CHEMICAL ENGINEERING COMMUNICATIONS
ISSN: 0098-6445 (Print) 1563-5201 (Online) Journal homepage: https://www.tandfonline.com/loi/gcec20
CATALYST EFFECTIVENESS FACTOR FOR LANGMUIR-
HINSHELWOOD-HOUGEN-WATSON KINETIC
EXPRESSIONS
K. MEENAKSHI SUNDARAM
To cite this article: K. MEENAKSHI SUNDARAM (1982) CATALYST EFFECTIVENESS FACTOR
FOR LANGMUIR-HINSHELWOOD-HOUGEN-WATSON KINETIC EXPRESSIONS, CHEMICAL
ENGINEERING COMMUNICATIONS, 15:5-6, 305-311, DOI: 10.1080/00986448208911076
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Chem. Eng. Commun. Vol. 15, pp. 305-31 1 0 Gordon and Breach, Science Publishers. Inc., 1982
0098-6445/82/15054305$06.50/0 Printed in the U S A .
CATALYST EFFECTIVENESS FACTOR FOR
LANGMUIR-HINSHELWOOD-HOUGEN-WATSON
KINETIC EXPRESSIONS
K. MEENAKSHI SUNDARAMt
Center for Catalytic Science & Technology
Dept. of Chemical Engineering
University of Delaware
Newark, DE 19711
(Received November 23, 1981; injinal form January 11. 1982)
INTRODUCTION
The influence of internal diffusional resistance on the rate of a reaction catalyzed by
heterogeneous catalysts has been considered by many workers [see Froment and
Bischoff, 1979; Aris, 19751. Attention has been mainly focused on power law kinetics.
Many heterogeneous catalytic reactions follow Langmuir-Hinshelwood-Hougen-
-
Watson (LHHW) or Rideal rate expressions. For a reaction A B, when the rate is
given by
Roberts and Satterfield [1965, 19661 have evaluated the effectiveness factors for var-
ious values of Thiele modulus numerically when the exponents m = n = 1 or 2, in
addition t o the explicit expressions for asymptotic cases. The value of m is related to
the number of sites involved in the reaction and hence restricted to integer values.
When the mechanism is more complex than the simple LHHW model, empirical ex-
pressions are resorted and the value of n is not restricted to integer powers in such
cases, and also the value of m need not be equal to n. In an earlier communication,
Narsimhan and Sundaram [I9751 considered the effectiveness factor for a reaction
following redox mechanism. Using the concept of critical Thiele modulus, they
showed that the effectiveness factor for a redox model can be expressed in the form
q = tanh (6*)/$,* where
A similar approach is considered here t o find the effectiveness factor, q, for the
reaction following the rate equation (1) where the cases considered by Roberts and
Satterfield are special cases.
t Present address: The Lummus Company, 1515 Broad Street, Bloomfield, NJ 07003.
306 K.M.SUNDARAM
ANALYSIS
For a general reaction
A+bB+...-pP+qQ+.-.
the rate equation is taken to be of the form
The continuity equation for species A for a slab catalyst of thickness 2L is given by
For other species the continuity equations can be written similar to Eq. (3) using
the stoichiometric coefficients v i
The boundary conditions are
CA = CAS,Ci = Cis at x = fL
Following the approach of Roberts and Satterfield [1965], Eq. (3) can be put in the
following dimensionless form.
where
@ = C A / C A Sand X = x / L
The boundary conditions are
CATALYST EFFECTIVENESS FACTOR 307
The effectiveness factor in terms of dimensionless parameters is
Eq. (6) cannot be integrated analytically except for integer values of m and n. The fol-
lowing cases will be considered for large values of d, (asymptotic value of 7).
Defining q = (d*/dX), Eq. (6) can be written as follows:
This can be integrated to give
where I is the constant of integration. Only for certain values of m and n, the integral
in Eq. (1 I) can be evaluated analytically. In addition, for large values of 4,, the con-
centration gradient is very steep within the slab, and it is assumed that both (d$/dx)
and Jr tend to zero at X = 0. Therefore, in Eq. (1 I), the limits of integration are from
0 to 1 and I = 0.
Example: m = n = l
Using the boundary conditions (S), evaluation of the derivative at x = 1 leads to
Therefore, the asymptotic expression for the effectiveness factor is given by
This is the same expression obtained by Roberts and Satterfield [I9651 for this case.
For various values of (I, the asymptotic
. . solutions are parallel to each other and there-
fore by defining a critical Thiele modulus &, which varies with a,they can be re-
duced t o a single line.
0.5
(I
308 K.M. SUNDARAM
and
Eq. (15) is identical in form t o the asymptotic expression for first order kinetics and
therefore by analogy the effectiveness factor can be generalized for other values of dm
to
The values of d, gives the upperbound of Thiele modulus above which certainly dif-
fusion limitation exists. However, below the critical modulus, presence of diffusional
limitation depends upon the value of m, n a n d a.The fit of Eq. (16) for various values
of d and a to the exact values are shown in Figure 1. The exact values are obtained
FIGURE 1 Effectiveness factor versus modified Thiele modulus as a function of a. Rate expression
given by Eq. ( 2 ) : m = n = 1.
: exact solution
-.-.. . calculated by Eq. (16)
----: calculated by Eq. (17)
(when not shown, dotted lines coincide with solid line)
CATALYST EFFECTIVENESS FACTOR 309
by numerical integration of the differential equation (6) by a variable grid size finite
difference method discussed in detail by Sundaram and Froment [1981].Though the
calculated asymptotic effectiveness factors by Eq. (16)are in excellent agreement with
the exact values, they deviate much at low values of 4,. To be applicable over a wide
range of parameters, an empirical correction factor is introduced in Eq. (16).
where
The correction factor is obtained by matching Eq. (17) with exact values and min-
imizing the residuals by Marquardt algorithm. The best function obtained is given by
Eq. (18). This correction factor tends to unity for both small and large values of 4*,
and therefore it reduces to Eq. (16)for asymptotic cases. When a = 0, this also re-
duces t o the standard Eq. (16) for the slab geometry for first order kinetics with
&J* = +,,,. With this correction factor, predicted values of 11 for the same range of 4,
and a are also shown in Figure 1. It is clear that Eq. (17)predicts the exact values in
good agreement for the entire range.
For other integer values of m and n, the integral in Eq. (I I) can be evaluated ana-
lytically and therefore the asymptotic effectiveness factors are exact. For non-integer
values of n, a two-term series expansion is used in evaluating the integral and the crit-
ical Thiele modulus are summarized in Table I. The same correction factor Eq. (17)is
found t o be sufficient for other values of m and n shown in Table I. In addition, the
critical Thiele modulus for the general case n, for the values of m = 1 and m = 2
shown in Table I reduces to the specific values also shown in Table I when n = 0, I,
o r 2. Representative values of effectiveness factor obtained from Eq. (17) with the
critical Thiele modulus shown in Table I for various values of n and a are compared
TABLE I
Critical Thiele modulus 4, for various values of m, n. and a
. ~
0 n Also for a = 0 when m # 0
1 0 &(I + a ) [I/a - log (I + a)]"'
1 I 4 ( 1 + a ) [l/al(a - log (I + a)]"'
I 2 &(I + a ) [l/a'(a2/2 - a + log (I + a))]"'
I n &(I + a ) [(BI - Bz + B,) log (I + a ) + (El - B,) a + .5Bla1]
BI = (1 - 1.5n + 0.5n1)/a
BI = (2n - n')/a2
Bj = 0.5(n1 - n)/a3 for 0 5 n 2 2
2 n fi(l + a)' [(Bz - 2B3) log (I + a ) + (BI - 81- B,)/(1 + a )
+ BI + &(I + a)] for 0 In 1 2
310 K.M. SUNDARAM
FIGURE 2 Effectiveness factor versus modified Thiele modulus as a function of n. Rate expression
given by Eq. (2); m = 1.
: exacl solution
----: calculatcd by Eq. (17)
(when not shown, dotted line coincides with solid line)
with exact values in Figure 2. The agreement between the approximate and exact
values is good. For values of m > 2, critical Thiele modulus similar t o those shown in
Table I can be obtained, but more than two terms are necessary when n is not an in-
teger for satisfactory results.
CONCLUSIONS
The above analysis indicates that effectiveness factor for a heterogeneous reaction
over a slab catalyst can be expressed by a single relation, Eq. (17). By suitably defin-
ing the correction factor f and the critical Thiele modulus, 4, effectiveness factor de-
fined in Eq. (16) reduces to their standard correlations. Modification of the rate ex-
pression affects the critical Thiele modulus strongly. Above the critical Thiele rnodu-
lus diffusional resistance exists, but below this value it depends upon the reaction pa-
rameters. Now not only the shape of the particle but also the form of kinetic expres-
sion can be grouped in defining the Thiele modulus, so that a single curve is sufficient
to evaluate the effectiveness factor.
CATAL YST EFFECTIVENESS FACTOR 311
ACKNOWLEDGMENT
The author acknowledges the generous support of Department of Chemical Engineer-
ing of University of Delaware.
NOMENCLATURE
C, concentration of i·th species
C, concentration of i-th species at pellet surface
D, diffusion coefficient of i-th species
f correction factor defined in Eq. (17)
k specific reaction rate constant
K, adsorption equilibrium constant of i-th species
L half the width of the pellet
m exponent in Eq. (2)
n exponent in Eq. (2)
r reaction rate
x length coordinate
X dimensionless length xlL
Greek Symbols
ClI parameter defined in Eq. (7)
Vi stoichiometric coefficient for i-th species
</J dimensionless concentration, CAl CAS
lJ effectiveness factor
</>m modified Thiele modulus defined in Eq. (7)
tf>c critical Thiele modulus
tf>* reduced Thiele modulus, tf>ml</>c
REFERENCES
Aris, R.• The Mathematical Theory ofDiffusion and Reaction in Permeable Catalysts. Clarendon Press, Ox-
ford. 1975.
Frornent, G.F. and Bischoff, K.B., Chemical Reactor Analysis and Design. J. Wiley, N.Y., 1979.
Narsimhan, G. and Sundaram, K.M., Chem. Eng. Sci. 30, 1425 (1975).
Roberts, G. and Satterfield, CN., Ind. Eng. Chem. Fundam. 4,288 (1965); 5, 317 (1966).
Sundaram, K.M. and Frornent, G.F., Variable Step Finite Difference Methodfor Solving Boundary Value
Problems. to be published (1981).
