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I J. D. TINKLER and A. B.

METZNER
University of Delaware, Newark, Del.

Reaction Rates in . .
Nonisothermal Catalysts
Temperature gradients within a catalyst particle can be important factors
in a chemical reaction. “Effectiveness factors” for nonisothermal catalyst
particles will be useful in achieving optimum reactor design and operation

I N THE DESIGN AND OPERATION Of as only a few sample calculations were sures of about 10 atm. (77) ; as similar
chemical reactors using porous catalyst made, no general design criteria were conditions of pore size prevail in most
pellets, rates of both mass transfer and developed. Pigford and Tinkler (9) good catalysts this mechanism is one
of some generality, and it is for this
chemical reaction must be considered. considered the case in which the tem-
case that the assumed temperature and
Because of resistance to mass transfer perature difference across the pellet is concentration independence of the
within the catalyst structure, diffusion of small but not negligible. By means of a diffLisivity is either a good approxirna-
reactants and products into and out of perturbation technique, they developed tion or a well established fact, re-
the pellet is often the slow or rate-control- a simple extension of Thiele’s result to spectively. Transport by thermal dif-
ling step. As a result, the reaction rate account for heat generation in the case of fusion and by surface migration of
may be much smaller than it would be a first-order, irreversible reaction inside physically adsorbed layers is ignored
if a diffusional resistance were not a spherical pellet. in this work. The latter may not be
present, I n the work reported here the non- small under low temperature con-
ditions, but as neither its importance
The effectiveness factor, first used by linear differential equations expressing nor mechanism is well defined at
Thiele (74) in 1939, is defined as the conservation of mass and energy for the present time no alternative as-
ratio of actual conversion rate to the reactions in nonisothermal particles sumption is possible.
rate which would occur if reactant were considered. Solutions were ob- .Heat transfer within the particle
concentrations everywhere inside the tained for first- and second-order ir- occurs by conduction through the
pellet were the same as a t the surface. reversible reactions taking place in spheri- solid portion of the pellet only.
Equations for the effectiveness factor cal catalyst pellets. Calculations were Simple calculations show that the
have been derived by Thiele and by also made for a first-order reaction tak- additional enthalpy transport of the
Wheeler (77, 78). However, in both ing place in a “flat-plate,” to obtain gases is negligible unless heat capacities
of reaction products differ enormously
cases it was assumed that the catalyst some insight into the effect of particle from those of the reactants. This
particle is isothermal and, therefore, geometry. The reader may compare the would require that the heat of reaction
that the reaction rate constant does not present results with those obtained in- be a much stronger function of tem-
vary with position. dependently and approximately simul- perature than for any catalytic reac-
Prater (10) has pointed out that a taneously by Carberry (6) and Weisz tion known a t the present time.
significant temperature difference may (76)* .Constant values of the thermal con-
exist between the interior and the ductivity and heat of reaction are
surface of the pellet because of the heat used. These approximations are ex-
of reaction. For instance, in dehydro- Working Equations pected to be excellent under the con-
ditions encountered.
genating cyclohexane on a platinum-
Derivations of the differential equa-
.The temperature dependence of the
alumina reforming catalyst, Prater esti- reaction rate constant is expressed
mated that the center temperature may tions are based upon the following as- by the Arrhenius equation.
be 53’ C. lower than that of the sur- sumptions : .Specific reaction rate and stoichio-
rounding fluid. Obviously, the assump- metric expressions must be chosen.
tion of no temperature gradients within 0 Catalyst particles have a porous, The problems analyzed herein are for
the pellet is not valid here. Thus, homogeneous structure in which the first- and second-order reactions
a theory which accounts for heat as catalytic activity per unit area is whose stoichiometry and mechanism
independent of position in the par- are both given by:
well as mass transfer is needed. The ticle.
nonisothermal effectiveness factor is 0 Surface concentrations of reactants
defined as the ratio of conversion rate and surface temperature are known.
to the rate which would occur if both If external resistances to mass and
reactant concentrations and temperature heat transfer exist, the surface con- Since the common application of
were the same everywhere inside the ditions may be calculated by means of these equations is in catalysis of gaseous
pellet as a t the surface. transfer coefficient correlations pre- reactants, concentration terms are ex-
Schilson ( 7 7 ) calculated the effective- sented in a variety of standard ref- pressed in terms of partial pressures for
ness factor, as well as intraparticle erences and recent reports (3,5,8,73). convenience of application. However,
0 Mass transfer within the pellet no restriction to gaseous reactants or
temperature and concentration profiles, occurs by diffusion only and may be
by solving an integral equation by the expressed by means of a constant products is either intended or necessary,
method of successive approximations. diffusion coefficient. I n many com- and the results may be directly applied
This approach clearly illustrates the mercial silica-alumina catalysts, Knud- to liquids by making self-evident and
magnitude of the effects involved, but sen diffusion prevails up to gas pres- consistent changes in the concentra-

VOL. 53, NO. a AUGUST 1961 663


tioiis, reaction rate constants. and yields an equation containing tempera- just as in thc isothermal case. However,
diffusion coefficients. The assumption ture as the only dependent variable: the partial pressure gradient (dPA/dr)n
of a constant diffusjvity is not a particu- will be different for nonisothermal
larly good one in this case, however. 1 (r2 $) - AHk [PI. + particles and is related to the tempera-
Derivation for Spherical Pellets. ture gradient a t the surface, (dT/dr),.
T h e conservation of mass and ecergy nX through Equation 5. Combination of
( T - T,L]? = 0 (10)
equations for a differential spherical DAAH Equations 15 and 5 and the introduction
shell of radius r and thickness dr are Introducing the dimensionless variables: of the dimensionless variables, 0 and p ,
( 4 ): yield the final Lvorking equation:

v = -3(d6jdp),=1.0 (16)
Equation 10 becomes
in which (dO,'dp),= 1.0as evaluated from
1 d Equations 13 or 14 will be a function
of cy and p.
(where f; is the rate of formaiion of (11) The classical result of Thiele ( 7 4 ) is a
component i caused by reaction per special case of these equations cor-
unit volume and v i is the whole number where 01 = R2k, P.4z-1/DA, a dimen-
responding to 0 = 0. Thus, for the
stoichiometric coefficient of component sionless parameter. The ratio of rcac.ion-
rate constants may be expressed as a first-order case, integration of Equation
i in the general chemical reaction, 13 produces :
Zv,Mi = 0 ; vi is positive for products, function of dimensionless temperature
negative for reactants. The value of by means of the Arrhenius equation: e = sinh d i p 1
(17)
the ratio, fi/vi, is the same for all com- ap sinh +

ponents), The boundary conditions are :


dPi/dr = dT/dr = 0 u-henr = 0 and the effectiveness factor is obtained
from Equations 16 and 17 as:
because of symmetry, and:
at r = R T=T,
and Pi = Pi, sionless parameter.
The error introduced by the approxi-
Sincefi is a function of both tempera- mation in Equation 12 is not particularly and 4; reduces to the Thiele modulus,
ture and partial pressure, the energy significant in calculating particle effec- R \/k,lDa. I t may appear that a
balance and the material balances are tiveness. LVhile k / k g may be appre- paradox exists, in that Equation 17
coupled. The equation connecting them ciably in error under fairly extreme may be used to calculate a finite tem-
is derived as follows: Multiplication of reaction conditions. any effect on the perature difference whereas Thiele pre-
Equation 1 by AH/:vi and addition to effectivenms factor is an integrated one supposed an isothermal pellet. How-
Equation 2 eliminate the term contain- and much smaller in magnitude in view ever, the same reaction rates are cal-
ing fi: of the small effect which the reaction culated whether ihe particle is isothermal
conditions in the central part of the or whether it is not but the activation
pellet have on over-all rate for the energy is zero (rate constant independ-
entire pellet. This is especially true in ent of temperature). One is somewhat
(3) the case of the second-order reaction. more internally consistent if one admits
Integration from Y = 0 to r = r gives: Finally, for the first-order reaction : the necessary coexistence of temperature
and concentration gradients, hence the
temperature differences of Equation 17,
and simply lets the rate constant be
A second integration from 1' = r to non-temperature dependent.
r = R results in an expression relating and for the second-order reaction : Derivation for the Flat Plate. This
partial pressure of component i to tem- geometry applies to all particle shapes
perature and known surface values, in the limiting case of very high reaction
rate (low penetration of reactants into
P,, and T,:
the particle), and comparison with
spherical pellet results also shows the
The boundary conditions in dimension-
effect of particle geometry. T h e balances
less form are:
Before proceeding further, specific representing conservation of mass and
At p = 0 d6/dp = 0 energy are derived for a differential
reaction mechanisms must be chosen.
Considering the stoichiometric and mech- Atp = 1.0 e=o slice of m.idt!i d.x located a t a distance Y
anistic equation: from the mid-plane of the plate and
The dimensionless temperature profile become analogously to Equations
(73:).

nA+B n = l , 2 (6) is a function of only two parameters, 1 and 2 for the case of spherical ge-
then fB = k P.kn v.t, = --n vg = +1 a and 0. (If the simplifying assumption
employed in Equation 12 were not used,
ometry :
(7) a third parameter would necessarily
Substitution of these relationships appear.)
into Equations 2 and 5 gives: The effectiveness factor of the catalyst
particle is given as:

with the boundary conditions


dPi/dx = d T / d x = 0 at x = 0

Combination of Equations 8 and 9 Pi = Pia and T = T, at x = L

664 INDUSTRIAL AND ENGINEERINGCHEMISTRY


N O N IS0 TI4 ERMA L CATALYSTS
10.00 10.00

1.00 I .oo

F F

0 IO 0.10

\I \
EAHPA, DA Y.

1111 I i i I
mTe2X
BROKEN LINES INDICATE
BROKEN LINES LNDICATE EXTRAPOLATED REGION
EXTRAPOLATED REGION
I

0.01
0.2 I .o 10.0

Figure 1. Values of a and E determine magnitude of Figure 2. For a second-order reaction within a spherical
effectiveness factor for first-order reaction within a spherical pellet, the effectiveness factor curves change shape
pellet

iManipulations similar to those used in ever, accuracy must be examined iiide- reduced to a small fraction. Throughout
the case of spherical geometry give, in pendently because it is a function of the this range analytical and analog solutions
dimensionless form : type of equation being solved, electronic agree very well.
circuit used, and transformation scale To illustrate his numerical procedure,
factors, as well as being dependent Schilson worked several sample hypo-
on the approximation introduced by thetical problems using fictitious nu-
Equation 12. Analog computer solu- merical values. Only two of his prob-
tions are compared with the analytic lems are within the range of variables
solutions of Thiele (74) and two numeri- likely to be encountered in practice and,
Again, for the special case /3 = 0 the cal solutions of Schilson ( 7 7) in the table therefore, included in the present cal-
equations may be solved analytically, for spherical pellets and for first- and culations. The results are presented
and one obtains Thiele's result: second-order, irreversible reactions. as cases 5 and 6 in the table. For
I n cases 1 through 4, cy values extend case 5 , in which Schilson considered
17 =
tanh
~-
l/o( (23)
from the kinetically controlled region, in the temperature dependence of the Knud-
6- which the effectiveness factor is approxi- sen diffusion coefficient, the coefficient
mately unity, to the diffusion-controlled evaluated at the surface temperature is
Results region, in which the effectiveness factor is used in calculating cy.

Method of Solution, Accuracy. The


equations developed represent nonlinear
boundary value problems in one dimen- Comparison of Computer with Analytical and Numerical Solutions for Reactions
sion. Since partial pressure profiles and within a Spherical Pellet Shows Agreement
effectiveness factor may be calculated Re-
ac- e, 17 -
from temperature distribution, the only
differential equation to be solved is the
tion
Case O r d r a: p %
Calcd.
?
Analog Diff." Crtlcd. Analog Diff.a Ref.
dimensionless energy balance. An ana- 1 1 1.0 0.0 0.149 0.149 0.0 0.939 0.936 0.3 (14)
lytical solution to a nonlinear, ordinary 2 1 9.0 0.0 0.0778 0.0778 0.0 0.672 0.666 0.6 (14)
differential equation of this type is very 3 1 100 0.0 0.0100 0.0100 0.0 0.270 0.272 0.7 (14)
difficult, if not impossible, to obtain. 4 1 900 0.0 0.00111 0.00111 0.0 0.0967 0.0975 0.8 (14)
5 1 18.4 -27.9 0.0531* 0.0540" 1.7 0.709 0.747 5.4 (11,
For this reason the equations were Probl.
solved on an Electronic Associates' 2)
Model 16-31R PACE computer using a 6 2 13.1 -33.5 0.0327d 0.03226 1.5 0,461 0.435 5.6 (11.
programming procedure reported else- Probl.
1)
where (75).
computer result - calculated result
The PACE computer is capable oi a 70Difference = X 100. * T , = 352' C.: T, = 390.4' C .
calculated result
very precise and accurate solutions; T , = 352' C.; T, = 391.0' C. d T , = 327' C . ; To = 370.3' C. e 7'8 327" C ; Tc =
component accuracies arcs on the order 369.6' C .
of *0.01% of full scak value. How-

VOL. 53, NO. 8 0 AUGUST 1961 665


I0.00 10.00

I O 0

F
aio

0 IO
0.10

I E-
EAHPAs Dn

I BROKEN L I N E S INDICATE
, 1
1 I
0.01
0.2
' E X T R A P O L A T E D REGION

I .o
I I
~ ~ I ' I

! I l l
10.0
~

1 1
~

' 1

0.01
0.2 I O IO 0
f i = R T f i
Figure 3. Effectiveness factors for first-order reaction Figure 4. Temperature a t the center of a spherical pellet
within a "flat plate" differ from those for spherical geom- for first-order reaction i s determined b y vclucs of Q and e
etry, except when E lies between - 2 and $2

I n cases 5 and 6, differences between T h e characteristic dimension in this second-cm.-atm. The thermal conduc-
analog computer solutions and numerical modulus was taken as equal to R for tivity of silica-alumina cracking catalysts,
solutions are due not only to machine the spherical pellet and as 3L for the as determined experimentally by Sehr
error but also to the approximation flat plate solution, as suggested by Aris (72),is 4 X lop3cal. per second-cm.-' C.
introduced into Equation 12 for the (2). He noted that in the "isothermal" A heat of reaction of +10 kcal. per
ratio of rate constants. This approxi- case, the effectiveness factor is nearly gram mole and an activation energy of
mation is very good for small activation independent of particle shape if the 40 kcal. per gram mole give E = 0.017.
energies and/or small temperature dif- characteristic dimension of the particle is Love and Emmett (7) studied am-
ferences across the pellet, but for the large defined as 3Vp/Sp, where V,, and S, monia decomposition on an iron am-
differences in temperature combined are volume and external surface area, monia synthesis catalyst at 387' C.
with high activation energies as en- respectively, of a single particle. and atmospheric pressure. For one
countered in these examples (AT = The introduction of a new parameter catalyst. calculated activation energy
40' C., E = 30, and 18 kcal., respec- defined as: was 31.7 kcal. per gram-mole. Using
tively), the approximation is not partic- a diffusion coefficient of 6.5 X 10-7
ularly good, and percentage error in gram-mole per second-cm.-atm., a ther-
the effectiveness factor exceeds 5%. mal conductivity of cal. per second-
However, even this is not excessive in cm.-O C., and heat of reaction of +11
view of other uncertainties generally is made so that the particle dimension kcal. per gram mole of ammonia one
involved in reactor design. appears in only one of the two param- obtains E = 0.26.
I n general, the present calculations eters required to describe the physical The vapor-phase hydrogenation of
may be assumed accurate whenever the situation. This parameter may be called benzene at 112' C. and 1 atm. on an
effectiveness factor does not exceed that a heat generation parameter, since it alumina-supported platinum catalyst was
for isothermal conditions by more than a includes the activation energy, heat of studied by Amano and Parravano ( 7 )
factor of about 2.0. At higher values, reaction, pellet thermal conductivity, who found the activation energy to be
the simplifying assumption of Equarion and surface temperature; it is negative 12 kcal. per gram-mole. The heat of
12 is no longer quantitatively valid for exothermic reactions and positive reaction, -50 kcal. per gram-mole, is
because of the large temperature dif- for endothermk reactions. To deter- unusually large. At 112' C. and for a
ferences in the pellet under these condi- mine the range of parameter values pore radius of 30 A., the effective
tions. There is no such limitation on which should be included in the calcula- Knudsen-diffusion coefficient of hydro-
the present calculations in the endo- tions to cover essentially all reactions of gen is 3.1 X 10-7 gram-mole per second-
thermic region, as the central portions of practical interest, consider the numeri- cm.-atm. Since the catalyst support is
the catalyst contribute negligibly to cal values arising in three typical kinds of alumina, the value of the thermal
over-all reaction rate under conditions reactions. conductivity for silica-alumina cracking
of a large temperature drop. M'heeler (77) considered a gas-phase catalysts may be used here. A value of
Ranges Covered. T h e Thiele modu- cracking reaction at 500' C. and atmos- B = 1.9 results.
lus, which is identical to &, was varied pheric pressure. For a molecule like I n these three examples, the absolute
over a wide range, extending from the cetane (C16H34)and a mean pore radius value of E changed by two orders of
completely kinetically controlled region of 30 A., the effective Knudsen-diffusion magnitude. For most practical cases,
well into the diffusion-controlled region. coefficient is 2 X 10-8 gram mole per the absolute magnitude of E will not

666 INDUSTRIAL AND ENGINEERING CHEMISTRY


N ON I S O T H ERMAL CATALYSTS
exceed that in the third example be- effectiveness factor may be several times perature may cause great decreases in
cause of the large heat of reaction and larger than that calculated by neglecting over-all reaction rate. Obviously, de-
the low temperature level of this reac- heat effects, as the over-all reaction sign conditions must be well removed
tion. However, to be sure that virtually rate is greatly increased. The tempera- from the regions of these maxima.
all reactions of interest may be included, ture rise increases the reaction rate Additionally, the large temperature
E was varied from - 5 to + 5 in this work. constant sufficiently to offset the effect rises occurring within the pellet under
The value of E will probably exceed these of decreased partial pressures created by these conditions may, of course, cause
limits only if the larger diffusion co- the diffusional resistance, a t least until degradation or undesirable side reac-
efficients of ordinary diffusion, through very high values of the Thiele modulus tions: if operation under such condi-
large pores, are substituted for the are reached. tions really was feasible, one would
smaller Knudsen coefficients used in the At small values of the Thiele modulus, normally operate with a higher surface
present study. The entire validity of the heat generation parameter and the temperature and a more nearly iso-
studies like the present rests on the Thiele modulus have little effect upon thermal particle to take advantage of
assumption of constant diffusivities, how- reaction rate. I n this region, the ef- higher reaction rates everywhere in the
ever, and this assumption is likely to fectiveness factor approaches unity be- pellet and not just a t its center.
be grossly in error under conditions cause the particle offers negligible resist- At large values of the Thiele modulus,
of ordinary gaseous diffusion. Ob- ance to heat and mass transfer. the effectiveness factor is inversely pro-
viously, there would be no point to At intermediate values of the Thiele portional to the modulus; thus, the rate
extending the ranges over which E is modulus in the exothermic region, the per particle is proportional to external
varied unless the Stefan-Maxwell equa- effectiveness factor may pass through a surface area. In this region, chemical
tions for multicomponent diffusion maximum a t a given value of the heat reaction is confined to a thin shell
were employed simultaneously. generation parameter, as the Thiele a t the pellet surface.
Tabulated a n d Graphical Results. modulus changes. Therefore, for a The curves of dimensionless center
Effectiveness factors are shown graph- given reaction occurring in a specific temperature bear a striking resemblance
ically in Figures 1-3; curves of the catalyst at set operating conditions, to those of the effectiveness factor.
dimensionless temperature at the center there may be an optimum pellet size. At small values of the Thiele modulus,
are plotted in Figures 4-6; several Pellet size becomes more critical as the neither the heat generation parameter
typical temperature profiles are given e value increases. Because of the nor the Thiele modulus has much effect
in Figure 7 . More complete profiles, as sharply peaked nature of the maxima, upon the dimensionless center tempera-
well as the tabulated results, are avail- operation a t this optimum condition ture. At intermediate Thiele modulus
able elsewhere (75). presents difficulties. For example, small values, maxima may appear in the exo-
Figures 1 and 3 clearly show that for changes in the rate constant caused by thermic region; it is here that large
the case of first-order reactions the catalyst fouling or changes in fluid tem- temperature rises may occur within the

6 = R m

Figure 5. Center temperature and maximum temperature Figure 6. Midplane temperature for first-order reaction
rise for second-order reaction within a spherical pellet are within a “flat plate”
obtained from these curves

VOL. 53, NO. 8 AUGUST 1961 667


x = normal distance from mid-plane
0 16 of plate, ft.
LY = dimensionless parameter;
= R2k, PAsrL-’/DAfor sphere
0 14 = Lzk,PA.n-l/DA for flat plate
@ = dimensionless parameter;
0 12 - -E AHR2kaPAan
_ 8, TS2X for sphere
0 10
EAHL2k,P,,”
for flat plate
CD
- RgT,2h
_____
E = dimensionless parameter = @,‘a
0 08 7 = effectiveness factor
0 = dimensionless temperature
0 06 = T, - T for sphere
AHR2k,PA& “/A
0 04 T, - T
= __-___ for flax plate
AHL2k,PA,”/ X
A = thermal conductivity of pellet,
B.t.u./(sec.) (ft.) (” F.)
Y = whole number stoichiometric co-
efficient of component in gen-
0 02 04 06 08 eral chemical reaction, 2 v L M 2
P = 0. Positive for products,
negative for reactants
p = dimensionless distance = 7, R for
P sphere, x / L for flat plate
Figure 7. Typical dimensionless temperature profiles are shown as functions of a:
for first-order reaction within a wherical pellzt when E = - 1 (left) and E = - 3 Subscripts
(right)
c = evaluated at center or mid-plane
of pellet
i = component
pcllct. At large values of the Thiele difficult to interpolate or extrapolate for s = evaluated a t pellet surface
modulus, all the curves approach the fractional-order reactions or to make
curve for E = 0 ; in this region the predictions for reactions following a
central portion of the pellet is isothermal Langmuir type of rate expression.
since the chemical reaction occurs only
Literature Cited
Figure 7 shows complete dimensionless
near the surface of the particle. temperature profiles (for two values (1) Amano, A , Parravano, G., “Advances
The curves of the effectiveness factor of the heat generation parameter) for in Catalysis,” Vol. I X , pp. 716-26,
for a spherical pellet, Figure 1, and the case of a first-order reaction in a Academic Press, New York, 1951.
those for a flat plate, Figure 3, qualita- sphere. (2) Ark, R., Chem. Eng. Sci. 6 , 262 (1957).
tively have the same shape. In the endo- (3) Bar-Ilan, M.. Resnick, W., IND.ENG.
CHEM.49, 313 (1957).
thermic region, the agreement is within (4) Bird, R.B., Stewart, W.E., L,i,ghtfoot,
Acknowledgment
about 7 076 ; however, in the exothermic E. N., “Transport Phenomena, Wiley,
region the maxima for the flat plate are D. E. Lamb provided advice and New York, 1960.
larger, more peaked, and occur at (5) Carberry, J. J., A.I.Ch.E. Journal F,
assistance pertaining to the programming 460 (1960).
larger values of the Thiele modulus than and operation of the computer. (6) Ibih., in.press.
those for the sphere. Thus, particle (7) Love, E(. S., Emmett, P. H., J . Am.
shape has little effect only if the heat ,-.. .,.
Chem. Soc. 63, 329; 7 (1941).
generation parameter lies between + 2 Nomenclature (8) Perry, J. H., “Chemical Enginfers’
Handbook,” 3rd ed., p. 547, McGraw-
and -2, unless ct is very large (values of Hill, New York, 1950.
the abscissa near 10).
D = effective diffusion coefficient in
pellet, 1b.-mo1ejsec.-atm.-ft. (9) Pigford, R. L., Tinkler, 3. D.. Chern.
A comparison of Figures 1 and 2 or of E = activation energy of reaction, Eng. Sci.,in press (1961).
4 and 5 shoivs that reaction order has a (IO) Prater, C. D., Ibid., 8, 284 (1958).
B.t.u./lb.-mole (11) Schilson. R. E.. Ph.D. thesis, Lniv. of
very pronounced influence on both f = rate of formation per unit volume, ’ ~~innesota,’Minneapolis.. Minn., 1957.
effectiveness factor and temperature 1b.-mole ’cu. ft.-sec. (12) Sehr, R. A,: Chem. Eng. Sci. 9, 145
profile within the particle. For a second- AH = heat of reaction, negative for I1 9581.
order reaction, the spread of the curves exothermic reaction, B.t.u. ’1b.- (13) Shu-lman, H. L., A.I.Ch.E. Journal 1,
mole 253 (1953).
is very small, and no maxima occur in (14) Thiele, E. W., IND.ENG.CHEM.31,
k = reaction rate constant, 1b.-mole/-
the exothermic region even at the largest 916 (1939).
cu. ft.-sec.-atm.” (15) Tinkler, J. D., M.Ch.E. thesis, Univ.
value of E studied. This difference is L = normal distance from mid-plane
due to the fact that the presence of heat of Delaware, Newark, Del., 1960.
to surface of plate, ft. (16) Weisz, P. B., Chem. Eng. Soc., in press.
effects is diminished by the quadratic iM = chemical symbol for component (17) Wheeler, A., ”Advances in Catalysis,”
dependence of the reaction rate on the n = empirical order of reaction Vol. 111, pp. 250-327, Academic Press,
partial pressure of the reactant: maxima P = partial pressure, atm. Kew York, 1951.
would only be expected a t values of the R, = gas constant, B.t.u./lb.-mole-’R. (18) Wheeler, A,: “Catalysis,” Vol. 2 ,
(indicated as script R o n figures) pp. 105-65, Reinhold, New York, 1955.
heat generation parameter well below
- 5. R = pellet radius, ft.
r = radial distance from pellet center, RECEIVED
for review hIarch 15! 1961
I n general, heat effects become less f t. ACCEPTED June 7,1961
important as reaction order increases;
S, = external surface area of particle, 139th Meeting, ACS, St. Louis, M o . ,
however, because of the large differences sq. ft. March 1961. Work supported by fellow-
between the effectiveness factor curves T = absolute temperature, R. ship to J . C. Tinkler from National
for first- and second-order reactions, it is V, = volume of catalyst particle, cu. ft. Science Foundation.

668 INDUSTRIAL AND ENGlNEERlNG CHEMISTRY