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ESTIMATION OF KINETIC PARAMETERS FOR ELEMENTARY

SURFACE PROCESSES FROM INTEGRAL REACTOR DATA.
CO OXIDATION OVER Pt/ Al2O3
a
BYONG K. CHO
a
Physical Chemistry Department , General Motors Research Laboratories , Warren, Michigan,
48090
Published online: 16 May 2007.

To cite this article: BYONG K. CHO (1986) ESTIMATION OF KINETIC PARAMETERS FOR ELEMENTARY SURFACE PROCESSES FROM
INTEGRAL REACTOR DATA. CO OXIDATION OVER Pt/ Al2O3 , Chemical Engineering Communications, 47:4-6, 201-217, DOI:
10.1080/00986448608911764

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 Chem. Eng. Commun. Vol. 47 pp. 201-217
0098-6445/86/4706-0201$20.00/0
1986, Gordon and Breach Science Publishers S.A
Printed in the United Slates of America.

ESTIMATION OF KINETIC PARAMETERS FOR

ELEMENTARY SURFACE PROCESSES FROM
INTEGRAL REACTOR DATA: CO OXIDATION
OVER Pt/A1203
BYONG K. CHO
Physical Chemistry Department
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General Motors Research Laboratories

Warren, Michigan 48090
(Received October 17, 1985; infinal form February 20, 1986)

A novel method has been developed which can be used for kinetic parameter estimation from
laboratory reactor data. It is based on discrete modeling and variational techniques applied to an
integral reactor packed with supported catalyst pellets. This new method, similar to the McCabe-
Thiele method in distillation column design, has been used to determine kinetic parameters of
adsorption, desorption and surface reaction steps for C O oxidation over PtIAI,O, catalysts at 500°C
and atmospheric pressure. The results clearly indicate the importance of the coverage dependency of
C O desorption activation energy in the steady state kinetics of C O oxidation. The good agreement of
the results with those on single crystal Pt surfaces indicates no significant metal-support interactions
for the Pt/AI,O, system during C O oxidation.
KEYWORDS Integral reactor Kinetic parameters C O oxidation Pt/AI,03

INTRODUCTION

The catalytic oxidation of carbon monoxide over noble metals such as platinum is
an important factor in the design of automobile catalytic converters (11. Partly
because of this practical importance, C O oxidation over platinum catalysts has
been investigated extensively; there is a wealth of information available on C O
oxidation over single-crystal Pt surfaces under ultra high vacuum conditions
[2,3,4,5]. The literature related to adsorption and oxidation of C O on
single-crystal surfaces has been reviewed recently by Engel and Ertl [6].
In contrast, little kinetic information is available on C O oxidation over
supported Pt catalysts at atmospheric pressure. Voltz er al. [7] obtained a kinetic
expression for C O oxidation over PtlAI,O, catalysts based on the assumptions
that the rate determining step was the surface reaction between adsorbed C O and
oxygen, and that the adsorption of CO and oxygen closely approached equi-
librium during the reaction. However, the assumption of adsorption equilibrium
may not be valid when the surface reaction rate is relatively fast compared with
the adsorption rate, as is the case with C O oxidation at high temperatures and/or
at low C O partial pressures. For example, Golchet and White [2] observed that,
at low partial pressures of C O where the rate-limiting step is the adsorption of CO,
 202 BYONG K. C H O
the surface concentrations of C O were considerably smaller than they would be in
adsorption equilibrium. Schlatter and Chou [8] found that the adsorption-
equilibrium Langmuir-Hinshelwood (LH) kinetic expression, similar to the one
used by Voltz et al. [7], could not fit their rate data for C O oxidation over
Pt/A1203 and PdlA1203. They attributed this failure to diffusion resistances in the
porous catalyst pellets, but did not address the validity of the adsorption-
equilibrium assumption.
It is evident that the adsorption-desorption process can deviate significantly
from equilibrium conditions when the rate of surface reaction is fast. When such
nonequilibrium-adsorption L H kinetics prevail, the individual rate parameters for
the adsorption and desorption processes (rather than adsorption equilibrium
constants) play an important role in addition to the surface reaction rate constant.
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Recently, a surface chemistry reaction model by Herz and Marin [9] which
accounts for all these elementary surface processes was shown to fit quite
adequately the steady-state rate data for C O oxidation over PtlA1203. More
recently Cho [lo], and Cho and West [ I l l showed both theoretically and
experimentally that the performance of the cyclic operation of Pt/A1203 catalysts
for C O oxidation depends strongly on the adsorption-desorption rate processes.
Though an integral reactor is commonly used for the laboratory evaluation of
catalysts, its usefulness as a means of kinetic parameter determination has not
been seriously considered mainly due to the need for seemingly complicated data
analysis procedures. In this work we have developed a simple method whereby
the kinetic parameters for adsorption, desorption and surface reaction steps can
be estimated from integral reactor data. This new method is based on a discrete
modeling technique similar to that used previously for catalyst poisoning
problems (12,131 and on a variational technique applied to the packed-bed
reactor. It is not necessary, in this method, to invoke the adsorption-equilibrium
assumption commonly adopted by many engineering kinetic studies [7,8]. This
method enables one to determine the oxygen sticking coefficient and surface
reaction rate constant as well as the coverage dependency of the CO desorption
activation energy from a known value of the initial C O desorption activation
energy.

EXPERIMENTS

Steady-state activity measurements for C O oxidation were carried out at 500°C

using a laboratory integral reactor made of a quartz tube packed with Pt/A120,
catalyst pellets. The catalysts were prepared by impregnating Pt on a y-A1203
support using the nonaqueous impregnation method [I41 in order to obtain a
shallow noble metal band (40pm) at the periphery of the pellet. Following the
impregnation, the catalysts were dried overnight in air at room temperature,
heated slowly in flowing air up to 500°C, and then calcined in air at 500°C for 4
hours. Dispersion of platinum was determined from C O chemisorption measure-
ments. The noble metal impregnation depth.was determined by scanning electron
microprobe analysis. Reactant concentrations at the reactor inlet and outlet were
 KINETIC PARAMETERS FOR SURFACE PROCESSES 203
TABLE I

Experimental data

Reactor: integral reactor (2.5crn I.D. quartz tube)

Temperature: 500°C (isothermal)
Pressure: 101.3 kPa (1 atm)
Feed Flow Rate: 4M1 cm3/min (STP)
Catalyst Bed Depth: 5 layers of catalyst pellets
Feed Composition: 0.6% CO (9.46 x mollcm3 at 500°C)
0.3% 0, (4.78 x mol/cm%t 500°C)
Conversion of Reactants: 92.45%
Catalyst: 0.1 wt % of Pt on AI,03
50% dispersion of Pt
1600 pm radius
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40 pm impregnation depth

measured by an IR detector for CO and an electrochemical sensor for 0 2 . The

feed composition was maintained at the stoichiometric point (0.6% CO, 0.3%
02), and the feed temperature was controlled by a preheater. The reactor bed
temperature was measured by a thermocouple located in the middle of the bed.
The detailed experimental data are listed in Table I.

ESTIMATION OF KINETIC PARAMETERS

The analysis of the integral reactor data will be based on the following facts and
assumptions.
The adsorption-desorption processes follow Langmuir kinetics, with molecular
adsorption of CO and dissociative atomic adsorption of oxygen [6].
The CO oxidation occurs primarily through the Langmuir-Hinshelwood mech-
anism [6].
The pressure drop along the reactor is negligible. This assumption is valid for
our experiments where the bed depth is very shallow.
The size of the gas-phase mixing cell is one pellet layer [MI.
The reactor is under isothermal conditions. This assumption is valid for the
turbulent flow regime encountered in our experiments, where the Peclet
number for axial thermal dispersion is about 5 to 10 times smaller than the
Peclet number for the axial molecular dispersion.
We have reliable sources of information on the initial activation energy of CO
desorption (i.e., activation energy at the low-coverage limit), on the desorption
rate of oxygen, and on the sticking coefficient of CO on Pt surfaces. We will
elaborate further on this as our analysis proceeds, but it suffices to note here
that there are independent literature values of the initial CO desorption
activation energy which are generally in good agreement [ 6 ] , and that our final
results of the parameter estimation is rather insensitive either to the rate of
oxygen desorption or to the CO sticking coefficient within the range of practical
interest.
 204 BYONG K. CHO
1. Phase Relation
The steady-state mass balances for a porous catalyst pellet for CO oxidation can
be described by the following:
for CO (molecular balance);

for oxygen (atomic balance);

where the primed variables denote those associated with oxygen. The mass unit in
Eq. (1) is in g-mol of CO, while that in Eq. (2) is in g-atom of oxygen. The
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adsorption rate constants (k,, k:) are related to the sticking coefficients (S, S') by
the kinetic theory of adsorption for a perfect gas:

In Eqs. (1) and (2) we described the steady state of the catalyst and
surrounding gas phase in terms of three rate processes: external mass transfer
rates (left-hand side), net adsorption rates (middle), and surface reaction rates
(right-hand side). It should be noted that the effects of intrapellet diffusion
resistances are implicitly accounted for by introducing the catalyst effectiveness
factor, q.
The mass action law requires that Eq. (I) be identically equal to Eq. (2). In
other words, Eqs. (1) and (2) are not independent but coupled through this
identity condition; the mass balance of CO and O2 are coupled with each other
through the surface concentration of the reactants. It is useful to decouple the
two equations from each other, for we can then describe the steady-state behavior
of the catalyst in terms of the kinetics associated with only one reactant without
any knowledge of the kinetics associated with the other reactant. This can be
done as follows.~
For convenience we introduce kd, k; and kR such that

Then Eqs. (1) and (2) reduce to

km(c, - c,) = ~,[Kc,(N - n - n ' ) - n] = kRnnl (6)
2kk(cA - cj) = ~;[K'C:(N - n - n')' - nqZ]= k n n ' (7)
where K and K ' are the adsorption equilibrium constants of CO and oxygen on
PtlAI2O3, respectively. By eliminating n' from Eq. (6), we get
 KINETIC PARAMETERS FOR SURFACE PROCESSES 205
where
a = %k,(l + Kc,)
b = k&cb - c,) - N ~ , & K c ,
c = k , f d Kc,(cb - c,)
Our experience indicated that there is a unique steady state under the
operating conditions of our experiments. T h i s i s consistent with the literature
report [16] that neither rate multiplicities nor spontaneous oscillations were
observed at temperatures above 300°C. A quick examination of Eqs. ( 6 ) and (7)
indicates that the surface concentration of CO ( n ) must always have a unique
value for the given steady state. Based on the above argument, we impose the
uniqueness criterion on Eq. (8). That is, we obtain from Eq. (8) the condition
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under which the surface concentration of CO ( n ) has a unique value for a given
set of reaction rate and surface concentration of oxygen ( n ' ) ;

where

By solving Eq. (10) for ub with the constraint that ub must be equal to u,
whenever a = 0 , we get

This is the relationship (hereafter referred to as the phase relation) which must
be satisfied between the bulk gas-phase concentration of C O (u,) and the
gas-phase concentration at the external surface of the catalyst (u,).
It is important to emphasize that in Eq. (13) the phase relation of CO can be
expressed exclusively in terms of rate parameters for CO, and thus the knowledge
of kinetic parameters associated with oxygen is not needed.

2. Reactor Operating Characteristics

An integral reactor can be simulated by a cascade of axial mixing cells [12, 171.
The steady-state mass balance for CO around the i-th cell is

or in dimensionless form,

where
 206 BYONG K. CHO
Note that Eq. (15) describes the reactor operating characteristics by relating
the conditions of the i-th cell of the reactor to those of the preceding cell, and is
hereafter referred to as the reactor operating condition.

3. Reactor Performance Diagram and Reaction Rate Constant

The reactor performance diagram can be constructed from the phase relation
[Eq. (13)] and the reactor operating condition [Eq. (IS)]. In combining these two
relations, the possible variation of the catalyst effectiveness factor along the axial
direction of the reactor is represented by its reactor-average value. The phase
relation for the i-th cell is
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The right-hand side of the reactor operating condition can be expressed in

terms of u , , ~by substituting Eq. (17) into Eq. (15);

where

A stepwise procedure similar to that developed previously for the poisoning

studies [12,13] can be constructed from the fundamental relations, Eqs. (17)
through (19), as illustrated in Figure 1.
For the first cell,

i-th Cell

FIGURE 1 The reactor performance diagram for the i-th cell.

 KINETIC PARAMETERS FOR SURFACE PROCESSES 207
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Phase Relation if) or Reactor Operating Condition (h)

o r Dimensionless Bulk Gas-Phase Concentration (Ub)
FIGURE 2 Estimation of surface reaction rate constant from the input-output data of an integral
reactor experiment using the stepwise graphical procedure.

and for the i-th cell (2 5 i 5 J),

Equations (20) and (21) suggest that, for a given feed concentration of CO, the
dimensionless surface concentration of C O in each cell can be obtained through
the repeated use of the stepwise procedure from the first to the last cell, based on
the f - and h-curve calculated from known parameters K, a and 8. On the other
hand, if we know the values of K, B and the exit concentration of CO, then we
can estimate a and thus k, (or k,) by matching the exit concentration through a
simple trial-and-error procedure. Note, however, that we have to assume q to fix
the value of /3 since /3 is a function of q.
Figure 2 shows how such a stepwise procedure can be used to obtain the
reaction rate parameter (k,) from the experimental data listed in Table I and the
known parameter values listed in Table 11. The trial-and-error procedure yielded
a reaction rate constant (k,) of 1.201 X 10" (mol/cm2 Pt)-Is-'. The value of q
listed in Table I1 was determined by a consistency test for the initial sticking
coefficient of oxygen, as will be discussed later. The sensitivity of the reactor
operating line and the phase relation line to the value of k, is shown in Figure 3.
Note that the horizontal distance between the reactor operating line and the
phase relation line is a direct measure of the catalyst performance in each cell of
the reactor.
 BYONG K. CHO
TABLE 11
Known parameter values

Np,i= 43
qS, = 3 . 5 1 5 ~(assumed
~ value; to be checked later)
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In Table I1 the external mass-transfer coefficients were obtained from the

correlation by DeAcetis and Thodos [20]. The molecular diffusivities were
calculated from the Wilke-Lee modification [21.] of the Hirschfelder-Bird-Spotz
method [22]. The estimated value of k , is relatively insensitive to the C O sticking
coefficient over the range of practical interest (S >0.2), as shown in Figure 4.
It should be noted here that in the above analvsis the desorution activation --. - --

energy of C O was assumed to be independent of the surface coverage of CO. The

case of coverage-dependent C O activation energy will emerge naturally as our
analysis proceeds.

Dimensionless Bulk Gas-Phase

Concentration (Ub)

FIGURE 3 The effect of reaction rate constant (k,) on the reactor operating line and phase relation
line (- reactor operating line, - - - phase relation line).
 KINETIC PARAMETERS FOR SURFACE PROCESSES 209
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0 0.2 0.4 0.6 0.8

3
1 .O
CO Sticking Coefficient (S)

FIGURE 4 The effect of CO sticking coefficient on the estimated value of the reaction rate
parameter.

4. Initial Oxygen Sticking Coefficient

The information available from integral reactor experiments is usually the input
and output concentrations of reactants. However, we can use such input-output
data to extract kinetic information about the elementary surface processes by
analyzing the reactor behavior using the stepwise graphical procedure illustrated
in Figure 2.
From the points 1 , 2 , 3 , 4 and 5 in Figure 2 we can determine the dimensionless
gas-phase concentration at the external surface of the catalyst (u,) and the
dimensionless bulk gas-phase concentration ( u b ) of C O at the first, second, third,
fourth and fifth cell of the reactor, respectively. From these we calculate the
intrinsic surface reaction rate (a,)for the i-th cell of the reactor, i.e.,

Furthermore, the unique solution of Eq. (10) gives the surface concentration of
co,

and thus the surface concentration of oxygen,

 BYONG K. CHO
lo-3x20
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0 0.1 0.2 0.3 0.4 0.5

CO Surface Coverage (6')
FIGURE 5 Required relationship between the oxygen sticking coefficient and CO surface coverage
to match the observed conversion.

From the steady-state mass balance we also get

Finally, the sticking coefficient of oxygen is obtained from Eq. (4);

Figure 5 shows the relationship between the oxygen sticking coefficient (S/)and
the surface coverage of CO (Bi) along the reactor from the first to the last cell
(i = 5). The relationship can be correlated by
St!= 0.00157 e~p(4.3730~). (28)
Equation (28) implies that, in order to match the experimentally observed
conversion level, the oxygen sticking coefficient is required to vary exponentially
along the reactor with the surface coverage of CO. This requirement is physically
unreasonable, and therefore we suspect that this might be an artifact which could
have come from some other phenomena that we did not appropriately take into
account during our data analysis. We will elaborate on this in the next section.
 KINETIC PARAMETERS FOR SURFACE PROCESSES 211
It should be noted that since the surface reaction rate (k,) is much faster than
the desorption rate of oxygen (k;), Eq. (26) can be approximated by

Thus, the oxygen sticking coefficient obtained from Eq. (27) is insensitive to
the oxygen desorption rate constant (k;).

5. Coverage-Dependent Actiuation Energy of CO Desorption

Recall that in the previous section we assumed the activation energy of C O
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desorption was independent of the surface coverage of CO. In general, however,

the desorption activation energy of simple gases on transition metals normally
decreases with increasing coverage due to the non-uniformity of the adsorption
sites and repulsive interactions between the adsorbed species [23]. A surface
coverage dependence of the C O desorption activation energy has been reported
on clean Pt surfaces under high vacuum conditions [6,18], while some inves-
tigators [4] have obtained a coverage-independent desorption activation energy of
CO.
For supported Pt catalysts, no reliable information is yet available about the
value of the desorption activation energy of CO and its dependence on the
surface coverage. In order to find out whether there is a correlation between the
C O desorption activation energy (Ed) and the surface coverage (O), we need only
to check whether there is a correlation between Ed and the oxygen sticking
coefficient (S'), for we already have the relationship between S f and 8 in Eq.
(28).
In order to correlate Ed with S' we employ the variational technique as follows.
Equation (26) indicates that the reaction rate parameter I;, can be expressed in
terms of Ed and S' if all the other reactor operating conditions (including the
conversion) are held constant. In other words,

Since the reactor is under the isothermal condition, kR must be constant. Then
it immediately follows from elementary differential calculus that

The values of (3) and (2)can be obtained from the experimental

d k ~.s EA

data by varying infinitesimally the value of $ to obtain the corresponding

such a way that the experimentally
observed conversion is-kept constant. The variation we used in this analysis
corresponds to 10 cal/mol in desorption activation energy. For example, from the
 BYONG K. CHO
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Variation of Oxygen Sticking Coefficient due to

Variation of CO Desorption Activation ~ n e (AS')
r ~ ~
FIGURE 6 Correlation between the oxygen sticking coefficient and its variation due t'o the variation
of CO desorpti'on activation energy.

positive variation of Ed we obtain aEd + and from the negative variation of

(K)
.
(2). (2)
.

Ed we obtain The final value of is the average value of

(2) and (aEd)-. The change of the variation in Ed from 20cal/mol to

l O c & n o l did ndt significantly influence the final result of our analysis. The
results are

In Eq. (32) we used the data correlation between S' and AS', corresponding to
A& that in turn corresponds to AEd in Eq. (31), which can be represented by
S' = 0.00157 + 42.751 AS' (33)
as shown in Figure 6.
Equations (30), (31) and (32) now yield an ordinary differential equation,
 KINETIC PARAMETERS FOR SURFACE PROCESSES 213
namely,
S'
(%)& = - G G x lo-' (mollcal).
The appropriate initial condition for Eq. (31) is
Ed = 35,300 callmol, when S' = 0.00157. (35)
By solving Eq. (31) with the initial condition (35), we get
S' = 0.00157 exp{(35,300 - Ed)1855). (36)
By equating Eq. (36) to Eq. (28), we get the relation between Ed and 9 ;
Ed = 35,300 - 3,7009 (callmol). (37)
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It should be mentioned here that the assumed value of qS, listed in Table I1
was obtained by carrying out a trail-and-error procedure until the initial oxygen
sticking coefficient obtained by Eq. (28) for 9 = 0 was consistent with that
obtained by Eq. (33) for AS' = 0.

DISCUSSION

Listed in Table 111 are the parameter values estimated from the integral reactor
experiments, along with some literature values reported on clean Pt surfaces. The
kinetic parameters on the Pt/A120S catalyst are in reasonably good agreement
with those on clean Pt surfaces, indicating no significant metal-support interac-
tions for the Pt/A1203 system during C O oxidation.
In Figure 7 the dependence of CO desorption activation energy on C O surface
coverage obtained in this work is compared with literature values. The good
agreement in the slope of the straight line between this work and McCabe and
Schmidt's work on single crystal Pt surfaces suggests the possibility that the size of
Pt particles dispersed on AI,03 in the supported catalyst may be large enough to
make the repulsive interactions of adsorbed C O on Pt1A1,O3 be as strong as those
on clean Pt surface.

TABLE 111

Kinetic parameters (T = 773 K)

On PtIAI,O, On Pt
(this work) (literature) References

S' 0.0016 0.0078 1241t

Ed, kcallmol 35.3-3.78 35.2-6.58 Pt(211) i18i

36.2-3.08 Pt(210) [I81

t Extrapolated value from 200 K to 773 K using S' = 0.00404 cxp(10001RT).

 BYONG K. CHO

40 7
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CO Surface Coverage (81

FIGURE 7 Coverage dependency of CO desorption activation energy.

In a recent study by Cho and West [ l l ] it was experimentally observed that, for
C O oxidation on Pt/A120,, steady operation performed better than cyclic
operation for stoichiometric time-average feed composition at warmed-up tem-
peratures. This observation is not in agreement with the previous modeling study
[lo], in which the coverage dependency of C O desorption activation energy was
not taken into account. Now it appears that one of the major reasons for this
discrepancy between the experimental observation and theoretical prediction of
the dynamic response of the catalysts is related to the coverage dependent
activation energy of C O desorption. That is, the repulsive interaction between
adsorbed C O molecules is a very important and integral part of the processes
occurring during C O oxidation on Pt/A1,03 catalysts.
It should be noted, however, that the kinetic parameter values obtained in this
work is based entirely on the value of Ed reported by Fair and Madix [4]. Even
though this value is in good agreement with most of the literature values [6], it is
desirable to conduct independent experiments in order to measure Ed on
supported Pt.
In summary, we have developed a simple method which can be used in
estimating kinetic parameters from the integral reactor experiments. We have
obtained by this method kinetic parameters of C O oxidation on PtlA1203. It was
found that the kinetic parameters of C O oxidation on Pt/A1203 are similar to
those on clean Pt surfaces. This technique can, of course, be applied to different
temperature levels in order to obtain the activation energy of the surface
reaction. However, we have decided not to pursue this until the activation energy
of C O desorption is measured by independent experiments, in view of the fact
 KINETIC PARAMETERS FOR SURFACE PROCESSES 215
that the resulting activation energy of surface reaction is strongly dependent on
the assumed value of the activation energy of CO desorption.

ACKNOWLEDGMENTS

The catalysts were prepared by M.J. .D'Aniello and K.D.T. Dang, and the
reactor experiments were carried out by L.A. West.

NOTATION
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external surface area of a pellet, cm2.

bulk gas-phase concentration of CO, mollcm3.
bulk gas-phase concentration of OZ,mol/cm3.
gas-phase concentration of CO on the external surface of a pellet,
mol/cm3.
gas-phase concentration of O2 on the external surface of a pellet,
mol/cm3.
activation energy of CO desorption, cal/mol.
phase relation between cb and c, defined by Eq. (13).
total number of mixing cells in the reactor.
adsorption rate constant for CO, (mol/cm3 gas)-'s-'.
adsorption rate constant for 0 2 , (mollcm3gas)-' (g-atom/cm2Pt)s-'.
desorption rate constant for CO, s-l.
desorption rate constant for O,, (g-atomlcm2Pt) s-'.
adjusted desorption rate constant for CO as defined in Eq. ( S ) , s-l.
adjusted desorption rate constant for 0, as defined in Eq. (5), (g-
atom/cm2 Pt) s-I.
external mass transfer coefficient for CO, cm/s.
external mass transfer coefficient for 0 2 , cmls.
surface reaction rate constant, (mol/cm2Pt)-' s-'.
adjusted reaction rate constant as defined in Eq. (5), (mollcm2Pt)-Is-'.
adsorption equilibrium constant for CO, (mol/cm3gas)-'.
adsorption equilibrium constant for O,, (mollcm3gas)-'.
molecular weight of CO.
molecular weight of 0,.
surface concentration of CO, mollcm2Pt.
surface concentration of oxygen, g-atom/cm2Pt.
surface concentration at saturation. mollcmZPt.
 BYONG K. C H O
total number of catalyst pellets in the i-th cell.
volumetric gas flow rate, cm3/s.
intrinsic surface reaction rate defined in Eq. (22), mol/cm2 Pt . s.
sticking coefficient of C O adsorption.
sticking coefficient of oxygen adsorption.
platinum surface area in a pellet, cm2 Ptlpellet.
temperature, K.
dimensionless bulk gas-phase concentration, Kcb
dimensionless gas-phase concentration on the external surface of a pellet,
Kc,.
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Greek Letters
dimensionless parameter defined in Eq. (12).
dimensionless parameter defined in Eq. (12).
dimensionless parameter defined in Eq. (12).
catalyst effectiveness factor (reactor-average value).
surface coverage of CO, nlN.
Boltzmann's constant.
dimensionless parameter defined in Eq. (16).
dimensionless parameter defined in Eq. (12).

Subscripts
f feed condition.
I i-th cell of the reactor.

REFERENCES
I. Taylor, K.C., "Automobile Catalytic Converters." Caralysis-Science and Technology (Edited by
Anderson, J.R. and Boudart, M.), Vol. 5, Springer-Verlag, Berlin (1984).
2. Golchet, A , , and White, J.M., I. Caral. 53, 266 (1978).
3. Matsushima, T., Surf. Sci. 79, 63 (1979).
4. Fair, J.A., and Madix, R.J., I. Chem. Phys. 73, 3486 (1980).
5 . Gland, J.L., and Kollin, E.B., I. Chem. Phys. 78, 963 (1983).
6. Engel, T., and Ertl, G., Adv. Caral. 28, 1 (1979).
7. Voltz, S.E., Morgan, C.R., Liederman, D., and Jacob, S. M.. Ind. Eng. Chem. Prod. Res.
Develop. U,294 (1973).
8. Schlatter, J.C., and Chou, T.S., "Measuring CO Oxidation Rates in an External Recycle
Reactor." Paper presented at the American Institute of Chemical Engineers 71st Annual
Meeting, Miami Beach (November 1978).
9. Hen, R.K., and Marin, S.P., I. Caral. 65, 281 (1980).
10. Cho, B.K.. Ind. Eng. Chem. Fundam. 22, 410 (1983).
I I . Cho, B.K., and West, L.A., Ind. Eng. Chem. Fundam. 25, 158 (1986).
12. Cho, B.K., Hegedus, L.L., and Aris, R.. A.1.Ch.E.J. 29, 289 (1983).
13. Cho, B.K., and Oh, S.H., Ind. Eng. Chem. Proc. Des. Deuel. 24, 897 (1985).
 KINETIC PARAMETERS FOR SURFACE PROCESSES 217
14. D'Aniello. M. J. and Dang, K.D.T., private communication, General Motors Research
Laboratories, Warren, MI (1984).
15. Amundson, N.R., and Aris, R., A. I.Ch.E.J. 3,280 (1957).
16. Sheintuch, M., and Schmitz, R.A., Coral. Rev.-Sci. Eng. 15, 107 (1977).
17. Sinkule, I., Hlavacek, V., Votmba. J., and Tvrdik, I., Chern. Eng. Sci. 29, 689 (1974).
18. McCabe, R.W., and Schmidt, L.D., Surf. Sci. 66, 101 (1977).
19. Wilf, M., and Dawson, P.T., Surf. Sci. 65,399 (1977).
20. DeAcetis, J., and Thodos, G., Ind. Eng. Chem. 52, 1003 (1960).
21. Wilke, C.R., and Lee, C.Y., Ind. Eng. Chern. 47, 1253 (1955).
22. Hirsehfelder, J.O.,Bird, R.B., and Spotz, E.L., Tram. ASME 71, 921 (1949); Chem. Rev. 44,
205 (1949).
23. Tompkins, F.C., Chernisorprion of Gases on Meralr. Academic Press, New York (1978).
24. Gland, I.L., Surf Sci. 93, 487 (1980).
25. Schwaha, K., and Bethtold, E., Surf. Sci. 65,277 (1977).
26. Bowel, H.P., and Ku, R., Surf. Sci. 33,91 (1972).
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