k = specific rate constant in appropriate units
k,, kc’, k l l = specific rate constants, liters;/mole sec.
Kg, K9’, K l o = equilibrium constants in concentration units
r)nijuctl,,n = rate of reaction in induction period, moles/
liter sec.
R = gas constant, 1.987 cal.;/mole OK.
T = temperature, OK.
0 = time, sec.
literature Cited
(1) EerrnAk: V., Chem. Zfiesli 8, 714 (1954).
(2) Fischer, O., DraEka, O., FischerovA, E., Collection Czech.
Chem. Commun. 25, 323 (1960).
EFFECTIVENESS FACTOR FOR
POROUS CATALYSTS
Langmuir- Hiizshelwood Kinetic Expressions
GEORGE W. ROBERTS A N D C H A R L E S N. S A T T E R F I E L D
Department of Chemical Engineering. Massachiisetts Institute of Technolog). Cambridge. Mass.
A generalized method of predicting the catalyst effectiveness factor has been developed for kinetic ex-
pressions of the Langmuir-Hinshelwood type for the case of a single reactant in which adsorption of prod-
ucts or reactant may be significant. Generalized charts for computation are presented and the method i s
illustrated by a typical set of data for the reaction of carbon dioxide with finely porous carbon.
HE relationships between the “effectiveness“ of a porous
Tcatalyst and the characteristics of the catalyst and of the
reaction were first developed mathematically in the United
States by Thiele (73).and have since been extended by IVheeler
(78), LYeisz and coworkers (76: 77), and many others. T h e
present state of development of the theory has been sum-
marized in a recent book ( 7 7 ) . Given knoivledge of the
effective diffusivity of the reacting species in the porous cat-
alyst, a body of mathematics exists today that permits the effec-
tiveness factor of the catalyst, q , to be calculated for a wide
range of conditions. including various pellet geometries and
reaction orders. various degrees of volume change on reaction,
temperature gradients within the pellet, and various diffusion-
flux equations.
Almost all of the present solutions are based on the assump-
tion of an integer-po\ver kinetic equation-i.e., a zero-: first-:
c)r second-order reaction. Only limited attention has been
given to determining the effectiveness factor for cases in Lvhich
the kinetics follo\vs a more complex expression, as represented
for example, by the Langmuir-Hinshel\vood type of rate
equation. To be sure, over a narroiv region of concentration,
the Langmuir-Hinshelwood form may be well approximated
by an integer-poivei equation. Ho\vever. if the diffusional
resistance xvithin the pellet is high-viz., the effectiveness
factor is lou-the reactant partial pressure may vary from its
value a t the pellet surface dowm to a value approaching zero
in the interior of the catalyst. If such is the case, the range
of partial pressure \vi11 not, in general, be small and it is
necessary to consider the effect of the more complex rate
equation on the effectiveness factor.
Several analyses of this type of problem have been made
288 l&EC FUNDAMENTALS
(3) Jellinek, K., Z. Anorg. Chem. 70, 93 (1911).
(4) Kolthoff, I. M., Miller. C. S., J . A m . Chem. Sac. 63, 2818
(1941).
(5) Lynn. S., Ph.D. thesis, California Institute of Technology,
1954
(Gf-ginker, K. G.: Gordon. T. P.. Mason, D. M., Sakoida. R. K.,
Corcoran. \V. H.. J . Phys. Chem. 64, 573 (1960).
(7) Schonbein. J.. J . Prakt. Chem. 61, 193 (1852).
(8) Schutzenberger. P.. Compt. Rrnd. 69, 196 (1869).
(9) Semenoff, N. N., “Chemical Kinetics and Chain Reactions,”
Oxford Clarendon Press. New York; 1935.
RECEIVED
for review July 13, 1964
ACCEPTED March 1. 1965
previously. T h e procedure is basically the same as for integer-
po\ver kinetic expressions. in that the differential equation
for simultaneous diffusion and reaction of the reactant inside
the catalyst pellet must be solved. T h e mathematics, however,
are much more complex. Chu and Hougen (4) used a numeri-
cal technique to calculate values of the effectiveness factor for
the reaction .4 + Q , \vhen the rate equation is of the form
r = kK.4.b~. (1 + KAPA + KQPQ)
Their results are presented as plots of q us. a dimensionless
parameter, M , for various values of the mole fraction of re-
actant a t the pellet surface. and for various values of K A P .
All of their solutions are for KQ = 0-that is. no product ad-
sorption-and constant total pressure throughout the pellet
is assumed. If diffusion is in the Knudsen or transition region?
the total pressure does vary through the pellet to a degree
which may be significant in some real cases. This point has
been illustrated in a recent article by Otani, \Vakao, and
Smith (6). Furthermore, Chu and Hougen used three
parameters to specify q , although it is shoivn below that, by
a judicious choice of variables. two parameters suffice.
Sumerical techniques have also been used to calculate 7
for specific reactions obeying rate equations of the Langmuir-
HinshelFvood type-namely, the oxidation of NO to NO2 ( d )
and the cracking of cumene to benzene and propylene (7).
Several investigators have obtained closed-form solutions for
the effectiveness factor by making various assumptions to
simplify the mathematical treatment. .4kehata, Namkoong.
Kubota, and Shindo ( 7 ) suggest expanding the kinetic equa-
tion in a Ta!dor series around the outside concentration,
neglecting all but the first tkvo terms. S o comparison of this
method with the more accurate numerical technique is avail-
able. Rozovskii and Shchekin (70). using a series of approxi- Substituting the resulting expressions into Equation 1 gives
mations, derived a formula for the effectiveness factor that
might be expected to be valid a t low values of 7 ) if the reactants 7 = kPA (1 + - DA
I
(Kzut D2)1 +
and products all have the same diffusivities. Again, no
aiialysia of the accurac!- of this method is available, but the c K,[P,,s + (Pa S~IDA:D*)ll (5)
result almost certainly breaks down a t high effectiveness
factors. since zero partial pressure of reactant a t the center of
the pellet is implicitly assumed. I n addition, the linearization
technique of Schilson and Amundson (72) could be applied T h e value of w will normally be positive, but in the case of a
to Langmuir-Hinshelwciod rate expressions. reaction having a reactant in addition to A. a negative value
l ' h e purpose of the present Lvork was: (1) to develop a of w could result if the second reactant had a very large value
general method of predicting the effectiveness factor for ki- of K i and a very small value of Dp, Y. Results of the present
netic expressions of the Langmuir-Hinshelwood type. involving computations cannot be used for negative values of w.
as feiv restrictive assumptions as practicable, a n d (2) to com-
Further let k' = k w (7)
pare the efrectiveness factors as calculated for Langmuir-
Hinshelwood expressions with those for integer-power equa- and let K = [ K A - DA (Kivi/Di)]/w (8)
tions. in order to assess the degree of error incurred by the i
common procedure of assuming an integer-power relationship Since w is dimensionless, K has the dimensions of a n adsorption
for the kinetics. constant, and k' has the dimensions of a rate constant. 4 s
the values of K A and the various Kl become so small that the
Mathematical Derivation reaction approaches simple first-order, K approaches zero ;
T h e case to be developed in this paper is the particular kinetic a negative value of K indicates that the sum of the groups
relationship represented by Equation 1. This expression KvDA Dlfor the products is greater than that for the reactants.
includes reactions in which 4 decomposes or isomerizes by a Qualitatively. a negative value of K indicates inhibition by
first-order process. or rtaction of A \t.ith B in which the con- reaction products.
centration of B does not appear in the numerator, b u t may Using these definitions, Equation 5 reduces to
appear in the denominator. For the reaction of A a n d B,
such an rxpression might result, for example, if adsorption of
r = k'Pa/(l + K'bA) (9)
A on the catalyst is the rate-controlling process. A subsequent Let a modified Thiele modulus Q . be
~ ~defined by
paper \vi11 consider the reaction of A and B, when the nu-
merator contains the partial pressures of both reactants.
T h e general chemical equation describing reactions under When K = 0, the reaction is simple first-order, a n d $.+I be-
consideration is comes identical to the familiar Thiele modulus. pL, defined by
A + bB 4- . . . + XX + JY + . . . Equation 15. Equation 9 may be substituted into Equation 2
a n d integrated. Substitution of Equation 10 into the result
T h e rate equation is taken to be gives
d(KPA)! d ( x / L ) =

where index i is used to denote any reaction product or reactant

other than A . Slab geometry is assumed-i.e., that the catalyst
is infinite in t\vo directions, exposed to the gas stream on one
face and sealed a t the other. T h e thickness of the slab is L.
I t is further assumed that the effective diffusivities of all
species are constant bui. not necessarily equal. that the pellet
is isothermal, a n d that i.he ideal gas la\vs are applicable.
.4 material balance on component A , over a differential
thickness Lvithin the catalyst, gives
where Pa,o is the partial pressure of A a t the sealed face.
T h e effectiveness factor, 7, of the catalyst pellet is defined
as the actual reaction rate (which equals the rate of diffusion
of A into the slab a t the gas-stream face) divided b)- the rate
that ivould result if internal concentration gradients \vere
absent. I n terms of present nomenclature

= DA
d2cA
Da dx2
( ) d"pA
-1
RT dx2
= I
7 =

Taking the stoichiometric coefficient, Y : of a reactant other

than .A to be negative, a similar balance on any other species
gives This equation is not useful in itself, since is not known.
However! PA .o can be determined by numerical integration
(3) of Equation 11: subject to the boundary conditions given in
4. Equation 11 shows that K,bA,o is a function only of oY
Equations 2 a n d 3 ma) be combined and integrated subject to and K P ~ , therefore,
~ ; from Equation 12. 7 is also a function
the boundary conditions of 4 to yield a n expression of these two parameters only.
in terms of P A . \t-hen the effectiveness factor is OM.? the reactant partial
pressure a t the sealed face, P A , * , approaches zero and Equation
PA = Pa.s; PI = P i , qa t x = 0 (exposed surface) 12 reduces to

dpa dx = dp, d~ = 0 at x = L (sealed surface)

VOL. 4 NO. 3 AUGUST 1965 289

 1.0

1.00

0.50

0.1c
F:
;0.100
c
u
L? 0.05

t I Flr?tI O r d e r 4 1 m
Lo
m
c
m
...2
E
r
0.010
w
0.005

1
1 I l l 0.0010
0.010 0.05 0.10 0.50 1.00 5.00 10.0 50 100
Modified Thiele Modulus, .#M

Figure 1 . Ratio pA.o/pA,. as a function of modified Figure 2. Effectiveness factor, q, as a function of modified
Thiele modulus, +.$f, for various values of K P . ~ . ~ Thiele modulus, +.$f, for various values of K ~ A , ,

Values of pa,o were calculated by numerical integration of (74) and has been used extensively by Weisz and coworkers
Equation 11, using a digital computer. Details of the nu- (76, 77). T h e new dimensionless modulus, aL, is defined as
merical technique are given by Roberts ( 9 ) .
@L = ( L 2 / D A C ~ , ,X
)
Results (observed reaction rate, gross catalyst volume) (14)
T h e results of the numerical calculations are shown in Figures For any integer-power rate equation of order n, Equation 14
1, 2, and 3. Figure 1 is a graph of (pA,,,/pA,,) us. q M for each reduces to
of a number of values of K p A , , ranging from -0.98 to +50.0.
@L = adL2
T h e lines for KpA,8 of -0.10 and + O . l O are essentially coin-
cident with the first-order line. T h e lines for KpA,, of -0.98 where
and -0.95 are coincident with that for -0.90 as shown on
Figure 1. T h e lines for a constant value of Kp,,, are drawn of
finite length. T h e left-hand terminus of a liqe occurs a t the
value of @u corresponding to 7 greater than 0.95. T h e right- and for the type of Langmuir-Hinshelwood rate equation
hand terminus occurs a t a value of +,lf for which (< - 7 ) is considered here
less than 0.005. Thus, for values of 4.,< exceeding the right-
hand terminus, Equation 13 is very accurate. For values of
@L = 7@.VAJ(1 + KPA.8)

KpA,, greater than +50.0 Equation 13 is also accurate to aL, as

within 5y0,except for values of 7 greater than 0.95. T h e ends
of the K p A , , = -0.95 line occur a t G.,~ values of 1.00 and
0.02; that of the -0.98 line a t q.rr values of 1.00 and 0.008.
Figure 2 shows the effectiveness factor, 7 , LIS. for the same
range of values of KpA,, that is represented in Figure 1 .
Equation 1 3 is accurate to within about 0.005 for the region to
the right of the dashed line in Figure 2. T o compute the
effectiveness factor, k' a n d KpA,, must first be calculated.
T h e values of k' and DA are then used to calculate $.M. T h e
values of and K p A , , may then be used to locate 7 on Figure
2 . If interpolation between lines of constant Kp,,, is neces-
sary, the calculation of several values of 6 will help fix the
position of the desired line. I n some cases it may be more
accurate to interpolate a value of from Figure 1 ,
and use Equation 1 2 to calculate 7 , but the relative accuracy
of these procedures has not been checked. Interpolation is
not necessary if the point falls to the right of the dashed line;
Equation 13 can be applied with good accuracy in this case.
Comparison of Effectiveness Factors Using Different
Kinetic Expressions. An illuminating way to compare
effectiveness factors for Langmuir-Hinshelwood kinetics with
those for integer-power equations is by relating 7 to a modulus
containing only quantities which can be either observed or
predicted. This approach was first suggested by TVagner
defined by Equation 14: is for slab geometry and
differs from the modulus a, which has been used extensively
by \.t-eisz and coworkers for analyses in spherical geometry.
T h e latter is given by Equation 16.
(observed reaction rateigross catalyst volume) (16)
Aris (2) sho\ved that the functions of 7 11s. q for a first-order
reaction in a sphere, a slab, a n d a cylinder of infinite length lie
very close together when the Thiele modulus, @! is based on a
characteristic dimension equal to the ratio of the volume of
porous mass to the outside surface through which reactants
have access. T h e use of slab geometry greatly simplifies the
mathematics in any analysis of effectiveness factors, so it has
been tempting to apply the results of calculations on slab
geometry to make predictions for other shapes by defining the
characteristic dimension in the above fashion. However, the
effect on the 7 - 4 relationship of changing geometrical shape
has not been generally established for kinetic expressions other
than first-order.
For the infinite slab sealed on one face, the characteristic
dimension of .4ris is exactly equal to L , while for a sphere it is
equal to R,i'3. Thus, if the effect of pellet geometry on v
could be essentially removed by using this characteristic
dimension, the present results on slab geometry could be

290 I&EC FUNDAMENTALS


compared directly with previous analyses on spheres by re-
placing ar,with 9.
\\'eisz (77) has suggrsted that the criterion for the absence
of difEusion effects is a value of '7 exceeding 0.95. For a second-
order reaction in a sphrre. this corresponds to about 5 0.3;
for first order. to Qs 5; 1.0; and for zero order. to @\ 5 6 .
T'hr corresponding-values of become 0.033:0.1 1, and 0.66.
respectively. Since the range from -zrro. to second order
seemed to cover most cases of interest. \Vrisz siiggrstrd that.
if 2 6. diffusion eftpcts \vi11 definitely be present. and if
Q T 5 0.30. difTurion efTectr are insignificant.
Figure 3 is a graph of 7 2 ' 1 . for various values of K p A , s
and for first-. second-. and zero-order reactions. l ' h e curves
for first- and zero-order expression5 may be regarded as specific
members of the famil)-. T h a t for z t ~ oorder corresponds to a
value of Kp.4,a approaching infinity and that for first order:
to a value approaching zero. T h a t for a second-order ex-
pression. ho\vever. cuts across the family of curves. A negative
value of Kp, , s indicates significant product adsorption effects.
as sho\vn in the discussion of Equation 8. T h e minimum
possible value of Kp;PA,s is -1. Using this plot, 7 can be esti-
mated directly for any experimental run \\ithout a trial-and-
error procedure. T h e error involved in the use of a n integer-
power approximation can also be estimated for any case from
Figure 3.
Several conclusions can be drawn from Figure 3.
~ ,
1. Unless K F , , ~ > 0.10, the 7 us. Q L curve is essentially
coincident with the first-order line. Moreover, if KPA,x >
50.0, the 7 - aL curve is essentially coincident with the zero-
order line.
2. .411 curves for positive values of Kp,,, are bracketed by
the first- and zero-order lines.
3. T h e actual valuer, of Q L for bvhich second-, first-, and
zero-order reactions have 7 = 0.95 are Q L = 0.075. 0.15,and
2.1. respectively. \Vhen the actual values of @ L for these
reaction orders are compared with the values of Q L that \vere
calculated by transforming from as to @I,. good agreement re-
sults only for first-order reactions. This comparison is sho\vn
in Table I .
I n other words. the difference betlveen the numbers in
columns 2 and 3 is a measure of the effect of geometry on the
Figure 3. Eftectiveness factor, r ~ ,as a function of modulus a,,
~
Table I. Values of @ I , Corresponding to Effectiveness
Factor of 0.95
R m t i i o n Ordrr +I, for Slab +I f o r Sfihves
0 2 1 0 66
1 0 15 0 11
2 o 075 0 033
functional relationship between effectiveness factor and
modified l'hiele modulus for each of three integer reaction
orders. Althoiigh the functions of '7 1 s . for the three shapes
studied by Aris fall close together for first-order reactions.
Table I shokvs that they depart from one another substantially
for reactions of other orders; for a given vaiue of QI, the true
effectivenes. factor in a spherr \vi11 be less than that calculated
for slab geometry, but the amount of the difference is only
knokvn for the simple cases above.
4. For $lab geometry. and probably for other simple shapes,
strong product adsorption (large negative values of Kpa , s )
results in '7 versus Q 1 ~curves jvhich are low relative to zero-,
first-: or second-order curves. .\s a n example, '7 = 0.95
at = 0.085for a second-order reaction. For strong product
adsorption-for example. \vith h;bA,, = -0.95--~ becomes 0.95
a t Q L = about 0.008. Therefore. \\'eisz' criterion that
diffusional effects \vi11 be absent if a, 5 0.3 must be extended
to considerabl! IoLver values of Qs if strong product adsorption
is involved-e.g.. diffusional limitations \sill be encountered
a t substantially lo\ver rates of reaction than heretofore pre-
dicted.
Appendix
Illustrative Example. An example of a system in \vhich
the rate of reaction is retarded by a product is the reaction of
carbon dioxide \vith solid carbon Xvhich is retarded by carbon
monoxide. T h e effect is particularly marked a t relatively
lo\ver temperatures. L-se of the method developed in this
paper for calculating the effectiveness factor may be illustrated
by taking a set of data for one run from LValker. Rusinko. and
Austin ( I T ) . 'I hey studied the reaction of COSwith spectro-
scopic carbon. a fincly porous material, a t temprratures rang-
ing from 950' to 1305' C.. and a t various CO? partial pres-
sures. I'he mathematical relaticnships for this reaction are
@L
VOL. 4 NO. 3 AUGUST 1965 291
the same as those for decomposition or isomerization of a T h e authors did not determine a rate equation for the reac-
single reactant on a porous catalyst, except that the porosity tion, but several other investigators have reported that on
and hence the effective diffusivity will increase as reaction each of various types of carbon it is of the form
proceeds. T h e reaction d a t a of Walker et al., however, are
for only the first 11% of reaction, so the change in diffusivity
during a run is relatively insignificant.
T h e carbon was cylindrical in shape, 2 inches in height, T h e form of carbon most similar to that studied by \\'alker
and '/z inch in diameter. A '/*-inch hole was cut in the et a l . on which kinetic information is available, is probably
center, and a mullite rod was inserted in this hole. T h e top electrode carbon. \ V u (79) reports valdes of the constants
and bottom faces of the cylinder were sealed off with mullite for electrode carbon over the temperature and pressure range
plates so that access to the interior of the carbon was available of interest. \2'ith Figure 35 of ( 7 9 ) the values a t 1000O C.
only through the lateral exterior surface, and diffusion was can be estimated as
truly radial. T h e initial weight of the carbon annulus was
about 8.8 grams. Kco? = 2.4 atm.-'
Figure 22 (75, p. 197), shows that a t a COS partial pressure
of 0.75 atm. and a t temperature of 1000' C., the rate of reac-
tion was 0.125 g r a m of carbon per hour. Presumably, the
partial pressure of carbon monoxide a t the exterior of the
carbon was zero during the run, and it will be assumed that I t will be assumed that these can be applied to the \vork of
nitrogen, which was present in the feed stream, does not Austin et al. A value of KpA can now be calculated.
enter into the rate equation. Rates were measured over about
the first 11% of burnoff, so that a t the midpoint of this interval

Rate/gram = 0.125/(8.8 X 0.945) =

0,1251'8.32 = 0.015 g r a m C/gram C hour

Figure 13 (75) shows that the average porosity (cc./cc.) of

this sample during the period of the burnoff is about 0.36. If it is assumed that the diffusivity is approximately propor-
Taking 2.27 as the true density ( p t ) of carbon, the apparent tional to the square root of molecular weight
density of the particle is then
p = (1 - 0) pL = (0.64) (2.27) = 1.45 grams per cc. (Dco, Dco) = d 2 8 44 = 0.80
T h e observed reaction rate per gross volume of carbon
K = (2.4 - 0.80 X 63 X 2) w = ( 2 4 - 101) w = -99 w
(0.015) (1.45)
-
12 3600

= 5.04 X 10-7 mole/(cc.) (sec.)

From Figure 16 (75) the effective diffusivity D = 0.013 sq.
c m per second a t NTP. Diffusion apparently occurs in the
transition region between Knudsen and bulk diffusion. T h e = 1 + 0.80 X 0.75 X 63 X 2 = 77
authors suggested that D is proportional to about but
i n a more recent study on a similar graphite electrode, for
COz counterdiffusing through helium between 30" and about
400" C. a t a total pressure of 1 a t m . , Nichols (5) reported the Interpolating between Lhe curves for K p d , s = -0.95 a n d
temperature exponent to be about 0.98. Using this value -0.98 in Figure 3, the effectiveness factor, 7 , for this run is
about 0.35. If the temperature coefficient of the diffusivity
D (1000" C.) = 0.013 X 8$2( = were taken to be 1.3 as suggested by ivalker. aL would be
0.0715 and for 7 : about 0.5. Therefore, internal diffusion
0.013 X 4.20 = 0.0545 sq. cm./sec. effects are significant. This conclusion has been confirmed in
a subsequent paper by Austin and b'alker ( 3 ) .
T h e external concentration of carbon dioxide is
If the reaction \vere assumed to be of simple first order,
C A , s = 0.75j(82.06)(1273) = 7.16 X l o p 6 mole/cc the effectiveness factor would erroneously be calculated to be
nearly unity-i.e.! diffusional effects would be thought to be
T h e dimension L , given by the ratio of volume to surface,
insignificant. Even if a simple second-order reaction were
can be approximated by
assumed, the effectiveness factor would be taken to be about
0.92.
Another study in which intrinsic reaction rate data are
available on electrode carbon is that of Reif (8). Using his
T h e value of aLcan now be calculated values for the constants in Equation A-1. the value of KpA,s=
-0.970, which is very close to the value calculated from \\'u's
L2
@L = ~ (observed ratel'gross carbon volume) = data. .4ctually, IVu's correlation for coal coke gives a t this
OCA ,s temperature a value of KpA,s = -0.965. identical to the value
(0.298)*(5.04 X lo-') for electrode carbon. For the same observed rate of reaction.
(7.16 X (0.0545) the effectiveness factors for these two types of carbon would
aL = 0.114 therefore be very close to the one calculated above.

292 I&EC FUNDAMENTALS

Acknowledgment aL = modulus defined by Equation 14
as = modulus defined by Equation 16
T h e machine computations necessary in the preparation of qjL = Thiele modulus, defined by Equation 15
this paper were performed a t the Massachusetts Institute or $.,f = modified Thiele modulus, defined by Equation 10
Technology Computation Center. Acknowledgment is also w = parameter defined by Equation 6
made to the Sational Science Foundation for providing finan- SUBSCRIPTS
cial support to George W. Roberts in the form of a fellow-
z = index denoting any chemical species other than A
ship during the period of the project. o = sealed surface, x = L
s = exposed surface, x = 0
Nomenclature
literature Cited
Any consistent set of units may be used. Those specified
below are those used by Satterfield and Sherwood ( 7 7). (1) Akehata, T., Namkoong, S., Kubota, H., Shindo; S.; Can.
J . Chrm. Eng. 39, 127 (1961).
ENGLISH
LETTERS (2) Ark. R., Chem. Eng. Sci. 6 , 262 (1957).
(3) Austin, L. G.: Walker, P. L.. Jr., A.Z.Ch.E. J . 9, 303 (1963).
A = geometrical surface area of catalyst mass, sq. cm. (4) Chu. C., Hougen, 0. .4., Chem. Eng. Sci. 17, 167 (1962).
C , = concentration of ith species, g. moles!(cc.) (5) Nichols, J. R.?Ph.D. thesis, The Pennsylvania State University,
D i = effective diffusivity of ith species, based on total cross 1961.
section of catalyst mass. sq. cm./sec. (6) Otani, S., Wakao, N., Smith, J . M . , A.I.Ch.E. J . 10, 130
(1964),
I; = parameter defined by Equation 8, (atm.)-I (7)' Prafer, C. D., Lago. R. M.. Advan. Catalysis 8, 293 (1956).
K i = adsorption constant for ith species in Langmuir- (8) Reif, -4. E., J . Phys. G e m . 56, 778 (1952).
Hinshelwood rate expression, (atm.) (9) Roberts. G. LV.. Sc.D. thesis, Department of Chemical
k = reaction-rate constant, g. moles l(cc.) (sec.) Engineering, Massachusetts Institute of Technology, 1965.
k' = modified rate constant (see Equation ?), (g. moles) (10) Rozovskii, A. Ya., Shchekin, V. V.. Kinetics Cataiysis (USSR)
(arm.) (cc.) isec.)
I 1, 313 (1960) : p. 286 of Consultants' Bureau English trans-
L = thickness of catalyst mass. cm. lation.
p 1 = partial pressure of ith species, arm. (11) Satterfield. C. N.. Sherwood, T. K.; ''Rolr of Diffusion in
Catalysis." Addison-Wesley. Reading. Mass., 1963.
R = gas constant, (atm.) ( c c . ) ! ( g . moles) (OK). (12) Schilson. R. E.. Amundson, N. R., Chrm. Eng. Scz. 13, 226,
R,? = radius of sphere. cm. 237 (1961).
I = reaction rate: (g. moles), (cc.) (sec.) (13) Thiele: E. W.; Znd. Eng. Chem. 31, 916 (1939).
7 = absolute temperature, OK. (14) Wagner, C.. Z. Phyr. Chem. A193, 1 (1943).
V = volume: cc. (15) Walker. P. L.. J r . : Rusinko. F.: Jr., Austin, L. G., Aduan.
.Y = Cartesian dimension, cm. Catdysis 11, 134 (1959).
(16) LVeisz. P. E.. Hicks, J . S.. Chem. Eng. Sci. 17, 265 (1962).
GREEKLETTERS (17) LVeisz, P. B., Prater, C. D., Adam. C ~ t a l y6s, ~143
~ (1954).
(18) Ll'heeler, A . H.. Zbzd.. 3, 249 (1951).
17 = effectiveness factor (see Equation 12) (19) \Vu, P. C.. Sc.D. thesis, Massachusetts Institute of Tech-
4 = approximate effectiveness factor, defined by Equation 13 nology. Cambridge, Mass.. 1949.
6' = void fraction of catalyst mass, (cc.)/(cc.)
RECEIVED
for review August 17, 1964
v i = stoichiometric coefficient of ith component ACCEPTED February 8, 1965
p = apparent densi1.y of catalyst mass: g./(cc.)
p t = density of solid material in catalyst, g./(cc.) First in a series on effectiveness factor for porous catalysts.

DIFFUSIONAL EFFECTS IN GASISOLID

REACTIONS
J 0 H N S H E N AND J . M . S M I T H , University of California, Dar?is, Car$,

The interaction of physical transfer processes and chemical reaction is considered for the reaction of a gas
and spherical pellet of solid reactant. The conversion-time relationship is derived for both isothermal and
nonisothermal conditions for which mass and energy transfer as well as reaction resistances are important,
For isothermal conditions the conversion can be expressed in terms of a dimensiontess time and two param-
eters, while for nonisothermal systems three additional parameters are necessary. For an exothermic
reaction, there is a region of unstable operation bounded at the upper temperature level by a stable diffusion-
control regime and at the lower level by a stable kinetic-control regime. Approximate criteria are derived
for the limits of instability. A numerical application is given showing the transition from the diffusion to
kinetic regimes.

HE rates of gas-solid reactions in which one reactant and porous solid around the shrinking core of B, according to the
T o n e product are solids are particularly susceptible to diffu- reaction
sion resistances. For nonisothermal, exothermic examples
also. the interrelationship between mass and energy transfer
A(g) + bB(s) + G(g) + rcb'(s) (1 1
can lead to interesting stability problems. T h e analysis that Further conversion occurs by diffusion of A through the
follows is restricted to a single. spherical pellet in a gas stream product layer to the core of reactant. T h e reaction at the
of constant composition. Initially the pellet consists of non- surface of B is assumed to be first-order and reversible, so that
porous reactant B. As reaction proceeds, product W forms as a the local rate is given by

VOL. 4 NO. 3 AUGUST 1965 293