κa. In these cases, eqs 1 and
2 are equaled, giving
0rζE
u∞ ) (3)
η
which is the usual result in the case of no double-layer overlap.
The relative velocity µ, by definition, is given by
(9) Stevens, T. S.; Coates, H. J. Anal. Chem. 1983, 55, 1365-1370.
Analytical Chemistry, Vol. 69, No. 3, February 1, 1997 361
Figure 1. Variation of relative velocity with electrokinetic radius.

Figure 2. Variation of relative velocity with particle diameter for

interparticle porosities of 0.26, 0.40, and 0.48 (from the lower to the
upper curve), where κ ) 0.10 nm-1 is assumed.

µ)
u
u∞ [
) 1-
2I1(κa)
κaI0(κa) ] (4)

The relative velocity has a limiting value of unity in the absence

of the double-layer overlap and approaches zero at extremely small
values of κa. In Figure 1, the relative velocity µ is plotted against
electrokinetic radius κa, which clearly shows that double-layer
overlap has a profound effect on electroosmotic velocity only in
the low range of κa. For κa ) 10, the electroosmotic flow is
reduced by 20%.
In order to evaluate the relative velocity using eq 4 in relation
to experimental conditions of capillary electrochromatography, one
needs to know magnitudes of flow channel diameters in a packed
column. As shown elsewhere,10 the mean channel diameter d may
be estimated by the following equation: Figure 3. Variation of relative velocity with electrolyte concentration
for interparticle porosities of 0.26, 0.40, and 0.48 (from the lower to
n the upper curve). (a) dp ) 1 µm; (b) dp ) 3 µm; (c) dp ) 5 µm.
d ) 0.42dp (5)
1-n
porosity. It appears that the channel diameter is directly propor-
where dp is the mean particle diameter and n the interparticle tional to the particle size, with the proportionality mainly deter-

362 Analytical Chemistry, Vol. 69, No. 3, February 1, 1997

mined by the interparticle porosity. The interparticle porosity of
a chromatographic column is known to vary widely, depending
on the packing method, particle shape, and size distribution.11
Due to the heterogeneous nature of the random packing, the
local values of porosity are even more variable and unpredictable.
As pointed out by Giddings,11 the geometrical complication of pore
structure has defied all efforts to come to grips with it mathemati-
cally, and our practical understanding of porosity must be limited
to inexact and intuitive concepts supported by experience. As a
starting point, we may consider simple models, such as regular
packings of uniform spheres. According to Graton and Fraser,12
the least compact arrangement of such spheres is that of simple
cubical packing with a porosity of 0.48, whereas the most compact
packing is the rhombohedral one (where each sphere is tangential
to 12 neighboring spheres), which has a porosity of 0.26. A
random packing of spherical particles in a chromatographic
column has an average interparticle porosity around 0.40, a value
falling in between these limits. It seems reasonable to assume
that the tightly fitted particles in the column will have a porosity
approaching the minimum value of 0.26. It is these densely
packed regions that become our concern, as the electroosmotic
velocities in these regions may be markedly reduced due to
double-layer overlap effects.
The effect of packing density and particle size on electroos-
motic velocity can be shown by substituting 0.5d from the above
equation for a in eq 4. The relative velocity is plotted as a function
of dp in Figure 2 for three porosity values between 0.26 and 0.48,
assuming κ ) 0.10 nm-1. The relative velocity is increased with
interparticle porosity in the lower range of dp. With respect to
the effect of particle size, all the curves show the same trend,
whatever the n values. The relative velocity increases rapidly with
dp at low dp values and more gradually for high dp values. From
the curves in Figure 2, it is also evident that the transcolumn
variation of electroosmotic velocity caused by the variation of the
interparticle porosity is less than 30% for dp > 1 µm. This
magnitude of variation is, indeed, very small as compared with
that in pressure-driven chromatographic systems, where the mean
velocity is proportional to the square of the channel diameter.11
However, the velocity inequality increases considerably with
submicrometer-sized particles as a result of a substantial double-
layer overlap occurring in narrow channels.
The electrolyte concentration affects the relative velocity
through the electrical double-layer thickness. The reciprocal of
the double-layer thickness is related to the molar concentration
(10) Wan, Q. H. J. Phys. Chem., submitted.
(11) Giddings, J. C. Dynamics of Chromatography; Marcel Dekker: New York,
1965; Chapter 5.
(12) Graton, L. C.; Fraser, H. J. J. Geol. 1935, 43, 785-909.
(13) Hunter, R. J. Zeta Potential in Colloid Science: Principles and Applications;
Academic Press: London, 1981; Chapter 2.
by eq 6 for an aqueous solution of 1:1 electrolyte at 25 °C:13
κ ) 3.29c0.5(nm-1) (6)
The values of µ as a function of log c were calculated by
substituting eq 6 for κ in eq 4, and the results are shown Figure
3 for three values of dp between 1 and 5 µm. These calculations
assumed the same values of n as in Figure 2. In general, the
relative velocity increases with the electrolyte concentration over
a reasonable range covered. As can be seen, electrolyte concen-
tration has a major influence on electroosmotic velocity for low
values of dp and n. In these cases, the use of higher electrolyte
concentrations is essential to minimize the undesirable effects of
double-layer overlap. However, the upper limit of allowable
electrolyte concentration is set by other factors such as thermal
effects and bubble formation. From these considerations, it is
obvious that electrolyte concentration is an important operating
parameter that needs to be optimized for best performance in
CEC.
In conclusion, the present theoretical study predicts that the
effect of electrical double-layer overlap on electroosmotic velocity
in a packed-capillary column decreases with increasing interpar-
ticle porosity, particle diameter, and electrolyte concentration. To
our knowledge, there exist no measurements of these effects
under the conditions specified here to confirm the predicted
trends, but we anticipate that systematic experimental studies
aimed at addressing the issues raised in this work will appear in
the near future. It is important to note that the theoretical model
presented here is highly simplified. No constriction of the flow
channel is taken into account, and that particles are of equal size
is assumed. Despite these approximations, the model provides a
detailed understanding of the dependence of electroosmotic flow
on various CEC operating parameters; therefore, we believe is a
useful starting point for the more refined analysis of double-layer
overlap phenomena.
ACKNOWLEDGMENT
I thank Professor H. Poppe (University of Amsterdam) for his
encouragement and support during the research. The work was
supported by a postdoctoral fellowship from the University of
Amsterdam. Part of the work was presented at the 5th Interna-
tional Symposium on High Performance Capillary Electrophoresis,
Orlando, FL, January 25-28, 1993.
Received for review May 16, 1996. Accepted November 7,
1996.X
AC960478E
X
Abstract published in Advance ACS Abstracts, December 15, 1996.
Analytical Chemistry, Vol. 69, No. 3, February 1, 1997 363