I nt . J. He at Ma s s Transfer. Vol. 17, pp. 1093 1103. Pergamon Press 1974.

Printed in Great Britain

ANALYSIS OF DI FFUSI ON IN MACROPOROUS MEDIA
IN TERMS OF A POROSITY, A TORTUOSITY AND A
CONSTRICTIVITY FACTOR
J. VAN BRAKEL and P. M. HEERTJES
Laboratory of Chemical Technology, University of Technology Delft,
Julianalaan 136, Delft, Netherlands
(Received 29 October 1973 and in revised f orm 2I January 1974)
Abstract--The ratio between the effective bulk diffusion coefficient in macroporous media and the
diffusion coefficient in the absence of the porous medium is analysed in terms of the porosity, the
tortuosity and the constrictivity. The necessity of distinguishing these three parameters is supported by the
description of diffusion in partly saturated homogeneous isotropic monodisperse sphere packings.
The results are generalized to bulk diffusion in all homogeneous isotropic porous media in the
porosity range 0 50 per cent.
N O ME N C L A T U R E
A, area [ m 2] ;
c, mol ar densi t y [ mol m- 3];
Di j , diffusion coefficient of component i i n com-
ponent j [ m 2 s - 1] ;
De~, effective diffusion coefficient [m2s-l];
L, l engt h par amet er of por ous medi um [ m] ;
Mi, mol ecul ar weight of component i [kg mo l - t ] ;
Ni, mol ar flux of component i relative to st at i on-
ary coordi nat es [ mol m- 2 S - 1] ;
Q, diffusibility;
q, mat ri x factor;
Ri j , = Ni / Nj ;
u, l i qui d cont ent of por ous medi um [vol. %] ;
x~, mol e fract i on of component i;
co, angl e;
fl, rat i o of maxi mum and mi ni mum cross section
of a pore space segment ;
6, const ri ct i vi t y;
e, porosi t y;
e~, mol ecul ar di amet er of component i I r a] ;
z, t ort uosi t y.
Subscri pt s
A, B, species A, B;
S, surface;
V, vol ume.
I N T R O D U C T I O N
IF DIFFUSION takes place i n por ous medi a t he effective
diffusion coefficient, Deft, is lower t han the diffusion
coefficient, DAB, i n the absence of a por ous medi um.
Fol l owi ng Hoogschagen [1] we will call the rat i o
D~fr/DAB t he diffusibility, Q, of the por ous medi um.
I n order to predict the diffusibility many equat i ons,
based on pore space model s or empi ri cal correl at i ons,
have been proposed; the general t endency bei ng to try
to give Q as a uni que funct i on of the porosity, e. The
di sadvant age of most model s is t hat they cont ai n at
least one adj ust abl e par amet er t hat cannot be est i mat ed
i ndependent l y. Hence t he sense of devel opi ng such
model s can be di sput ed [ 2- 4] . Moreover, i n general,
the experi ment s do not differentiate bet ween different
model s [5]. Therefore t here is no need for still mor e
compl i cat ed models, with still more adj ust abl e par-
ameters, especially if there is no sound physical basis
for such models.
The fact remai ns, however, t hat the diffusibility can
be very different for one por ous medi um or anot her.
The cent ral t heme of this paper will be t hat to account
for this it is necessary to i nt roduce, apar t from the
influence of the porosity, a t or t uosi t y and a con-
strictivity factor. None of these t erms is new, but the
di scussi on about the i nfl uence of these pore space
characteristics is hi ghl y confusi ng; especially the t erm
t or t uosi t y is used for al most any concept related to the
charact eri zat i on of the pore space.
These factors must have a sound physical meani ng
i ncl udi ng i ndependent met hods to det ermi ne them.
Unl ess otherwise stated, the di scussi on will be re-
stricted to (bulk, mol ecul ar) uni di r ect i onal bi nar y gas
diffusion i n homogeneous, i sot ropi c macr opor ous
medi a with a cont i nuous pore space. Tot al pressure or
t emper at ur e gradi ent s are assumed to be absent.
1093
1094
THEORETICAL CONSIDERATIONS
The diffusion equation
If for a homogeneous and isotropic porous medi um
it is assumed t hat the numbe r of collisions of the
mol ecul es among themselves is much higher t han the
numbe r of collisions with the wall (hence bul k diffusion)
it can be deri ved t hat [6, 7]:
- cDe~ grad XA
NA -- (1)
XA RSA + XB
wi t h RBA = --NB/ N A, Fur t her , the diffusibility, Q, i n
DeN = QOAn (2)
is det er mi ned onl y by the st ruct ural propert i es of the
por ous medi um. That is to say the general propert i es
of gas t r anspor t derived from the Bol t zmann equat i on
do not depend on the special shape of t he solid
surfaces; onl y t he numer i cal coefficients change.
Fur t her mor e, accordi ng to the der i vat i on of equat i on
( 1 ) , RBA is i ndependent of the pore space st ereomet ry
and, assumi ng har d sphere molecules, [6] :
/ (M A CrB~
Rsa ~/ \ M. a A] ' (3)
Hence the mass t r anspor t can be det er mi ned a priori
except for t he val ue of Q. The st udy of Q is the
subj ect of this paper.
Proposed expressions f or Q
The present ed expressions for Q can be di vi ded i nt o
three classes: (i) empi ri cal correl at i ons, (ii) semi-
empi ri cal equat i ons based on a pore model, and (iii)
theoretical expressions.
(i) All empi ri cal correl at i ons express Q as a funct i on
ore. Some represent at i ve examples are given i n Tabl e 1.
Table 1. Empirical correlations for the diffusibility
Dependence
Author, yr of Q on e, Remarks
Buckingham [8],
1904 e 2 soils
Penman [9], 1940 0.66c soils; 0 < e < 0.6
various, cf. [10], ae + b a = 0'53 ~ 0"97
1948-1952 b = -0"13 ~ 0"04
Van Bavel [11], 1952 0-58e
Currie [10], 1960 7e ~ 0 < e < 1 ; ~ = 0.8 1
Satterfield [12], ae catalysts:
1970 a = 0"14 0"33
(ii) The equat i ons falling i n this class all take the
form Q = ?e", i n which e" is general l y said to represent
t he i nfl uence of the smal l er cross sectional surface
avai l abl e for diffusion.
Most l y ~ is set equal to 1 and then, i nt r oduci ng q
called t he mat r i x factor, the rel at i on bet ween Q and e
J. VAN BRAKEL and P. M. HEERTJES
can be gi ven as
Q = - . (4)
q
Many vari ant s of equat i on (4) are present ed i n the
literature.
(iii) Strictly theoretical equat i ons for Q have been
derived for porous medi a of which t he solid phase is
dispersed in the form of spheres or ot her regul arl y
formed solids. I n most cases the expressions were
derived for the dielectric conduct i vi t y of por ous media.
I n Tabl e 2 some represent at i ve equat i ons are given.
Recently Neal e and Nader [16] have deri ved t hat for
a homogeneous, i sot ropi c swarm of spheres Q =
2e/ ( 3- e) for the whole porosi t y range. Thi s is the same
rel at i on as found by Maxwell and ot hers for a limited
porosi t y range. The aut hor s report, however, t hat the
experi ment al conf i r mat i on ( by electric conduct i vi t y
measurement s) is satisfactory for e < 0-45 while ex-
cellent for e > 0.45.
Table 2. Some theoretical diffusibilities for sphere packings
Dependence
Author, yr of Q on e Remarks
Maxwell, Rayleigh, 2E/(3 - e ) e ~ 1; ordered
cf. [13] packings
Bruggeman [14], e3/2 not for monosized
1935 spheres
Weissberg [ 15], ~/( 1 - ~ In ~) overlapping spheres
1963 possible
Neale and Nader 2e/(3-e,) all random homo-
[16], 1973 geneous isotropic
sphere packings
Marshall [171, 1959 e3/2 pseudo theoretical
Millington [18],
1959 e 4/3 pseudo theoretical
When Q is pl ot t ed vs e the different Q- ~, rel at i ons
can hardl y be di st i ngui shed from each ot her ; therefore,
for compar i son, a plot of e vs 1/q has been chosen as
given in Fig. 1.
The experi ment al results report ed hi t hert o permi t
no concl usi on as to which rel at i onshi p is confi rmed
best. Most often Bruggeman' s equat i on (curve e i n
Fig. 1) is preferred for practical appl i cat i ons [ I , 19, 20].
It will be argued below t hat for por ous medi a a
funct i on of t he ki nd Q = f (e) does not exist. Fur t her -
more it will appear t hat the pragmat i c val ue of the
proposed Q- e rel at i ons is not very great (cf. curve g
i n Fig. 1).
The porosity
The mol ar flux i n equat i on (1) is related to the t ot al
cross sectional surface of the porous medi um perpen-
di cul ar to the di rect i on of t ransport . Thus the diffusi-
bility has to account for the fact t hat onl y part of this
Analysis of diffusion in macroporous media 1095
' . 2 '
O 3
1 . 0
0 . 8
0 . 6
0 , 4
0 . 2
J 7
-
~ _ ~ - ~ _ ~ _ _ . : _ . . . . . . I
= f __. , . _/__
, " g~
_ / / . i
I
0 0 . 4 0 . 8
E
FIG. 1. Some relations between the inverse of the
matrix factor and the porosity as given by theor-
etical and empirical expressions for the diffusi-
bility, cf. Tables 1 and 2. (a) q - l = 2/(3-~:);
(b) q 1=0. 66; (c) q- 1=0. 58; (d) q l = e u 3 ;
(e) q l = c~i2;(f) q 1 = ~:;(g) experimental results
for partly saturated porous media (obtained from
Fig. 6).
surface, i.e. t he part t hat intersects t he por e space, is
avai l abl e for diffusion. In a homogeneous, i sot r opi c
por ous medi um each pl ane i nt er sect i on has t he same
surface porosi t y, ~s, which is equal to t he vol ume
porosi t y, e~,.
In t he l i t erat ure there have been several suggest i ons
t hat e= e, [18, 21 24]. Such suggest i ons ar e i ncorrect .
Al t hough t here exist some pr obl ems in strictly pr ovi ng
t hat e,~ = ~,,, [25] these are on a level of strictness t hat
does not concer n us here.
The reason t hat for e~ val ues like e~/3 [18], 1/2 8 t , ,
~; , [24] have been pr oposed is t hat these values have
been based on some pore model and because all por e
model s used are ani sot r opi c e,~ will depend on t he way
t he i nt ersect i ng pl ane is taken.
Those suggest i ons t hat Q - e 2 and vari ant s [18, 21,
22] on t he gr ound t hat "a furt her rest ri ct i on on the
effective size of each por e sequence by a fract i on
is necessary because of t he poor fit of one pore to the
next " [26] all go back to t he per meabi l i t y por e model
of Chi l ds and Col l i s- Geor ge [27].
Such model s are based on the assumpt i on t hat t he
por e size di st ri but i ons in t wo adj acent pl anes are
r andom rel at i ve to each other. Thi s is in general not
t he case, because the di spersi on of t he solid and t he
por e space is not r andom on a mi cr oscopi c scale (which
has been recogni zed l at er on [26, 28]). In fact such a
r andom adj acent pl ane concept assumes pores of
infinite shortness, t he ext ra fract i on q i n Q t hen t aki ng
account of the combi ned const ri ct i vi t y and dead- end
pore effect.
The tortuosity
For a homogeneous i sot r opi c por ous medi um with
a cont i nuous pore space t he t or t uosi t y and t he con-
st ri ct i vi t y are always bot h to be recogni zed. Al t hough
it may somet i mes seem artificial in t he di scussi ons t hat
follow, it will appear t hat t he i nt er pr et at i on of experi-
ment al l y found diffusibilities is clarified great l y if these
two par amet er s are distinguished.
As far as defi ni t i ons of t he t ort uosi t y, T, occur in t he
l i t erat ure t hey are al ways gi ven ei t her wi t h reference to
ani sot r opi c cyl i ndri cal por e model s or using t he con-
cept of the short est di st ance bet ween t wo poi nt s in t he
por ous medi um, whi ch concept has no cl ear meani ng.
The present aut hor s suggest t he fol l owi ng appr oach
for t he defi ni t i on of t he t ort uosi t y.
Assume t he por e space of t he por ous medi um t o be
compl et el y filled wi t h what we will call diffusion paths.
The mai n di r ect i on of t he diffusion pat hs is t he same
as t hat of t he concent r at i on gradi ent . In t he way t he
diffusion pat hs wi nd t hr ough t he por e space t hey can
be compar ed wi t h t he st reaml i nes for l ami nar flow in
por ous medi a.
An i nt ersect i on of t he por ous medi um, per pendi cul ar
to the di r ect i on of t he concent ) at i on gradi ent , of area A
will cont ai n an i nt er sect i on of t he por e space of ar ea
cA. Thi s area ~A is const i t ut ed by the i nt ersect i ons of
t he diffusion paths, t he surface of i nt er sect i on of a
diffusion pat h bei ng A(eA). The or der of magni t ude
of t he l engt h par amet er s of the i nt ersect i ons of t he
diffusion pat hs is i nt er medi at e bet ween t hose of t he
free pat h of t he mol ecul es and the di mensi ons of t he
por e space segments. * The diffusion pat hs do not all
have equal A(eA) values, but for each i nt er sect i on of
t he por ous medi um t he z~(eA) di st r i but i on is t he same,
The number of diffusion pat hs is t he same in each
i nt ersect i on. Di fferent diffusion pat hs have different
di rect i ons rel at i ve to t he concent r at i on gradi ent , but
the di st r i but i on of angles, c~, bet ween t he di rect i on of
t he diffusion pat h and the concent r at i on gradi ent , is
t he same in each i nt ersect i on. At each poi nt of each
diffusion pat h t he local Q in this poi nt is l i near in
cosZc~: over a di st ance dl per pendi cul ar to the inter-
sect i on eA t he l engt h of t he diffusion pat h is d/ / cos ~
and t he surface for diffusion per pendi cul ar to the
di r ect i on of t he diffusion pat h is A(~A) cos c~. Thus we
can assign to each i nt er sect i on and hence to t he por ous
medi um as a whol e a cos 2 c~ di st ri but i on.
In t erms of the above model t he mat r i x fact or is a
*A pore space segment is an element of the pore space
and has a volume that is of the same order of magnitude
as the largest possible inscribed spheres in the pore space.
For example, in a densest sphere packing the pore space
is constituted by tetragonal and rhombohedral pore space
segments. For random particle packings rules can be chosen
to divide the pore space in segments in a unique way.
1096
f unct i on of the cos2~ and the A(eA) di st ri but i on. It
will not be possi bl e to specify these di st r i but i ons; the
model was i nt r oduced onl y to clarify the not i on of the
t ort uosi t y, which is i n fact a restricted t or t uosi t y
because it is not based on all diffusion pat hs but onl y
on what we will call the mai n diffusion paths. The
mai n diffusion pat hs are the shortest diffusion pat hs
i n t he por ous medi um. The t ort uosi t y, z, can t hen be
defined by st at i ng t hat r - 2 is equal to the average of
the values of cos2ct for the mai n diffusion pat hs and
hence Q is pr opor t i onal to r - 2.
It will be clear t hat z as defined above is a funct i on
of e. And hence it is not necessary to decide whet her
is equal to x/2 [29 31] or # 3 [22, 32]. These values
are rel evant onl y to pore model s of unconnect ed
cyl i ndri cal pores and do not give a physical meani ngful
charact eri zat i on of a homogeneous, isotropic, con-
t i nuous pore space.
The constrictivity
That the mai n diffusion pat hs of a pore space segment
are not paral l el to the concent r at i on gr adi ent has been
account ed for by the t ort uosi t y. The const ri ct i vi t y, 6,
account s for the fact t hat the cross section of a segment
varies over its length. That is to say the const ri ct i vi t y
is defined as 6 = (Defr/eDaB)~=l.
Hence we have for the diffusibility:
e6
Q = ~ , (5)
The form of the pore space segment s varies and is in
general not known. However, if these segment s are
charact eri zed by the rat i o of the maxi mum and the
mi ni mum cross section, fl, it appears t hat 6 is mor e
or less i ndependent of the segment form. I n Fig. 2
some exampl es are gi ven: Curri e [10] cal cul at ed 6 for
si nusoi dal segments. Pet ersen [33] for hyperbol as of
r evol ut i on and Mi chael s [3] for a repet i t i on of cylin-
drical capillaries. Therefore we may assume t hat i n
using, e.g. Pet ersen' s curve to find 6 the devi at i on of
the t rue val ue will be smal l for most por ous media.
Independence of e, ~ and
That the diffusibility can be anal ysed i n t erms of
e, r and 6 can be verified onl y if they can be deter-
mi ned i ndependent l y.
Pr obabl y all three variables can be det er mi ned from
represent at i ve phot omi cr ogr aphs of i nt ersect i ons of the
por ous medi um. The porosi t y can be det er mi ned
di rect l y; for r and 6 (i.e. fl) this is not possible. Especially
will be t oo low if det er mi ned from the appar ent
mai n diffusion pat hs i n a t wo- di mensi onal picture.
If ~ is known the values of r and fl can be estimated
for "r easonabl e" part i cl e packings. We will r et ur n to
this poi nt presently.
J. VAN BRAKEL and P. M. HEERTJES
I O - ~ i ~ ' P e t e r s e n
i ~ \ - C u r r i e
II ' ~ . . . . Michaels
I \
I \ \' ~-,,,,.
I ' \ \ .
0 4 - \ ~ ~
I
0"2 I
o l ~ I I I I [
o 5 lO 15 20 25
FIG. 2. Constrictivity, 6, as a function of the ratio,
fl, of the maximum and minimum cross section
for different pore forms. Petersen [33] : hyperbola
of revolution; Currie [10]: sinusoidal; Michaels
[3]: cylindrical capillaries connected in series,
length ratio of capillaries is 5.
The val ue of fl and hence of 6 can be det er mi ned
by means of mer cur y por osi met r y: the penet r at i on
curve gives the mi ni mum cross section and the retrac-
t i on scanni ng curves the maxi mum cross-section.
Thi s met hod has been verified for r andom sphere
packi ngs [34].
An i ndi rect ar gument for the di st i nct i on bet ween z
and 6 is t hat by compar i ng diffusion and viscous flow
i n por ous media, the val ue of z is the same, but t hat
of 6 is different i n the two cases.
Or, mor e general, the t ort uosi t y, like the porosity,
is a par amet er charact eri zi ng the pore space i n an
absol ut e sense while the val ue of the const ri ct i vi t y
depends on t he ki nd of t r anspor t phe nome non studied.
E X P E R I M E N T A L P R O C E D U R E
Methods and materials
Diffusion experi ment s were performed under st at i on-
ary condi t i ons i n a modi fi ed Wi cke- Kal l enbach
apparat us.
The porous medi a used for the experi ment s had a
di amet er of 21 mm and a l engt h of 14ram. They con-
sisted of sintered glass beads (i.e. sintered together, but
wi t hout significant def or mat i on of the spheres); the
part i cl e di amet er was in the range of 40- 400 lain.
The homogenei t y of these por ous medi a was
measured usi ng an X-ray abs or pt i on t echni que [35].
In some of the experi ment s to test the measur ement
t echni que por ous medi a of si nt ered br onze spheres
were used.
Analysis of diffusion in
In all exper i ment s hel i um diffused in a ni t r ogen
at mospher e: one side of t he por ous medi um being
swept wi t h pur e ni t rogen, t he ot her wi t h ni t r ogen con-
t ai ni ng 0' 5 to 2% vol. of hel i um.
The same ki nd of diffusion cell was used as t hat of
Fost er et al. [24], whi ch cell had been desi gned to
avoi d boundar y- l ayer effects and st agnant areas at the
surface of t he por ous medi um as much as possible.
A di sadvant age of t he cell i s - - i n our case the risk of
"i nf l ow" of t he passi ng gas.
The vel oci t y of t he gas at t he surface of t he por ous
medi um was in t he r ange 3 13 cm/s.
All exper i ment s were per f or med at 46.5C.
Di ffusi on experi ment s were also carri ed out with
part l y sat ur at ed media. For t he sat ur at i ng l i qui d di-
chl or o acet i c aci d was chosen based on the fol l owi ng
cri t eri a: (i) wet t abi l i t y (ii) l ow vapour pressure (iii) possi-
bility to det er mi ne t he homogenei t y of t he l i qui d dis-
t r i but i on by means of an X-ray absor pt i on t echni que
(iv) easy absor pt i on of t he vapour from t he gas stream.
Di fferent sat ur at i ons coul d be obt ai ned using a suct i on
t echni que, for very low sat urat i ons fol l owed by
evapor at i on.
Flow sheet
In Fig. 3 a flow sheet of t he exper i ment al appar at us
is given. The ni t r ogen flow, br ought to about 4a t m
by r educi ng val ve VI, is kept on a const ant flux by a
needl e cont r ol val ve B~. Thi s flux is di st ri but ed over
l i ne( l ) and l i ne(2)i n about equal pr opor t i ons by means
of t he valves A ~ and B2.
The hel i um st ream is br ought to about 0"2 at m by V2.
Aft er passing a filter (F) the hel i um st ream is br ought
on t he desi red level by means of B3. The flow rate is
measur ed by means of t he pressure dr op (M~) over a
capillary. The pressure difference bet ween t he t wo sides
of t he por ous medi um (P) is kept below 0.1 mm H2 0
by means of B2 and A2.
The concent r at i on of hel i um in flow (1) is measur ed
by means of a conduct i vi t y cell (K,,, reference Kr). The
~
[ U L-j []
[ M 2
U ~2
H~
FIG. 3. Flow sheet of diffusion apparatus. See main text for
explanation.
macroporous media 1097
gas flows (1) and (2) ar e measur ed via r ot amet er s or
soap bubbl e met ers (R1, R2).
When t he por ous medi um is part l y sat ur at ed wi t h
di chl or o acetic acid the vapour of t he l at t er is absor bed
at D with sodi um hydroxi de.
A compl et e meas ur ement - i ncl udi ng t he set t i ng and
r emoval of t he porous medi um can be carri ed out
wi t hi n 15 min.
Reliability and accuracy
The diffusibility of the por ous medi a was cal cul at ed
using equat i on (1). For t he ni t r ogen- hel i um system
RBA is about 2"5 [21, 23]. Because t he mol e fract i on
of hel i um is 0.018 at a maxi mum it is not necessary
to know t he val ue of RBA to any great accuracy.
The presence of di chl or o acet i c acid creates a t hree
component system. Because t he mol e fract i on of t he
acid vapour was onl y 0.0013 (no gr adi ent in t he por e
space) it was assumed t hat equat i on (1) remai ns val i d
and t hat t he val ue of DAB remai ns the same.
The largest er r or source is t he possi bi l i t y of a t ot al
pressure gr adi ent over t he por ous medi um; this can
give an er r or of 3 per cent at a maxi mum.
In or der to test the rel i abi l i t y of the meas ur ement
t echni que ei ght een experi ment s were per f or med with
one and the same por ous medi um. The st andar d
devi at i on for the det er mi ned diffusibilities was 2.5
per cent. Est i mat es based on known er r or sources gave
st andar d devi at i on 2 per cent, " ma xi mum" er r or 8
per cent.
These ei ght een measur ement s i ncl ude a var i at i on of
bot h t he t ot al gas flow and t he concent r at i on gr adi ent
with a fact or 4, cover i ng t he range of all exper i ment al
condi t i ons used.
Fur t her mor e experi ment s were performed wi t h seven
"i dent i cal " por ous media. The st andar d devi at i on for
the det er mi ned mat r i x fact or was here 5 per cent to
be compar ed with an est i mat ed maxi mum er r or of
10 per cent. The difference bet ween the reproduci bi l i t y
for one and t he same por ous medi um and t hat for
numer i cal l y different but ot herwi se as far as is
known i dent i cal por ous medi a is caused by the in-
accuracy in est abl i shi ng t he l engt h and t he porosi t y
of the por ous medi um.
RESULTS AND DISCUSSION
The diffusibility of monodisperse random sphere packings
Por e space segment s in r andom monodi sper se pack-
ings will resembl e t hose in regul ar sphere packings.
Regul ar sphere packi ngs ar e ani sot ropi c, hence Q is
di r ect i on dependent . Never t hel ess val ues of ~ and 5
obt ai ned for regul ar sphere packi ngs will give some i dea
of t hose for r andom packi ngs of r ound particles. Exact
cal cul at i ons of t he diffusibility (by i nt egr at i on over the
boundar i es of a pore space segment) have been made
1098 J. VAN BRAKEL and P. M. HEERTJES
by Kessl er [36] for different segment s i n regular
packings. His experi ment al results as well as the
est i mat es made by Adams [19] and Cur r i e [-10]
cor r espond to these cal cul at i ons wi t hi n 5 10 per cent.
Accordi ng to t he estimates of Adams 6 is for the cubi c
(e = 48 per cent) as well as for the hexagonal (e = 26
per cent) packi ng about 0-75 (using Pet ersen' s curve,
cf. Fig. 2). Al t hough Kessler' s experi ment al results
suggest t hat this val ue can be on the low side we will
assume t hat the val ue of 6 = 0.75 can be used for all
r andom monodi sper se sphere packings.
Between the two ext reme sphere packi ngs of 26 and
48 per cent porosi t y the val ue of r varies from 1 to 1.3
(and is, agai n, di rect i on dependent , e.g. when it is said
[10, 19] t hat t he t or t uosi t y of a cubi c packi ng is 1,
t hat is of course t rue onl y for a t r anspor t di rect i on
per pendi cul ar to a pl ane t hrough the sphere centers).
Whet her or not t here is a uni que rel at i on bet ween
T and ~ for r andom packings, the error i n Q will not
be very large when we assume a l i near change i n r from
1 to 1"3 over the range e = 48- 26 per cent, because
the change i n T is anyway small.
Under these assumpt i ons we obt ai n for the effective
diffusivity i n the porosi t y range 38-43 per cent (which
covers the porosities nor mal l y found for r andom sphere
packings):
Oetr = (0"57_+0'04)eDA~. (6)
Our experi ment s wi t h sphere packi ngs of 40 80, 100-
150 and 300- 400 gm particles all confi rmed equat i on
(6) as do t he mor e numer ous and sophi st i cat ed experi-
ment s of Bennet and Bolch publ i shed recently [37].
The compi l at i on of fifteen different sources, gi ven in
[37], for diffusion experi ment s with sphere packi ngs
shows a var i at i on in Q from 0"5 e to 0"8 ~.
We may concl ude t hat for r andom monodi sperse
sphere packi ngs an anal ysi s in terms of ~, z and 6
al t hough i n this case perhaps not necessar y- - cor r e-
sponds wi t h the experi ment al results as far as accuracy
permits.
It may be r emar ked t hat the val ue for Q derived
from equat i on (6) i s - - i n the specified porosi t y r a nge - -
much lower t han the val ue of 2~/ (3-e), which woul d
be t he t heoret i cal val ue accordi ng to [16].
We di d not find any significant change i n q for
mi xt ures havi ng porosities bet ween 30 and 43 per cent.
Nei t her woul d we expect a significant change for still
lower porosities.
1.8--
1.6--
1.4--
t, (b)
o (c)
+ (d)
1 2 - -
1. o I
o lO
,

o +* 4.
x
t~ t~ x ,


t~ x A
o ~
o 8
o
I l I ~ I
20 30 40 50
E , / o
FIG. 4. The matrix factor as a function of the
porosity for polydisperse sphere packings.
(a) Currie [10]; (b) Vilain and Druelle [40];
(c) Shimizu et al. [41]; (d) this work.
The results reported i n the l i t erat ure are not con-
sistent. Curri e [10] report ed a l i near i nt er dependence
of q and e, but when his results are compar ed with
those of ot hers (see Fig. 4) the onl y possi bl e concl usi on
seems to be t hat for porosities bet ween 20 and 50
per cent the mat ri x factor will lie somewhere bet ween
1 and 1-9.
l nhomogeneous porous media
Theoret i cal l y we may expect the diffusibility of an
i nhomogeneous porous medi um to be hi gher t han t hat
of a homogeneous porous medi um with t he same
average porosity.
If we assume t hat the por ous medi um can be di vi ded
i n parts t hat are i nt er nal l y homogeneous, each part has
its own e, z and (5. The s ummat i on over the different
parts will yield a hi gher overall Q because of what
we mi ght call a macroscopi c const ri ct i vi t y (for i n-
homogenei t i es i n the t r anspor t direction) and a macro-
scopic t or t uosi t y (for i nhomogenei t i es per pendi cul ar to
the t r anspor t direction). For exampl e when the porous
medi um is i nhomogeneous in the t r anspor t di rect i on
only, we have
The diffusibility of polydisperse packings
Measur ement s with mi xt ures of r ound particles of
different di amet ers confi rm equat i on (6) when they
have porosities i n t he specified range [38]. Wi t h
mi xt ures it is, however, possible to obt ai n much lower
porosities [39]. Theoret i cal l y one may expect t hat for
such packi ngs i n which the smal l er particles fill the
voids bet ween the larger particles bot h T and 6 will
increase.
n
~) = (7)
1 1 1
Cal cul at i on examples, however, show t hat t he i nhomo-
geneity of the porous medi um will sel dom change the
overall diffusibility by mor e t han 10 per cent.
Some experi ment s were carri ed out in which the
i nhomogenei t y (expressed i n t erms of t he local porosity)
was varied over the l engt h of the por ous medi um (i.e.
Analysis of diffusion in
al ong the t r anspor t direction), part l y by changi ng the
packi ng, part l y by def or mat i on of t he spheres duri ng
si nt eri ng (the l at t er mi ght decrease 5 in an absol ut e
sense).
The por osi t y di st r i but i on for two ext r eme cases is
gi ven in Fig. 5. The val ues of Q as a funct i on of the
por osi t y var i at i on ar e gi ven in Tabl e 3. As can be seen
t he i nfl uence of t he i nhomogenei t y is negligible.
4 3
39
3 5
3 1
J . . . . "4
~ 3 6 t 7 1 7
. ~ I I !
0 4 8 12
L~ mm
FiG. 5. Porosity distribution along the transport
direction for a homogeneous and a heterogeneous
porous medium.
Table 3. Matrix factor for
inhomogeneous sphere packings
Porosity ('~'/,,) Matrix factor
367 1-72
38.43-7 1.85
41.92.4 1.77
30-5+1.5 1.75
35.60.9 1.84
40-20.5 1.65
39.20.2 1.77
Hence t he r epor t ed " i mpor t ant i nfl uence of t he
nat ur e of the packi ng" on Q [9-1 l ] is not conf i r med;
it is mor e pr obabl e t hat the high st andar d devi at i on
for experi ment s with numeri cal l y different por ous
medi a is t he cause of bad reproduci bi l i t y (cf. also
Fig. 4).
The diffusibility of partly saturated sphere packings
( pendular liquid)
When a packi ng of particles, i ni t i al l y compl et el y
sat urat ed with a wet t i ng liquid, is dr ai ned some l i qui d
will remai n behi nd ar ound t he cont act poi nt s of the
macroporous media 1099
particles. These i sol at ed rings of l i qui d have been called
pendul ar l i qui d in di st i nct i on of funi cul ar liquid, in
which case t he l i qui d phase in t he porous medi um is
cont i nuous. The change of t he funi cul ar to t he pendul ar
phase for r ound particles is at about 8 per cent of the
l i qui d cont ent [42, 43].
Some exper i ment al results for t he mat r i x fact or in
the "pendul ar st at e" are gi ven in Fig. 6. It appears
t hat q changes linearly wi t h the l i qui d cont ent , u. The
homogenei t y of the l i qui d di st r i but i on appear ed to have
no significant influence.
C'J
2.9
2.5
2.1
I . 7 i
x o
J J
O 4 8 12
U, %
FIG. 6. The matrix factor for a partly saturated
porous medium as a function of the liquid content
(pendular state). Different symbols ( , / ~, x, A) in-
dicate experiments with different porous media; for
easy comparison the results were corrected in such
a way that the points for r2/6 at u = 0 per cent
coincide for the different porous media.
We may emphasi ze t hat t he (gas phase) por osi t y
changes onl y from, for exampl e, 38 to 34 per cent when
u goes f r om 0 to 10 per cent. Thi s implies t hat none
of the funct i ons depi ct ed in Fig. 1 are appr opr i at e in
descri bi ng diffusion in the pendul ar state [cf. cur ve g in
Fig. 1). Al t hough t he absol ut e val ues for Q in the
pendul ar state as found by Cur r i e [44] are about 10
per cent l ower t han ours, it can be deduced from his
dat a that he also observed a linear rel at i onshi p bet ween
q and u in t he pendul ar st at e; mor eover with the same
sl ope as we do (Curri e hi msel f analyses his results, for
pendul ar as well as funi cul ar liquid, in t erms of the
empi ri cal cor r el at i on Q = 7c").
The change in q as a funct i on of u can be whol l y
at t r i but ed to a change in ~$, cf. Fig. 7. The liquid in
t he pendul ar rings will not or hardl y change the
posi t i on of t he mai n diffusion pat hs and hence T will
remai n const ant . On the ot her hand it can be seen
1100 J . V A N B R A K E L a n d

7
I I
/ \ I I
A 13
P. M. HEERTJES
t he same u, Q can vary consi der abl y dependi ng on t he
l i qui d di st r i but i on in t he por ous medi um.
The const ri ct i vi t y will not decrease furt her in t he
funi cul ar state. The mi ni mum cross sect i on cor r esponds
wi t h t ouchi ng pendul ar rings (cf. Fig. 7). At hi gher
l i qui d cont ent s t he now annul ar ring in t he mi ni mum
cross-sect i on will become unst abl e soon and will
collapse, thus closing a connect i on. I f anyt hi ng, one
woul d expect 6 to i ncrease because, t he mi ni mum cross-
sect i on remai ni ng const ant , t he ma xi mum cross-sect i on
can onl y decrease with i ncreasi ng l i qui d cont ent .
At l ow u in t he funi cul ar st at e one can expect first
a smal l and when u increases a st r onger i ncrease in z
caused by t he closing of cell connect i ons one after
anot her . At hi gher l i qui d cont ent s t he mor e or less
r andom di st r i but i on of t he l i qui d will cause t wo effects:
FIG. 7. Intersections of regular sphere pack-
ings with pendular liquid. (A) tetrahedral cell;
(B) cubic cell.
t hat t he pendul ar l i qui d does change the mi ni mum
cross sect i on whi l e for t he great er part of a por e space
segment t he cross-sect i onal area remai ns the same.
Assumi ng t hat ~ remai ns const ant t he exper i ment al
results show a change in 6 from 0.75 to 0.48 over
t he range u = 0- 10 per cent. Thi s can be c o mp a r e d - -
fol l owi ng Adam' s met hod of cal cul at i on [ 19J - - wi t h a
ma xi mum change in 6 for the cubic, t et rahedral , and
r hombohedr al por e space segment s (cont ai ni ng pendu-
lar liquid) of 0. 7-0. 75 to 0.49-0.57.
We may concl ude t herefore t hat t he var i at i on of t he
mat r i x fact or in t he pendul ar state is due to a var i at i on
in t he const r i ct i vi t y and for the l at t er:
= 0. 75- 0. 027u, 0 < u < 10. (8)
The diffusibility in partly saturated sphere packings
(funicular liquid)
Regar di ng t he diffusion in por ous medi a wi t h funicu-
l ar l i qui d onl y a semi quant i t at i ve account is possible.
The reason for this is t hat t he l i qui d di st r i but i on in
t he por ous medi um depends st rongl y on t he "hi st or y"
of t he liquid. If we t hi nk of t he por e space as con-
sisting of "cel l s" and "connect i ons" t hen at a cert ai n
l i qui d cont ent cer t ai n cells and connect i ons will be filled
wi t h liquid. But whi ch cells and whi ch connect i ons
cannot be said a priori. It may be emphasi zed t hat a
si mpl e analysis in t erms of a so called por e size dis-
t r i but i on is onl y confusi ng and disguises t he i mpor t ant
st at i st i cal and hi st ori cal aspects of t he pr obl em as well
as t he fact t hat t here do not exist i sol at ed meni sci
( cor r espondi ng wi t h "pores") in t he por ous medi um.
It is, however, not t he pur pose of this paper to discuss
t he pr obl ems of the statics and dynami cs of capi l l ary
l i qui d in por ous medi a. It is enough to realize t hat at
(i) An i nhomogenei t y effect whi ch can be t hought of
as a macr oscopi c t ort uosi t y. Fo r this ki nd of
t or t uosi t y an analysis in t erms of a r a ndom
adj acent pl ane concept seems appr opr i at e.
(ii) The occur r ence of " de a d- e nd por es": a gas phase
regi on in t he por ous medi um t hat is onl y access-
ible from one side.
Some exper i ment al results for q in t he funi cul ar st at e
ar e gi ven in Fig. 8 and Fig. 9. Fi gur e 8 is for a very
homogeneous por ous medi um. The al most const ant q
bet ween 8 and 15 per cent cor r esponds wi t h t he physi cal
pi ct ure out l i ned above, but this may be acci dent al .
Fr om Fig. 9 it can be seen t hat t he scat t er is much
l arger t han can be account ed for by t he accur acy of
t he measur ement t echni que. The scat t er has to be
at t r i but ed to t he i r r epr oduci bi l i t y of t he pr ocedur e by
tO
CO
4. 0
3. 2
2 . 4
1 . 6 I I I
0 8 16 24
U, %
FIG. 8. Ma t r i x f act or f or a ver y homogeneous par t l y
saturated porous medium as a function of the liquid
content.
Analysis of diffusion in
/
o~,--
o / ~ o o
/ / x
x~'o oo o
t~
/
/
/
+
/
/
J
I I I I
0 10 20 30 40
U, %
FIG. 9. Matrix factor for partly saturated sphere packings
as a function of the liquid content (flmicular state). The line
from 0 to 10 per cent has been taken from Fig. 6. DiffErent
symbols (C), , A, +) indicate experiments with different
porous media.
whi ch t he por ous medi a were drai ned. Some experi-
ment s were per f or med at a l i qui d cont ent of 60 per cent.
The results in this case were compl et el y unpr edi ct abl e:
the mat r i x fact or varyi ng bet ween 12 and m. Thi s is
in conf or mi t y with t he r epor t ed var i at i on in the liquid
cont ent at whi ch Q becomes zero [45, 46].
In concor dance with t he account gi ven above pub-
lished results for t he diffusibility of part l y sat urat ed
sphere packi ngs are not consistent. Cur r i e [44] ob-
t ai ned for q about t he same wdues as we did. However
bot h Vi l ai n and Dr uel l e [40] and Reist [38] obt ai ned
l ower values.
Some general i zat i ons to more compl ex porous media
I n many cases one is not concer ned with diffusion
in part l y sat ur at ed por ous media. Nevert hel ess the
results for part l y sat ur at ed sphere packi ngs are rel evant
to t he i nt er pr et at i on of the diffusibility of por ous medi a
wi t h a mor e compl ex por e space. One can t hi nk for
exampl e of cat al yst s and t he ki nd of medi a encount er ed
in geol ogy.
I n conduct i vi t y as well as in diffusion experi ment s
val ues of q up to 20 and hi gher have been report ed.
Because t he mat r i x fact or is, in general , anal ysed onl y
in t er ms of t he t or t uosi t y this may lead to concl usi ons
like t hat of Car man that [31] "The physical meani ng
of t hese hi gh t ort uosi t i es is not at all clear". What
will, however, be clear is t hat a val ue of 10 or even 20
for q is not so strange, gi ven t he consi der at i ons
present ed above. It we t ake for 6 a mi ni mum val ue of
0"35 (cf. Fig. 2) and z at low porosi t i es at a maxi mum
of ,,/3 it is anyway r easonabl e to expect a val ue of
10 for q, even for a homogeneous i sol r opi c por ous
medi um.
Much hi gher values can be expect ed for i nhomo-
geneous por ous medi a or por ous medi a in which dead-
macroporous media 1101
end pores are present t hat ar e not account ed for via
t he porosi t y used in equat i on (5). In anal ogy with t he
results for t he funi cul ar st at e one may expect t hat
especially for low porosi t i es t he influence of dead- end
pores can be consi derabl e.
It is of interest to not e that it is a well known fact
in geol ogy t hal t he electric conduct i vi t y (and hence the
diffusion) in porous stones depends st rongl y on the
measur e of " c e me nt a t i on" [47, 48], e.g. in conduct i vi t y
measur ement s a val ue of 22 for q was obt ai ned on a
por ous medi um (having a por osi t y of about 15 per cent)
t hat had been const r uct ed by addi ng a cement i ng
agent to a mi xt ure of glass beads [47]. As in the
pendul ar state the cement i ng agent will first concent r at e
at t he cont act poi nt s of t he particles and t hen st art to
close connect i ons.
CONCLUSI ONS
(i) The diffusibility, Q, of a homogeneous i sot r opi c
por ous medi um can be anal ysed in t erms of t hree
paramet ers, all havi ng a sound physical basis: the
porosity, t;, the t ort uosi t y, r, and t he const ri ct i vi t y, 5.
(ii) Q is pr opor t i onal to t:. The porosi t y is t he specific
vol ume avai l abl e for diffusion. Ar gument s cont endi ng
the surface porosi t y to be different from the vol ume
porosi t y for i sot ropi c medi a are inwdid.
(iii) Q is pr opor t i onal to r 2. The t or t uosi t y can be
defined in t erms of the aver age mai n diffusion path.
For homogeneous i sot ropi c medi a r is a funct i on of
~:, and can t ake wdues bet ween 1 and ,,/3. For most
part i cl e packi ngs r will be close to 1"15.
(iv) Q is pr opor t i onal to 6. The const ri ct i vi t y can be
defined in terms of the rat i o of the maxi mum and
mi ni mum cross-sect i onal area of a pore space segment.
For homogeneous i sot ropi c round part i cl e packi ngs 5
is about 0.75 (lower boundary).
(v) The i mpor t ance of di st i ngui shi ng bet ween r
and gi is suppor t ed, i nt er alia, by the fnnct i onal i sm in
descri bi ng diffusion in part l y sat urat ed sphere pack-
ings; by the possi bi l i t y of est i mat i ng z and/ or 6 a priori;
and by t he possi bi l i t y of det er mi ni ng 6 i ndependent l y
by means of mer cur y porosi met ry.
(vi) None of t he pr oposed Q- ~: rel at i ons is sui t abl e
for descri bi ng the diffusibility of part l y sat urat ed
por ous media.
(vii) For sphere packi ngs cont ai ni ng pendul ar l i qui d
is i ndependent of t he liquid cont ent , u, and 5 changes
linearly with u.
(viii) For por ous medi a cont ai ni ng funi cul ar l i qui d
no a priori st at ement s can be made about Q because
the liquid di st r i but i on depends st rongl y on its hi st ory
and small i nhomogenei t i es in t he por ous medi um.
acknowled,qemem We thank If. O. R. Booi for performing
most of the cxpcrimental work in the final year of his studies.
1102
J. VAN BRAKEL and P. M. HEERTJES
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Anal ys i s of di ffusi on in ma c r o p o r o u s medi a 1103
ANALYSE DE LA DI F F US I ON GAZEUS E DANS DES MI LI EUX MAC R OP OR E UX A
L' AI DE D' UN F ACT E UR DE POROSI TE, DE T ORT UOS I T E ET DE RETREC1 S S EMENT
R6sum6 Le r appor t ent r e le coefficient de di ffusi on effcctif da ns des mi l i eux ma c r opor e ux et le coefficient
de di ffusi on en abs ence de mi l i eu por eux est ddcrit en f onct i on de la porosi t d, de la t or t uosi t 6 et d ' u n
f act eur de r6t r6ci ssement .
La necessi t 6 dc di s cer ner ces t roi s par am~t r es cst s out e nue par la descr i pt i on de la di ffusi on da ns des
e mpi l c mc nt s homog~nes , i sot r opi ques, et par t i el l ement sat ur ds de billes dc verre monodi s per s 6s . Les
r dsul t at s s ont g6n6ral i s6s it t ous los mi l i eux por eux homog~ne s el i s ot r opi ques pour les por osi t es de
0 ~'l 50 pour cent.
ANALYSE DER DI F F US I ON 1N SCHI ~I TTUNGEN UND
P ORI GE N G[ ' J TERN MI TTELS DER POROSI T/ kT,
E1NES UMWE GF AKT OR S UND EI NES E R WE I T E R UNGS F AKT OR S
Zu s a mme n f a s s u n g Das Verh~_iltnis zwi schen de m Di f f us i ons wi der s t and ci nes por i gen Gut e s und der
Di f f usi onszahl wird bcschr i cben al s ei ne Fu n k t i o n der Porosit{it, ei nes Umwe gf a kt or s und ei nes
Er wci t er ungsf akt or s. Di e Not wendi gkei t , di ese drei Pa r a me t e r zu unt er s chei den, i st d u t c h di e Fu n k t i o n
fiir di e Bes ehr ei bung der Di ffusi on in homoge ne n, i sot r open, teilweisc ge<i t t i gt en Schi i t t ungen yon
monodi s pe r s c n Gl a s kuge l n bedi ngt .
Di e Resul t at e wer den i m Hi nbl i ck a u f di e Di ffusi on in al l en homoge ne n, i sot r open, por i gen Gt i t er n
mi t Porosit~itcn von 0 50~!,; vcr al l gemei ner t .
AHAS1 H3 ZIJ/IC, qbY3HH B KAHHS I J I , q P HO- F I OP / 4 CTBI X TEJ 1 AX FI PH F1OMOI I I H
C T P YKT YP HB I X XAP AKT E P HC T HK: F 1 OP HCT OCT H, F I P OCBETA H H3 BI 4 J I HCTOCTEI
AnnoTallI4~ - - COOTttOHJCrlPI(2 Me~J]y 3f~fI)eKTHBHBIM KO3qbqbHHHeHTOM kll,lqbqby3HH r a 3a 13KarlHJ1JlflpHO-
FIOpHCrblX Te~ax n KO3(I)~HHHelITOM )J, Hqb~y3HH FIpH OTCyTCTBHH HOpHCTOFO TeJla aHa. n~3Hpyexca
f l pH FIOMOIUH cTpyKTypr l bl X xapaKTepHcTHK: HopHcTOCTH, npocBeTa H H3BH~IHCTOCTH, He o 6 x o ~ n MO
pa3AnqaTb 3TH TpH na pa Me r pa ~lna OllHCaliHfl kl.H{bqby3HH B qaCTHqllO tlaCblLL{eHHblX, OZI, HOpOj1H.blX,
H3OTpOI1HblX MOttO,/1.HCFlepCHblX ynaKoBKax cc~epHqecKHx qaCTHH.
Pe3yJlbTaTbl O606LuaK)TCn ~n~ Bcex oitnopoYl, HblX H3OTpOHHI,IX IlOpHCTblX Te~ 13 O6.rlaCTH
o/
r l opr t cTocr l 40T 0 50/ <, .