ChemicalEngineering Science, 1972, Vol. 27, pp. 763-778. Pergamon Press.

Printed in Great Britain

A structural model for gas-solid reactions
with a moving boundary-III
A general dimensionless representation of the irreversible
reaction between a porous solid and a reactant gas
H. Y. SOHN and J. SZEKELY
Department of Chemical Engineering and Center for Process Metallurgy, State University
of New York at But&lo, Buffalo, New York 14214, U.S.A.
(Firs? received 13 May 1971; in revisedform 16 J uly 1971)
Abstract-A general structural model is developed for the description of non-catalytic gas-solid
reactions; which allows for spherical and flat plate like pellets, made up of spherical or flat plate-like
grains.
The numerical solution of the dimensionless form of the governing equations results in a plot of
the dimensionless time to achieve complete reaction against a gas-solid reaction modulus, which is
valid for all the geometries considered.
The use of this plot could be useful for the planning of experiments or for the interpretation of
experimental data, in terms of structural models, without the need for digital computation.
It is shown that for extreme values of the gas-solid reaction modulus, the results of the model
reduce to the asymptotic solutions corresponding to the shrinking core and the uniform reacting
pellet models respectively. Thus the gas-solid reaction modulus is helpful for the quantitative
definition of the range of these asymptotic regimes, in terms of the chemical and structural parameters
of the system.
1. INTRODUCTION
IN RECENT years a great deal of work has been
done on the development of alternatives to the
shrinking core model for non-catalytic gas-solid
reactions[l-71. Much of the earlier work was
purely analytical, and only in two very recent
studies was there an attempt made to compare
the predictions of the models with actual
experimental measurements [6,73.
A common feature of all these models is the
postulate that the reaction takes place on a
distributed surface, within the porous body,
which is represented as an assembly of individual
particles or channels.
In the majority of cases the mathematical
representation of these systems led to a set of
simultaneous differential equations which had
to be solved numerically. The computed results
shown in the previous publications served
primarily an illustrative purpose, indicating
certain trends, for given specific situations.
It follows that in their present form the struc-
tural models available at present are not
immediately accessible for the interpretation of
experimental data or for the prediction of the
behavior of a given system.
Therefore it would be desirable to consolidate
ideas currently available on structural models
into a general dimensionless representation.
Ideally such treatment should provide both an
overview of the interaction of the various
parameters and a convenient framework for
prediction and interpretation of experimental
data, without recourse to numerical computation
in each instance.
The purpose of the paper is to attempt the
development of such a general model, at least
for systems undergoing first order irreversible
reactions and where structural changes occurring
in course of the reaction may be neglected.
2. FORMULATION
Let us consider a porous pellet of volume VP
and of superficial area Ap, made up of individual
763
particles (grains) having a volume and surface
area V, and A, respectively. The shapes to be
considered for the pellets and the grains in
the subsequent treatment will include spheres,
long cylinders and slabs, the behavior of which
should provide good guidelines for most practical
systems.
of the small size of the grains. Recent work by
Calvelo and Smith[7] has shown that the
importance of intragrain diffusion is negligible,
provided the grain Biot number, r,k/D, is smaller
than 1.
Let us consider that the solid material forming
the pellet reacts with a gas, irreversibly,
according to the scheme:
Within the framework of these assumptions
the problem may be stated by combining an
expression for the conservation of the gaseous
reactant with a mass balance for the reacting
solid. Thus we have
A(gas) + bB(solid) + Products.
(1)
D,QC, - VA =0
(2)
The following additional assumptions are made:
(1) the pseudo-steady state approximation is
appropriate for describing the concentration of A
within the pellet
where D, is the effective diffusion coefficient
within the porous medium, CA is the reactant
concentration, and VA is the local rate of con-
sumption of A.
(2) The resistance due to external mass
transfer is negligible. (This simplilication will
be relaxed in Section 4 where its effect will
be studied.)
(3) Diffusion within the pellet is either equi-
molar counter-diffusion or at low concentration
of the diffusing species.
Regarding the conservation of the solid, we
shall assume that within each grain the reaction
front retains its original geometrical shape
(i.e. concentric spheres, or coaxial cylinders, or
parallel planes) for successive times.
Then the local rate of reaction at a solid
surface may be expressed as
(4) The system is isothermal.
(5) The solid structure is macroscopically
uniform and is unaffected by the reaction.
p,,,g = bkc,
(3)
(6) Diffusion of the gaseous reactants through
the product layer of the individual grains is not
rate-limiting.
The consequences of and the limitations
imposed by these assumptions will be discussed
subsequently. At this stage it is noted that
assumption (1) is generally acceptable for
gas-solid systems& 93. The effect of external
mass transfer (i.e. 2) may be readily incorporated
into the analysis, but at this stage this would
have introduced one additional parameter.
Ishida and Wen[2] have shown that the effect
of external mass transfer is negligible if the pellet
Sherwood number, k,,,RJ De, is greater than 100.
While assumptions (3)-(5) are restrictive, they
are thought to be appropriate to a range of
problems of practical interest. Finally, it is
thought that it would be safe to neglect the effect
of diffusion through the product layer, because
where pm is the molar density of the solid,
r is the distance coordinate perpendic-
ular to the moving reaction front,
b is the stoichiometric factor, and
k is the reaction rate constant.
The boundary conditions for Eqs. (2) and (3)
have to express the stipulations that initially all
the grains are unreacted, and that the reactant
COnCeMiXtiOII iS maintained at CA0 at the OUter
surface of the pellet, and the gaseous reactant
concentration profile is symmetrical about the
centerline (center) of the pellet. These con-
straints are readily expressed mathematically
but, for the sake of brevity, will be only given in
their dimensionless form.
It is noted that a further assumption is implicit
in Eq. (3) through the form chosen for the rate
expression.
A relationship is readily established between
H. Y. SOHN and J. SZEKELY
764
A structural model for gas-solid reactions
the local rate of reaction and the consumption r) is the length coordinate in the V operator;
of A, provided the geometry of the grain is since radial or cylindrical symmetry has been
specified. For flat plates, cylinders and spheres, assumed, the angular terms are not con-
aA is given as sidered, and
R is the dimensional length coordinate within
nA,
VA = (I --E)eA jyg
(4)
the pellet.
Finally,
Here, E is the porosity of the pellet, and Fg is
the shape factor, which has the values of 1,2 and
r* = bkC% A, t
( > Pm FJg
(11)
3 for flat plates, cylinders and spheres, res-
pectively. is the dimensionless time.
Equations (2) and (3) may be expressed in The boundary conditions for Eqs. (5) and (6)
dimensionless forms given by Eqs. (5) and (6) are readily written down as follows:
below :
v*2,)- ,3,y5Fg-l = 0
e= l,att* =0
(12)
and +I= l,atr)= 1
(13)
where
(7)
i.e. the dimensionless concentration, normalized
with respect to the fixed value at the outer
surface of the pellet,
Ar
5,--8-
FJ ,
(8)
i.e. the dimensionless position of the reaction
front within the grain, and
$$ = 0, at r) = 0.
The system of Eqs. (5), (6) and (12)-(14) is
analogous to that derived earlier[5] in a dimen-
sional form. It does, however, provide a more
general treatment in that it allows the considera-
tion of spherical, cylindrical and flat pellets,
made up of spherical, cylindrical or flat grains.
It is noted that the dimensionless representa-
tion of the governing equations shows that the
dependent variables 5 and I/J are related to t* and
7 and the single parameter, which appears in
this formulation as cr.
FJ ,
This quantity u incorporates both structural
a=A,
J
( 1 - l ) kc& A,
D, v,
(9) and kinetic parameters and, on the analogy of
the Thiele modulus in heterogeneous catalysis,
should be helpful in the characterization of the
Here, u is a parameter which has a role akin to system.
that of the Thiele modulus in heterogeneous
In general the governing equations have to
catalysis, and F, is the shape factor for the
be solved numerically. For most practical
pellet, which has the values of 1, 2 and 3 for purposes the results sought are not the time
plates, cylinders and spheres respectively.
and spatial dependencies of I,!J and 6, but rather
the extent to which the pellet has reacted at
(10)
a given time.
In terms of the parameters used in the formula-
765
CX.5 Vol. 27 No. 4-H
tion, the overall extent of reaction is defined as
I
1
X= O
+Fp-l(l -p) drl
s
:
(15)
$FP- &-,
3. RESULTS
In this section we shall present solutions for
the governing equations, obtained generally by
numerical techniques, together with some
analytical solutions available for certain special
cases.
Before the presentation of the results it is
worthwhile to examine the asymptotic behavior
of the system as this may provide useful guide-
lines, both for the range to be covered by com-
putation and for the most convenient form in
which the results may be presented.
3.1 Asymptotic behavior
(i) When u approaches zero, the overall rate
is controlled by chemical kinetics, and diffusion
within the pellet is rapid compared with the rate
of the chemical reaction. Under these conditions
the reactant concentration is uniform throughout
the pellet (9 = 1). Furthermore, 5 is independent
of 7, although still a function oft*.
Under these conditions Eq. (6) is readily
integrated to obtain
5 = 1 - t*, for 0 d t* d 1
andt=O, fort* 2 1 * (16)
Upon using Eq. (15) we obtain the following
relationship between X and t*:
t* = l- (l-x)F~.
(17)
For subsequent use, let us define
&?QJX) = l- (l-XX)lFs
(18)
where the quantity gFg (X) refers to the value of
t* within the asymptotic regime where u --j 0.
It is noted that Eq. (17) provides a convenient
means for determining F,, i.e. the grain or
H. Y. SOHN and J. SZEKELY
particle shape factor from experimental data
obtained under conditions where diffusion within
the pellet was not rate-controlling.
(ii) When u approaches in$nity, the overall
rate is controlled solely by the diffusion of the
gaseous reactant within the pellet; this case
corresponds to that accurately represented by
the shrinking core model, thus the solution may
be written as:
pFp(X) = 2FF*
(19)
where
pFp(X) = X2, for Fp = 1
(20)
pFz,(X) =X+(1-X)ln(l-X),forF,=2
(21)
p+(X) = 1-3(1-X)23+2(1-X),
forF,=3. (22)
The form of Eq. (19) suggests the following
generalized definition for the parameter CT:
Vp
= d2iQFp = A,
J
(23)
In teIIm of &, p&(X) may now be written as
pFp(X) = t*@.
(24)
Equation (24) provides a convenient yardstick
to which other overall extent vs. dimensionless
time curves may be compared.
3.2 Analytical solutions
Equations (17) and (24) correspond to
asymptotic solutions for pure chemical control
and pure diffusion control respectively.
Analytical solutions may be obtained for certain
special geometries of the general case, where
both diffusion and chemical kinetics play a role
in determining the overall rate.
Thus for a spherical pellet (Fp = 3) containing
766
grains shaped as flat plates (F, = l)*, and for of the pellet, f2C1, is given by the following ex-
a first order reaction, Ishida and Wen[2] ob- pression for both the above cases (i.e. spherical
tained a solution, which may be put in the pellet, plate type grains, and slab, with plate
following form. type grains):
X=&[&coth (&&)-lJt*,O dldl
(25)
andforr L 1,
t;=, = l+Y.
(33)
The solution for a long, cylindrical pellet with
t* = 1+a(l--q,)2(1+2?jm)+ (l--r)&
x [&&qm coth (<?&/,) - l]
(26)
flat plate-type grains is expected to be an inter-
mediate between that for a sphere and a slab;
it is thought likely, therefore, that Eq. (33)
should also hold valid for this case.
3.3 The general case- numerical solutions
and X = 1- qm3 + %[tiirn coth (tibm)
-11 (27)
where q,,, is the position of the boundary between
the reaction zone and the completely reacted
layer.
A solution may also be generated for a slab,
made up of flat plate shaped grains, i.e. F,, = 1,
and FB = 1. For a first order reaction, i.e. n = 1,
we have the following:
forOGt*G 1
5= 1_coSh (--$*
cash (fib>
(28)
and
x,tanh (*h)t*
v% *
(29)
Fort* 2 1,
t* = 1+*-2(1-7jm)2+V%(1-rJm)
x tanh (fibm)
(30)
5 = 1 _ cash <fiM
cash (fiti,)
(31)
and
X= l-,,+A& -tanh (fiti,). (32)
The time required to achieve complete reaction
A structural model for gas-solid reactions
In the preceding Sections, 3.1 and 3.2, we
presented asymptotic solutions for & -+ 0 and
u += w and analytical solutions for the particular
cases of flat-plate-type grains, for which the
interfacial area available within a grain does not
change in course of the reaction.
In the general case, the system of equations
(5)-(6) with the boundary conditions (12)-(14)
has to be solved numerically. These equations
are identical in form to those solved previously;
indeed with minor adaptation, the same com-
puter program was used in order to generate
the solutions. The computational details are
available elsewhere [6], therefore we shall
confine ourselves to the presentation and
discussion of the computed results, which are
shown in Figs. l-8. Figures 1 and 2 show
computed results for small and large values of 6,
respectively. The coordinates for these plots are
so chosen as to allow the convenient presentation
of the appropriate asymptotic solutions, which
were derived in 3.1.
*The shape of the grains is an interpretation supplied in
the present paper; in their original article Ishida and Wen[21
merely postulated that the rate of reaction is independent of
the solid reactant concentration.
Thus Fig. 1 shows a plot of gFg(X) against t*
+th 6 as a parameter, for various values of
the two shape factors, Fp and F,. Also shown is
the line for & = 0, i.e. gFg(X) = t* which,
according to Eq. (18) is valid for all the geomet-
ries. It is readily seen from Fig. 1 that the 6 = 0
asymptote should be appropriate, provided
6 > 0.3; this information is helpful, since it
obviates the need for any detailed computation
within this region of & values.
Another important feature of Fig. 1 is that
767
H. Y. SOHN and J. SZEKELY
0.0 0 2 0.4 0.6 0.6 1.0 1.2 1.4 1.6 1.6 20
i
Fig. 1. Conversion function vs. reduced time for small values of B.
0.0 0.2 0.4 0.6 0.6 1.0 1.2 1.4 1.6 I.6 2.0
t/ 6
Fig. 2. Conversion function vs. reduced time for large values of $.
Fig. 3. The dependence of time for complete conversion on &.
the straight-line relationship between gFg (X) and
t* persists for t* < 1. For small values of u
(say & < 0*7), the straight-line relationship exists
until the conversion becomes 90 per cent or
higher. This shows that the existence of a
Stkght-fine relatiOnShip between gFg(x) and t
does not necessarily mean that the system is
under a chemical-reaction control; even when
there is a substantial effect of intrapellet diffusion,
one may obtain a linear relationship. This is
consistent with the findings reported by St.
Clair[lO].
For pellets made up of flat grains (F, = 1)
the linear relationship is given by Eq. (29) for
slablike pellets and by Eq. (25) for spherical
pellets. Approximate equations may be obtained
for small values of B:
ForF,= FQ= 1,
768
A structural model for gas-solid reactions
Fig. 4. The dependence of time for 90 per cent conversion
on 6.
Fig. 5. The dependence of time for 75 per cent conversion
on B.
x= 1+++L.. . .
(
>
t*
(34)
andforF,=3andF,= 1
Fig. 6. The dependence of time for 50 per cent conversion
on B.
Fig. 7. The dependence of time for 30 per cent conversion
on 6.
x=
21 8,
l-y++&-*. (35)
As diffusion becomes important (& becomes
large), the slope of the straight line becomes
769
Fig. 8. Generalized plot for reaction time vs. conversion.
smaller than would be in the absence of the
diffusional effect. Thus, for the reduction of
Fe& by hydrogen, St. Clair[lOl, obtained
an activation energy of 25 Kcal/g mole consider-
ing the diffusional effect, compared with a value
of 15 Kcal/g mole obtained by McKewan 1111
assuming the reaction to be controlled by
chemical reaction alone.
Figure 2 shows a plot of pFP(X) against 1*/?
with & as a parameter, for large values of &.
As in the previous graph, the choice of the
coordinates was dictated by the form of the
asymptotic solution, i.e. Eq. (24).
It is seen on inspection of Fig. 2 that the & -+
00 asymptote is approached when 6 > 3.0 for
all the geometries considered.
This finding is again helpful, because it
provides a definition for the range of validity of
the shrinking core model, in terms of the struc-
tural and kinetic parameters of the system.
Again, it is of interest to note that the straight-
line relationship between pFP(X) and t persists
even when the value of + does not correspond
to infinity (& > 2). This shows that the existence
of a straight-line relationship betweenp,JX) and t
does not necessarily prove that the system is
H. Y. SOHN and J. SZEKELY
controlled by intrapellet diRusion alone, unless
the straight line passes through the origin and
extends up to X = 1. When 2 < 6 < m, a straight
line will be obtained which upon extrapolation
does not pass through the origin. The data on the
reduction of iron oxide obtained by Kawasaki
et al. [ 121 clearly show this effect, indicating that
chemical reaction played a significant role, in
contrast to their conclusion that the system was
controlled by diffusion alone.
For pellets made up of flat grains (F, = 1)
the approximate equation for the linear relation-
ship can be obtained from Eqs. (30) and (32),
or Eqs. (26) and (27) to give
$ = PFB(X) +&
In case of such straight line relationship the form
of Eq. (36) provides a convenient way of
obtaining the reaction parameters for the system.
Thus the extrapolation of the linear portion of
the curve to &,(X) = 0 will give the kinetic
parameters, whereas the effective diffusion
coefficient may be deduced from the slope.
Except for the asymptotic regimes, in Figs. 1
and 2 the different geometries had to be re-
presented by different curves. A more unified
representation is possible, if we consider the
time required to achieve complete reaction, or
a given degree of reaction, as the dependent
variable. Such plots are shown in Figs. 3-7.
Figure 3 shows a plot of l/f$_1 against 6. Also
shown, with the broken line, is the asymptote
corresponding to cr 4 00, i.e. the relationship
given by Eq. (24). As indicated by the single
continuous line, the curves for Fp = 1 and FB = 1,
Fp = 3 and F,=3, and F,=l and F,=3 all
coincide, thus it appears that the quantity
l/& may be represented as a unique function
of 6 irrespective of the pellet or grain geometry,
at least for the geometries considered in the
formulation. The actual equation describing
the continuous line in Fig. 3 has been previously
given as Eq. (33):
t& = 1+@.
(33)
770
A structural model for gas-solid reactions
Since the ordinate may be regarded as the ratio
of the time taken to complete the reaction for
i? = 0 to the time taken to complete the reaction
for the actual value of 5, the quantity may be
regarded as the overall effectiveness factor for
the complete reaction.
This behavior shows a marked analogy to that
found in heterogeneous catalysis, with regard
to the role played by the Thiele modulus.
Figures 4-7 show similar plots to that given ;n
Fig. 3, but for the times required to achieve
a given fractional completion of the reaction.
As seen on inspection of these graphs, the
quantity t* can no longer be represented as
a unique function of C although the results for
the different geometries may be brought quite
close by the appropriate choice of the co-
ordinates, in particular, for the range, X > 0.5.
The coordinates used in this instance were
&
tx*
,
i.e. the ratio:
time required to achieve a given degree
of reaction with & = 0
time required to achieve a given degree
of reaction for the actual value of 6
and
The results shown in the preceding Figs. 3-7
are summarized in Fig. 8, with X as a parameter.
In these curves we have averaged out the
scatter observed for the various geometrical
factors, which as noticed would become signifi-
cant only at low levels of fractional reaction.
It is thus noted that the following general
relationship may be used for predicting the
extent of reaction:
(37)
or t* = gFg (x) + ?pFp(x).
Thus we may conclude from our computation
that the time required to achieve a given frac-
tional reaction may be predicted through the use
of Eq. (37). Figure 9 shows the comparison
between the exact solution and Eq. (37) for Fg =
1 and Fp = 3, and Fg = Fp = 3. It is seen that
Eq. (37) gives a satisfactory representation of
the exact solution, especially for X > 0.5.
The comparison is made for the intermediate
region (a = 1 and 2), where the difference is
largest. For smaller and larger values of & the
agreement is better than shown in this figure.
Furthermore, Eq. (37) is asymptotically correct
as I? + 0 or 6 + m.
4. THE EFFECT OF EXTERNAL MASS
TRANSFER
In the preceding discussion we assumed that
external mass transfer was not rate controlling.
Fig. 9. Comparison of Eq. (37) with exact solutions for (T = 1 and 2.
771
In laboratory scale experimental studies such
conditions are readily realized by using sufficient-
ly high gas velocities; however, external mass
transfer may be fully or partially rate controlling
in practical systems involving packed or fluid-
ized beds of solid particles.
When the effect of external mass transfer
cannot be neglected, the governing Eqs. (5) and
(6) and the boundary conditions (12) and (14)
still apply but boundary condition (13) must
be replaced by the following:
~=ml-6),
atr)= 1
(38)
where
(39)
Figure 10 shows the effect of the modified Sher-
wood number, Nib on the plot of the conversion
vs. time for three different values of 6.
---F.*3, Fp*3
Parameter:
;
-*
p
0.0 1.0 2.0
t/ BL
Fig. 10. Effect of external mass transfer on the relationship
between conversion and time.
H. Y. SOHN and J. SZEKELY
The solution for a spherical pellet made up
of flat grains may be obtained analytically[2]
whereas the case of a spherical pellet containing
spherical grains was solved numerically.
It is seen in Fig. 10 that when 6 is small,
variations in Nib will play only a minor role,
which is to be expected, because in this case the
system is chemically controlled.
While N& may play an important role in deter-
mining the overall rate for larger values of u,
the effect of external mass transfer becomes
unimportant when NL,, > 30.
Let us now generalize the results obtained in
the preceding sections for Nib + CO to allow for
finite values of the Sherwood number.
The rate of reaction can be expressed in terms
of the overall rate of conversion X or the rate
of diffusion through the gas film.
dN..+ _
---
(l-E)PJ* dX
dt b dt
(40)
dNA _
- - --Apkm(C~o--AS)
dt
(41)
where CA8 is the gaseous IWAant concentration
at the external pellet surface. Upon assuming
quasi-steady state, the term dX/dt in Eq. (40) can
be obtained from Eq. (37) with CA, replacing CA,
in the definition of t *, to give
1
g;,(x) + ?&J(x) * (42)
Substituting Eq. (42) into Eq. (40) and equating
with Eq. (4 1) we obtain
23 + N;/,{&,((x) +&$,(x)} (43)
Finally, on combining Eqs. (42) and (43) we
obtain an approximation for t *.
t* = &W) +s
(4)
Figure 11 shows the comparison between the
772
A structural model for gas-solid reactions
5.3 5=3
Exact solution - -a-
f*OF*w+&*(PFp(XI+~) _-__ -+-
0.0 0.5 1.0 1.5 2.0
f
Fig. 11. Comparison of Eq. (44) with exact solutions.
exact solution and Eq. (44) for 6 = 1-O and
NLh = 3. It is seen that Eq. (44) gives a satis-
factory representation of the exact solution.
For smaller and larger values of 6 the agreement
is better than shown in this figure. Furthermore,
Eq. (44) converges to the exact solution as 6 + 0
or & + 03. The asymptotic relation for large 6
can be obtained analytically from the solution
of Ishida and Wen[2]. For X = 1 Eq. (44) again
becomes identical to the exact solution. This was
also checked for the case of FB = Fp = 1 for
which an analytical solution is possible [ 171.
The implications of the above findings are
discussed in the subsequent section.
5. DISCUSSION
In the paper a dimensionless representation
was developed for the reaction between a porous
solid and a reactant gas. The formulation was
quite general, in that it allowed the pellet to be
a slab or a sphere (cylinder by interpolation) and
the grains making up the pellet could also assume
a spherical, or slablike shape.
By the appropriate manipulation of the
governing equations it was possible to obtain
a general set of solutions on the plot of the extent
of reaction against a suitably chosen dimension-
less time, with a single quantity & as the para-
meter.
The dimensionless time required to attain
complete reaction of the pellet could be re-
presented as a unique function of a generalized
reaction modulus, 6 through a relationship
which was valid for all the geometries considered.
The potential practical application of these
results appears to be threefold.
(i) Prediction of the reaction characteristics
of porous solids.
(ii) Providing insight into the general behavior
of gas-solid reaction systems.
(iii) Providing a framework for the interpreta-
tion and planning of experimental studies involv-
ing gas-solid reactions.
(i) prediction of the behavior of gas-solid
systems. If information is available on the
quantities that make up &, the time taken to
achieve complete reaction, or a given fractional
reaction, may be calculated with aid of Eq. (44),
without recourse to any digital computation.
If the overall rate of reaction is desired, this
may be readily obtained by the differentiation of
Eq. (44):
dx 1
dt = g;,(X) + S-Q&(X) +2/N:,,} * (45)
Another useful feature of the dimensionless
representation, given here is that the value of &,
the generalized gas-solid reaction modulus,
provides quantitative guidance whether the
system falls within one of the asymptotic
regimes.
It has been shown earlier that when & < O-3
the pellet will react at a uniform rate throughout,
and when 6 > 3-O chemical kinetics are not rate
controlling and the use of the shrinking core
773
H. Y. SOHN and J . SZEKELY
asymptote would be appropriate. As discussed
in the paper, these considerations apply to both
spherical and slablike geometries, and are likely
to hold, at least as a reasonable approximation
for most other geometries to be encountered in
usual practice.
(ii) Some general characteristics of gas-solid
reaction systems. In a previous publication[5]
it was shown that one attractiveness of the grain
model was its ability to suggest certain optimal
geometric configurations, which would give
the fastest overall reaction rate for a given
situation. The dimensionless representation
given in this paper allows a more general
statement of this problem.
In order to find the optimum values of the
structural parameters giving the maximum
average rate of reaction up to the complete
conversion, we write this quantity, R,,,, as
follows with the aid of Eq. (37):
For a given value of k and structural parameters,
u is specified provided D, the effective diffusivity
is known. The effective diffusivity is independent
of the grain size, if diffusion within the pellet
in the molecular regime; however, D, will be
a function of the grain size, if diffusion is in
the Knudsen or in the transition regime.
Let us consider a pellet made up of spherical
grains; then the Knudsen diffusion coefficient
may be estimated with the aid of the dusty gas
model proposed by Mason et al. [ 131:
where DeK is the effective Knudson diffusivity
r, is the radius of the grain,
E is the porosity of the pellet,
T is the tortuosity,
MA is the molecular weight of the species
A,
R, is the universal gas constant, and
T is the absolute temperature.
The effective diffusivity may then be obtained
with the aid of the Bosanquet interpolation
formula:
1
_1+1
D,- De+, D~K
(48)
where DeM = ED,&- is the effective molecular
ditfusivity.
We may now proceed to obtain the conditions
for the maximum R,,, in terms of the grain size;
thus by using Eqs. (23), (47) and (48) we have
F kCn-Kr
rAol3t= (1-e) p
J 2:
(49)
where r,lOPt is the optimum grain size for a given
constant porosity. It is noted from Eq. (49) that
for a given pellet porosity the optimum grain
size is proportional to the pellet size, and is
independent of the molecular diffusivity; this
behavior is consistent with physical reasoning,
since the grain size will not have an effect on
the performance of the system, at constant
porosity and under conditions where the overall
rate is controlled by molecular diffusion. By
analogous considerations we may also obtain
an expression for the optimum porosity, for
a fixed value of r,, which is given as
E
-1 =!NJ~) (50)
1 - l opt r o
where
K= (l+$)($$$z
(51)
(iii) The use of the model for the planning of
experimental studies and the interpretation of
experimental data. As discussed earlier, all the
previously available structural models had the
inherent drawback of requiring extensive com-
putation before they could be used for the
interpretation of experimental data. The model
described in this paper could be useful for both
the planning of experimental studies and the
interpretation of experimental data, without
recourse to digital computation.
774
(a) Planning of experimental studies
In the study of a given system it is desirable
to define the range of variables over which a
given mechanism controls the overall rate.
Ideally, one would wish to carry out a series
of rate measurements under conditions, where
the process is chemically controlled, i.e. when
& + 0. Within this regime a straight line plot,
according to Eq. (17) should enable one to
obtain a suitable average value for F,.
While it is desirable to corroborate such find-
ings through the use of electron microscopic
techniques, this latter procedure may become
quite cumbersome, especially in the case of
irregularly-shaped grains.
The intrinsic reaction rate constant, k could
also be obtained from such data, through the use
of Eq. (17) and the definition of t* given in
Eq.(ll).
Once information is available on F,, the other
grain parameters, and on the intrinsic chemical
rate constant, the model would enable one to
predict the behavior of the system over the whole
spectrum of possible operating conditions -
within the limitations contained in the simplifying
assumptions made in the derivation.
The procedure outlined above should be rather
more satisfactory than experimental studies
working exclusively with pellets, where the
principal variable would be the operating
temperature. Factors other than the reaction
rate constant may be strongly temperature-
dependent (sintering, etc.); thus the apparent
activation energies obtained from reaction
studies at different temperatures could be quite
misleading.
(b) I nterpretation of experimental data
The model can be used for the interpretation
of experimental data obtained using pellets or
larger particles. Typically, these data would
consist of information on conversion vs. time,
and possibly data on the structural parameters
Under these conditions, in the absence of
separately measured kinetic constant and
diffusion coefficient, Eq. (37) enables one to
determine these parameters from the data of
A structural model for gas-solid reactions
time taken for complete reaction. Thus Eq. (37)
may be put in the following form:
bP tx=l_ 1
- T - k,,e-ERgT A,
R,P,
The use of Eq. (52) should enable one to estimate
the value of the group [ (1 - l )FJ/2D, from
experiments carried out with pellets of different
sizes; it is noted, however, that such procedure
is unsatisfactory means of estimating D, when
diffusion is not rate controlling, although this
state of affairs would be readily deduced from
the small values obtained for the above group
under such conditions.
In principle the use of Eq. (52) would allow us
to obtain information on the V,F,/A&, and the
E/R0 groups from experiments conducted at
different temperatures, although this procedure
may not be entirely satisfactory because at
extreme temperatures other effects may come
into play. Thus at very low temperatures one
may encounter induction periods [ 141 requir-
ing the nucleation of a new phase, whereas at
higher temperatures sintering may occur.
The representation of these phenomena would
require rather more involved kinetic expressions
than what were given in this model.
It is noted, however, that the form of Eq. (52)
conveniently separates the diffusional and the
chemical kinetic terms, so that the relative
importance of these variables may be readily
assessed, even under conditions where the
accurate evaluation of the individual groups is
not possible.
Having the approximate expression given by
Eq. (37), one might be tempted to put it in the
following form:
gFgo_ bG, A, t
PFp (X)
---(ye
pm FJ , PFJ X)
(53)
A linear plot of gFg (X)/pFp(X) against t/pFp(X)
for a single experiment would give the values
of k and 6 (hence D,). Unfortunately, however,
this does not work, due to the approximate
nature of Eq. (37), especially at a low conversion,
775
H. Y. SOHN and J. SZEKELY
where the term on the left hand side is the ratio
of two small numbers, and thus is very sensitive
to errors. However, as shown in Section 3.3 of
the text, when 6 approaches 0, or infinity, the use
of Eqs. (34) or (35) and (36) respectively, would
provide a reasonable estimate of these para-
meters.
6. CONCLUDING REMARKS
In the paper a structural model was proposed
for describing the first order, irreversible
reaction between a porous solid and a gas. The
model was stated in quite general terms, so that
allowances could be made for both the grains and
the pellets having slablike and spherical shapes.
The behavior of cylindrical grains may be
estimated by interpolation.
The formulation was developed in a dimension-
less form and all the systems considered could
be represented on a curve, relating the time
required to achieve complete reaction of the
pellet to a general reaction modulus.
The time required to achieve a given fractional
conversion of the solid could not be uniquely
described on a single curve, but rather as a family
of curves with a geometric factor as a parameter.
The model is thought to have potential for
both the interpretation of experimental data and
for the prediction of the behavior of gas-solid
reaction systems, on the basis of a limited
number of measurements.
The simplifying assumptions made in the
derivation of the model will clearly limit its
applicability and it may be worthwhile to
comment on the most critical of these.
(i) The assumption of first-order kinetics for
the chemical reaction may not be appropriate
to many practical systems, nonetheless, judging
from prior experience on hetergeneous catalysis
[ 15, 161 the net effect of higher order rate
expressions is unlikely to alter drastically the
general nature of the relationships found in this
investigation.
(ii) Perhaps the most critical assumption has
been the neglect of structural changes in course
of reaction; such structural changes could either
increase the diffisional resistance (sintering) or
alternatively could lead to a more open pore
structure.
Appropriate allowance for these factors would
be desirable, but any such work has to be pre-
ceded by investigations concerning the kinetics
of these structural changes.
(iii) The isothermality assumed for the system
may also be an oversimplification for many cases,
and corrections for nonisothermality should
be made in future studies.
Nonetheless, it is felt that the model given here
will apply to a number of practical systems and,
at the same time, it should provide a useful
starting point for further work in this area.
Acknowledgements-The authors wish to thank the A. E.
Anderson Foundation for financial support, and Dr. J. W.
Evans for providing the computer program for the numerical
solution.
&, 4
b
C*
c
A8
C
A0
Dt?
D
t?K
D
au
D&7
DM
E
Fw Fp
&?Fg (x)
k
NOTATION
external surface area of the individual
grains and the pellet respectively, cm2
stoichiometric coefficient in Eq. (1)
gaseous-reactant concentration, g
moles/cm3
gaseous-reactant concentration at the
outer surface of the pellet, g mole/cm3
gaseous-reactant concentration in the
bulk, g moles/cm3
effective difIusivity of A in the porous
pellet, cm2/sec
effective Knudsen ditfusivity of A,
cm2/sec
effective molecular ditfusivity of A
(ED&), cm2/sec
effective diffusivity of A in the product
layer of individual grains, cm2/sec
molecular diffusivity ofA, cm2/sec
activation energy, Cal/g mole
shape factor for the grains and the pellet
respectively (= 1, 2 and 3 for flat
plates, cylinders and spheres, respec-
tively)
conversion function for small 6 defined
by Eq. (1%
reaction-rate constant, (cm3/g mole)-
cmlsec
776
ko
km
K
n
dN,lclt
%t
PFp (x)
HI
121
131
141
VI
El
171
181
191
1101
[ill
WI
r131
t::;
V51
u71
A structural model for gas-solid reactions
pre-exponential factor, (cm3/g mole)-l T absolute temperature, K
cm/set
external-mass-transfer coefficient,
set
VA reaction rate for the species A, g moles/
cm/
cm2/sec
V,, VP volume of the individual grains and the
pellet respectively, cm3
the X conversion of solid reactant
rate
Greek symbols
factor defined by Eq. (44)
reaction order with respect to
gaseous reactant concentration
rate of formation or mass transfer
per pellet, g moleslsec
modified Sherwood number defined by
Eq. (39)
conversion function for larger $ defined
by Eqs. (20)-(22)
total pressure, atm
E
7)
%?I
porosity of the pellet
dimensionless distance coordinate de-
fined by Eq. (10)
dimensionless position of the boundary
between the reaction zone and the
completely reacted layer
dimensionless position of the reaction
front within the grain defined by Eq.
(8)
distance coordinate perpendicular to
the moving reaction front in the
t
individual grains, cm
radius of the grain, cm
distance coordinate in the pellet, cm
Pm
average reaction rate defined by Eq.
(39), g moles/cm3/sec u
universal gas constant
time, set 6
dimensionless time defined by Eq. (11)
time for complete conversion, set
dimensionless time for a given degree of
;
conversion
REFERENCES
molecular density of the solid, g moles/
cm3
gas-solid reaction modulus defined by
Eq. (9)
generalized gas-solid reaction modulus
defined by Eq. (23)
tortuosity factor
dimensionless concentration of gaseous
reactant
AUSMAN J. M. and WATSON C. C.. Chem. Enann Sci. 1962 17 323.
ISHIDA M. and WEN C. Y.,A.Z.Ch.bJ I 1968 14311.
CALVELO A. and CUNNINGHAM R. E.. J. Caral. 1970 17 1.
SZEKELY J. and EVANS J. W., Chem. E&g Sci. 1970 25 1091.
SZEKELY J. andEVANS J. W.,Chem. EngngSci. 197126 1901.
SZEKELY J. and EVANS J. W., Met. Trans. 19712 1691; 1698.
CALVELO A. and SMITH J. M., Proc. Chemeca In press.
BISCHOFF K. B., Chem. Engng Sci. 1963 18 7 11.
LUSS D., Can. J. Chem. Engng 1968 46 154.
ST. CLAIR H. W., Trans. metall. Sot. A.I.M.E. 1965 233 1145.
MCKEWAN W. M., Trans. metall. Sot. A.I.M.E. 1960 218 2.
KAWASAKI E., SANSCRAINTE J. and WALSH T. J., A.1.Ch.E J l. 1962 8 48.
MASON E. A., MALINAUSKAS A. P. and EVANS R. B., III, J . them. Phys. 1967 46 3 199.
EVANS J. W., Ph.D. Thesis, State University of New York at B&do, 1970.
PETERSEN E. E., Chemical Reaction Analysis, Chap. 4. Prentice-Hall 1965.
SOHN H. Y., MERRILL R. P. and PETERSEN E. E., Chem. Engng Sci . 197025 399.
SOHN H. Y. and SZEKELY J., Met. Trans. submitted for publication.
RQum6-Les auteurs dkveloppent un modble structural general pour d&ire des reactions non-
catalytiques gaz-solide; ce modble tient compte des pastilles spheriques ou plates faites de grains
spheriques ou plats.
La solution numerique sans dimension des equations gouvemantes donne une courbe qui montre
la relation entre le temps, sans dimension, necessaire a laccomplissement de la reaction et le module
de reaction gaz-solide; cette courbe est valable pour toutes les geometries considerees.
777
H. Y. SOHN and J. SZEKELY
Lutilisation de ce graphique pourrait &tre utile au planning dexperiences ou a linterpretation de
don&es experimentales, par rapport a des modbles structuraux et sans la necessite de calculs numer-
iques.
Les auteurs montrent que pour des valeurs extr8mes du module de reaction gaz-solide, les resultats
du modele se rtduisent aux solutions asymptotiques correspondant respectivement aux modeles du
noyau retrecissant et des grains reagissant uniformement. Ainsi le module de reaction gaz-
solide est utile a la definition quantitative de la gamme de ces regimes asymptotiques par rapport aux
parambtres chimiques et structuraux du systeme.
Zusammenfassung-Es wird ein allgemeines Strukturmodell zur Beschreibung von nichtkatalytischen
Gas-Feststoffreaktionen entwickelt, das kugelfiirmige sowie flache, plattenfiirmige Platzchen, die aus
kugelfiirmigen oder flachen, plattenfdrmigen Kiimem bestehen, beriicksichtigt.
Die numerische Losung der dimensionslosen Form der massgebenden Gleichungen ergibt ein
Diagramm der dimensionslosen Zeit zur Erzielung vollstandiger Reaktion gegen einen Gas-Feststoff
Reaktionsmodulus, gtiltig fur alle in Betracht gezogenen Geometrien.
Die Verwendung dieses Diagramms konnte sich bei der Planung von Versuchen oder bei der
Auswertung von Versuchsdaten im Sinne von Strukturmodellen als niitzlich erweisen, ohne digitale
Datenverarbeitung erforderlich zu machen.
Es wird gezeigt, dass fur Extremwerte des Gas-Feststoff Reaktionsmodulus, die Ergebnisse des
Modells sich auf die asymptotischen Lijsungen entsprechend den Modellen mit schrumpfenden
Kern bzw. gleichfi%rnig reagierendem Pfatzchen reduzieren. Der Gas-Feststoff Rwaktions-
modulus ist daher brauchbar fiir die quantitative Bestimmung des Bereichs dieser asymptotischen
Systeme, ausgedriickt durch die chemischen und strukturellen Parameter.
778