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6661
R T In y1 =
In this integral Nu is the number of solvent molecules in the system
of total volume V, ulu(r)is the potential energy of a molecule of
species 1 and a solvent molecule separated by distance r in the
absence of any other molecules (Le., a vacuum potential energy),
and gluois a weakened radial distribution function. We refer
elsewhere for the meaning of the weakening, or coupling, parameter X.30~31The important point for us here is the correspondence between the superscript on g and the limiting operation
of eq 39: glue, hence Zloo, reflects the mean potential energy of
interaction of a molecule of species 1 with a pure solvent environment (one mole of species 1 added to an infinite amount of
pure solvent). Note that when two different solvents are compared,
E l l j + ( I I u- ZlUo)
j- 1
(44)
The integrals I look just like Ila0in eq 43, but with j replacing
(r (and the obvious meanings for Nj and u,,) and without a superscript on g,,, the weakened radial distribution function for
solute molecules of species 1 and species j (where j can be 1 or
some other solute species). The first sum in eq 44, then, represents
the effect of solute-solute interactions in the solution at the
specified concentrations. These interactions are mediated by, and
so y 1 depends on, the solvent species, which appears implicitly
in g l j . The second term in eq 44 is the effect of the change in
solute-solvent interaction due to the nonzero concentrations of
all solute species.
The lattice theories for polymer adsorption of Roe and of Scheutjens and Fleer have been extended to include an electrical
term. Equilibrium segment profiles and adsorbed amounts are computed as a function of chain length, solvent quality, electrolyte
concentration, chain charge, surface charge, and adsorption energy. The most conspicuous difference with the adsorption
of uncharged polymers is that, due to the repulsion between chain segments, loop and tail formation is suppressed, so that
flat adsorption ensues with no influence of molecular weight. Addition of electrolytes screens this repulsion but very high
ionic strengths are required to approach the behavior of uncharged polymers. Agreement with experiments is satisfactory.
Introduction
The adsorption of polyelectrolytes is a matter of considerable
practical and theoretical interest. The phenomenon plays a role
in fields as disparate as water purification (adsorption of polyelectrolytes can lead to flocculation of particles, rendering them
more easily filterable), food technology (e.g., as emulsifiers in food
emulsions), pharmacy (also as emulsifiers), medical science (the
polyelectrolyte heparine is an anticoagulant), soil structure, paint
manufacture, etc. For a good understanding it is usually mandatory to have an insight into the conformation of the polyelectrolyte at the phase boundaries involved.
From the theoretical side, very few attempts have been made
to describe polyelectrolyte adsorption. The relatively most elaborate picture has been put forward by H e s ~ e l i n k - ~Although
this theory is able to explain a number of influences on the adsorption at least semiquantitatively, it has a number of limitations,
the most serious one being that a step function is assumed for the
polymer segment distribution in the adsorbate whereas this distribution is just one of the principal parameters sought. As in
Hesselinks model, Silberbergs4model does not contain an ab initio
derivation of the segment profile.
6662 The Journal of Physical Chemistry, Vol. 88, No. 26, 1984
i = 1, 2, ..., M , 1 representing the surface layer and the layers
beyond M constituting the bulk. Each lattice site can be occupied
by either a polymer segment or solvent molecule. In order to better
imitate real molecules, variations are possible in which polymer
segments occupy more than one site or where the small ions have
a finite volume. Backfolding is allowed, which is a restriction of
the theory, especially in the case of polyelectrolytes, but this
limitation is partly offset by the fact that it is also accepted in
the bulk to which all interfacial quantities are normalized. At
present, we discuss homopolymers only.
In SF theory, the conformation of a molecule is taken as fully
defined by the number of segments the molecule has in any layer
i. A molecule is counted as adsorbed if it has at least one segment
in i = 1. The probability P, of finding a certain conformation
c is given by
P, = w,
i = 1 2 3 4
n p;'
i1
with
w,
xoqx1F-1-q
(2)
In these equations, p I is the weighting factor for individual segments in layer i (referred to p* = p M + 1 = p M + 2 = ... l), also
called free segment probabilities. They represent the probability
of finding a segment in i if this segment were not covalently bound
in the polymer chain. ri is the number of segments that conformation c has in i. The factor w, accounts for the lattice-determined number of steps that can be made along the chain from
a certain site to the next: Xo is the fraction of the number of
possible steps remaining in i, XI is the same for a step from i to
(i + 1) or ( i - l), e.g., for a hexagonal lattice Xo = 0.50 and A,
= 0.25. r is the number of segments per chain and q the number
of steps in i, all of this applying for conformation c. The degeneracy of conformation c is related to w, through
a, = Lz'lw,
(3)
-2x((4O,) - 4*)
where
(4OA =
W01-+1X04O1 + X14O1+1
(4)
PI =
41(40M)-1 exP[-2X((41)
- 4O*)1 exP(~1,Xs)exP[-a(Yl
- Y*)l
(5)
bulk
4 4
01
J/.
at the plates and their average
(6)
where a. is the area of the unit cell. Counterions and co-ions are
considered point charges and distributed between these plate
charges according to Poisson-Boltzmann (PB) statistics. As a
rule, the full PB equation is used, Le., the Gouy-Chapman (GC)
approximation is analyzed. As this equation cannot be solved
analytically in our case, some computations have also been done
using the Debye-Hiickel (DH) approximation. It is along the
lines of the model to treat the bulk solution in equilibrium with
the adsorbate also as a repeating array of plate charges; here the
D H approximation is used throughout.
In order to verify the quality of some of the above model
assumptions, some computations have also been done with polyelectrolyte charges not confined to lattice layers but smeared
out over the cells and another one with small ions of finite sizes.
Figure 1 visualizes the model. Let us first consider the bulk
situation. Following Moller et a1.,I0 we introduce averaged
(10) Moller, W. J. H. M.; van Os, G. A. J.; Overbeek, J. Th. G. Trans.
Faraday SOC.1961, 57, 325.
The Journal of Physical Chemistry, Vol. 88, No. 26, 1984 6663
- It-
f a&/aoro = 0
a.e
(7)
(8)
yM(bulk side) =
where tois the permittivity of free space and e the relative dielectric
constant. As in the bulk the potentials are usually small, (9) will
be analyzed in the D H approximation. Defining the reciprocal
Debye length aslo
= (fi+
K'
+ fi-)e2/ttokT
+
(11)
e(ii+
+ ri-)/kT
Levine and Neale" pointed out that for the space between two
layers (1 1) is valid to lower potentials than for a semiinfinite space
near one plate, where fi+ = E-. The choice of b is equivalent to
choosing a value for the average potential in the bulk. As our
analysis contains only the difference in potential between bulk
and adsorbate, this choice is arbitrary and for sake of convenience
we set b = 0. This quantity does, however, play a role in describing
the Donnan potential between bulk polyelectrolyte and dialyzate
where the equilibrium electrolyte concentration equals 2fi+fi-/(fi+
fi-). Setting b = 0 implies that
+ jj+)
= fi-(l - j j - )
p+ = j j -
I jj*
(13)
(14)
- bulk side)]
K ~ M
(20)
- K ( $ ~
- 2qM(bulk side)).
with
fi+(
[d~(x)/dxl,i,, = -
d2y(x)/dx2 = K ' ~ ( x ) b]
(19)
(10)
b=
ale
2tto~kT
-[exp(Kro) - 1]-'
ule
2toK k T
-exp[rK(x - Xi)]
Y(X) =
u0e
(16)
ale exp[-K(x - xi)] + exp(-xro) exp[x(x - xi)]
2tco~kT
1 - exp(-nro)
=-
exp(-xx) (22)
This equation applies to the region between xi and xi + r,, for any
(1 1) Levine, S.; Neale, G. J . Colloid Interface Sci. 1974, 49, 330.
CEOKkT
6664 The Journal of Physical Chemistry, Vol. 88, No. 26, 1984
0-
;-.c.
rl
-81,
-10
10
,
20
1s
10
15
0.01 M. SF theory.
OF,
h l
The ( i in the last term derives from the fact that the first
layer is at r0/2 from the surface.
In the SF picture these potentials are substituted in (5).
If the Roe theory is used, the free energy is needed. Extending
(21) to a multilayer system having in each layer an excess of
charge over that on bulk layers amounting to (ai - a,) dX, if X
is the charging parameter, gives
dFeI = C+j(X)(aj i
US)
dX
20
(24)
a=l
- a*)
(25)
Results
Figure 2 is a typical example of a segment density profile. In
order to exaggerate the qualitative features the plot is made
semilogarithmic. The most conspicuous conclusion is that at low
salt content, where charge effects of the polyelectrolyte count most
heavily, a region of negative adsorption occurs. Significant adsorption takes place only in the layer(s) adjacent to the surface.
In other words, polyelectrolytes adsorb in flat layers because the
mutual repulsion between the charges on the chain inhibits loop
formation.
If electrolyte is added, the profile progressively resembles that
of an uncharged polymer. For a = 0, the part at low i is linear,
Le., the $i(i)distribution is exponential, but at large i @i decays
more slowly to its bulk value 4..
Considering the experimentally established fact that hydrophobic colloids are coagulated by not more than 0.2 M (1:l)
electrolytes, the very high salt concentrations that are needed to
screen the polyelectrolyte charges completely are unexpected.
However, this feature seems well-established; it is also observed
if the theory is modified such as to let each small ion occupy a
J
LA
I
The Journal of Physical Chemistry, Vol. 88, No. 26, 1984 6665
-2
:1,
r.10
O01. 1
Q.
lo-'
5~10-~
-8
10
15
20
Figure 5. Comparison between profiles in the Gouy-Chapman and Debye-Hiickel approximation. Poor solvent (x = 2) x, = 5 a = l, r = 100,
otherwise as in Figure 3.
-3t I rl
tails only
-5
I
5
10
15
2o
25
added. SF theory.
more extended decay for CY = 0 in the S F case. However, for
polyelectrolytes, loops and tails are suppressed and then the adsorbed amounts are almost indistinguishable. The difference in
depth of the profile minimum does not measurably contribute.
Figure 5 illustrates the effect of invoking the DH approximation:
it overestimates the potentials and therefore predicts too deep
minima and too low adsorptions in the first two layers.
An interesting feature is observed at high 4. (Figure 6 ) . In
this case the contribution of the tails to the profile has a maximum
beyond the generally observed minimum. The high potentials at
a short distance from the surface tend to expel tail segments from
that region, but further away, where potentials are low, the chain
can "curl up". This phenomenon can have some relevance for
colloid stability, notwithstanding the fact that there are only few
of them (about one per ten chains) so that on a weight basis they
contribute by less than 0.3% and hence are easily overlooked.
Typical adsorption isotherms are presented in Figure 7. They
are of the high affinity type if r is not too low and, in agreement
with the conclusions arrived at above, the plateau value is then
insensitive to r.
As is the case with the adsorption of the uncharged polymers,
a certain critical value of the adsorption energy parameter xs is
needed to let the polyelectrolyte adsorb at all, but once this critical
value has been surpassed, the adsorption rises sharply with x,.
e,,:
CM-
-- ------__
x*=4
c*.10-'
0 . 7 ~
0.60.5-
---->,=4
--------
.--2s=lo-'
--_----.
a. ( c i a , )
x = 0.5, r
6666
1 .o
c
0
01
-3
-2
J
0
-1
log ( c , l M )
-dY1
= - dY
dx
dx
(A3
6667
This paper continues our recent work on the kinetics of free-radical chain polymerization in the gas phase. As in the previous
work, we avoid having the involatile polymers condense out of the vapor phase by employing a cloud chamber technique
which allows us to study the kinetics under conditions such that there are so few polymers growing simultaneously that they
cannot encounter one another. We detect the arrival of individual product molecules by having them nucleate macroscopic
drops of monomer liquid. The arrival of product molecules is so discrete that signal averaging must be employed in the
determination of the rate. As in the previous work, the polymer is poly(viny1 acetate). In the present study we employ a
nonsteady technique in which the reaction is initiated by a pulse of photons. Among other things, this approach makes it
possible to determine the degree of polymerization of the polymer capable of participating, along with monomer molecules,
in the binary nucleation process and therefore makes it unnecessary to rely on a difficult nucleation theory. The monomer
supersaturation has been deliberatelychosen to be high, so that high enough rates could be achieved to allow the signal averaging
to be performed by hand. As a result, the polymers responsible for nucleation are small, containing only about six monomer
units.
1. Introduction
0022-3654/84/2088-6667$01.50/0