Rate of Capillary Rise in Porous Media with Nonuniform Pores

F. A. L. D U L L I E N , M. S. EL-SAYED, AND V. K. B A T R A 1
Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario, Canada
Received June 21, 1976; accepted September 24, 1976

An equation for the rate of capillary rise in porous media with nonuniform pores has been derived
on the basis of a three-dimensional network model of pore structure, consisting of a repeating capillary
element with step changes in its diameter. The measured rates of capillary rise of water in a number
of sandstone samples have been accurately predicted by the model. The apparent capillary diameter
for the rate of the capillary rise has been found to be several orders of magnitude smaller than the
pore diameter corresponding to the peak of the mercury intrusion porosimetry curve. The perme-
ability of the sandstone samples has been found to be approximately directly proportional to the
apparent diameter of the rate of capillary rise. This approximate proportionality has been shown to
follow from the capillary network model of the pore structure used in this work.

INTRODUCTION the above way of looking at the pore structure

Various mass transport phenomena in con-
solidated porous media can seldom be inter-
preted in terms of a single "effective" or
hydraulic capillary diameter because of the
complexity of pore structure in such systems
(e.g., (1-3)). In consolidated porous media the
pore structure is probably best modeled by
three-dimensional networks of capillary tubes
of different diameters which are distributed
over the network according to some rule.
Regular two-dimensional networks of this type,
with the capillaries of different diameters being
randomly distributed over the network, were
introduced the first time by F a t t (4).
As pointed out by Dullien (1-3), in pore
networks there are parallel paths (in the sense
of the word used in electrical circuitry) of
different effective mean diameters and con-
ductivities and, along each path, capillary
segments of different effective diameters alter-
nate serially, in a quasi-periodic manner. Owing
to the well-known sensitivity of flow to the
value of the pore diameter, in Poiseuille flow
it varies as the diameter to the fourth power,
i PEDCO, Cincinnati, Ohio.
has been quite fruitful in interpreting and
predicting transport properties involving
viscous flow. The applications so far include
D a r c y permeabilities (1) and the "paradox,"
pointed out by Klinkenberg (5), of calculating
smaller pore sizes in sandstone from a miscible
displacement breakthrough profile than b y
conventional mercury intrusion porosimetry
(6).
In the present paper these pore structure
concepts have been applied to the rate of
capillary penetration (capillary rise, imbibition,
infiltration, wetting, etc.) in consolidated
porous media.
The rate of capillary rise in vertical cylin-
drical capillaries, after a very short initial
unsteady-state period (7), is given b y the
equation (22)
dh r2pg (he -- h)
-- = - - , [i]
dt 87 h
where h and ho are the height at time t and the
equilibrium height of the capillary rise,
respectively; r is capillary radius; p and ~ are
liquid density and viscosity, respectively; and
g is the constant of gravitational acceleration.

497
Copyright ~ 1977 by Academic Press, Inc. Journal of Colloid and Interface Science, Vol. 60, No. 3, July 1977
All rights of reproduction in any form reserved, ISSN 0021-9797
498 DULLIEN, EL-SAYED AND-BATRA

ADVANCING
For packing of narrow sieve fractions of
, MENISCUS
coarse, rotund particles, order-of-magnitude
agreement between values of k calculated from
capillary rise measurements via Eq. [2-] and
those predicted by Eq. [-3-] has been reported
(8).
It is well known (e.g., (9)) that the Carman-
?. Kozeny equation and the hydraulic radius
concept seldom apply to consolidated porous
media. As the permeabilities of a number of
sandstone samples had been determined in
these laboratories (10, 11) it was logical to
test the consistency of Eqs. ['2-] to [-4"] in the
case of sandstones. The rate of capillary rise
measurements performed with the same sand-
stone samples, however, resulted in hydraulic
diameters (in this work the term "apparent
diameter" will be used instead) that gave
completely unrealistic permeabilities via
Eqs. [-21 to [-4"].
FIG. 1. Capillary rise in a cylindrical tube with The expression derived in this work for the
periodic step changesin its diameter.
rate of capillary rise in a cylindrical tube with
periodic step changes in its diameter has
By equating d h / d t to the Dupuit-average
predicted the rates of capillary rise observed
pore velocity, van Brakel (8) has suggested
in various sandstone samples with a remarkable
that the corresponding equation for porous
accuracy, in most cases. The input for the
media (at least for packings of course, rotund
model consists of two pore size distributions,
particles) is
determined by two independent methods, i.e.,
dh he - - h (a) mercury porosimetry, and (b) photo-
- = k - - , [-2"]
micrography of polished sections, evaluated
dt h
by using the principles of quantitative stere-
where e is the void fraction of the packing ology or geometrical probability (12-16).
and k is a Darcy permeability with the dimen-
sions of velocity, and k is given by the Carman- RATE OF CAPILLARY RISE IN A
Kozeny model as CYLINDRICAL TUBE WITH
PERIODIC STEP CHANGES
pg e3 IN ITS DIAMETER
k = . [-31 The tube considered here consists of a basic
n k'(1 -- ~)2S~
unit which is repeated a very large number of
The Kozeny constant k' ~ 5 (3) and S is the times in a macroscopic system (see Fig. 1).
specific surface of the packing, ho is the equi- The basic unit has been assumed to consist of
librium height of the capillary rise, given by a series of cylindrical segments of different
the relationship diameters Dj (j = 1, 2, . . . , n).
The lengths li of segments j have been
ho = ~ cos O/rhog, [-4]
normalized on the arbitrary basis lm~,~ = Dm~,,,
where ~, is the surface tension of the liquid, 0 is where Dm~ is the diameter of the largest seg-
the contact angle; and rh is the hydraulic ment, i.e., l~ = ( V f f V ..... )(Dm~x3/Dj2), where
radius of the medium. Vj and Vm~ are the volumes occupied in the
Journal of Colloid and Interface Science, Vol. 60, No. 3. July 1977
 RATE OF CAPILLARY RISE IN POROUS MEDIA 499

sample by "pores" of diameter Di and D . . . .
respectively. It is important to point out that
the values lj (j = 1, 2, . . . , n) are not neces-
sarily in the same proportions as the lengths of
the individual "pores" of diameter Dj. in the
sample which have been found photomicro-
graphically (10, 13, 17) to be of the same order
of magnitude as the corresponding Di. The
length of the basic unit is negligibly small as
compared with the macroscopic height of
capillary rise, h, at any time during the
capillary rise experiment.
The rate of capillary rise in a consolidated
porous medium is modeled by a three-
dimensional interconnected network consisting
of tubes shown in Fig. 1. It has been shown (1)
that in isotropic media the random or irregular
network of capillaries present in an actual
sample can be simulated with regular cubic
networks of arbitrary orientation with respect
to the macroscopic flow direction. The theo-
retical value of the geometrical tortuosity
factor is equal to 3 for both random and cubic
networks (3).
This result is assumed in the present work
and, for simplicity, the rate of capillary rise is
calculated in a single tube of random orienta-
tion with periodic step changes in diameter,
as shown in Fig. 1.
Derivation of Rate Expression
The average rate of capillary rise, v,v, in a
tube such as that shown diagrammatically in
Fig. 1, is defined as

dheff length of periodically repeating basic unit

~)av - - [51
dt time it takes the liquid meniscus to travel the length of basic unit '

where heff is the effective distance traveled in of the basic unit, ~slj is the length of the basic
the tube by the liquid meniscus from time unit, and heff is that tube length, consisting of
t = 0 when it was at the same elevation as the a large number of basic units, over which the
bulk liquid surface. In Eq. [-51 it has been pressure drop is AP. It has been shown (e.g.,
assumed that the length of the basic unit is (8)) for cylindrical capillaries of uniform
very small as compared with the dimensions diameter, D, that the Hagen-Poiseuille equa-
of the macroscopic system and, therefore, v~v tion adequately represents the rate of capillary
will be treated as a point function of hell. In a rise if AP is expressed as
random network in general, heff> h, where h
is the macroscopically observed depth of A P = 4"y/D -- pgh, [.71
penetration measured perpendicularly with
respect to the front of the liquid advancing in where complete wetting by the liquid has been
the sample. assumed.
If the Hagen-Poiseuille equation is applied It is assumed here that Eq. [-7~, if used in
to each capillary segment, it can be readily conjunction with Eq. [-61, will result in the
shown that the volumetric flow rate Q, correct Q for the tube shown in Fig. 1.
through the tube shown in Fig. 1, is It is noted that the step changes in D result
in predicting stepwise variations in Q as the
7r zXP meniscus passes into a segment of a different
Y'~ l~/Y~ ( l j D i 4) [-6-] diameter; i.e.,
Q = 12s, ,
7r 4~,/Dk -- pgh
where li and Di are the length and diameter, Qk = - - lj/Z (ljD/) , [.8-]
respectively, of segment j (j = 1, 2 , . . . , n) 1287 s i heff
Journal of Colloid and Interface Science, Vol. 60, No. 3, July 1977
500
where Qk denotes the flow rate when the
meniscus is in a capillary segment of diameter
Dk (k = 1, 2 , . . . , n ) . The time spent, tk, by
the meniscus in segment k is found by com-
bining Eq. [8] with the relation
D21r lk
Q~ = - - -
4 t,
resulting in the expression
t~ = 32~lhoulk Y~. (lHD~)(Dk/D~)3/
$
(43' -- pghDk) ~_, lj.
Combining the definition of the rate of capillary
rise v,~ (Eq. [5]), using the appropriate
symbols, i.e.,
dheff
~av ~- .... X ldZ, t~,
dt k Dcpp = - -
with Eq. [-10] results in the following expres-
sion for va~.
dhaf
v~ = - - = (E l~)~
dt k houdhaf/hdh = T.
X [ 3 2 . h e f f ~ lk Z J (lJ/nj)(Dk/n$)3] -1
A few remarks are in order in connection
with Eq. [12-]. First of all, since the capillary
segments in actual porous media are short,
often with a length-to-diameter ratio of order 1,
it is not likely that Qk will be given accurately
by Eq. [8] because insufficient time is spent
by the meniscus in the individual segments for
a new steady state to be reached. It is evident
from Eq. [10], however, that tk increases very
rapidly with Dk. Hence, Y~.ktk in Eq. [11] is
determined by the time spent by the meniscus
in the largest segments. On the other hand,
physically speaking, the relatively long time
spent by the meniscus in the widest segments,
corresponding to the lowest value of Qk, can
be expected to determine the rate of a near
steady rise throughout a basic capillary unit.
Journalof Colloidand InterfaceScience,Vol. 60, No. 3, July 1977
DULLIEN, EL-SAYED AND BATRA
Thus, Eq. [12] can be expected to approximate
the physical reality reasonably well.
It was found convenient to test Eq. [-12-] by
performing capillary rise experiments in sand-
stone samples, using water at room tempera-
tures, and calculate the "apparent capillary
[9] diameter," D~pp from the measured rates by
the customary (Washburn) equation (e.g.,
(8)):
dh/dt = 3"Dapp/Snh, [13-]
where the term pgh has been dropped because
1-107 in the laboratory capillary rise experiments
i with sandstones it was found small compared
with the capillary pressure 47/D, i.e., h << he.
Making the same approximation in Eq. [123,
comparison between Eqs. [12] and [13] results
in the following theoretical expression for the
apparent capillary diameter.
[n] hdh
( ~ lk)2
he,dh., k
Z t~ Z q/Dj) (nk/Di)3] -'. [14]
k k
By the usual definition of "tortuosity," T,
[15-]
For random or regular cubic networks of
capillaries it has been shown that T = 3
[12] (e.g., (3)). Hence, Eq. ['14] becomes
(n,vp),~,ca = -~(Y'. lk)~
k
X [ E lk Z (lffn~)(Dk/n~)3-] -I. [163
k i
Equation [16] gives the apparent capillary
diameter in terms of pore structure data, based
on the model shown in Fig. 1. Values of the
apparent diameter calculated by Eq. [16-],
(D, pp)eal~, are compared below with the
corresponding measured values, (D~pp). . . . ,
obtained by Eq. [13-].
Pore Structure Data for Eq. [16]
The type of pore structure data required to
evaluate Eq. [-16] was not available until
recently. Dullien and co-workers (12, 14, 17)
 RATE OF CAPILLARY RISE IN POROUS MEDIA 501

have determined the pore size distribution of

i'~ I 2 5 4 5 6 Di
7 8
many sandstone samples by two different and i

independent techniques: (a) the conventional

E I 0.8 1.0 3.9 9.2 8.1 6.4 4.5 1.4!4.25
mercury intrusion porosimetry, and (b) a 2 0 0.3 5.4 9.5 8.6 6.6 3.1 i1.0 9.'/5
photomicrographic method, based on scanning 5 0 0 1.5 I0 8.6 6,0 4.5 1,9 15.5
polished sections of the sample and the use of
Dj 4.259.'/5 15.5 5 0 50 70 90 I10
methods of quantitative stereology to calculate
the distribution of three-dimensional pore Fio. 2. Bivariate pore size distribution of a sandstone,
sizes (e.g., 12, 14-16). For a few sandstones a calculated from the m e r c u r y porosimetry and the
more detailed "bivariate" pore size distribution photomicrographic pore size distribution (D in
has also been determined (13). The size distri- micrometers).
bution of such pores as have been invaded by
a nonwetting phase (in these experiments: lowest saturation (usually 10-15~o of the pore
Wood's metal) has been measured for various space) at which the mercury first forms a
values of the capillary pressure. (For more continuous conducting phase in the sample.
details see Ref. (13).) An example for a The capillary paths penetrated at this point
bivariate pore size distribution estimated on are relatively few and far apart. The second
the basis of the mercury porosimetry and point is the point of inflection on the cumula-
photomicrographic pore size distribution (1) tive intrusion curve, corresponding to a very
detailed penetration of the pore network
is shown in Fig. 2. Index i (i = 1, 2, . . . , m)
denotes the pore of entry and index j (j = 1, (usually around 50% saturation).
2 , . . . , n ) denotes any pore; D~ is the pore It has been assumed in this work that the
entry diameter and Di is the diameter of any rate of capillary rise of a completely wetting
pore. Vii is the pore volume percentage in thefluid is controlled by those pores which have
sample of "pores" having diameter Dj that been penetrated by the mercury (a nonwetting
were penetrated by the invading nonwetting fluid!) at the point of inflection of the mercury
phase through necks of size Di. The bivariate porosimetry curve. The physical reason for
pore size distribution concept is used in the this assumption is that whereas the rate of
numerical evaluation of Eq. 1-163. capillary rise is fastest in those capillaries
which are penetrated by the mercury at the
Rather than using the length, lj in the basic
(first) "critical," or "breakthrough," point,
capillary unit of capillary segments j, often it
is easier to visualize instead the length-to- most of the liquid rising in these is lost to the
diameter ratio as: neighboring narrower capillaries which make
up much of the network.
a ~ - l i D i. 1-17~ Hence the lower limit of capillary diameters
to be used in Eq. [-18~ is the value at the peak
After the introduction of aj., Eq. 1-163 of the mercury porosimetry curve, whereas
becomes the upper limit was found from the photo-
(D~pp)~lcd = ( E akDk) 2 micrographic pore size distribution of the
k sample. Both values were taken from Batra's
dissertation (17) and they are listed in Table I.
X E~-~akDk Z a~(Dk/Dj)3] -'. E18~
k j The coefficients aj have been estimated as
follows. The sum of the coefficients Vii in any
Cumulative mercury intrusion porosimetry column j of the bivariate distribution (Fig. 2),
curves of sandstones and many other porous summing from the bottom of the table up to
media exhibit two important characteristic the particular value of the pore entry diameter
points. The first one is the "critical," or (in the table denoted by D0 corresponding to
"breakthrough," point, corresponding to the the point of inflection, gives the volume
Journal of Colloid and Interface Science, Vol. 60, No. 3, July 1977
502 DULLIEN, EL-SAYED AND BATRA

TABLE I
Summary of Results
Sandstone h2/t Di~f pt /)max (Dapp)meM (D*pp)eal*d * k k/(Dapp)m~)
(cm2/sec) (~m) (~m) (~m) (zm) (fraction) (cm~ X l0 n) (pm)

Bandera 0.0010 5.0 120 0.0055 0.0069 0.191 8.6 1.564

Clear Creek 0.0055 8.0 110 0.031 0.029 0.191 95 3.065
Noxie 129 0.0060 8.5 120 0.033 0.035 0.283 148 4.485
Cottage Grove 0.010 11.0 120 0.056 0.073 0.216 116 2.071
Big Clifty 0.010 9.0 100 0.056 0.061 0.192 164 2.929
Torpedo 0.020 12.0 110 0.11 0.10 0.246 184 1.673
St. Meinrad 0,025 14.1 120 0.14 0.14 0.247 210 1.500
Berea 108 0.025 26.0 180 0.14 0.47 0.178 613 4,378
Boise 0.60 47.0 180 3.3 3.1 0.232 5372 1,628

percentage of all pores of diameter D~. which The normalized coefficients aj. are shown in
are p e n e t r a t e d b y the nonwetting phase a t Table I I for one of the sandstone samples.
this point. This sum of V~i, denoted here b y Vy,
is thus calculated as EXPERIMENTAL

(Di) inf pt
T h e rate of the capillary rise of aqueous
Vi= X Vii. [-191 2 % NaC1 solutions in rod-shaped sandstone
(D~),..~ samples was measured. As one end of the
sample was contacted with the solution, con-
Assuming cylindricalcapillaries,
tained in a large, tightly sealed glass vessel,
V~ = (Dj2~r/4)li. [-203 an electrical timer was started. A cathetometer
Thus, was used to determine the position of the
a~ = l/D~ = ( 4 / ~ ) ( V j / D ? ) . [21~ b o u n d a r y of the solution rising in the sample.
T h e b o u n d a r y was sharp in all samples. The
T h e coefficients a~-, obtained b y Eq. [21-], level of the solution in the vessel was used as
have been normalized b y multiplying every d a t u m ( h - - - 0 ) . All the readings were taken
one of them b y (1/aj), corresponding to the
along a straight vertical line drawn on the side
largest pore diameter, (D~-)..... in the sample.
of the sample, parallel to its axis. I t was
observed visually, however, t h a t often the rate
TABLE II of rise was n o t uniform a r o u n d the circum-
Sample Calculation Showing Dependence of ference of the sample. The irregular b o u n d a r y
(Dapp)~lcdon the Coefficients aja
Di (..m) (Dapp)ealed TABLE II[
(~m)
11 60 120 Rate of Capillary Rise in Boise Sandstone

54b 20b 1b 0.064 t h h~/t

(sac) (cm) (cm~/sec)
20 6 1 0.038
10 3 1 0.030 2 0.75 0.3
5 2 1 0.033 8 1.75 0.4
3 1.5 1 0,038 16 2.75 0.5
2 1 1 0.041 24 3.75 0.6
1 1 1 0.073 38 4.75 0.6
56 5.75 0.6
a Sandstone: Cottage Grove; (D.pp)me.~= 0.056 zm. 115 7.75 0.5
b These values were calculated by Eqs. [-19-]to [-21-] 162 8.75 0.5
from the bivariate distribution function.
Journal of Collold and Interface Science, Vol. 60, No. 3, July 1977
 RATE OF CAPILLARY RISE IN POROUS MEDIA 503

5"2 -

4.8

4,4

4-0
o
. 3 6

ta 3 2

0 2'8
)<
O
2-4
-o
.c 2.0

1'6

1"2--

0.8

0.4

o / ' I ' [ ' T T [ 1

0 0'1 0.2 0,3 0"4 0"5 0.6 0.7 0"8 0"9 1.0
I/h, cm-I

FIG. 3. Typical dependence of rate of capillary rise on reciprocal height of rise (Boise sandstone).

of the rising solution projected a very graphic
picture of the inhomogeneity of the sample.
I t is easy to show that if pgh m a y be neglected
compared with 47/D then the experimental
data m a y be reduced to the form
h2 ~(D~.,) .....
-- = - constant.
t 47
Otherwise, the quantity h2/t will decrease with
time t. The h~/t data showed no trend indicat-
ing inadmissibility of the above approximation.
An example, for the sandstone with the largest
pores (Boise), is shown in Table I I I . The best
values of h~/t for the samples studied in this
work are listed in Table I.
Another check was also run on the data,
consisting of plotting dh/dt vs 1/h. A straight
line could be fitted to the data in every case,
as shown in Fig. 3. Extrapolating the line to
dh/dt = 0 gave near zero intercept, 1/h,, in
every case.
On the basis of the above results it was
concluded that the equilibrium height of
capillary rise, h,, was much greater than the
heights h observed in these rate experiments,
and, therefore, neglecting the term pgh beside
4~/D was justified.
RESULTS AND DISCUSSION
The experimental apparent diameters,
(Dapp) ..... for the rate of capillary rise were
['22] calculated by Eq. [223, using the values h2/t
listed in Table I. The values obtained for
(Dapp) ..... are also listed in the table.
The apparent capillary diameters, (D, pp)~l~,
calculated from pore structure data, using
Eq. [-183, are listed in Table I alongside the
corresponding experimental value, (D, pp) ......
The agreement between the calculated and
experimental values is generally good, actually
better than can reasonably be expected from
the still very crude model of pore structure
used here.
When calculating (D,pp)~alcd it was dis-
covered that practically the same values were
obtained if all the coefficients aj were set equal
to 1 in Eq. [-187, resulting in the expression
(D~pp)~l.d = ~ (E Dk)2['E Dk E (Dk/DJ)3-]-'.
k k j
[-231
Journal of Colloid and Interface Science, V o l . 60, N o . 3, J u l y 1 9 7 7
504 DULLIEN, EL--SAYED AND BATRA
FIG. 4. Photomicrograph of polished section of "Berea 108" sandstone. (Magnification: X 118.8).
It was also found that it made but a negli-
gible difference if only three capillary diam-
eters, Dinf pt, D ...... and (Dinf pt -~- Dmax)/2,
were used instead of the more detailed distribu-
tion such as that shown in Fig. 2.
The effect of the values of coefficients aj on
the calculated values of (Dapp)calod is illustrated
by a sample calculation in Table II. The trend
displayed by these results is typical of all the
other samples as well. As is evident from the
table, the coefficients aj obtained from the
bivariate pore size distribution resulted in good
agreement with (Dapp)..... On decreasing the
a~. gradually toward unity, (D~pp)caloa also
decreased until, after reaching a shallow mini-
mum, (D~pp)o~loa started to increase again.
In the end, for a y = 1 ( j = 1 , 2 , . . . , n ) ,
(Dapp)~l~a was again quite close to (D~pp)......
The simplification offered by Eq. ['23] per-
mits considerable economy of labor, and it is
also important to be aware of the fact that an
accurate knowledge of aj. is not essential to
obtain a good agreement with experiment.
It is evident from the data in Table I that
D~pp is, in most cases, several orders of magni-
Journal of Colloid and Interface Science, Vol. 60, No. 3, July 1977
tude smaller than Din~ pt; indeed, it is probably
smaller than the diameter of the narrowest
capillary in the sample. The explanation of
this curious phenomenon is that whereas the
resistance to capillary rise is determined by
the smallest diameter along the capillary
("neck" diameter), on the other hand, the
driving force is determined by the largest
diameter ("bulge" diameter), resulting in the
observed abnormally low rates of capillary rise.
The photomicrographs of sections through
Berea 108 samples saturated with Wood's
metal show a different type of pore structure
than those of the other sandstones (see Fig. 4),
which may help to explain the discrepancy ob-
served in Table I for this sample. There was
also an abnormally great formation factor
(electric resistivity factor) found for this
material (21) (see also Ref. (2)).
As is evident from Table I, there is an
approximate proportionality between Dapp and
the measured permeability. The mean value
of the ratio k/(D~pp). . . . is 2.6 #m with a mean
deviation of 4-40%. This ratio shows no trend
as (Dapp)..... changes over a range of 600. The
 RATE OF CAPILLARY RISE IN POROUS MEDIA
permeability of a medium, however, is usually
proportional to some mean-square capillary
diameter (e.g., (3)) and, therefore, the simple
proportionality found here calls for an explana-
tion. It was pointed out to the senior author
(F.A.L.D.) by his colleague, Dr. I. F. Mac-
donald, that this result suggests the existence
of a linear dimension which is of about the
same magnitude in all the sandstone samples.
This can indeed be shown to be the case by
comparing Eq. El8] with the expression
derived for the permeability ki in Ref. (1).
Written for that part of the pore space
which is penetrated by the mercury at the
point of inflection of the cumulative porosim-
etry curve, and using Eq. [19], this expres-
sion takes the form
kin~ pt = - - (~_, Vk/Dk~)2/Y:~ Vk Z (Vk/Ok 6)
96 k ~ A theoretical expression was derived for the
XSinf
where Sinf pt is the fractional saturation of the
sample with respect to mercury at the inflection
point.
Equation [18] can be readily brought into
the following form by using Eq. [21].
(D~pp)~,~a = (Y:~ Vk/Dk2)2/
k quantitative photomicrographic pore size dis-
Y:~ VkDk ~_, (Vk/Dk6).
k k
Comparing Eqs. E24] and [25] results in the
following simple relation between kinf pt and
(D~vv)al,te
~ i n f pt - -
32
X S~, pt ~ V,Dk/Y~ V,.
k k
As the size of the large pores (bulges) varied in
all the samples only from 100 to 180/~m, the ex-
pression ]~,kVkD~/~kVk is approximately con-
stant for the samples. Similarly, e varies only
from 0.191 to 0.283. The relative (mercury)
permeability at the point of inflection, ki,f ,t/k
and Si~e ,~ are also approximately constant
505
for the various sandstone samples (17). Hence,
the approximate proportionality between k
and D~pp has a plausible explanation in terms
of the model used.
CONCLUSIONS
The rate of capillary rise of 2% NaC1 solu-
tions in various sandstone samples has been
measured. The "apparent" capillary diameters,
(Da,p) ..... obtained from the measured rates
by the Washburn equation, were found to be
several orders of magnitude smaller than the
pore diameter corresponding to the point of
inflection of the cumulative mercury intrusion
porosimetry curve. The measured apparent
capillary diameters were found to be approxi-
mately proportional to the Darcy permea-
bilities, k, of the samples.
rate of capillary rise in cylindrical capillaries of
pt, [24] arbitrary orientation with periodic step changes
in their diameters. By comparing the result
with the Washburn equation, a theoretical
expression was obtained for the apparent
capillary diameter, (D~pp)cal~d,in terms of pore
structure data. Two pore size distributions,
the mercury intrusion porosimetry and the
tribution, were used to calculate (Dapp)~aCd.
[25~ No adjustable parameters were used in the
calculations. Assuming that the diameter of a
rate-controlling capillary ranged from a mini-
mum value, given by the point of inflection of
the mercury porosimetry curve, to a maximum,
given by the largest pore size obtained from
the photomicrographs, the values obtained
for (Davp)~l~ were generally in good agreement
with the corresponding values of (D~p,)......
[26] According to the model, the abnormally low
values of D~pp result from the fact that the
resistance to capillary rise is controlled by the
"necks," whereas the driving force (capillary
pressure) is determined by the "bulges" in
the capillaries.
The approximate proportionality between
(Day,) . . . . and k was shown to follow from the
model of pore structure used for predicting
Journal of Colloid and Interface Science, VoL 60, No. 3, July 1977
506 DULLIEN, EL-SAYED AND BATRA
both the rates of capillary rise and the permea-
bilities of the sandstones.
ACKNOWLEDGMENTS
The financial support of the National Research
Council of Canada is gratefully acknowledged. F.A.L.D.
wishes to thank Dr. E. G. Baker of the Exxon Research
and Engineering Company for directing his attention
to the problems of the rate of capillary rise.
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