Dynamics of Adsorption of Colloidal Particles in Packed Beds

RAJ RAJAGOPALAN 1 AND RICHARD Q. C H U

Department of Chemical Engineering, Rensselaer Polytechnic Institute, Troy, New York 12181
Received February 18, 1981; accepted August 13, 1981

This paper presents a combined theoretical and experimental study of deposition of colloidal
particles in packed beds. It is shown experimentally that the rate of deposition declines rapidly
with surface coverage even when the surface forces are favorable for deposition and that this decline
is largely due to an excluded-area effect introduced by the surface-borne particles. The experimental
data reveal that the above decline in the local rate can be expressed adequately in terms of a
"desorption" term (that is linearly proportional to the surface concentration) in the rate equation;
the coefficient of proportionality can be estimated a priori through a charge balance on the grains.
In addition, the (local) rate of transport of the particles toward a typical grain in the bed is repre-
sented in the rate equation in terms of a cell model for the porous media. The above rate equation,
in combination with an overall elemental mass balance in the bed, leads to a linear-chromatography-
approximation for the dynamics of deposition in packed beds. This formalism permits one to take
advantage of the extensive amount of work on packed bed adsorption already available in the
literature and also leads to a closed form solution to the deposition problem. Although the experi-
mental data reported here are obtained for deposition from aqueous suspensions, our experimental
and theoretical results are shown to be in general agreement with a recent experimental study on
nonaqueous suspensions as well.

The use of packed beds and porous media
for the physical separation of colloids dis-
persed in liquids has been known for some
time. This method of separation was origi-
nally thought to be dominated only by
mechanical modes of separation and con-
sequently the mechanics of the deposition
phenomena was the first to attract the sci-
entists in this area [see Rajagopalan and
Tien (1) for an extensive review of the mod-
ern theories of packed bed filtration]. How-
ever, experience over the years has amply
demonstrated that the deposition rate in this
phenomenon (and in other related phe-
nomena such as mutual coagulation, bac-
terial and viral adsorption, and fouling of
heat exchanger and mass transfer surfaces)
is critically influenced under certain cir-
cumstances by the physicochemical inter-
actions between the suspended particles and
1 To whom correspondence should be addressed.
299
Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
the retaining substrates. Most important
of these interactions for the case of deposi-
tion (or adsorption) are the long-ranged
forces such as London-van der Waals
attraction and coulombic (electrostatic)
attraction or repulsion. (The L o n d o n -
van der Waals interaction can be repulsive
when the solvent-substrate and the solvent-
particle intermolecular forces are stronger
than substrate-particle forces. However,
this is extremely rare in the types of sepa-
ration problems that form the focus of this
paper.) Shorter-ranged forces such as Born
repulsion and "hydration" forces usually
exert no influence in this case but are
thought to be relevant in the case ofdesorp-
tion of already adsorbed particles.
The calculation of deposition rates in
packed beds can be accomplished by divid-
ing the process of deposition into two
sequential s t e p s - - a transport step, in which
the particles are transported from the bulk of
0021-9797/82/040299-19502.00/0
Copyright © 1982 by Academic Press, Inc.
All rights of reproduction in any form reserved.
300
the liquid to the substrate, and an attach-
ment step, in which the particles overcome
any repulsive surface forces that may
prevail near the substrate and make contact.
The former is controlled by convection,
gravitational and buoyancy forces, drag,
and torque on the particle and diffusion (if
the particle is sufficiently small). The
attachment step, however, is usually dom-
inated by the surface forces and can be quite
critical in the case of submicron particles.
In the case of large particles (over about
2 p.m in size) the deposition rate can be
computed with the help of the equation of
motion of the particles. [This procedure
is called "trajectory analysis" and is de-
scribed in detail in Rajagopalan and Tien
(1, 2)]. An appropriate convective diffusion
equation replaces the trajectory equation in
the case of submicron particles, but in both
cases the calculations lead to only the rate
of transport of the particles to the sub-
strate. The actual deposition rate, on the
other hand, can be substantially lower when
strong repulsive forces dominate in the
interfacial region between the particle and
the substrate at short distances of separa-
tion, and this interfacial resistance and its
interaction with the transport step depend
on the shape of the surface potential pro-
files [Ruckenstein (3); Rajagopalan and
Kim (4)]. Rajagopalan and Kim (4) have
presented a simple equation for the net
adsorption rate applicable when the inter-
action potential has negligible secondary
minimum. Their calculations also show that
when the depth of the secondary minimum
is substantial (-~0.5 kBT) the influence of the
transport mechanisms extends into the in-
terracial region. This overlap does not sig-
nificantly decrease the resistance offered by
the surface interactions; however, it does
prevent one from obtaining the net adsorp-
tion rate in terms of simple asymptotic
solutions.
It must be emphasized that the above-
mentioned theoretical studies are confined
to the initial deposition rate (i.e., when the
Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
RAJAGOPALANAND CHU
particles begin to deposit on clean sub-
strates). In most applications this initial
period is a small fraction of the total time
involved and consequently the rate of depo-
sition on partially "loaded" substrates and
the mechanisms that affect this rate are
considerably more important from the prac-
tical standpoint. For instance, as discussed
in detail later in this paper, experimental
studies based on reasonably well-character-
ized substrates of simple geometry have
shown that the adsorption rate falls off very
rapidly as particles start accumulating on
the substrate, and one generally finds much
less than a monolayer coverage when the
substrate is completely saturated.
In the case of deposition in packed beds,
the complex geometry of the pores generally
promotes other (physical) mechanisms of
deposition (such as interception), and con-
sequently one might expect a combination
of the physical mechanisms and the previ-
ously mentioned surface chemical effects
to control the rate [see Rajagopalan and
Tien (1)]. In addition, it is not clear how
the observations based on experiments with
simple substrates of well-defined geometry
are to be extended to more complex situa-
tions prevailing in the tortuous pores of
packed beds. In fact, it would be desirable
to be able to design simple laboratory-
scale experiments (such as measurement of
deposition on rotating disks, for example)
whose results could be used to design large-
scale separators of more complex features.
The objective of this paper is to present
some theoretical and experimental observa-
tions which address the above, general goal.
In particular, our focus will be on obtain-
ing some (at least partial) answers to the
following questions:
(a) To what extent do the particles that
are already deposited in the pores of a
packed bed affect further deposition and
the rate?
(b) If a strong influence of this nature
exists, is it primarily due to the resultant
 ADSORPTION OF COLLOIDALPARTICLES
surface chemical changes or are there other
factors that should be accounted for?
(c) Can the surface chemical effects be
adequately accounted for by suitably adjust-
ing the charge density and the surface poten-
tial of the substrate?
(d) How does the limited amount of ex-
perimental data and observations available
on deposition on isolated substrates relate
to deposition in packed beds?
(e) Is it possible to predict the break-
through a priori?
A T H E O R E T I C A L T R E A T M E N T OF
ADSORPTION IN PACKED BEDS
Adsorption and desorption of colloidal
particles in packed beds can be treated theo-
retically from two different points of view.
The older of the two, the so-called "macro-
scopic (or, phenomenological) approach,"
is based on a mass balance on an elemental
slice of the bed and follows the overall
(average) concentration history at any
arbitrary location in the bed. On the other
hand, the newer, "microscopic" approach
aims for a closer scrutiny of the individual
processes that occur in the interstices of the
bed and is based on an elaborately struc-
tured sequence of theoretical procedures
that start with an appropriate geometric
model of porous media. The advantage of
the latter is that the rates of adsorption
and desorption are not accounted for in
terms of undefined (or empirical) mass
transfer coefficients but are expressed in
terms of the relevant mechanisms that
cause the adsorption or desorption to occur.
Nevertheless, since one usually measures
only the concentration history in packed
bed operations, it is essential that the
microscopic procedure be integrated with
the macroscopic for comparing the predic-
tions with experimental results. Both these
methods are discussed in some detail in
Rajagopalan and Tien (1). What follows is a
brief treatment of a theoretical formulation
that combines the above two approaches
301
for interpreting the experimental break-
through curves reported later. The specific
model presented here is not discussed in
Rajagopalan and Tien (1); however, some
of the general concepts and the details on
relating the adsorption rate coefficient to
the individual collection mechanisms can
be found there.
Macroscopic Formulation o f Adsorption
in P a c k e d Beds
A mass balance on the flowing suspen-
sion in an elemental slice of the packed bed
leads to the familiar continuity equation:
OC OC pgas(1 -- e) OCs
--+u~--+ ---0, [1]
Ot Oz e Ot
where
ui = Us/e, the interstitial velocity in the bed
(us is the superficial velocity ob-
tained by dividing the volumetric
flow rate by the overall cross-sec-
tional area of the bed); assumed con-
stant across the cross-section,
as = the specific surface area; area (avail-
able for adsorption) per unit mass of
the grains of the bed,
c = concentration of the suspended parti-
cle in the liquid; number per unit
volume of suspension, and
cs = concentration of the captured particles
on the grains; number per unit area
of the grain.
Axial and radial dispersions and the radial
variation of concentration have been as-
sumed negligible in Eq. [1]. The term
(OCs/Ot) represents the local flux (i.e., at any
position z) as a function of time and has
to be defined in terms of the relevant param-
eters that determine the rate of deposition.
For our purpose here we shall consider a
simple rate equation of the type
Ocs
- kfc - krcs, [2]
Ot
where kf and kr are adsorption (forward)
Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
 302 RAJAGOPALANAND CHU

and desorption (reverse) rate coefficients is fairly homogeneous so that local varia-
which have to be specified as functions of tions in flow are negligible, kf and kr can be
the parameters that affect the deposition and assumed to be independent of the position.
resuspension mechanisms (see below). In addition, since the adsorption rate in
The choice of the above rate equation dilute dispersions is not affected by par-
implies that a specific mode of adsorption/ ticle-particle interactions, it is reasonable
desorption has been assumed, and thus Eq. to assume that it is directly proportional
[2] is more than a mere mathematical con- to the first power of the concentration in
venience. In particular, Eq. [2] assumes a the bulk, i.e., kf is not a function of c. On
simple interpretation for the kinetics of the the other hand, if this rate is affected strongly
deposition/resuspension process, namely, by the area available for adsorption (i.e.,
that the rates of deposition and resuspen- equivalently, by the number of particles
sion are linearly proportional to c and cs, already adsorbed on the substrate) the coef-
respectively (unless of course one chooses ficient kf may be expected to depend on cs.
kf and kr as functions of c and Cs). For convenience, we shall assume, subject
We shall see subsequently that this assump- to verification, that any such influence can
tion, although seemingly restrictive, is suf- be adequately represented by the "desorp-
ficient for interpreting and predicting tion" term " - k r c s " in Eq. [2], where kr is
experimental breakthrough curves. In addi- assumed constant.
tion, the form of Eq. [2], under appropriate Under these conditions one can relate
conditions on kf and kr (see below) and the coefficient kf to the various transport
boundary conditions, permits an analytical mechanisms (such as convection, gravity,
solution of the system of equations. diffusion, and London-van der Waals
Since the above form of analysis is com- attraction) using the theory developed by
mon in the theory of linear chromatog- Rajagopalan and Tien (1, 2):
raphy [see Aris and Amundson (5)], we shall Sh = 0.25 a 7k[1/8NT15/81)~
.~t SZ v LO 1"~ R I t :
refer to this model as the linear-chromatog-
raphy approximation. + 0.85 × 10-WbW~°'4Pe + A]laPe l/a, [4]
In addition to the above equations the where
following boundary conditions are taken to
Sh = kfdg/D. [51
be valid:
c =c0 at z = 0, t >0, A brief description of the conceptual basis
of Eq. [4] and how it is derived is pre-
c=0 sented in Appendix A; the notations are
for z>0, t=0. [3]
Cs = 0 explained in Nomenclature. The first two
terms on the right-hand side of Eq. [4] ac-
Microscopic Theories for Forward and count for deposition due to geometric
Reverse Rate Coefficients interception and gravitational force and
buoyancy [see (1)] and are important for
The solution of the set of equations
relatively large particles (~ 1/zm). Brownian
[1]-[3] for the concentration profiles c(z, t)
diffusion becomes progressively more im-
and c~(z, t) depends on the choice of the
portant for smaller particles and the third
form of the forward and reverse rate coef-
term, which results from the convective
ficients in Eq. [2]. More specifically, if kf
diffusion of the particles, becomes gradually
and kr are functions of c, cs, and t (and,
more significant in magnitude for sizes be-
possibly, of r and z as well), a numerical
low 1 p,m:
procedure may be necessary for obtaining
the solution. However, if the porous medium Sh = A]ISpe113; ap < 1 /.Lm [6]
Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
 ADSORPTION OF COLLOIDAL PARTICLES 303

Further, Eq. [4] has been derived under the c~.~at (i.e., Oc~/Ot = 0). The forward rate
assumption that there is no significant sur- coefficient, kf, is still defined by Eq. [4].
face interaction barrier against adsorption. It must be noted that if one wishes to
This restriction can be removed by using modify the surface potential of the grains as
the following equation, which has been sug- particles are adsorbed then kf would become
gested by Kim and Rajagopalan (6) for the an explicit function of time t. Then an
case of surface interaction potentials with analytical solution of Eqs. [ 1]- [3] is difficult
negligible secondary minima: to obtain. To avoid this and for the sake of
simplicity we shall assume, as a first ap-
Shnr/ Shr proximation, that Eq. [8] in combination
= 1 + 0.5NaB(NLo)exp(0.96Vmax), [7] with Eq. [2] describes the change in the
deposition rate adequately. We shall return
where
to this point in the Discussion section of
Shnr = Sherwood number when there is this paper.
no repulsion (Eq. [4]),
Sh~ = Sherwood number when repul- Solution f o r B r e a k t h r o u g h and
sion is significant, Saturation C u r v e s
B(NLo) = a function of the London group
Equations [1]-[3] can be solved easily
that depends on the shape of
using Laplace transform to obtain c(z, t) and
the potential of interaction
cs(z, t). In fact, the solution to Eqs. [1] and
= N ~ "~2 + 0.05N~,7; NLo < 2,
[3] with a more general rate equation was
V m a x = maximum in the interaction en-
presented by Thomas (8) in closed form
ergy profile, in multiples of
and is reproduced in Sherwood et al. (9).
kBT, and
For the case of the linear chromatography
N a = ap/ag.
approximation it reduces to
Expressions similar to the one for kf can n ( x , o) = C/Co = J ( ~ , [3) for ~->0
be obtained in terms of the surface poten-
=0 for ~<0 [9]
tials for the desorption rate constant, kr
[see Dahneke (7)]. However, as shown in and
the Discussion section of this paper, the
ns(x, z) = Cs/(Lco)
actual desorption of adsorbed particles is
negligible when favorable surface interac- =l-J([3, c0 for 0->0
tions exist between the substrate and the
=0 for ~<0, [10]
particles and consequently a high level of
where
theoretical sophistication for the determina-
tion of k~ seems unwarranted at this stage. a = P K f x , number of transfer units
In fact, it seems sufficient to look upon the up to position x, [11]
desorption term in Eq. [2] as a convenient [3 = Kr~, [12]
method of accounting for the decrease in P = (1 - E)pga~L/E, [13]
adsorption rate as surface coverage in- Kf = k f / u i , dimensionless forward
creases. If this is assumed, one can easily rate coefficient, [14]
relate kr to the saturation value of surface Kr = krL/ui, dimensionless reverse
concentration by rate constant, [15]
x = z/L, dimensionless axial distance, [ 16]
kr = kfco/Cs,sat, [8]
"0 = z - x, dimensionless "elapsed"
where it has been assumed that the local time, and [17]
bulk concentration c reaches Co as cs reaches z = uit/L, dimensionless time. [18]
Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
304 RAJAGOPALAN AND CHU

0.999
0.995 ......7~_~iI
~~-
--'-- 0.9980.99
0.98
~--~ 0"95
0.9
0"8
0.7
0"6
¢& 0.5
,g 0"4
0.3--
v
-3,
/ 0"2
0.1--

¢;/
0"05
0.02
0"01
0.005
0.002
0.001
2 5 I0 20 50 I00 200 500 1000

FIG. 1. The J function needed for computing the concentration profiles and breakthrough curves
[from (10)].

The function, J ( a , fl), in Eqs. [9] and [10] and saturation curves for most values of the
is defined by two relevant parameters, PKf and Kr.
The J function defined in Eq. [19] has
J ( ~ , fl) = 1 - e -~
f;
e-ffo(2(fl#)ll2)d#, [191 been studied extensively since the partial
differential equations satisfied by it (i.e.,
where I . ( y ) is the modified Bessel function Eqs. [1] and [2]) describe a wide range of
of zeroth order and argument, y. Figure I engineering operations such as ion exchange,
presents a plot of the function J ( a , fl) and adsorption in packed beds, and heat trans-
can be used to produce the breakthrough fer in cross flow heat exchangers. Klinken-

"°1 '" .... ' 'Sf"FY' '" ....

°'I 77 77
N
04

0.2 .....

o l - - - - r ~ , . I , , , i. ~,1 ~ . ~ .... I , . , I ....

I00 3(3 102 103 104 105
1"]= T - I

FIG. 2. Theoretical breakthrough curves, c/co vs ~: Effect of rate of transport. P = 4.18 x ]0+3;
Kr = 5 × 10-a; V a l u e s o f Kf: C u r v e (a): 1 x 10-a; (b): 5 x 10-4; (c): l × 10-a; (d): 5 x 10-3; (e): 1 x 10 -2.

Journal of CoUoid and Interface Science, Vol. 86, No. 2, April 1982
 ADSORPTION OF COLLOIDAL PARTICLES 305

0.8

_/_//S;,
Cs 06

OOo
~ . - , - + - T - - - - " r ' ~ ~ .--L--"'~, , , i,~i .~, , ..a" . . . . i
o.
I0 o 101 I0 z 10 3 I0 4

"~: r-I

FIG. 3. Theoretical saturation c u r v e s , Cs/Cs,sat VS "O: Effect of rate o f transport. The p a r a m e t e r s are
the same as t h o s e in Fig. 2.

berg (10) has presented a collection of use- Fig. 2. The "shallow bed" behavior repre-
ful asymptotic expressions for the J function. sented by curve a can result, for instance,
A table of some computed values is given from a low adsorption rate constant or low
in Sherwood et al. (9). Equation [19] can specific surface area available for adsorp-
however be evaluated without any difficulty tion, both of which can be caused by un-
using numerical quadrature. favorable surface conditions on the grains.
Figures 2-4 show a set of typical results The effect of variation in Kr is not shown
computed from Eqs. [9], [10], and [19] for since a change in Kr leads merely to an
a fixed value of Kr; the change in these pro- expedition or delay in the breakthrough
files is thus completely determined by the curve (a change in Kr amounts to a cor-
parameter PKf. A properly designed packed responding change in the capacity of the
bed, when operating efficiently, should lead bed). It can be shown from Eq. [19] that a
to a breakthrough curve of the type d or e in reduction (or an increase) in Kr is accom-

10-3 • ' • i .... [ • , , i .... I ' ' 'l .... I ' ' ' I .... I ' ' ' I

10-4

On s

Or

I0-~ I

I
I0 -6
I0 ° iot I0 2 IO 3 I0 4 I0 5

FIG. 4. Theoretical flux Ons/aTvs ~: Effect o f rate of transport. T h e p a r a m e t e r s are the same as t h o s e
in Fig. 2.
Journal of Colloid and Interface Science, V o l . 8 6 , N o . 2, A p r i l 1982
306
panied by an increase (or a reduction) in the
elapsed time, 7, in the same proportion, i.e.,
J(ot, K1~1) = J(c~, K2~2) implies that
~q~ = (K1/K2)~l.
Finally, it can be seen from Figs. 3 and 4
that the particles that are already adsorbed
on the grain begin to influence the net flux
relatively quickly. For example, in the case
of a sufficiently " d e e p " bed (say, curve e
in Figs. 3 and 4) the flux increases initially
at any location because of the gradual in-
crease in the local concentration; the influ-
ence of the surface-borne particles, i.e.,
- k r c s , is relatively unimportant at this
stage. However, as the surface concentra-
tion increases the rate of increase in the flux
begins to diminish (this occurs at ~ ~ 7
× 103 in Fig. 4 for curve e). Subsequently
the flux attains a maximum and begins to
drop because of the increasing competition
between the transport of particles toward
the grain and the retardation of adsorption
by the surface-borne particles. The sur-
face concentration in the case of curve e at
the onset of this retardation (i.e., at 9 = 7
× 103) is seen to be only about 10% of the
maximum (saturation) concentration (see
Fig. 3). Since usually the saturation con-
centration itself amounts to a relatively low
surface coverage (=20-40% of the area of
the substrate), it is evident that the adsorbed
particles begin to influence further adsorp-
tion at very low surface coverage (=2-4%).
We shall see later, during the discussion of
the experimental results, that this early
influence cannot be attributed to the surface
chemical change on the substrate and must
result from a geometric effect.
EXPERIMENTAL WORK
In order to examine the questions regard-
ing the decrease of deposition rate on par-
tially saturated substrates in packed beds
a series of experiments was conducted
using packed columns of uniform glass beads
and monodispersed suspensions. The de-
Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
RAJAGOPALAN AND CHU
tails of these experiments and some of the
data reported here are presented in Chu
(11). What follows below is a brief sum-
mary of the major points of the procedure
[20] used in these experiments.
The suspensions used in the experiments
contained monodispersed hydrous chro-
mium (III) oxide particles with an average
diameter of 0.3 ~m. The method of prepara-
tion of the suspension followed that given
by Demchak and Matijevi6 (12). Table 1
lists the physical characteristics of the
particles.
The packed bed column was an acrylic
(Plexiglas) cylinder with an inside diameter
of 2.57 cm and a packing height of 20 cm.
A Teflon screen (210-/zm mesh opening)
was used to support the beads in the column.
To distribute the feed suspension evenly
over the top of the column, a thin Teflon
disk with random perforations was placed
at the inlet head. Pressure and sample ports
were drilled down the length of the column
o n two sides. The port tubings were poly-
ethylene with an inside diameter of 0.086 cm.
The glass beads were obtained from Pot-
ters Industries, Inc. (see Table I). These
were washed with 5 × 10-2 M hot chromic
acid, rinsed thoroughly with deionized,
distilled water, washed with 4 × 10-1 M
nitric acid, and rinsed thoroughly again
with water. These were drained, covered,
and stored. Just before use, the cleaning
procedure was repeated and was followed
by an equilibration step. To ensure thorough
rinsing, the conductivity of the rinse water
was monitored; rinsing was stopped when
the conductivity approached that of fresh
water.
Care was taken to make sure that no metal
parts came into contact with the suspension
and the beads.
To load the beads, the column was first
filled with an electrolyte solution which
had the same concentration as that to be
used for the suspension of a particular run,
and then wet glass beads, previously equil-
ibrated as mentioned, were spooned in and
were packed hydrodynamically.
 ADSORPTION OF COLLOIDAL PARTICLES 307

TABLE I
Physical Characteristics of the Colloid and the Glass Beads

I. Hydrous chromium (III) oxide particles

Mean diameter 0,3 ~m

Salts used in preparation CrK(SO4)2.12H20
Specific gravitya 2,42 ___0.02
Shape Spherical
Size distribution 0,24-0.36 ttm

II. Glass beads

Source: Potter Industries, Inc. (Carlstadt, N. J. 07072)
Soda lime glass spheres (uncoated)
Technical quality, composition: (SiO2 72.8%
Na20 13.3
CaO 8.0
MgO 3.9
A1203 1.3
K20 0.3
S04 O. 1)
Density (sp. gray.) 2.46-2.49
Nominal diameter 500-355 ~m, average 400 #m
U. S. screen number 35-45
a Kolakowski and Matijevi6 (13).

Procedure 24 hr in a large volume of an electrolyte

Glass has a porous structure, which per-
mits the diffusion of ions in or out of it, and
an active charged surface; therefore, ad-
sorption or ion exchange may occur (14).
To maintain the composition of the ions in
the suspension to be fed into the column,
the glass beads were equilibrated first. This
was done by immersing the beads for at least
solution of the same concentration as that
of the feed suspension. The procedure was
repeated until the pH of the electrolyte
solution remained constant during the
equilibration period.
A schematic diagram of the deposition
apparatus is shown in Fig. 5. The feed
suspension flowed from the feed tank into

FEE0VALVE3 PUM~ I--VEE0 T'NK

PRESSUREPORTS--, [ ~ ~ --
coN.,o,. 4 ,.ow,

CONTROL V A L V E

FIG. 5. Schematic diagram of packed bed deposition apparatus.

Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
 308 RAJAGOPALAN AND CHU

meter. For large flow rates, a variable speed

drive pump was used; for low flow rates, a
gravity flow arrangement (Mariotti principle)
30 which maintains constant head was used.
2O
Experimental runs lasted roughly 4-15
hr. These runs were kept in the laminar flow
regions (Re ~< 1).
The Peclet numbers at the experimental
conditions were large enough to satisfy the as-
-I0 sumption that axial dispersion was negligible.

-30
FIG. 6. Zeta potential as a function of pH for the
Cr(OH)a particles used in the experiments. (At 250C;
1 × 10-4 M KCI; with HAc/NaAc buffer.)
the column. At various time intervals dur-
ing the run, samples from a particular bed
depth were taken and stored in 20-ml vials
for particle number concentration analysis.
Pressure was monitored with the mercury
manometer and the flow rate with the rota-
Methods o f Analyses
Determination o f particle number con-
centration. The number concentration of
the monodispersed hydrous chromium (III)
oxide particles was determined from angular
light-scattering-intensity measurements us-
ing a light-scattering duophotometer.
Particle electrophoretic mobility meas-
urement. The average electrophoretic mobil-
ity of the particles was measured using the
recently introduced System 3000 electro-
phoresis unit (manufactured by Pen Kem,
Inc., Croton-on-Hudson, N. Y.). The ap-
paratus is fully automated and average
mobility readings are received via a con-

TABLE II
Summary of Experimental Parameters and Observations

I. Experimental parameters
Length of the bed: 7-12 cm
Us 0. ! - 0 . 3 cm/s
E 0.35
Co 107-109 particles/cm 3
Electrolytes KC1, NaNO3; 10-4 M-10 -2 M
pH 3.5-10.5
T(°C) 20-25
Grain zeta potential - 2 5 - - 1 1 0 mV
Particle zeta potential - 3 0 - + 4 5 mV
Run time 4-15 hr

II. Experimental observations

kf (experimental) cm/s
5 X 1 0 - 5 - 5 X 10 -4
Theoretical prediction (from Eq. [6]) ~1.1-1.7 X 10-4 cm/s
kr 1 X 10-5-3 X 10-~ 1/s
c,.,,t (experimental) 7 X 107-7 X l 0 s particles/cm 2
[Based on charge balance: 1 X 10g-5 X 109 particles/cm 2]
Coverage at saturation (%): (experimental) 5-50%
Based on charge balance: 20-100%

Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
 ADSORPTION OF COLLOIDAL PARTICLES 309

I.O ' ' ' I .... I ' ' ' I .... I ' ' ' I .... I ' ~ ....

° °ATA
0.8

0.6
C o o o
Co
o o
0.4
o

0.2

O. , , llllll I i i I .... I , , I .... I , , , I,,,

IO ° I 01 I0 z IO 3 IO 4

'r] = "t- - I

FIG. 7. A typical experimental breakthrough curve for initially favorable surface inter-
action. The zeta potentials of the particles and the grains for the run shown were +38 mV and
-30 mV, respectively. The line shown corresponds to K~ = 4.5 × 10-4 and Kr = 1.5 × 10-3;
the theoretical value of Kf is 2.8 × 10-4; the actual capacity was 25.6%, whereas the value
based on charge balance (for a final zeta potential of + 10 mV for the grain) is 37.4%.

nected printer or CRT terminal. The instru- colloid/substrate systems. For instance,
ment is also capable of giving the actual the particles in a given batch of colloid,
mobility distribution for polydispersed sus- h o w e v e r carefully prepared, seldom have a
pensions using peripheral equipment (see single, well-defined zeta potential. As illus-
Fig. 8). A p H - z e t a potential profile for the trated by the measurement shown in Fig. 8,
hydrous chromium oxide particles is shown often a small fraction of the colloid has po-
in Fig. 6. tentials in a range favorable for adsorption,
Streaming potential measurements were even if one discounts the possibility of
used to determine the zeta potential of the heterogeneity of the substrate. As a result,
glass beads. experiments in which the average surface
Table II presents a brief summary of the potentials indicate conditions unfavorable
relevant experimental variables and param- for adsorption often lead to trace amounts
eters. An example of the experimental of adsorption that can in effect show a dif-
breakthrough curve is shown in Fig. 7. ference of many orders of magnitude in the
rates from those predicted theoretically.
DISCUSSION OF RESULTS This was in fact observed in our experi-
ments (see the comments under Fig. 8).
Initially Unfavorable Surface Interactions
H o w e v e r , whether adsorption rates under
Because of the exponential dependence of adverse surface interactions can be pre-
the adsorption rate on the interaction energy dicted accurately or not is o f minor con-
barrier, the initial deposition rate predicted sequence in many instances. For example,
by Eq. [7] becomes negligibly small when in the case of packed bed filtration one
the particles and the grains have potentials would not start the operation at unfavorable
of the same sign. In addition to the fact that surface conditions. In addition, even at
these low rates are difficult to measure, more advanced stages of adsorption (at
there exist other experimental difficulties which presumably the surface-borne par-
which restrict a meaningful scrutiny of the ticles would have changed the effective
rates of adsorption in similarly charged surface potential to a less favorable state)
Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
310 RAJAGOPALAN AND CHU

0.08 I ! bed" behavior (i.e., the initial exit concen-

0.07
Hydrous Chromium( I I I )
Oxide Particles
Radius, 0.15 pm
4- 0.06 pH =10.3
"6 1.4 M KCe
> behavior could have been modified by in-
E 0.05
o. 0.04
Z
I- 0.03,
(..)
rY
LL 0.02
0.01
-6O -40 - 20 O 20
PARTICLE ZETA POTENTIAL
mV
FIG. 8. An example of the actual zeta potential
distribution obtained for the colloid. Notice that for any
given value of the zeta potential of the grain a fraction
of the particles in this batch would have potentials
in the favorable region. In the particular experiment
(grain: - 4 5 mV) particles with potentials less than
about - 5 mV (numerically) or with positive potentials
would be expected to be adsorbed. About 5-10% of
the particles were in fact found to be adsorbed in the
experiment.
geometric effects seem to play a more domi-
nant role than surface chemical effects. In
view of these the discussion that follows
will focus primarily on adsorption under
favorable surface chemical conditions.
Initially Favorable Surface Interactions
When the grains and the particles are
oppositely charged, the adsorption rate is
completely transport-controlled. A typical
breakthrough curve for such a case is shown
in Fig. 7. As noted under Fig. 7 and shown
in Table II, the initial experimental mass
transfer coefficients in this case and in other
similar runs agree very well with the coeffi-
cients calculated from Eqs. [5] and [6]; it
was found that the empirical values were
generally within a factor of 2 from the theo-
retical ones. It is further evident that the
breakthrough curve indicates a "shallow
Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
tration is relatively high) because of the
relatively low deposition rate (the initial exit
concentration is equal to e-eKf). This
creasing the parameter PKf (i.e., by reduc-
ing the grain size, by increasing the particle
size, etc.). This, however, was avoided in-
tentionally since these changes are normally
accompanied by increased retention by
interception or gravitational effects, thereby
obscuring the primary objectives of this
study (listed in the beginning of this paper).
We shall return to the role of additional
transport mechanisms (represented by the
first two terms of the right-hand side of Eq.
[4]) later in this paper.
The Meaning of the "Desorption" Term
The eventual decrease in the adsorption
rate, signaled by the increase in the exit
concentration in Fig. 7, has been attributed
in the past to two possible effects:
(i) the desorption of adsorbed particles,
and
(ii) the progressive change in the surface
chemical state of the grain toward an un-
favorable condition.
However, the surface chemical conditions
that existed in the initial and subsequent
stages of the experiments discount the pos-
sibility of any significant desorption of the
adsorbed particles. In fact, our attempts
to wash the saturated bed using a solution
identical in ionic strength and pH to the
original suspension led to negligible desorp-
tion. Furthermore, experiments conducted
in our laboratory on adsorption on and
desorption from rotating glass disks show
that the captured particles are not resus-
pended in detectable amounts unless the pH
of the liquid is changed so that a strongly
repulsive interaction develops between the
substrate and the particles (15). These ob-
servations are also corroborated by the
evidence available in the literature. For
 ADSORPTION OF COLLOIDAL PARTICLES 311

example, the recently reported experi-

1.0
ments of Bowen and Epstein (16), in which
the escape of silica particles deposited on --Packed Bed Expt. "~\

smooth plastic substrates was studied using 0.9 - - - - - Using Charge Balance -
0 M s o r p t i O n in Channel Flow
a radioactive tracer technique, and the work 0 Rotating Disc Expt.
of Kolakowski and Matijevi6 (13) on the 0.8 ---Excluded-Area Model -
desorption of hydrous chromium oxide par- n

ticles (similar to the ones used in our study) ~- o.7

from glass beads both show that no desorp- c- 0
tion occurs under conditions similar to the ~ 0.6
ones maintained in our experiments.
As mentioned above, it has also been
~0 05
suggested previously that slow accumula- 0
tion of particles on the surface of the glass
o
beads gradually shifts the interaction to a I1~ 0.4

less favorable one (18). The assumption here \

is that the observed reduction in flux can be ~ 0.3
\ t~
traced to the changing ionic (charge) con- W

centration on the substrate because of the 0.2 \

continual arrival of particles with charges
of the opposite sign. Wnek et al. (18) have
attempted to incorporate this in their trans-
port equations for deposition in packed
beds. However, Wnek's (17) comparison
of this method with the experimental data
available at that time led to only partial
success. Wnek could indeed predict the time
for breakthrough sufficiently accurately
in the case of the data reported by Heertjes
and Lerk (19). But this method was in-
adequate for explaining the data of Burns
et al. (20). Although a part of this failure
is certainly due to the lack of sufficient sur-
face chemical data in (19) and (20), there
are other reasons for questioning the
adequacy of the charge-accumulation con-
cept for explaining the breakthrough suf-
ficiently accurately. In particular, our analy-
sis of the present experimental results and
those of Heertjes and Lerk (19), based on
the above approach, suggests the following:
(i) The charge balance is indeed helpful
for estimating the actual capacity of the
grain, and the capacity thus estimated can
be used to compute the magnitude of the
coefficient kr (using Eq. [8]). This value of
kr can then be used to determine the design
\
\
\
0.I
O 0.5 1.0
Fractional Saturation, O
FIG. 9. The rapid decline of the adsorption rate at
low surface coverage. (Notice that charge balance
alone is insufficient to explain this decline.) ©, Run
111-6 of (16)., rq, From (15)., - - - , From data shown
in Fig. 7.
parameters (such as time for breakthrough)
using the linear-chromatography approxi-
mation presented in this paper.
(ii) On the other hand, the charge-balance
concept is not sufficient to explain the rapid
decline in the adsorption rate as particles
accumulate on the substrate.
The latter observation is brought out
clearly in Fig. 9 which shows the actual
decline in the effective adsorption rate
coefficient as a function of the fractional
saturation. The effective adsorption rate
coefficient, for the rate expression given in
Eq. [2], is defined by
-~ - k~.c =
[(
k~ 1 ~ -c
Cs) c. [211

Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
312
Therefore, R, the ratio of kerr to the initial
coefficient, kf, is
R=(1 - ----krcs)kf
c "
The fractional saturation, 0, is defined as
0 = Cs/Cs,sat,
where the surface concentration at satura-
tion is obtained from Eq. [8]:
Ca.sat = kfco/kr.
(Notice that 0 = 1 does not imply a com-
plete monolayer coverage since Cs,sat may
not necessarily correspond to a complete
coverage of the substrate.)
The solid line in Fig. 9 shows the varia-
tion of R defined in Eq. [22] as a function
of 0. (The concentrations c and ca are ob-
tained from Eqs. [9] and [10], respectively.)
Also shown in Fig. 9 are the effective ad-
sorption rates obtained using other experi-
mental setups [rotating disk experiments
(15) and deposition in channel flow (16)] in
which the rates were measured directly. As
evident from this figure, the decline in R is
sharp and the qualitative behavior is identi-
cal regardless of the experimental technique
(the surface chemical conditions, however,
are quite similar in all cases). In contrast,
the effective adsorption rate computed on
the basis of the charge-accumulation con-
cept predicts a fairly constant rate until the
surface potential of the substrate becomes
large enough for the formation of a repul-
sion energy barrier.
This sharp drop in the rate and the fact
that the maximum surface coverage is gen-
erally only about 20-40% of the total area
available indicate that the rate and the satu-
ration are influenced heavily by what may
be called an "excluded-area" effect arising
from the finite size of the particles already
adsorbed.
E x c l u d e d - A r e a E f f e c t on the
Adsorption Rate
A particle already adsorbed on the sub-
strate reduces the area available for further
Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
RAJAGOPALAN AND CHU
adsorption by an amount that is generally
larger than its projected area. This effect,
which is the result of the finite size of the
[22] particle, has been called "the shadow effect"
by Tien et al. (21) in their work on aerosol
deposition. In the case of colloids this ef-
fect is enhanced by the ionic cloud sur-
[23]
rounding the adsorbed particle. An exact
solution to the problem of obtaining the
shielded area is very difficult and in fact is
not necessary for demonstrating the im-
[24]
portance of the excluded-area effect over
that due to charge accumulation. For our
purpose here we shall borrow a somewhat
simplified model already available in the
area of gas adsorption. Recently Thakur et
al. (22) have derived a simple expression
for the surface-shielding f u n c t i o n , f (p), for
the fractional area excluded by the adsorbed
molecules which occupy a fractional pro-
jected area of p:
f(p) = 1 - (1 - p) exp[-5p/(1 - p)], [25]
where p is defined as the projected area of
the adsorbed particles per unit area of the
substrate, i.e.,
p = cs~rag [26]
with
ap = particle radius.
Equation [25] allows, at saturation, a maxi-
mum coverage of 100% of the total area of
the substrate (i.e., f ( p ) = 1 implies that
p = 1)--a coverage that is clearly physically
impossible (even for a tightly packed mono-
layer coverage). Despite this, the area avail-
able for further deposition [i.e., 1 - f ( p ) ]
as predicted by the above equation de-
creases rapidly to a very small fraction of
the total area by the time p reaches roughly
0.35. This "saturation" coverage is consis-
tent with the magnitude of the maximum
coverage observed in our experiments.
Furthermore, a saturation coverage in this
range is also consistent with what one may
project for the present t h r e e - d i m e n s i o n a l
problem from the recent computer experi-
ments performed by Feder and Giaver (23)
on an analogous t w o - d i m e n s i o n a l problem.
 ADSORPTION OF COLLOIDALPARTICLES
This latter study, on the random sequential
filling of a two-dimensional region by non-
overlapping disks, shows that the "jamming
limit" (i.e., the value of p at saturation) is
approximately 0.55. In the case of random
filling of the surface with spheres--cor-
responding to the problem addressed in the
present paper--one would expect a smaller
jamming limit since the excluded area
depends also on the angle of arrival of the
particles (because of the protrusion of the
adsorbed particles in the normal direction).
Thus use of Eq. [25] for estimating the
shielded area is adequate.
If the adsorption rate is therefore as-
sumed to be proportional to the area avail-
able for adsorption, one obtains from [25]
OCs
Flux - - kfc[1 - f(p)].
Ot
Since, as mentioned above,
Cs,satTra~ -~ 0.35
one has, f o r p ,
p = 0.35Cs/Cs.sat = 0.350.
Equation [27] thus implies that the normal-
ized effective adsorption rate, R, is given by
R = keff/kf = (1 - g(O)),
where
g(O) = f(0.350).
Equation [30] is not restricted to any par-
ticular experimental arrangement as long as
the substrate can be assumed to be planar
with respect to the particle size and there-
fore should apply to all the data shown in
Fig. 9. The broken line on Fig. 9 shows
the prediction of Eq. [30]. Although the
excellent quantitative agreement (partic-
ularly for the data from the packed bed
experiment) is perhaps a little fortuitous,
the qualitative agreement itself offers a suf-
ficient support for the thesis that the ex-
cluded-area effect is more responsible for
the reduction in the adsorption rate than
the charge-accumulation effect.
313
A Priori Description o f the
Adsorption Dynamics
The above description implies that the
complete dynamics of the adsorption proc-
ess can be predicted in advance either by
assuming a rate equation of the type specified
in Eq. [27] or by using the original rate equa-
tion [2] in combination with kr = kfco/Cs.sat.
The latter is of course simpler than using
Eq. [27] since the functionf(p) in Eq. [27] is
sufficiently complex to preclude an analyti-
cal solution to the associated transport
equation.
With the choice of Eq. [2] as the rate
equation one obtains the closed-form solu-
tions specified in Eqs. [9] and [10]. The sur-
face concentration at saturation, needed for
estimating kr, can be obtained from
[27]
Cs.sat = Q/(Qp47ra~), [32]
where
Q = charge (per unit area of the grain)
[28]
necessary to take the surface po-
tential of the grain to the unfavor-
able region (coulomb/cm2), and
[29] Qp = charge density of the particle (cou-
lomb/cm2).
Equation [32] leads to saturation concentra-
[30] tions that are within a factor of 2 to 3 times
the experimental values (see Table II). The
choice of Eq. [2] and of the relations [8] and
[31] [32] for predicting breakthrough curves
rests on empirical evidence and is sufficient
for the determination of the relevant design
parameters. Although the conclusions pre-
sented here are based on experiments em-
ploying aqueous colloids, the recent experi-
mental results of Chowdiah et al. (24)
indicate that these are valid in the case of
nonaqueous colloids as well. A brief discus-
sion of their results follows.
Adsorption in Nonaqueous Systems
Chowdiah et al. (24) report experimental
results on the filtration of carbon particles
in tetralin through sand beds. Their theo-
retical procedure, which is an extension of
Journal of CoUoid and Interface Science, Vol. 86, No. 2, April 1982
 314
the one originally presented in (18), resorts
to a numerical solution of a slightly simpli-
fied form of the transport equation used in
this paper. A numerical solution is required
in their case since the associated rate equa-
tion has been written in terms of the progres-
sive accumulation of charges on the grain
surface. In addition, the rate equation con-
tains an empirical factor, f, which has been
included in order to remove the consistent
difference observed between the experi-
mental capacity and the estimation derived
from charge balance.
The theoretical calculations reported in
(24) predict both the breakthrough time and
the streaming potential of the bed at satura-
tion sufficiently accurately, although the
actual, local rate of deposition differs from
the predictions (as evidenced from the dif-
ference between the slopes of the computed
and the actual breakthrough curves). Never-
theless, Chowdiah et al. attempt to account
for the excluded-area effect through the
inclusion on the empirical factor, f, and their
observation that the macroscopic design
parameters can be estimated using a charge
balance supports the use of Eq. [32] sug-
gested above. In addition it is worth noting
that their conclusions are based on experi-
mental data on nonaqueous systems.
There is, however, one observation in (24)
that is at odds with our results and the re-
sults of Kim 05), Bowen and Epstein (16),
and Karis (25). While the latter studies in-
dicate that charge neutralization at the sub-
strate requires larger deposition than ob-
served experimentally, the experimental
results of Chowdiah et al. (24) are con-
sistently higher (by a factor of about 2.5)
than the theoretical estimates. It is possible
that this is due to the charge-independent
deposition mechanisms (such as intercep-
tion) that become significant at large values
of the particle/grain size ratio [as was the
case in (24)]. In fact, as observed by Chow-
diah et al., the charge-independent mecha-
nisms continue to operate even after charge
neutralization, and as a result the exit con-
Journal of ColloM and Interface Science, Vol. 86, No. 2, April 1982
RAJAGOPALANAND CHU
centration at the time of charge neutraliza-
tion is less than the inlet concentration. This
implies that deposition continues beyond
this point aided by the effects of the first
two terms of Eq. [4]. Eventually the bed
would lose its effectiveness as the pores
get blocked and simultaneously the inter-
stitial velocity would rise above the thresh-
old value beyond which further deposition
would decline rapidly [see (1) and (26)].
SUMMARYAND CONCLUSIONS
The experimental results and the theo-
retical calculations reported here on the
adsorption of hydrous chromium (III) oxide
particles on glass beads indicate that the
rate of adsorption declines very rapidly
due to an excluded-area effect introduced
by the adsorbed particles. This observation
is also consistent with similar experimental
data published in the recent literature.
Further, it is evident that the adsorbed
particles do not desorb readily unless the
physicochemical properties of the liquid are
so changed that a net repulsion between
the substrate and the particles develops.
These conclusions are not restricted to the
particular experimental system used in this
study.
In addition, this paper presents a simple
model with a closed-form solution that can
be used to predict the dynamics of adsorp-
tion of colloidal particles in packed beds.
A simple procedure is suggested for ac-
counting for the excluded-area effect men-
tioned above, and this leads to a linear-
chromatography approximation of the
packed bed adsorption problem (see Eqs.
[1] and [2] and the discussion following
them). Consequently, the full power of the
extensive theoretical analyses available on
this class of problems can be easily ex-
tended to the adsorption problem discussed
here. The conclusions of this paper apply
also in the case of nonaqueous systems
(24). The procedure for estimating the
capacity of the substrate (see Eq. [32] and
 ADSORPTION OF COLLOIDAL
related discussion) requires further study
since the excluded-area effect would be
expected to depend on the physicochemical
properties (such as ionic strength, p H , etc.)
of the suspension. H o w e v e r , this p r o c e d u r e
is adequate for estimating the time of break-
through, length of the bed, and other param-
eters that would be required for the design
o f p a c k e d bed filters.
NOMENCLATURE
a g = grain r a d i u s
ap = particle radius
as = specific surface area of the grain,
area p e r unit mass of the grain
As = a geometric factor that is used in
Eq. [4]; a function of bed
porosity, ¢; see Eq. [A.5]
B(NLo) = a function of the L o n d o n group,
NLo, defined following Eq. [7]
c = concentration o f particles in the
suspension; n u m b e r per unit
volume of suspension
Co = inlet concentration of the suspen-
sion (i.e., c at z = 0)
cs = concentration of particles on the
substrate; n u m b e r per unit area
of the substrate
Cs,sat = concentration on the substrate at
saturation
dg: diameter o f the grain, 2ag
D = Brownian diffusion coefficient of
the particles
f ( p ) = surface-shielding function defined
in Eq. [25]; a function o f the
extent of surface coverage, p
J = function defined in Eq. [19]; the
breakthrough curves are given
in terms of J
kB = B o l t z m a n n constant; 1.380458
× 10 -1G erg/°K
keff = effective adsorption rate constant
defined by (OcJOt) = keffc
k f = transport rate coefficient
k~ = rate coefficient that accounts for
retardation o f adsorption due
to the effect of surface-borne
particles
PARTICLES 315
K f = dimensionless k f defined in Eq. [ 14]
Kr = dimensionlesskr defined in Eq. [15]
L = length of the bed
n = dimensionless bulk concentra-
tion c; see Eq. [ 9 ]
ns = dimensionless surface concentra-
tion cs; see Eq. [10]
NG = gravity group defined in the
Appendix
NLo = L o n d o n group defined in the
Appendix
N a = ap/ag
p = fractional surface coverage de-
fined as projected area o f the
surface-borne particles per unit
area o f the substrate; defined
in Eq. [26]
P = dimensionless p a r a m e t e r defined
in Eq. [ 13]
Pe = Peclet n u m b e r used in Eq. [4];
see the Appendix
R = keff/kf
Sh = S h e r w o o d n u m b e r defined in
Eq. [5]
t = time
T = absolute t e m p e r a t u r e of the sus-
pension, °K
ui = interstitial velocity o f the sus-
pension in the bed, us/¢
us = superficial velocity of the sus-
pension in the bed, flow rate
per unit cross-sectional area of
the bed
Vmax = value of the m a x i m u m in the sur-
face interaction energy, in
multiples of kBT
x = dimensionless axial distance, z/L
z = axial distance
Greek letters
a = n u m b e r o f transfer units defined
in Eq. [11]
/3 = p a r a m e t e r defined in Eq. [12]
• = porosity of the bed
r/ = elapsed time defined in Eq. [18]
pg = density of the grain
r = dimensionless time, uit/L
Journal of Colloid and Interface Science, Vol. 86, No. 2, April 1982
316 RAJAGOPALAN AND CHU

0 = fractional saturation, defined as from which it follows that

Cs/Cs,sat
Sh = k f d g / D = (1/4)(1 - E)-2/3pe,], [A.7]
APPENDIX A: THE PHYSICAL AND where
MATHEMATICAL BASIS OF
EQUATION [4] FOR THE P e = Peclet number = usdg/D. [A.8]
SHERWOOD NUMBER
Equation [A.2] considers, as mentioned
As briefly outlined in the introductory in the text, the following three deposition
part of the paper the flux toward a typical mechanisms, each represented by the in-
grain in the bed can be obtained from the dicated dimensionless groups:
solution of the trajectory equation for the
particle motion. The fluid velocity field Interception: NR = ap/ag, [A.9]
necessary for these calculations is ob- Gravity and Buoyancy:
tained with the help of a suitable geometric
model for the packed bed [see (1) and (2)]. NG = 2a2p(pp -- pf)g/(9ftUs), [A.10]
One such geometric model is the so-called London attraction:
Happel sphere-in-cell model in which a
spherical grain of radius, as, is assumed to NLo = H/(9"n'/za~s), [A. 11]
be imbedded in a spherical liquid shell of where pp and pf are the particle and fluid
radius, b, where b is related to the porosity, densities, respectively, g is the fluid viscos-
E, and ag by ity, and H is the Hamaker constant.
b = ag(1 - E)-1/3. [A.1] One can add the transport rate due to
Brownian diffusion given by [see (1,27-29)].
Rajagopalan and Tien (2) present the flux
computed for this model in terms of the T~Diff = 4Als/3pe-213(1 - - E) 213 [A. 12]
following interpolating equation to those given in [A.2] to obtain the total
rI = ,rh{(2/3)N~oSN~ 1Is rate. Now, the combination of [A.2], [A. 12],
and [A.7] leads to the expression for Sh
+ 2.25 x 10-3N~'ZN~Z'4}, [A.2] given in Eq. [4] in the text.
771 = interception efficiency
ACKNOWLEDGMENT
= 1.5N~A~(1 - e)z/3, [A.3]
We would like to acknowledge the timely support
where the efficiency, ~, is defined by of this work by the National Science Foundation
through Grant ENG77-06953. We are also grateful to
"0 = number of particles transported toward Dr. Ralph DeBlois of the Corporate Research and
the grain per unit time + 7rb2usco. [A.4] Development Center, General Electric Company,
Schenectady, New York, for bringing Ref. (23) to our
The factor As is a function of porosity and attention.
depends on the geometric model chosen.
REFERENCES
For the Happel cell model used above
1. Rajagopalan, R., and Tien, C., "Progress in Filtra-
As=2(1-yS)/(2-3y +3y 5-2y6), [A.5] tion and Separation" (R. J. Wakeman, Ed.),
Vol. 1, pp. 179-269. Elsevier, Amsterdam,
where 1979.
y = a g / b = (1 - E)1/3. 2. Rajagopalan, R., and Tien, C., AIChE J. 22, 523
(1976).
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