THE B E H A V I O U R O F P O R O U S CATALYST PARTICLES IN

VIEW O F I N T E R N A L MASS A N D HEAT D I F F U S I O N EFFECTS

P. B. WEISZ and J. S. HICKS

Socony Mobil Oil Company, Inc., Research Department, Paulsboro Laboratory,
Paulsboro, NJ 08066, U.S.A.

(Received 27 February 1961)

Abstract--The reactivity behaviour of porous catalyst particles subject to both internal mass concentration
gradients as well as temperature gradients, in endothermic or exothermic reactions has been analysed. The
analysis uses the exponential relationship between intrinsic reaction rate and temperature without approxi-
mations. Criteria for the existence of appreciable mass and heat diffusion effects, their quantitative
appraisal, and their significance and importance in various types of actual catalytic solids are discussed.
Regions of inherent instability of operation are shown to exist, and the conditions for their existence are
demonstrated.

R~sum6--Le comportement r6actionnel de particules de catalyseur poreux soumises/l des gradients de

concentration massiques internes ainsi qu'/t des gradients de temp6rature a 6t6 examin6 pour des r6actions
exothermiques et endothermiques. L'analyse utilise les relations exponentielles entre la vitesse de rb,action
intrins~que et la teml~rature, sans approximations. Les auteurs discutent ~galement les crit~res d'existence
d'effets appreciables de diffusion de chaleur et de masse, leur 6valuation quantitative ieur signification et
leur importance dans les divers types de catalyseurs solides. II existe des r6gions d'instabilit6 inh&entes
/t l'op6ration et les conditions de ieur existence sont discut6es.

1. INTRODUCTION various geometric forms [5, 6] so that the spherical

When a chemical reaction process occurs within a particle is a good approximation [7, 8] for most cases
porous particle, its behaviour may deviate appreciably encountered, such as cylindrical pellets or irregular
from true chemical kinetics, when interpretation is granules.
based on externally observable quantities. For It was shown by Weisz [9] that the conditions
example, the intrinsic chemical behaviour of the reac-
dN 1 R 2
tion rate per unit volume of a porous catalyst dN/dt, <1 (1)
may follow--or be closely approximated b y - - a first- dt Co D
order law, dN/dt = kc, where c is reactant concentra- offer a useful and general order of magnitude criterion
tion and k is the reaction rate constant. However, which for a reaction system tests or defines conditions
the observed rate may not be equal to kco, where Co is for which no appreciable modification of chemical
the reactant concentration known externally of the kinetics will be observed (i.e. r / ~ 1), and which
particle. This situation will occur if mass transport criterion contains only observable quantities and
resistance creates an appreciable concentration drop does not presuppose knowledge of the intrinsic rate
within the particle. Expressions which take mass law.
transport into account have been derived by Dam- For experimental rate data for which eq. (1) is
k6hler I-1"1,Thiele [2"1, Zeldowitsch 1-3] and Wheeler not satisfied, an Arrhenius plot will not represent
1-4"1, leading to a modification of intrinsic kinetics true chemical kinetics and its slope will not yield the
taking the form chemical "activation energy", Qo. A value which
is too small will be obtained ranging between Qo
dN
dt F(c)~l and ½Qo.
The analysis of diffusion effects has been frequently
where F(c) is the intrinsic chemical kinetics ( = kco, in and successfully applied in experimental work (e.g. by
the case of first-order); r/has been termed the utiliz- Wicke and Brotz [61 and Weisz and Prater [5]). In
ation factor and is a function of the dimensionless such work the entire catalyst particle has been as-
quantity ~b = R ( k ~ with D the effective diffusivity sumed to be isothermal. When the chemical reaction
and R a length parameter (radius in case of a sphere). is accompanied by a heat effect, not only a mass
The exact functional form of r/(¢) depends on concentration gradient, but also appreciable temper-
the functional form of the intrinsic chemical kinetics ature gradients can exist within the particle. The anal-
F(c) and the particle shape. The approximate behav- ysis of the behaviour of such a system becomes more
iour of the functional forms is sufficiently similar for complicated since now both reactant concentration
and the rate constant, which generally is exponenti-
ally dependent on temperature, will be functions of
position within the particle.
This report is concerned with the solution of the
Reprinted from Chem. Engng Sci. 17, 265-275, 1962. non-linear equations for simultaneous mass and heat
3951
3952 P. B. WEISZand J. S. HIcKs
diffusion effects. Specifically, the dependence of the temperatures at any point within the granule,
utilization factor in relation to catalyst properties and
HD
reaction conditions is developed, the practical circum- AT=T-To= -~(Co-C) (7)
stances leading to measurable or profound effects due
to internal temperature gradients are discussed, and with To and Co being the boundary values. This rela-
the consequences of such effects on the "Arrhenius tionship was proved by Prater [11] to apply to any
plot" of experimental data are examined. particle geometry. The use of this relationship enables
us to write the reaction rate (6) in terms of one vari-
2. T H E PROBLEM AND ITS S O L U T I O N able instead of both, c and AT, namely
In the usual analysis of chemical kinetics with diffu- dn
sion effects one usually obtains the reaction rate per - - = kocoy exp{~fl(1 - y)/[1 + fl(1 - y)]}
dt
unit volume of the catalyst particle by deriving the
concentration gradient of the reactant, grad c, at the coHD (AT I c
particle boundary, and setting Q fl = = , y = - - . (8)
7 = R To' K To \ To/max Co
dN The parameters ~ and fl each have convenient phys-
dt - [grad c]ats ical significance; y expresses the sensitivity of the reac-
tion rate to temperature; it is the exponent in the
where S is the particle surface and V its volume. From
Arrhenius expression of the true chemical rate. fl is the
this, one obtains the utilization factor, as maximum temperature variation (AT)mal which could
(DS/V) [grad c].t s exist within the particle relative to the boundary tem-
~l = - F(co) perature; this follows from eq. (7), by c --, 0.
We can now formulate the conditions represented
For a spherical particle with radius R, by eqs (4) and (5) in terms of a single variable, by using
the rate expression (8) in the mass diffusion equation
3Dco r ,
r/- R--~o) tgrau C.ls (2) (4); in this manner we obtain the equation for spheri-
cal particles
For first-order kinetics, F(co) = kco, eq. (2) becomes 1-y
D [-~,2
f d 2 y ±7-2 d y ~ = k o y e x p [ ' f l + fl-0 --- Yi]
3 \,~, r dr] 1
~/= ~-~ [grad] Ys. (3)
or

If heat transport is also taken into account the

system must satisfy not only the diffusion equation for d2y +
-dx
~ ~
= ~o2y exp yfl
(ly)1 +-tffi- y)
(9)
the mass transport (4) but also the analogous equa-
tion for heat diffusion (5), where ~bo = R ~ ; y = C/Co; x = r/R.
We have solved this equation by numerical integra-
dn
D V2c - ~-~ = 0 (4) tion (see Section 6 below) for [grady],ta, subject to
the boundary conditions y(1)= 1, (dy/dx)x=o = O,
dn and have obtained relationships between the utiliz-
kV 2T - H-~ = 0 (5) ation factor ~/ and the characteristic variable ~bo
for a range of values for the parameters ? and ft. At
where K is the thermal conductivity, H the molar heat this point it is well to review the physical significance
of reaction and dn/dt is an exponential function of of r/. It represents the ratio of actual reaction rate
T (the actual per unit volume reaction rate in a vol- to that which would be produced by the catalyst
ume element), particle if negligible temperature or concentration
gradients existed within the particle; i.e. if the
entire particle "saw" the reactant concentration
Co and temperature To, which are the externally
We can introduce the boundary temperature To, measurable conditions.
and the corresponding rate constant ko = k(To), as
fixed reference points, 3. RESULTS AND INTERPRETATION
Figures 1-4 summarize the results of calculations
for 7 = 10, 20, 30 and 40, and fl in the range from 0 to
dt acexp R(To + A T + 0.8 (exothermic reaction) and 0 to - 0 . 8 (endother-
mic reaction).
=kocexp R-To To I + A T / T " (6)
Utilization factors larger than unity
DamkiShler [10] has pointed out that for For the case of exothermic reactions it is seen that
the spherical particle eqs (4) and (5) lead to a relation- r/ can become larger than unity for large enough
ship between the reactant concentrations and the values for 7fl and specific values of ~b. For a sufficiently
 The behaviour of porous catalyst particles in view of internal mass and heat diffusion effects 3953
iO00.O ~ , ,,i,,, , , ,I,,,, , ,,(,,,, , ,,I,",-

5o0.0 y,~o ~ooo ~ "r=3o -

100.0 too.o \
50,0 oo

I0.0 iO.O ~' \

1.0
05 ~ 0.5
=0.8
0.1 =0.8 0.1 .
0.05 ~ =0.~ 0.05 ~-
~=0
~ =-0.2
~ =-0.4
O.OI "~=-O.g
0.01
=-0.8
0.0O5
0.005

)
I i [ lllll l l i I ii,l I i , } ,,ii I i i i i l]
(1001 , i i |1111 i i i |lilt i i t IiJ|l I I 11|1~
O.z 0:5 1.0 S.WOI0.0 {0 I00 500 1000 lO.O 50 iO0
0.01

Fig. 1. Relationship of utilization factor and dimensionless

diffusion parameter. Fig. 3. Relationship of utilization factor and dimensionless
diffusion parameter.
4'o=R/ko;7=lO
~/u 4,o=R/~;~=30

,ooo.o , ,,I,,,, I , ,,I . . . . . . . I . . . . . . . I'"

iO00.O ' ''f'"' ' ' 'I'"' ' ' ~I'"' ' ' 'I'"-
L
5000 500.0 ¥= 40
y, 20

ooo

500
500 E
bOO0 ~ ~O)

IO.O

1.0 ~ ' ~ ~
05 o._~
tO //3
T) 0.5 ~=0.8 9
~=0.6
--,0.4
0.1 ~--'0.3 O.t
~,0.2 O.OS
3.05 ~:0.1

-:°o ~
,, ~ = - 0,4.
O.Ot ~ =- 0.~' 0.0 ~ "<
-: =-0.8
0.005 0.00.'

0001 , , ,l,,~ , . ,h,*t i i tlL,,t , , ,l,h 0.001 r" , , =ll,,A t i ehlH I I |l,|ll f = ;ll,t
0.1 0,5 i.O 5.0 iO0 50 iO0 500 iO00 O.OI 0.05 0.1 03 LO 5JO IO.O 50 IO0

FiE. 2. Relationship of utilization[actor and dimensionless Fig. 4. Relationship of utilization factor and dimensionless
diffusion parameter. diffusion parameter.

~bo = R . / ~ ; 7 = 20 ~bo = R j ~ ; 7 =40

3954 P. B. WEISZand J. S. HIcKs
fast exothermic reaction the average internal temper- corresponding to an actual Q = 37 kcal/mol, as it
ature will be above the boundary temperature To, would be modified due to heat and mass diffusion
and the resulting increase in the internally "effective" effect for a case offl = 0.2 and ~bo = 0.1 at 723 K. It is
rate constant over the value of ko can, for certain noteworthy that the transition of slope from Q' = Q
combinations of mass diffusivity and thermal con- to a maximum value above Q takes place over a range
ductivity, outweigh the drop in the overall "effective" of about 0.2-20 in ~bo,i.e. over a range of a factor 102.5
reactant concentration below the value of Co, to pro- in reaction rate, or a temperature interval of 200 K.
duce a reaction rate greater than koco. The range of temperature, or reaction-rate en-
compassed by most practical measurements, is often
Consequences on Arrhenius plot much smaller and experimental accuracy sufficiently
In an attempt to observe the variation of reaction limited so that the investigator cannot easily recog-
rate with temperature one varies ko and therefore q~o. nize his operation as taking place in this range of
Weisz and Prater has shown that one can deduce transition.
rather simply the behaviour of the resulting Arrhenius
slope Q' over a range of variation of ~bo from the Criteria for existence of significant thermal effects
conventional functional plots of In q vs In ~o, from It is of interest to find criteria which would dofine
Q' 1 dlnr/ conditions for which we need not be concerned about
--=I+--- internal thermal effects, or which would define condi-
Q 2 dln~bo
tions which must be analysed further with due consid-
i.e. from the slopes of the plots of Figs 1-4. For eration to the internal temperature gradient. A cri-
no-thermal effect ( f l = 0 ) and for endothermic terion containing only observable quantities, analog-
reactions (fl <0) the slope d In ~//dIn ~bo varies mono- ous to that of eq. (1) for the case of mass diffusion
tonically from 0 to - 1 , and thus the Arrbenius "ac- effect alone, is particularly desirable for exothermic
tivation energy" varies from Qo, at sufficiently low reactions.
temperature, to Qo/2, for sufficiently high temper- If in the case of no-thermal effect (fl = 0) the cri-
atures. For exothermic reactions and moderate values terion ~o ~< 1 is acceptable as indicating conditions
of fl < 0 the slope dlnr//dlnq~o can take up positive for negligible diffusion effect we can derive a modified
values; with rising temperature, the Arrhenius slope condition for the size of ~o ~< I x P(7, fl) which takes
may rise in value above Q and pass through into account possible thermal effects. Equation (9)
a transition to ultimately again approach the value differs from the case of no thermal effect by the pres-
Q/2. Figure 5 shows an example of an Arrhenius plot ence of the exponential term. Over the entire range of
y the exponent cannot be greater than Vfl/(1 + fl).
Thus, where ~o ~< 1 was a sufficient criterion for fl = 0
104
~2 exp[vfl/(1 + fl)] ~< 1
NO MASS OR HEAT
TRANSPORT EFFECTS or

~bo ~< exp[ - ½yfl/(1 + fl)] (10)

10"* ~ M A S 5 AND HEAT should now be a sufficient criterion for exothermic
TRANSFER EFFECTS
reactions. This should be "safe" and conservative inas-
much as in fact, y > 0 (i.e. the exponent must be
"O smaller than the value above) for most or all of the
v; range of y. Inspection of Fig. 2 demonstrates how, for
bJ
I,- MASS TRANSPORT example, a case like V = 20, fl = 0.3 becomes conser-
<: I0a
n," EFFECT ONLY"
vatively "safe" at q~o ~0.1 as predicted by eq. (10)
Z
O above.
I--. This criterion can be reformulated in terms of "ob-
w servables" by eliminating ko from dN/dt = kocoq and
10 ~bo = R ~ , to
dN 1 R 2
Oo~,S= ~, (11)
dt Co D
from which we obtain with eq. (10) the criterion
I I I
dN 1 R 2
800 700 600 500 dt Co D exp[vfl/(1 + fl)] < 1. (10a)
TEMPERATURE, "C

Thus a criterion is available to define the range of

Fig. 5. Modification of the Arrhenius plot of activity due to
mass transport effect, and due to both mass and heat trans- "safe" operating conditions of a rate process, i.e. for
port effect for the case Q = 37 kcal/mol, fl = 0.2, $0 = 0.1 at behaviour free of mass and heat diffusion effects, in
723 K. terms of properties and operating parameters which
 The behaviour of porous catalyst particles in view of internal mass and heat diffusion effects 3955
can be measured or defined independently of an ac- of heat removal by conduction for a given temperature
tual rate operation. differential between adjoining volume elements will
therefore be able to intersect this curve up to three
Behaviour for large diffusion inhibition times. Thus we can obtain a physical rationale for
For large values of ~b0, the slope d In r//d In ~bo ap- obtaining up to three steady-state solutions, which are
proaches - 1 as in the standard case without thermal defined by the equalities of heat production and re-
effect. This suggests that for an experimental inquiry moval rates. The same picture leads to insight into the
into the activation energy, one may not only proceed nature of the instabilities implied by the presence of
by designing conditions satisfying the criterion (10a) multiple roots, such as has been described by Frank-
to measure Q, but may at times find it more expedient Kamenetskii [12] for an analogous problem in
to go to conditions of strong diffusion inhibition and exothermic surface reactions and ignition. The point
there to measure Q/2. b is metastable; an initial temperature condition be-
low b will result in stabilization at a; initial conditions
Multiple solutions corresponding to a point above b will send the system
For exothermic reactions, with severe thermal ef- to condition c.
fects defined by f17 > 5, there exists a region of ~bo- This indicates that in observing reaction rates as
values associated with values of ~/>> 1, where multiple a function of rising temperature, one may obtain a dis-
solutions result for r / = ~/(~b).In this range of multiple continuous temperature change when a metastable
solutions, the physical situation of the steady-state condition is passed, i.e. when the system is in a state
concentrations and temperatures within the particle is characterized by multiple steady-state solutions.
not sufficiently defined by eq. (9), i.e. by eqs (4) and (5).
The applicable stable solution may depend on condi- 4. APPLICABILITY TO VARIOUS OPERATING SYSTEMS
tions from which steady state is approached; or, the
We shall discuss the type of porous solid reaction
condition may be intrinsically unstable as defined,
systems which are "safe" from, and those subject to,
stabilization resulting from second-order phenomena
significant internal thermal effects. The parameter fl is
such as temperature dependencies of D, K, etc. The
determined by two properties of the solid, D and K,
physical situation leading to multiple solutions may
and by chemical reaction parameters To, Co and H.
be understood as follows:
Magnitudes encountered in various physical systems
With every temperature To + AT of a volume ele-
will be of interest. The magnitudes of effective dif-
ment there is associated a reaction rate given by eq.
fusivities of porous catalyst particles have been dis-
(6), which in view of the interrelationship of temper-
cussed and studied by several authors [4, 5, 9]. The
ature and reactant concentration (7), has the form
upper bound to the magnitude of possible diffusivities
is the free gas-phase diffusivity, corrected (downward)
~ = pexp R(To + A T ) (q - AT). for the fraction of void space in the solid (porosity),
and for "tortuosity" I-4]. Thus a reasonable upper
Thus the functional relationship of rate of heat pro- magnitude is of the order of Dmax~0.2.½.½-
duction and temperature begins with an exponential 5 x 10 -2 cm2/s at atmospheric (or higher) pressure.
rise, but is subject to an inflection, as illustrated by the Thermal conductivities will vary greatly, their mag-
sketch A in Fig. 6. A straight line representing the rate nitude depending mainly on solid composition rather
than macroscopic structure. The available spectrum
ranges from metals with K ~0.1-1.0 cal/(cm s K) to
insulators with values down to Kmin ~ 10 -4. The heat
conductivity of the non-metallic solid will depend
mainly on the degree of order in crystalline structure,
RATE ~A decreasing with increasing disorder toward that of the
completely random assembly corresponding to a gas
(K ~0.2-0.7 x 10-4).
Thus we may estimate an uppermost limit offl to be
encountered, with H ~70kcal/mol and at atmo-
spheric pressure (Co ~ 2 x 10-s mol/cm 3)

HcoDmax 700
/3m,x (12)
Kmin To To

B or of the order of unity. At higher pressures Co will

rise, but D will drop proportionately. At lower pres-
sure the inverse compensation will occur until gaseous
TO --~ To+AT mean-free-path approaches and exceeds internal pore
Fig. 6. Functional shape of heat generation rate, A, with dimensions, whereupon Dmax will no longer increase
temperature above the boundary temperature, and depend- as Co drops, thus decreasing/~ below the above limit.
ence of heat removal rate on temperature differential, B. As exceptional cases there remain conditions of
3956 P. B. WEISZand J. S. HICKS
a highly exothermic reaction, with D at Dm,x and K at may be particularly important in the case of carbons
Km~x as above, at unusually low temperatures. which vary in structure and type of crystalline order
It is with this in mind that our calculations cover sufficiently to have important effects on temperature
the range 0 <fl < 1. It is noted that cases of fl <0.03 coefficients.
are not likely to be experimentally significant devi-
ations from fl = 0. Solid-liquid phase reaction systems
For a contact between a porous solid and a liquid
Porous solids with Knudsen diffusion phase reaction system we can examine the magnitude
Typical examples of non-metallic catalytic solids of fl in the light of the magnitudes of the constants
with pore structures of small enough dimensions to be applicable to liquids. We shall have K ~0.2-1 x 10- 3,
operating in the Knudsen diffusion range are the D < 10- 5_ 10- 6, Co< 5 x 10- 2 mol/cm 3, and therefore,
oxides or mixed oxides of silicon, aluminium and/or again with H = 70 kcal/mol,
magnesium, derived by drying and calcination from
hydrous gels, without precipitation or flocculation [9] 7
(formation from "xerogels" or "jellies" [131). They
have a relatively narrow pore-size distribution around
Thus such reaction systems can usually be considered
an average dimension of, for example, 50 A, in the case
safe from internal thermal effects.
of silica-alumina cracking catalysts. With typical
effective diffusivities [8, 9] of about D ~ 1-5 x 10- 3,
and heat conductivity [14] or K ~ 5 - 9 x 1 0 -4, 5. THE UTILIZATIONFACTORIN TERMSOF
modifying eq. (12) to flmax~ 14/To to 2~To. Operation OBSERVABLE PARAMETERS
of this type of material would therefore be expected to The graphs of Figs 1-4 demonstrate the depend-
be free of internal thermal effects, and justifies neglect ence of the utilization factor r/on basic properties of
of this phenomenon when studying mass diffusion the catalyst material and catalyst reactivity, as repre-
effects, using this type of solid. sented by fl, ~, and q~0. Use of q~o implies some know-
ledge of the intrinsic rate constant ko which often is
Porous metals not available because the experimenter is in fact faced
In view of thermal conductivities of three to four with the problem as to whether his catalyst system
orders of magnitude above Kmin,it is clear from eq. reflects true kinetic behaviour. It is most practical
(12) that even for the highest attainable mass diffusivi- therefore to introduce a parameter which involves
ties, no thermal effects need to be anticipated in por- only "observables". The quantity q~o 2rt has been shown
ous metals, metal sponge, etc. by eq. (11) to contain only observable quantities,
namely the observed reaction rate, reactant concentra-
tion, particle size and diffusivity.
Porous solids with non-Knudsen diffusion Figure 7 shows the plots of ~/vs the quantity
In porous solids with pore diameters large com-
pared to the gaseous mean-free-path, D approaches
Dmax above. Such solids are common in many areas of
operation, including catalytic operation, and combus- The transformation of the abscissa to ~4~ has re-
tion of porous carbons. In many such instances pre- moved the multiplicity in the functions, in the sense
cipitates or fine particles are compressed by extrusion that a given observed rate
or by pressure pelleting operations, to produce the
ultimate granules. Inasmuch as precipitates generally
have a particle size of the order of 0.1-10 It, a pore i.e. dt co
structure of 103-105 A dimensions exists, leading to
the diffusivities just indicated. defines the system uniquely. However, there will be
It follows from eq. (12) therefore that the thermal a metastable region of rates, indicated by the dashed
conductivity can be a very decisive magnitude for portions between arrows, which corresponds to the
these solids, unless its magnitude is K > 3 x 10-3 cal/ regions of multiple solutions in r/ vs ~o, which we
cm s K. Measured values for catalytic oxides [14] lie believe cannot be realized by the steady-state catalytic
definitely below this limit; also the spectrum of results system.
from the few measurements on carbons span a range The graphs of Fig. 7 should be of most universal
which includes values below this limit. For the inter- utility in the appraisal of mass or heat transport
pretation of rate studies on these solids, with non- interference for a given or contemplated catalytic sys-
Knudsen pore structure, knowledge of its thermal tem. One may estimate fl for the catalyst and reaction
conductivity can become very important. We note conditions, and inspect on these graphs the likelihood
that such knowledge is indeed very sparse. In addi- and nature of the transport effects at any level of
tion, most thermal conductivity studies have been actual, observed or contemplated rate. Or, one may
confined to temperatures low compared to the operat- use the relationships to quantitatively explore kinetic
ing temperature which may be of interest in connect- behaviour when the absence cannot be assured by
ion with catalytic or combustion rate studies. This experimental design.
 The behaviour of porous catalyst particles in view of internal mass and heat diffusion effects 3957
I0
t l iO0 ,/.""-" "N.
'7 /" ~ ~"=40
,
t.O
IO ~ ,"
j,,
I /
\ \
0.1

o.ot ) ,! ° J, ,1
0.1 1.0 I0 I00 1000
(a)

~'20
o.o, ... \ 'N~°O.
o.2 2

I0 / / ~' 0.00[ I / Illlll , I llllti ? t /))ill I f t )1

O.I 1.0 10 IOO tO00

/' /
(d) CI) "

Fig. 7. (Continued.)
LO

6. M A T H E M A T I C A L METHODS
Solutions to eq. (9), subject to the boundary condi-
0.1 tions y'(0)= 0 and y(1)= 1, for various values of
y and fl, were obtained by numerical methods, because
an analytic attack did not appear feasible.
It was noted by Wei 1-15] of this laboratory that the
0.01i i , tJ,,,, ,,,
0.1 1.0 I0 I00 I000 transformation x = a~ applied to eq. (1) results in the
(b) equation

d 2 y + ~ dy [ 1-Y 1 (9a)
d~ 2 ~ = a2~p~y exp 7fl 1 + -fl-0 S_ y)
,oo~
r which is of the same form as eq. (9). This transforma-
tion makes it possible to treat the two-point bound-
';~ \ ze- ary-value problem as an initial value problem (more
IO /
tractable from the viewpoint of numerical analysis).
The procedure is the following:
(1) For desired values of~ and fl choose a value for
,o ~ ~ -, a
a~.
(2) Assume a value for y(0) and integrate eq. (9a)
until y(~) = 1.
(3) Set 1/a equal to the value of ~ for which
y(~) = 1.
(4) Calculate q~o
z.
This procedure solves the original boundary-value
0.01 ~N~O~4" problem for the calculated value of q~2. Then
-0.8 3 dy 1
~/ a~b2d¢ at ~ = - . a
O. I I.O I0 I00 1000
An additional problem is that of determining the
(c) ~ "
value of the indeterminate form (2/¢)(dy/d~) at ¢ = 0.
This can be done as follows: Expand dy/d~ in a Taylor
Fig. 7. Functional dependence of utilization factor on the
"observable" quantity. series about ~ = 0; then
dN 1 R2
# o~ --= -I-
dt co D de d-~ ¢=o d-~ ¢=o ¢ + \d-~//¢=o T + ""

CES 50-24-H
3958 P. B. WEISZ and J. S. HICKS

or, since odd derivatives are zero because of symmetry and call this the slope of the In ~/,In $ plot at
dr (d2y'~ r / = ~ and $o=~$o2).
d-~ = k-d-~J¢ =o ~ + "" 3. Calculate dy'(1)/d$o and for a given A$o calcu-
Therefore, late a new ~/by
3 {, d y ' ( 1 ) , , "~
lim 2dy t/d2y~ ~/,cw = ($o + AS) 2 ~ y (1) + - - ~ o zX~po:.

4. Set rh = r/and r/2 = r/. . . . $ol = $o and $02 =

and
$o + A$o. Repeat steps 2 and 3 until $o reaches the
desired value.
d-~J¢=o 3" ,eoyo exp ~fl 1 + 3(1 - Yo),]
No formal error analysis of the above procedure
and was made, but its validity was tested for each curve by

lim2dy z~2.k2,
( 1_,o )
exp~,fl l + f l ( 1 - y o )
repeating the calculation starting with the two r/
values corresponding to the third and second highest
$o values. In every instance, agreement to three signif-
icant figures was obtained between the two extrapola-
The numerical integration was performed on an
tions.
IBM 704 computer using a Fortran subroutine de-
The numerical integration of the equation for the
veloped by Slayton of Lockheed, and distributed by
sphere gave multiple solutions for certain ranges of
Share 1-16]. The Adams four-point formula for integ-
$o. This also turned out to be the case for the numer-
ration is used in the program, and double precision
ical solution for the slab, where V 2 = d2/dx 2, with the
accumulation of increments reduces round-off errors.
same boundary conditions. For the slab, however, it is
The program was arranged so that between 500 and
possible to establish analytically upper and lower
1000 increments of ~ were used between ~ = 0 and the
bounds to the solution. These bounds, it turns out,
value for which y ( ~ ) = 1. The solution was then
imply the existence of multiple solutions. This gives an
checked using double the number of increments.
heuristic argument that the multiplicity in the spheri-
Agreement to three or four significant figures was
cal case is real, and not a consequence of some pecu-
obtained in all cases.
liarity of the numerical analysis.
With the computer program using single-precision
floating-point arithmetic, the numerical integration
REFERENCES
could be carried out for any y(0) 1> 10 -37, covering
the $o range up to a point where din r//d In qbo ap- [1] Damk6hler, G., 1937, D. Chem. Ing. 3, 430.
12] Thiele, E. W., 1939, Ind. Engng Chem. 31, 916.
proaches - 1 . To extend the r/,$o plots up to [3] Zeldowitsch, J. B., 1939, Acta Physicochim. U.R.S.S. 10,
$o = 150, the following simple extrapolation method 583.
was used. Noting first that r / = (3/$2)y'(1), we obtain, 1-4] Wheeler, A., 1951, in Advances in Catalysis, Vol. 3, p.
by differentiating with respect to $o and multiplying 249. Academic Press, New York.
15] Weisz, P. B. and Prater, C. D., 1954, in Advances in
by So/t/, Catalysis. Vol. 6, p. 143. Academic Press, New York.
[6] Wicke, E. and Br6tz, W., 1949, Chem. lng.-Tech. 21,
dlnr/ = _ 2-1- - -3 dy'(1) 219.
dln$o r/So d$o [7] Aris, R., 1957, Chem. Engng Sci. 6, 262.
[8] Weisz, P. B., 1959, Chem. Engng Progr. (Symposium
Then Series) 55, 29.
19] Weisz, P. B., 1957, Z. Phys. Chem. 11, 1.
1. From the numerical integration data for a given [10"] Damk6hler, G., 1943, Z. Phys. Chem. A193, 16.
r/, $o curve choose those values oft/(call them r/l, and [11] Prater, C. D, 1958, Chem. Enono Sci. 8, 284.
r/2) corresponding respectively to the second largest 1"12"1 Frank-Kamenetskii, D. A., 1939, Zh. tekh. fiz. 9, 1457.
and largest values of $o obtained (call them $ol and [13] Weiser, B. H., 1935, lnoroanic Colloid Chemistry, Vol.
II, p. 15. Wiley, New York; Hauser, E. A., 1938, in
$02); Colloidal Phenomena, p. 213. McGraw-Hill, New York.
2. Calculate [14] Sehr, R. A., 1958, Chem. Enono Sci. 9, 145.
[15] Wei, J., 1961, private communication.
dlnr/ In rh/r/2 [16] Slayton, G. R., 1962 GL AIDE I, SHARE Distribution
dinS0 1n$01/1#02 No. 413.