JOURNAL OF POLYMER SCIENCE VOL.

XVIII, PAGES 527-534 (1955)

Sedimentation and Electrophoresis of Porous Spheres

J. J. HERMANS, Laboralorium voor Anorganische en Physiche Chemie,

Rijks Universiteit, Leiden, The A’etherlands

I. INTRODUCTION
Oseen’s‘ equations for the flow produced by forces acting on a liquid
have been used by Burgers,Z H e r ~ n a n s and
, ~ Kirkwood and Riseman4 to
account for the hydrodynamic interaction between chain segments in the
sedimentation of polymer molecules. According to these equations the
velocity v produced at a point r(x,y,z) by a force F acting at the origin is:
v = +
(8 7 r~ r)-l(F (F-r)r/r2] (1)
where q is the viscosity of the liquid. Kirkwood and Riseman’s procedure
consists in deriving an integral equation for the force F. In the following
we will use a somewhat similar but greatly simplified method. A different
procedure was developed by Debye and Bueche5 and, independently, by
Brinkman.G In their work the Navier-Stokes equations for the flow of
liquid inside the polymer molecule are supplied with an additional term to
account for the force that the segments exert on the liquid. The model
used is that of a porous sphere of radius R, containing I?‘. segments whose
density v in space is constant. Thus:
IN = (4’/3)7rBXV (2)
Iff is a frictional factor and v, is the relative velocity of the liquid with
respect to the polymer segments, the force acting on the liquid per unit of
volume inside the sphere is - vfvT. The final result for the resistance ex-
perienced by the sphere when moving with constant velocity U is:
W = 6nqRU$(u) (3)
where $(u) is a function of the “shielding ratio”:
u = (vfR2/V)1”2 (4)
When u is large, $(u) = 1 so that the molecule behaves like a compact
sphere and obeys Stokes’ law. When u approaches zero, the molecule is
free-drained and the frictional force becomes equal to Nf U.
The calculation is tedious, because the complete solution of the hydro-
dynamic equations both inside and outside the sphere must be obtained,
and the integration constants appearing in this solution must be adjusted
in such a manner that the velocities and the stresses are continuous a t the
527
528 J. J. HERMANS

surface of the sphere. The method developed below makes use of the same
model: a porous sphere with constant bead density. However, the calcu-
lation is based on Oseen’s equations and leads more readily to the final
answer.
According t o the result obtained by Kirkwood and Riseman the sedi-
mentation velocity in a polyrner homologous series obeys the relation :
U = a + bM‘/‘ (5)
where M is the molecular weight while a and b are constants. It has been
shown elsewhere’ that Debye’s result does not differ appreciably from
equation (5). I n fact, it can easily be shown that a plot of U versus M’/’
is equivalent with a plot of u 2 / # ( u ) versus u2, and it is found that this is
almost a straight line:
u * / + ( u ) % g/2 + u2
If this approximation is used, the frictional force becomes :
W +
~ T T , ~ ? U U ~u2)-l
(’/~
It will be shown in Section I11 that our own method leads to essentially
the same result although our final equation is simpler than Debye’s.
It is riot claimed that our result is an any w-ay an improvement on that
obtained by previous authors. The main purpose of the simplification
introduced is t o pave the way for a simple treatment of electrophoresis and
conductivity. The method of Brinkman and of Debye and Bueche has
already been extended by Fujita and Hermans* to calculate the electro-
phoretic velocity of polymer ions and the conductivity of polyelectrolyte
solutions. However, the results obtained are very complicated. The
equation arrived a t in Section IV gives similar results but is much simpler.

11. METHOD USED

We assume that the molecule has a velocity U in the direction of the x-
axis. The velocity of the liquid a t any point is a result of the forces acting
on the liquid and can be derived from Oseen’s equations. In our method
we need only consider the x-component of the force (X) and the x-compo-
nent of the velocity (u). Both in sedimentation and in electrophoresis the
force due to the external field has spherical symmetry, ie., it depends only
on the distance from the center of the molecule. As a result of this force,
however, a velocity field is produced which has no spherical symmetry (see
below). This flow in its turn causes the polymer segments to evert a force
on the liquid and as a result of this the total force will not be spherically
symmetrical. Our approximation consists in assuming that we may take
X to be spherically symmetrical and that in Oseen’s relation between X and
u we may replace u by its ayerage value over a spherical surface.
Thus, let a spherical shell of radius p be subject to a force 4 ~ p ~ X ( p ) d p ,
where X ( p ) is a funct,ion of p alone. First consider the x-component of the
flow produced a t a point Q(x,y,z) by the force X ( p ) acting a t the point P ,
 POROUS SPHERES: SEDIMENTATION AND ELECTROPHORESIS 529

where P is at distance p from the center of the molecule. This flow follows
from equation ( 1 ) and may be written in the simple form:
6u = (X/8nv)(b2h/by2 + b2h/bz2) (6)
where h is the distance between P and Q. If we integrate h over the sur-
face of the sphere with radius p we obtain:
4rp2(h),v = +
4?rp3 (4/3)7rpr2 wh e n p >r
47rp2 (h)*" = +
4?rp2r (4/3)7rp4/r when p <r
Here r is the distance from Q t o the center of the molecule; r2 = x2 y2 + +
2. D8erentiating twice with respect to y and to z,we find from equation
(6) that the x-component of the flow in Q produced by the force 4np2X(p)dp
acting on the entire spherical shell of radius p is:
( 2 / 3 d P X @ )dP whenp >r
+
(1/2q)p2X(p)dp[l/r x2/r3 + p2(1/3r3- x2/r5)J when p <r
Clearly, the spherically symmetrical force X does not produce a spheri-
cally symmetrical velocity u. However, as explained before, we average
the velocity over the spherical surface with radius r and obtain:
du = (2/3dPX(P)dP \\hen p>r
du = (2/37?)b2/r)X(p)dp \+hen p<r
Thus, finally, the total velocity produced by the forces X will be :
44 = (2/3rl)[ ( l / r ) S ; & P"b> +S 3 P P X b ) 1 (7)
The approximation introduced serves to simplify the problem to a
spherically symmetric one. In the treatment of Kirkwood and Riseman
something of a similar nature is done by averaging over all possible con-
figurations of the polymer molecule and assuming that in this averaging
process the force acting on a segment may be treated as independent of its
position. There is also a similarity with a device used by Burgerss to
derive Stokes' law. In this device the flow produced by the motion of a
solid sphere is replaced by that which would be produced by a force acting
on the liquid at the center of the sphere. When this is done, the velocity
of the liquid near the surface of the sphere does not coincide with that of the
sphere itself, but if the average of this velocity over the entire spherical
surface is made t o coincide with the velocity of the sphere, it is found that
the force needed to produce this flow is exactly 6~77RU.

111. SEDIMENTATION
In the case of sedimentation: X ( r ) = 0 when r > R and
X(r) = vf[U - u ( r ) J when r < R (8)
Combining equation (8) with ( 7 ) we obtain the following equation for
x:
530 J. J . HEHMANS

X(r) + X2[(l/r) SOr dP P"(P) + X" dP PX(P)I = VfU (9)

where use has been made of the abbreviation:
X2 = 2vf/3q (10)
If equation (9) is differentiated twice with respect to r , one finds:
AX = X2x (11)
which has the solution:
X(r) = (A/r)sinh(Xr) (12)
because X must be finite when r = 0. The constant A can be obtained by
inserting the solution for X in equation (9). In doing so, we introduce the
following dimensionless parameter :
p = XR
which is very simply related to Debye's shielding ratio CT:

p2 = 2/3CT2

The result found for A is:

A = vfU/(X cash p)

Fig. 1. The function p 2 / J ' ( M ) versus p 2 . This is equivalent with a plot of sedi-
mentation velocity versus square root of molecular weight.
 POROUS SPHERES: SEDIMENTATION AND ELECTROPHORESIS 531

To find the resistance W experienced by the molecule we integrate the

force X over the entire volume of tlic splierc. This gives:

1Y = 67rqIlUr(p) (15)
r(d = 1 - (tail P)/P (16)
When p approaches zero, W becomes equal to i\lflJ (free draining),
When p is large, r ( p ) becomes equal to 1, M hich leads to Stokes' formula.
To show that equation (5) is obeyed approximately we plot p z / r ( p ) against
p2 in Figure 1. The result is almost a straight line, which for most practical
purposes may be represented by the simple equatioii :

p2/r(p) s 3 + p* (17)
This would give:
qp)= py3 + p?)-l = u2(9i2 + ,2)-1

In this approximation, therefore, our result is identical w-ith that of Debye

and Bueche.

IV. ELECTROPHORESIS
When the polymer segments are charged, the bead density v corresponds
with a constant density p of charges fixed 011 the polymer ion. For this
model the charge density s due to the small ions has been calculated by Her-
mans and Overbeek'O on the assumption that the approximation of Debye
and Huckel is valid. They found
s = -p+ p(1 + 6) exp {-@I
sirih t / t for r <R (18)
s = -pp cosli p r ( p ) exp {-/I// for r >R (19)
Here r is the function defined by equatioii (16) and:
2 = Kr; fi = KR (20)
where K is the reciprocal characteristic length of the Debye-Huckel elec-
trolyte theory.
If an electric field E in the x-direction is applied, the density of the force
acting on the liquid in the direction of z will be given by :
X(r) = vf[U - u ( r ) ] + Es(r) for r <R (21)
X(r) = Es(r) for r >R (22)
The value of u(r) in equation (21) is determined by ( 7 ) . Using this in
(21) and differentiating twice with respect to r , it is found that, for r < R:
AX - X2X = EAs
With equation (18) for s this leads t o the solution:
 X(r) = + ( K / r ) sinh
( B / r ) sinh(h r ) (K r) MIIPII r .< I< (2:))
K = /!pK(l + pje-p(K2 - X?) -l (24)
The constant B must be derived from equation (21). Usilig equation
( 7 ) for u(r) it is found that:

(A cosh p)B = vfU - Ep + Epp2eCp cod1 p

The resistance experienced by the polymer ion is found by integrating
~f(I/- u ) over the entire volume of the sphere. Since the result must be
equal to the electric force (4/3)rR3pE,one arrives at an equation for U:

'? =
I.= vf
(1 P2
- - eCB r(p)
0
cosh p +

For future reference we give the expression for B which follows when
equation (26) is inserted into ( 2 5 ) :

Equation (26) may be simplified if for r we accept the approximation

given in (17). This gives:

I n most cases e-2@will be small compared with unity so that we end up

with a quite simple expression for U / E . Finally, in view of the applica-
tion to the conductivity of polyelectrolyte solutions, we write the expres-
sion for the relative velocity u7 = u - U of the liquid with respect to the
polymer ion:
uf = - ( l / v f ) [ E p + ( B / r ) sinh (Xr) + (Kh2/K2r)sinh (Kr)] for r < R
(29)
uf = - U + (2R3/3qr)Epexpf - K ~ I cosh p r ( p ) / p 2 for r >R (30)
These expressions can be derived from equation ( 7 ) by inserting the
values found for X inside and outside the sphere, if proper use is made of
equation (24) and (27).

V. LIMITING CASES FOR U / E

(a) p = 0. The molecule i$ free-drained, and equation (26) gives:
U/E = p/vj
as should be expected.
(b) /3 = 0. This is not of practical interest because the effect of the
 POROUS SPHERES: SEDIMENTATION AND ELECTROPHORESIS 533

counter ions is quite iuiportaiit cvcn a1 c.\trenici ctilritioii. T<q~iatioii26

leads t o the obvious rcsiilt:
l ‘/E = (4/3) 7rpH ’/67rvfI r y p )

(c) fl = a. Equation (26) gives the same answer as in case (a). It

has been explained by Hermaris arid l;ujita* that the molecule becomes
free-drained when 0 is large.
(d) p = 03. The molecule behaves like a compact sphere. Equation
(26) leads t o the result:
U / E = (2pR2/377)(e-’/b2) cosh pr(0)
This is exactly what Hermans and Fujita8 found from a m u d i more com-
plicated formula. The result agrees with Henry’s formula for a compact
sphere.
(e) When p and fl are both large compared with unity, equation (26)
becomes :

In the first place, this may be compared with the‘ result obtained by
Hermans and Fujita:

Since p2 = 2 / 3 ~ 2 , this is almost though not quite ideiitical wit11 equation

(31). Second, equation (31) gives some idea of the approximate clraracter
of (28), since for large values of fl this equation would give:
U/E = (P/vf)(l + P2/2P2) (32)
The difference between (31) and (32) is less proiiouiired than one might
think a t first sight. They become identical when p >> P. They give iden-
tical results also when p << P, namely, p / v f . It is only when p and /3 are of
the same order of magnitude that the results differ, but the difference in
U / E is always less than 15%.
References
1. C. W. Oseen, Hy$rodynamik, Akad. Verlagsgesell., Leipzig, 1927.
2. J. M. Burgers, Proc. Akad. Amsterdam, 43,425,6 1,s (1940).
3. J. J. Hermans, Rec. trav. chim., 63, 219 (1944).
4. J. G. Kirkwood and J. Riseman, J . Chem. Phys., 16, 565 (1948).
5 . P. Debye and A. M. Bueche, J . Chem. Phys., 16,573 (1948).
6. H. C. Brinkman, Proc. Acad. Amsterdam, 50, 618 (1947).
7. J. J. Hermans, Flow Properties of Disperse Systems, North-Holland, Amsterdam,
1953, p. 227; Interscience, New York.
8. J. J. Hermans and 11. Fujita, Proc. Akad. Amsterdam, B58, 182(1955). 13. Fujita
and J. J. Hermans, ibid., B58, 188(1955).
9. J. M. Burgers, Second Report on Viscosity, North-Holland, Amsterdam, 1938, p.
119.
10. J. J. Hermans and J. Th. G. Overbeek, Rec. trav. chim., 67, 762 (1948).
534 1. J. HERMANS

Synopsis
An approximate method is developed to calculate the velocity of a polymer niolecule
in a centrifugal and in an electric field. The model used is a porous sphere. The hydro-
dynamic interaction between the polyner segments is described by means of Oseen’s
equations. It is assumed that the force acting on the liquid has spherical symmetry
and that the flow derived from this force may be replaced by its average over a spherical
surface. The results of the calculation show that this approximation is legitimate.
For the sedimentation velocity an equation is obtained which is similar t o Debye’s
though somewhat simpler. I n the theory of electrophoresis all relaxation effects are
ignored, while for the charge density dne to the small ions an expression is used that has
been derived on the basis of the Debye-l-luckel approximation for electrolytes. The
expression derived for the electrophoretic mobility is quite simple and leads t o results
almost identical with those obtained in previous work by a straightforward extension of
the theories of Brinkman and Debye and Bueche.

RBsumB
Une mCthode approchke est dCcrite en vue de permettre le calcul de la vitesse d’une
molkcule polymCrique souniise A un champ centrifuge e t un champ Clectrique. Le
modhle utilisk est cehii d’une sphBre poreuse. L‘interaction hydrodynamique des seg-
ments entre eux est dkcrite au moyen des equations de Oseen. On adniet que la force
agissant sur le liquide prCsente une synietrie sphkrique, e t que 1’Ecoulernent resultant de
cette force peut 6tre remplad par sa valeur moyenne autour d’une surface spherique.
Les rCsultats du calcul montrent que cette approximitation est justifibe. Pour la vitesse
de sCdimentation on obtient une Cquation semhlable B celle de Debye, bien que plus
simple. Dans la thkorie de I’ClectrophorBse tous les efyets de rClaxation sont ignorks,
tandis qu’on utilise pour la densit6 de charge, due aux petits ions, une expression dCrivCe
de l’approximation de Debye-Huckel pour les Clectrolytes. L’expression obtenue pour
la mobilitC ClectrophorCtiqueest tr&ssiinple e t fournit des rksultats la plupart identiques
B ceux obtenus prCcCdemment par U I ~ Pextension directe des theories de Brinkman, de
Debye e t de Bueche.

Zusammenfassung
Eine angenaherte hfethode zur Berechnnng der Geschwindigkeit eines Polymermole-
kiils in einem zentrifugalen und in einem elektrischen Feld wird entwickelt. Das ver-
wendete Model ist eine porSse Kugel. Die hydrodynamische lnteraktion zwischen den
Polymersegmenten wird mittels der Oseen’schen Gleichungen beschrieben. Es wird
angenommen, dass die Kraft, die auf die Fliissigkeit einwirkt, spherische Syrnmetrie
hat, und dass das Fliessen, welches aus dieser Kraft entwickelt wird, auf einer spherischen
OberflBche durch seinen Mittelwert ersetzt werden kann. Die Resultate der Berech-
nung zeigen, dass diese Annaherung gereclitfertigt ist. Fiir die Sedimentationsgesch-
windigkeit wird eine Gleichung erhalten, welche der Debye’schen ahnlich, aber etwas
einfacher ist. In der Theorie der Elektrophorese werden all% Relaxationswirkungen
ignoriert, wiihrend fur die Ladimgsdichte. die durch die kleineri lonen bedingt wird, ein
Ausdruck verwendet wird, welcher auf der Grundlage der Annaherung von Debye-
Huckel fiir Elektrolyte abgeleitet wurde. Der fur die elektrophoretische MobilitBt
abgeleitete Ausdruck ist ziemlich einfach und fiihrt zu Resultaten, welche mit denen in
einer friiheren Arbeit durch eine direkte Ausdehnung der Theorien von Brinkman und
Debye und Bueche erhaltenen fast identisch sind.

Received April 20, 1955