COLLOIDS

Colloids and Surfaces

AND
SURFACES
A
ELSEVIER A: Physicochemical and Engineering Aspects 95 (1995) 101-111

Interpreting titration data of aqueous latices by coupling

ionization and ion-exchange equilibria
Marc Hlavacek *, Pascal Chenevi6re, Michel Sardin, John Dodds
Laboratoire des Sciences du Gknie Chimique, CNRS-ENSIC, 1 rue Grandville, B.P. 451, 54001 Nancy, France
Received 2 December 1991; accepted 9 September 1994

Abstract

Suspensions of colloidal latex particles with weak acid (carboxylic) and/or weak basic (amine) groups on their
surface have been titrated with HC1. Analysis of the ionic composition of the liquid phase shows variations in the
Na ÷ and C1- concentrations associated with variations in the pH of the suspensions. A model reaction scheme is
proposed involving ionization of the surface groups and ion-exchange between the solid surface and the surrounding
liquid. The numerical solution of this system gives a reasonably good agreement ( _ 5%) with the experimental results.
The predictions of the model for the effects of the solids concentration and ionic strength are in agreement with known
results concerning the "suspension effect". The surface charge values obtained from the model suggest that care should
be taken when extrapolating measurements of the electrophoretic mobility of particles made at low solids concentration
to higher solids concentrations.

Keywords: Coupling ion-exchange equilibria; Coupling ionization equilibria; Latices; Titration data

1. Introduction omena under well-defined and constant conditions.

Engineering problems involving colloidal par-
ticles in suspension must take into account specific
interactions between the particle surface and the
surrounding solution. For example, the transport
of colloidal particles flowing through porous media
has been shown to depend strongly on double
layer interactions [1]. The electrical potential at
the shear plane, called the zeta potential [2], is a
key parameter of the physicochemistry which is
generally calculated from experimental measure-
ments of the electrokinetic mobility of particles by
DLVO theory [3].
Such an approach gives a good understanding
of the stability of suspensions and filtration phen-
* Corresponding author,
However, it is more difficult to apply to cases
involving transient changes in solution composi-
tion and when the interface composition is inacces-
sible. A case in point is in the design of
underground nuclear waste repositories. The con-
tainment of radionuclides in underground forma-
tions can be predicted when they remain in ionic
form, but it has been shown that they can attach
themselves to colloidal particles present in ground-
water and migrate over large distances [4]. To
deal with such problems it is necessary to have an
overall representation of the phenomena involved
in the transport, capture and even "creation" of
colloidal particles, together with the equilibria of
fixation of ions onto colloidal particles during
transit through ill-characterized natural formations
where groundwater composition varies with time
and place during migration.

0927-7757/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved

SSDI 0927-7757(94)03027-8
102 M. Hlavacek et al./Colloids Surfaces A." Physicochem. Eng. Aspects 95 (1995) 101-111
An approach to the characterization of colloidal
suspensions originally proposed by workers in soil
science [5-7] can be of interest for dealing with
this sort of problem. The chemical equilibria of the
ionic processes at the solid-liquid interface are
taken into account using the assumption that there
is a homogeneous ionization of weak acid, weak
base or amphoteric groups at the solid surface,
and a heterogeneous reaction involving complex-
ation and compensating ions (also called site bind-
ing) [5].
For a monoprotic weak acid S this complexation
reaction has the following form:
S + Na~ = S Na + + H~
Kr~a.rt = [ S- Na + ] [H~- ] / [ S] [-Nas+ ]
where the index "s" refers to the ions present at
the solid surface,
In addition to the chemical equilibria, the elec-
trostatic effects at the solid-liquid interface are
represented by a double layer model such as that
of Gouy-Chapman or Stern-Graham. The relation
between the ionic concentration at the solid surface
and in the bulk of the solution is represented by
the Poisson-Boltzmann relation. Rather curiously,
experimental work and modelling has mainly been
based on the H ÷ ion concentrations and pH
measurements in soils without considering other
ionic species. This loss in generality is perhaps at
the origin of the ambiguities noted by Westall and
Hohl [8], who showed that several different double
layer models or several different combinations of
equilibrium constants can give an adequate expla-
nation of the variation in pH values measured
experimentally.
Yet another approach to the modelling of ionic
equilibria, prompted by the widespread use of ion-
exchange resins, involves considering two distinct
phases (solid and liquid) and neglecting the detail
of the ionic distributions at the interface. The
phenomenological behaviour of strong acid or
strong base ion-exchange resins is well represented
in this way, and the theory is in current use for
the design of industrial ion-exchange processes for
water softening or demineralization. In the case of
weak acid or weak base resins, which are becoming
more and more important in fine separations,
Hellferich I-9] proposed a coupling mechanism
between surface ionization and ion-exchange
involving ionized groups. He suggested determin-
ing the ionization constants of the weakly ionized
sites by titrating the resins in the presence of a
high concentration of NaC1. This simplifies the
equations by allowing the concentration of Na ÷
and CI- in the liquid phase to be considered as
practically constant during the titration. More
recently a complete numerical solution of the prob-
lem has been proposed for the general case of a
variable salt concentration in the liquid phase
[ 10,11 ].
To our knowledge this approach has not been
fully exploited and in particular we feel that in
( 1) many cases colloidal particles which carry ioniz-
able sites (clays, bacteria, latex, etc ..... ) may be
considered to be finely divided ion-exchange resins
in suspension in the liquid phase. The study of the
effects of these reactions and exchanges in the
liquid phase may be considered to be a necessary
prerequisite to the application of double layer
theory for understanding physical interactions
between particles in suspension and the porous
medium through which they are flowing. To exam-
ine this idea with a view to applying it to colloid
migration in natural geological formations, we
considered itinterestingto study syntheticcolloidal
suspensions by the titration techniques used for
ion-exchange resins.
2. Coupling ion-exchange and ionization equilibria
As a first approach we assume that the colloidal
particles under study can be treated as weak resins
with a weak acid site S and a weak base site P.
This reasoning can be easily generalized to take
into account a greater number of sites. In the
following we only consider the overall solid and
liquid phases without taking into account the detail
of the ionic distribution at the interface. The double
layer is assumed to be part of the solid phase. Two
equilibrium mechanisms are taken into account:
ionization of the sites in the solid phase and ion-
exchange between phases.
 M. Hlavaceket al./ColloidsSurfaces A: Physicochem.Eng. Aspects95 (1995) 101-111
Ionization equilibria
SH = S - + H ÷
Ki.s = [ S - ] [ H + ] / [ S H ]
P + HzO = PH + + O H -
K,,p = [PH + ] [ O H - ] / [ P ]
Ion-exchange equilibria
Na + + H + = Na + + H +
KN~.n = [ N a + ] [ H + ] / [ N a + ] [ H + ]
C I - + OH = C I - + O H -
Kcl.OH = [ C 1 - ] [ O H - ] / [ C 1 - ] [ O H - ]
where H + and Na + (respectively O H - and C1-)
are the compensating counter-ions for the charges
S~- (respectively PH +) in the solid phase. The
overbar indicates the solid phase species; the liquid
phase species are not overlined. Concentrations
are in mol 1-1.
Conservation of sites S and P
IS]tot = [ S~-] '~ [SH]
[P]tot = [ PH+] + [P]
Conservation of ions Na ÷ and Cl-
[Na + ] t o t = [Na ÷] + [Na + ]
[C1-]tot = [C1-] + [ E l - ]
The total concentration of chloride ions [C1-]tot
changes during the course of the titration by
addition of the titrating solution HC1.
Electroneutrality in the solid phase (compensation
of each ionized site charge)
[H +] + [Na +] = [S~] (6a)
[ C 1 - ] + [ O H - ] = [ - P H +]
Water dissociation
H + + OH- = H20
Kw = [H +] [ O H - ]
Electroneutrality in the liquid phase
[Na +] + [H +] =[C1 ] + [ O H - ] (8)
In Eqs. (4a) and (4b), IS- ] represents the cationic
103
ion-exchange capacity and [PH ÷ ] represents the
anionic ion-exchange capacity. Taken together, as
for example in Eqs. (6a) and (6b), they represent
(2a) the overall zwitterionic nature of the surface. The
total surface charge ao (in C m -z) is given by
eNa p
(2b) ao - ([PH + ] - IS-]) (9)
as C
where Na is the Avogadro number, p is the density
of the particles, C is their mass concentration in
(3a) the suspension, e is the charge on an electron and
as is the specific surface of the suspension (for
monodisperse spherical particles a t = 6/d, where d
(3b) is the particle diameter).
This system of simultaneous non-linear Eqs
(2a)-(8) has been solved by a computer program
called HYBRID which was developed in our labora-
tory and is fully detailed elsewhere [ 10,11 ]. This
determines the concentrations of the various
species in the two phases at each addition of
titrating solution.
(4a) 3. Determination of the system parameters
(4b) The mathematical formalism used here is basi-
cally the same as that for an isolated equilibrium
(5a) reaction, although further calculation is required
because the reactions considered are not indepen-
(5b) dent. The set of Eqs. (2)-(8) can be solved by a
trial and error procedure if we start with an
adequate estimation of the system parameters.
That means we must have some idea of the equilib-
rium constants (Ki,s, Ki,p, KNa,H, Kcl,OH)_the con-
centrations of each type of site ([S]tot, [P]tot) and
the counter-ion concentrations in the system
([Na+ ]tot, [[C1- ]tot), so as to be able to calculate
the system variables (pH, [ H + ] , [ O H - ] , [ O H - ] ,
(6b) [ N a + ] , [ N a + ] , [C1-], [C1-], [ S - ] , [SH],
[ P H - ] , [P]). This identification of the system
parameters and variables is similar to that of James
and Parks [7].
Fig. 1 gives an illustrative example of the method
(7) and shows the variation in the composition of the
liquid phase during the acid titration of a suspen-
sion of particles with one site S and one site P.
The curves were obtained by solving the set of
Eqs. (2)-(8) at each addition of an aliquot of HC1,
104 M. Hlavacek et al./Colloids Surfaces A." Physicochem. Eng. Aspects 95 (1995) 101-111

ratio 2.0 --
pH / phi ..." ....... "'"
Na + / Na+i .,..
C1- / Cl'i . . . . . . . . . " ' ~ - ~

1.5
.°

1.0

0.5

• . . . . .

o.o ! ! i ! I
0.0 0.2 0.4 0.6 0.8 1.0

ratio; acid added / total acid added

Fig. 1. Illustrative example of calculated variations in the composition of the aqueous phase during titration with HC1. Concentrations
of the ionic species are normalized to the initial composition (index i). , titration with suspended solids; ..., titration without
suspended solids.

by means of the program HYBRID. It would also
be possible to plot any other system variable such
as [ S - ] or [ P H + ], and thus determine the surface
charge density by means of Eq. (9).
In practical situations the reverse problem is
posed: how to calculate the system parameters
from the liquid phase compositions determined
experimentally during a titration. Thus, if we con-
sider Fig. 1 to be the results from the titration
experiment, the first step in the analysis is to plot
the differential curves, both with and without sus-
pended particles, as shown in Fig. 2. It is obvious
that there are two regions in which H ÷ is con-
sumed: one at high pH corresponding to the release
of C1- into the liquid phase, and the other at a
lower pH corresponding to the release of Na ÷.
[ Na+ ]tot, [El-]tot are given by ANa + x Na + and
AC1- x CI~-, where ANa + and AC1- are taken at
the final value of pH.
As a first guess IS]tot and [P]tot can be taken
as being equal to [ N a + ] t o t and [ C 1 - ] t o t respec-
tively. This assumes that the titration is complete
over the range of pH used and, therefore, that the
differential curves of Na + and C1- should begin
and end with a plateau. In the case where the
titration is not taken to completion, for example
when the particles risk being damaged by a wider
range of pH, then [-S]tot or [P]tot have to be
estimated risk being damaged by a wider range of
pH, then IS]tot or [P]tot have to be estimated by
higher values. However, in general, most sites are
titrated between pH 10 and 2, and the evaluations
can be made by starting with the first estimations
which are gradually increased by a trial and error
comparison with computer simulations, until
values are found which match experimental data
at the initial and final pH values.
It is no straightforward matter to estimate the
equilibrium constants because we only have access
to the composition of the liquid phase. Thus only
apparent constants are available:
Kapp, s = Ki,s'KNa,n
SH + Na + --S + Na + + H + (10)
 M. Hlavacek et al./Colloids Surfaces A: Physicochem. Eng. Aspects 95 (1995) 101-111 105

1.0
ratio
/ffl + / M-l+i
6aNa+/ANa+i
ACI-/ ACI-i 0.8

0.6 - H+

0.4

0.2

0.0 I I I I ~ ' \1
2 3 4 5 ~6 7 18 9 lO
Ki,s Ki,p
pH

Fig. 2. Differential plot of the curves in Fig. 1 for titration with and without suspended solids. Two regions of H + consumption are
found corresponding to the release of Na + or the release of C1 into the liquid phase. The ionization constants of sites S and P are
shown (Ki,s, Ki,p).

Kapp,v = Ki,p'Kcl,o" have been used (obtained from Serva

+ C1- + H 2 0 = P H + + C1- + O H -
These equations result from coupling ion-exchange
and ionization, and correspond to the experimental
observations of the variations of p H and the release
of N a + and C1- into the liquid phase. Thus each
pair of ion-exchange and ionization constants
which satisfy Eqs. (10) and (11) will give the same
liquid phase composition. As suggested by the
literature [-9] we take the constants KNa,H and
KCLOH to be unity, allowing us to attribute the
values of the apparent constants Kapp,s, Kapp,P to
the values of the ionization constants Ki,s, Ki,p.
To do this, we assume an initial value of the
apparent constant for each site which is in the p H
range of the site. This is re-evaluated by trial and
error to give a good fit with the experimental
results,
4. Experimental
4.1. Colloids used and pre-conditioning
Three different types of commercial monosize
polystyrene lattices with ionizable surface groups
(11) Feinbiochemica, Heidelberg): latex No. 1 ( 1.05 ~tm)
and No. 3 (0.37 gm) are based on a m o n o m e r
having carboxylic groups, and latex No. 2
(0.21 tam) on a m o n o m e r having aromatic amine
groups.
These particles were pre-conditioned in a
0.5 m M aqueous solution of NaC1 in a series of
three separations/re-suspensions using a Sigma
202 MC centrifuge at 13000 rpm for 30 min. The
solid concentration was determined by drying and
weighing ( 2 4 h at 60 °C).
4.2. Acid-base titrations and analysis
A 200 ml sample of preconditioned particles of
known concentration (about 3 g 1--1) was agitated
under ambiant conditions, and then brought to an
initial p H of about 10 by addition of 1 N N a O H .
The titration with 1 N HC1 was started at this
point and taken to a p H of about 2.5, with
continuous measurement using an Orion SA 520
p H meter having an Orion model 501/L811 double
glass KC1 electrode. Titrating solution was added
in aliquots of 10-100 ~tl by means of a Gilson
106 M. Hlavacek et al./Colloids Surfaces A." Physicochem. Eng. Aspects 95 (1995) 101-111

precision micro-pipette and a 0.5 ml sample of the Ct- Na"

suspension was taken after each addition when the (meq.t") ,H
p H reading had stabilized. These samples were t5~- 12
centrifuged and the composition of the supernatant 32
solution was analyzed. A Varian model AA 20 I0, ,---(~ /'~
Atomic Absorption Spectrophotometer was used t3~- "o
to determine the concentration of Na + ions in the 2.4 '~o
range 0.5-2.5 mg 1 t, and the concentration of u i - ! o / ~ . ~ )
C1 ions was determined by means of a Dionex ~, ®
4000 Ion Chromatograph with a AS 4A column, is
All the equipment used in the titration and analyses 0.9[-t ~ e/° ~ o
was either in Nalgene or Pyrex glass washed with 0.8 o" " ° ' ~ ' ° - ' - o - - - - o ~
0.1 N HCI. The suspensions and solutions were 0.7 2
prepared with 18 megohm de-ionized water filtered
through a 0.22 ~tm membrane. 0 0.5 01 , ~ t ,
0 0.6 1.2 1.8 2.4
HCLadded(meq.e"l)
5. Experimental results Fig. 4. Variation in composition of the liquid phase during
titration of a suspension of latex No. 2 (3.76 g 1 1). The points
The results of the titrations are presented in are experimental results and the curves are predicted by
the model.
Figs. 3-5. It can be seen that latex No. 1 exhibits
a low capacity for N a + ion-exchange of 0.15 meq
1 1 between pH 8.5 and 4.5. The commercial infor- Na÷
mation for latex No. 2 indicated it as having only (meq.f") pH
2.6-
anionic sites, but the proton consumption at acid 12I
p H indicates a mixed cationic/anionic surface. This ]

Na+ 2.~ - 10t ( ~

(meq.f -') ,H ~-.---- •
1~ ? 12 81 / •
1.8. {
104 ~ 6l
0.95 - ''"o\

e ~ * 1.4- 41 ,~

iOo
0.90 - ~b~O .,.,.o .._.,._. o
S "o 21 t --o--
0.85 -
4 ~o 1£ - ~ I ! I
" ~ o ~ o t'2 z4 31s 4.a ~o z2
Ct80 - 2 HCI added(meq.{-')
i ~°s Fig. 5. Variation in composition of the liquid phase during
0.75 - 0 I I .. , t i titration of a suspension of latex No. 3 (3.20 g 1-1). The points
0 0.16 0.32 0.48 0.64 0.80 are experimental results and the curves are predicted by
HCLadded(meq.e-I) the model.

Fig. 3. Variation in composition of the liquid phase during

titration of a suspension of latex No. 1 (3.36 g 1-1). The points latex was also observed to flocculate at about p H 4
are experimental results and the curves are predicted by and showed rapid sedimentation when the stirring
the model, was stopped. Latex No. 3 has an Na + ion-exchange
 M. Hlavacek et aL/Colloids Surfaces A: Physicochem. Eng. Aspects 95 (1995) 101-111 107

capacity of 1.15meq 1-1 between pH 10 and 3
accompanied by a sudden drop in pH. This cation
exchange at alkaline pH suggests that the cation
sites re-associate in this region. The interphase
exchange of C1- ions is masked by the amounts
added with the titrating solution. Only a slight
change in slope can be observed at the start of the
titration of latex No. 2. With respect to the pH
curves, it is obviously difficult to precisely identify
the plateau zones and the inflexion points which
are sometimes used to determine ionization con-
stants 1-12]. As pointed out earlier, a much finer
analysis is carried out by working with the
differential curves of the H +, Na + and C1- concen-
trations in the liquid phase. Thus the i o n i z a t i o n
constants and the concentrations of each type of
site were determined by the procedure given above
and are summarized in Table 1. For example, it
was found that latex No. 2 can be described by
one type of cationic site at a concentration of
0.65 meq 1-1 having an ionization constant of
Ki.sl = 4 × 10 - 4 , and one type of anionic site at a
concentration of 0.9 meq 1-1 with an ionization
constant of Ki.pl=5 × 10 4. For lattices No. 2 and
No. 3, two types of cationic site, SI and $2, were
found,
6. Interpretation oftheresnits
The full lines in Figs. 3-5 have been calculated
using the parameters given in Table 1 and are in
good agreement with the experimental results given
as points. In particular, the electroneutrality and
mass balances predicted by the model agree with
the titrations to within +5%. Higher values of
concentrations may be attributed to the effects of
atmospheric CO2, in particular to species such as
CO3 and H C O 3 which are not taken into account.
The behaviour of latex No. 2 shows that it does
not contain only the aromatic amide groups indi-
cated by the makers. The cationic exchange sites
on the surface could be due to several causes: the
presence of adsorbed surfactants used in the
making or to stabilize the particles in storage;
the effect of the flocculation; the alteration of amine
groups to become cation exchangers. However,
despite this problem it can be seen that the rela-
tively simple reaction scheme proposed here with
a limited number of sites can account for the
variations in the composition of the liquid phase,
and take the electroneutrality and mass balances,
into consideration.
In the treatment used here, Na + ions are consid-
ered to take part in only one chemical reaction,
that is ion-exchange, whereas H + ions take part
in two reactions, ion-exchange and ion-adsorption.
If the latex particles with carboxylic surface groups
can be considered to be a weak acid then, by
definition, the weak acid anions tend to associate
with H + ions to form weakly dissociated com-
plexes. As a consequence there will be a specific
liaison with the H ÷ ions which is not the case with
Na + ions (see Ref. [-9], p. 162). Nevertheless, it
should be acknowledged that ion-adsorption
should be included in the reaction scheme when
polyvalent ions susceptible to covalent binding,
such as Ca 2 +, Pb 2 +, etc ..... are present. The ioniza-
tion constants determined here, which have values
of the order of 10 -8 and e v e n 10 - 1 2 for the Ki,sl

Table 1
Characteristics of the suspensions used in the titrations and parameters determined using the model

Latex No, 1 (1.05 ~tm) carboxylic Latex No. 2 (0.21 gm) aromatic amine Latex No. 3 (0.37 gm) carboxylic

$1 Ki, s l = 1 0 12 K i . s l = 4 x 10 -4 Ki, s l = 1 0 -8
[$1 ]tot =0.04 meq 1-1 [S1]tot =0.65 meq 1-1 [Sl]tot = 0.80 meq 1-
$2 K i . s z = 6 × 10 -8 Ki, s2=10 -3
[Sl]tot = 0.14 meq 1-1 [Sl]tot =0.35 meq 1-1
PI K~.p~=5 × 10 _4
[-Pl ]tot =0.90 meq 1-1
Cpar 3.36 g I 2 3.76 g 1-1 3.20 g 1-1

Cpar = solid concentration.

108 M. Hlavacek et al. /Colloids Surfaces A." Physicochem. Eng. Aspects 95 (1995) 101-111
of latex No. 1, may seem to be surprising for
carboxyl groups since equivalent values for organic
acids in solution are around 10-3-10-4 (pKcoo H=
3-4). Nevertheless, it should be borne in mind that
for molecular acids only one phase, the liquid
phase, is considered. This means that their ioniza-
tion constants are related to the H + concentration
of their environment, that is the pH of the solution.
In the case studied here the ionization constants
are defined with respect to the local H + concen-
tration at the surface of the solid, namely [ H + ] .
Hence, because the concentration at the surface is
much higher (in the order of 100 times greater at
a low ionic strength of about 10 -3 mol 1 1) than
that in the bulk solution, a true ionization constant
of 10 -s is only 10 -6 when defined with respect to
the pH, i.e. by replacing [ H + ] by [ H + ] in
Eqn. (2a). However, at higher ionic strengths the
ratio [ H + ] / [ H +] is less and the corresponding
ionization constant will be different from 10 -6.
The same discrepancies occur in the conventional
graphical analysis of pH plots is used to determine
the ionization constant of ion-exchange resins; a
different value for the ionization constant is
obtained for each ionic strength [13]. For these
reasons, estimated ionization constants based on
the graphical analysis of titration data only cannot
be considered to be the true thermodynamic
constants,
Considering the solid phase composition, the
model allows us to determine the concentrations
of the different species present which cannot be
directly measured by experiment. Whether these
are ionized or not determines the ion-exchange
capacity and the electric surface charge (Eq. (9)),
both of which are very important parameters
involved in electrostatic interactions and the sta-
bility of the suspension. The surface charge densi-
ties can be calculated from the model and the case
of latex No. 2 is given in Fig. 6 for different titration
conditions. For all the curves the charge density
varies only slightly between pH 5 and 8, and has
a value of around 22.2 pC cm 2 corresponding to
a region where the sites are in the S- and PH +
forms at a stable concentration. The contribution
of the PH + form increases at more acid pH
whereas that of the S - form decreases. The oppo-
site occurs at alkaline pH. It can be seen that the
~ ~
~ ®
w latex n* 2
. ~ 23.c b
~,
~
t.,
~ 22.5
,~ ®
to | ~ ~ ~ ,)
22.o
F ' 3o 4.'0 2o do zb 80 9.0
Fig. 6. Numerical simulations of the charge density of latex
IQO pH
No. 2 during titration, for differentinitial ionic conditions and
solid concentrations. (1) pH19.92, [Na+]i=0.76meq 1 1,
ECl ]~=0.68 meq 1-1, 7.4 x 1011 partm1-1. (2) phi 9.92,
[Na+]i=7.6meq 1 1, [C1 ]~=7.5meq 1 ',
7.4 x1011part m1-1. (3) pH19.92, [Na+]i=76 meq 1 1,
ECl ]i=76meq I ~, 7.4 z 1011 part ml-1. (4) pH i 9.92,
[Na+ ]~= 0.38 meq 1-1, [C1- ]i= 0.31 meq 1-1 ,
7.4x 10" partml 1. (5) pHi9.92, [Na+]i=0.76meq 1-1 ,
[Cl ]~=0.68 meql ~, 3.0 z 10~2part ml-1..
charge depends on both the ionic strength and on
the solid concentration. This may seem surprising
for those used to using strong acid ion-exchange
resins where the ion-exchange capacity is constant,
but the idea of a variable ion-exchange capacity is
in agreement with the deductions of James and
Parks [7] who found that capacity depended on
both the pH and the ionic strength. This also
relates to earlier work [14,15], showing that the
composition of the liquid surrounding suspended
clay particles depended on the concentration of
the suspensions. These observations gave rise to
the term "suspension effects" and the empirical
rules derived for this are in agreement with the
theory developed here. For example, the pH of a
suspension could depend on the solid concen-
tration due to ion-exchange between the surfaces
of the particles and the suspending liquid. The
higher the solid concentration of the suspension,
the more likely it is that protons be consumed to
reassociate with the sites on the surface of the
particles. However, the addition of a salt to an
equilibriated suspension bearing type S sites would
 M. Hlavacek et aL/Colloids Surfaces A." Physicochem. Eng. Aspects 95 (1995) 101-111 109

displace protons from the surface by cation 4 " • latex n°l

exchange, thus causing the pH to fall. The sensitiv- -~ latex
ity of the pH of the suspensions to changes in the ~ 21~ ~ • latex n'3
ionic strength is very different from that is observed __---~ c ?='~lk,,.
with molecular acids and bases. In contrast to the
case of solid particles in suspension, molecules are
~'~°-2
"~ -\\.
*-*-.-| . . . . . . . . .
an intimate part of the liquid phase and ionic -~-4. ~-O--o-°-°--°
strength only has a limited effect on the pH. This ~r =.,~_= _
is demonstrated by the acid-base titration of pro- -6 4 6 8 10
tein solutions [16]. pH
When characterizing colloidal suspensions it is
necessary to consider electrokinetic measurements. Fig. 7. Electrophoretic mobility of latex No. 1, No. 2, and No. 3
as measured by Malvern Zetasizer IIC. Solids concentrations
In many practical cases it is the potential at the are 1% of those given in Table 1.
shear plane around a moving particle, or zeta
potential, which is the most important factor gov-
Oe Oo
erning the behaviour. The approach described (~.c/~,,~) (~.c/,,,~)
above has the disadvantage of being based on 0
hypotheses about the reactions occuring in a o.3s ---.'>. -'". -20
system which are only verified a posteriori. The - ' ~ t ~ ' % ~ X .'""'-~,,
surface charge is calculated from the solid surface 0.0 -40
-60
composition obtained by measurements of liquid -0.35 -
phase composition. A model of the double layer is ~ ~ -s0
therefore required to determine the zeta potential. -07o -100
Electrokinetic techniques, which measure the zeta a ~ ~ ~ 1o120
potential directly, remain the preferred and largely pH
predominant technique for characterizing colloids. Fig. 8. Variation in electrophoretic charge density (ere) and
One disadvantage is that m e a s u r e m e n t s a r e limited surface charge density (%) during titration at high and low
to dilute suspensions, although s o m e n e w tech- solid concentrations of latex No. 1: S o - - - , 3.36 mg 1 - 1 ; -
niques, such as acoustophoresis [, 17,18], have been 33 mg 1-1 (model simulation). ~re - I 1 - , 33 g l -x .
developed for measuring zeta potentials of particles
in concentrated suspensions; commercial instru- The electrophoretic charge density ae is the charge
ments are still rather rare and expensive, at a certain distance from the surface correspond-
To examine the correspondance between the two ing to the shear plane between the particle in
methods, the electrophoretic mobility of the par- movement and the surrounding fluid. This is taken
ticles used here has been measured with a Malvern to be approximately at the limit between the
Zetasizer IIC automatic laser doppler apparatus, compact (or Stern) layer and the diffuse layer. As
These measurements were made using particles the major part of the surface charge is compensated
treated in the same way as reported above, by counter-ions in the compact layer, then c% can
although, owing to the domain of measurement of be lower than the surface charge % by a factor of
the apparatus, the solid concentrations used were 100 or more [,6,20,21] depending on the concen-
100 times less. Fig. 7 shows the measured mobilities tration. Further, specific adsorption of ions in the
as a function of pH and these results were con- compact layer can lead to large variations in charge
verted to electrophoretic charge densities by the profile and even a complete charge reversal
standard method of Loeb et al. [19]. [,21-23]. Nevertheless, we may asssume that c% is
Fig. 8 shows the electrophoretic charge density the consequence of ao, and is subject to the same
of latex No. 1 deduced from the electrophoretic variations, meaning that the curves have the same
mobility and the surface charge density, as deter- shape (Fig. 8). The same sort of relation between
mined by titration and the model presented above, a~ and % has been found for latex No. 2 and No. 3.
110 M. Hlavacek et al./Colloids Surfaces A: Physicochem. Eng. Aspects 95 (1995) 101-111
In addition, as mentioned above, a o also depends
on the solid concentration, which probably affects
the position of the shear plane and consequently
the value of the electrophoretic charge,
Unfortunately this variation could not be directly
measured owing to the restricted domain of solids
concentration which can be used in the instrumen-
tation available,
This comparison indicates that there is reason-
able agreement between the method based on
measurements of the liquid phase composition and
electrophoresis. However, it also shows that a
rather delicate problem is posed when dealing with
concentrated suspensions by extrapolating electro-
phoretic charge measurements made on dilute sus-
pensions, where the liquid phase composition is
fixed with regard to pH or ionic strength [3]. In
concentrated suspensions the liquid phase
exchange capacity will play the role of a buffer
and may influence the liquid phase composition;
thus the state of the suspension which will not
only depend on the initial liquid composition, but
will also be the result of a complex series of
equilibria.
7. Conclusions
We have shown that variations in the composi-
tion of the liquid phase which occur during acid--
base titrations of the latex suspensions studied here
can be explained by a mechanism involving weak
acid or base ion-exchange reactions coupled with
surface ionization. Identification of the sites
involved and their thermodynamic constants
allows a good quantitative prediction of the experi-
mental results, and gives an explanation of the role
of ionic strength on the pH curves and an indica-
tion of the state of the solid surface. Ion-adsorption
has not been considered as it is generally negligible
for Na + ions and is not needed to interpret our
experimental results. However, when polyvalent
ions are present, e.g. Ca 2+, P b 2+, etc., such a
mechanism should be included in the reaction
scheme.
Systems involving colloids are often complicated
owing to the diversity of possible phenomena. In
the case of transient and complex solution condi-
tions, we feel that a global approach to equilibria
in colloidal suspensions by the method used here
(extended to include other groups such as ampho-
teric sites and other reaction mechanisms) will aid
in understanding their properties and behaviour.
A possible extension of this work would be to
compare the results of electroacoustic measure-
ments on concentrated suspensions with those from
the titration method, which would allow a more
direct comparison with measurements of the zeta
potential.
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