491

Shorter Communications
(c) For flow of single fluids in packed beds the dispersion
model should hold well, however, for the non-coalescing dispersed phase of-two phase systems the convective mode1 should
be used because difTerent sized particles or droplets move at
dierent
mean velocities.
(d) To see which model better fits a particular flow situation
we must ask Do the elements of lluld experience a constant
reshuftling of their identities, or do some elements always move
faster, others always slower?
(e) In recent years there has been mounting interest in flow
characterization
of multiphase
systems such as trickle beds,
bubble columns, spsry columns, and so on. A recent comprehensive Journal Review by Shah et al. (1978) lists hundreds of
studies in this area. But what is pertinent is the continual
reference throughout this review to the Gaussian dispersion
model and other stochastic type models to represent these Bow
systems. And what is remarkable is that, ss far as can be seen,
not one of these hundreds of studies ever considered using a
convection type model!
(f) So far we have only mentioned one-dimensional flow situations. However, the sane considerations apply to multidimensional flows. For example, in the air pollution literature and also
for liquid jets it is common practice to use Gaussian dispersion
expressions for the spread of material from a point source. With
such a model one usually iinds dispersion coefficients which are
not constant, but vary with distance from the source, indicating
that this model is inappropriate for these situations. It may well
be that a convection type model should be used, at least for the
spread of material io one of the directions.
(g) Let us return to our falling droplet example, the bigger
ones falling faster, the smaller ones falling slower, the RTD
Gaussian. With no coalescence the Convective-Gaussian
model
should hold with

On the other hand with frequent

coalescences

of drop breakup

*Author to whom correspondence should be addressed.

tPresent address: TRW Inc., Redondo Beach, California,
U.S.A.

Chemical Enrbuering
Science Vol.
Printed
in Great Britain

3S, No.

3, pp. 491-493,

A case of negative

the dispersion

models should hold with

What of the intermediate situation of a few coalescences

Should we develop a flow model in which
IT2= L,

only?

l~flS2

where n characterizes the location between these extremes? Or

should we use some other measure? This is an interesting question which we leave for others.
Acknowledgement-The authors would like to acknowledge their
gratitude to Prof. E. N. Lightfoot for his helpful comments.
Chemical Engineering Department
Oregon State Unioersity
Corvollis, OR 97331, U.S.A.

OCTAVE LEVENSPIEL*
T. J. FITZGERALDt

NOTATION

D
E,
Es
L
RTD
t
t =&
u
I(

axial dispersion coefficient, m2/s

the RTD or exit age distribution function, s-
the RTD in dimensionless time units
length of vessel or section of vessel, m
the residence time distribution
time, s
mean residence time, s
linear velocity

of fluid, m/s

Greek symbols
0 = 4 dimensionless time
I
ut standard deviation of RTD curve, s
~0 standard deviation of RTD curve measured in terms of 0.
Also the flow parameter of the convective-Gaussian
model
REFERENCE
Shah Y. T., Stiegel G. Y. and Sharma M. M., A.1.Ch.E. J. IV78 24
369.

1983

apparent

activation

energy due to pore diffusion

effects

(Received 18 March 1982; accepted 23 JUry 1982)

In a 1976 review paper, Rajadhyaksba

and Doraiswamy [ l]
considered
various sources of falsification
of apparent experimental
kinetic parameters.
One section treats the cases
of parallel first order reactions in the asymptotic
region of
pore diffusion control (effectiveness
factor < 0.5):

and

C will be
(De).

r&l= R(k,
(De;O

k,C,

+ k,)O.J
k2CA

r==R,(k,+k#-s

(3)
(4)

for the case k, % k,

As the disappearance
of A is given by the sum of the two
rates, k, + kz, the effectiveness
factor rl in the asymptotic
region is expected to be

(De).

R,

(k, + k,)O,

where De is an effective pore diffusion constant,

and
the radius of a catalyst Pellet. The rates of formation

(2)
R, is
of B

rc = (De).Sk&, -%,/R,

(5)

Assuming that k, and k, can be expressed

as Arrhenius
equations,
the activation
energy for (5) will be E2 - E, /2.
Thus, if El is more than twice as large as E+, we have the
unusual
case of an apparent
activation
energy changing
sign. due to pore diffusion
falsification,
in the case of
parallel, competing
reactions.

492

Shorter Communications

We believe to have discovered such a case, although the

kinetics of the two competing reactions are considerably
more complex than those of (l), ruling out an analytical
derivation, such as quoted above. The case in point is the
competitive oxidation of carbon monoxide by oxygen and
nitric oxide, in the oxidizing regime (CO -z 2 x Or + NO)
over an automotive three-way catalyst (l-WC). Here the
C&O,
reaction is the dominant one in the concentration
regime of interest, resulting in the necessity of assigning an
apparent negative activation energy to the CO-NO reaction.
EXPERIMENTAL
The catalyst was a commercial (Engelhard Industries type
lPD).monolithic
three-way catalyst with 310 channels per
square inch, coated with a 10 wt/, y-alumina washcoat. and
containing 20/.NiO, 0.6% CeOs. 0.1% Ft and 0.01% Rh. It
had been thermally aged at 780C for 16 hr. The experiments
were carried out under steady state flow conditions, in the
temperature range of 37&593C, at a space velocity of about
50,000 hr - for the CcrOr-NO
system, and 930,000 hr - for
the CO-O, and the C-NO
systems. The maximum inlet
concentrations of active gases were 2.5% CO, 2400 ppm NO,
and about 2%0,. The gases always contained 10% water
vapor, 12% CO,, and.20 ppm SO,, with nitrogen as the remaining diluent. These conditions are considered typical of
automotive exhaust in the very general neighborhood of
stoichiometric conditions where a TWC would be used. The
steam was produced by pumping water at a controlled rate
into a steam generator. The remaining gases were taken from
tanks, and their flow was controlled by Matheson mass flow
controllers. The analytical instruments used are typical for
this kind of work and have been described many times[2].
Integral conversion data were obtained by measuring concentrations before and after the catalyst.
REACTOR MODEL
In order to obtain kinetic information from the integral
conversion data, a reactor model was devclopul and applied
to the laboratory results. In this model the catalyst is divided
in the axial direction into a large number of cells. Within each
cell the solid and gaseous temperatures, the concentrations of
all active species in the bulk gas, as well as their concentrations at the geometrical surface of the supported catalyst,
are the dependent variables. The rate processes occurring
within the cell are then expressed mathematically in terms of
these dependent variables and the catalyst properties. The
rate processes included in the model are the transfer of heat
and mass by bulk gas flow, interphase heat and mass transfer
between the gas and the catalyst surface, chemical reaction on
the catalyst and the accompanying heat generation, and axial
heat conduction through the monolith. The rate expressions
are then related to each other by means of steady state mass
and energy balances applied to both the gas and catalyst
phases, resulting in a set of coupled nonlinear algebraic equations which may be solved for the concentrations and temperatures in each cell.
The form of the rate expressions are straight forward except for the chemical reaction rates (i.e. the catalyst kinetics).
In this model we have chosen to express the kinetics in terms
of catalyst temperature and ;;surface concentration of each
species. Thus the pore diffuston effects are not accounted for
explicitly by the model, but rather are folded into the kinetic
expressions. To determine these kinetics, a functional form of
the temperature and concentration dependence of the rate is
postulated and the best values of the adjustable parameters in
these functions are determined, using a parameter optimization program, by comparing the model predictions with
the measured conversions over a range of temperatures,
space velocities, and inlet concentrations. This press
may
then have to be repeated, using a different kinetic expression,
until a sufficiently good match is found for the experimental
data. In general, our kinetic forms have an Arrhenius temperature dependence and a concentration dependence which

is either a power law or is of the Langmuir-Hinshelwood

form.
The apparent kinetics thus determined will clearly be
subject to possible falsification by pore diffusion effects. The
next section presents the apparent kinetics for the system
CGNU,
in the oxidizing regime. The apparent activation energy for the N&CO
reaction, in the presence of
oxygen, is negative. Yet, in the absence of oxygen the
N&CO
reaction has a rate exuression which increases
monotonically with temperature.
RESULTS
Using the modeling procedure described above, the following expressions were found to be quite satisfactory in
describing the ternary systems CC%Nu,,
in the oxidizing

region. -

For the reaction CO + 0.5 0, = CO,,

d[CO]

2.00 x 1Orexp (-

dr

4.44 x 104/RT)[CO][0,]-*n

(1 + 3035[co])*

(6)

For the reaction CO + NO = CO, + 0.5 N,

--=WOI

-- d[NOl

dt

dt

2.67 x lo- 2exp(4.57 x l@/RT)[CO]llIO]-

(1 + 7.5977 x

1o[oJ)o*=2

(7)

[CO], WO] and [0,] represent concentrations in mole fractions, at the surface of the catalyst-containing washcoat.
Rate expressions (6), (7), (7) and (8) represent fluxes into the
pores, as a function of concentrations at the pore mouths, in
units of kg-mole/see/m* of geometrical surface area. In the
above scheme, the total rate of disappearance of CO is given
bv the sum of (6)
\, and f71.
., As stated before. our model
accounts for all known mass and heat transfer effects except
for pore diffusion. As shown by (7), the resulting apparent
activation energy for the C-NO
reaction, in the presence of
the competing CO-O, reaction, is - 45.7 kJ.
The solid lines of Fig. 1 illustrate the agreement between
a few of our observed and calculated NO conversions, using
(6) and (7). The reader may think that a zero, or even a small
positive activation energy in (7) would lead to similar results.
After all, the larger activation euergy of the CO-Or reaction
assures that a greater fraction of CO is oxidized by Or, with
increasing temperature, leading to concomitant smaller conversions of NO. This argument is quantitatively incorrect,
however. To illustrate this, we eliminated the activation term
in (7), and readjusted the remaining three parameters to give
their best possible fit of the experimental data. The resulting
equation,

dWO1
dt

2.33[CO]~O]895
(1 + 1.13 x 108]Or]O.4

(7)

when inserted into our model, leads to the dashed lines of

Fig. 1. The agreement is substantially worse than that provided bv_ (7).
. ,_with its negative activation enerav.
__ In fact. a
statistical test[3] on the complete data base of the hypothesis
that the improvement in agreement upon using (7) over (7)
is negligible can he easily rejected at the 0.005 significance
level.
What about the CO-NO reaction in the absence of oxygen? Our relatively small data base for that subsystem can he
modeled by the expression
-~=WJOI
dt

8.84 [CO] lfJO]

(1 + O.l94[CO] exp (5.26 x lO/RT))

(8)

with some of the calculated and observed integral conversions shown in Fig. 2. Note that (8) is quite different from

Shorter Communications

Fig. 1. Space velocity: M,OOOhr-.

Inlet concentrations:
major diluent: N,, with 10% H,O, 12%CO,, 2Oppm SO*,
plus: A, 1.33% CO, 1000 ppm NO, variable Or, at 37 1Oc; 0,
1.33% CO, 1000 ppm NO, variable O,, at 482C; 0, I .CU&
CO, 1000 ppm NO, variable Or, at 593C: p,
modeled
with eqn (7); -----,
modeled with eqn (7).

493

our kinetics are much more complex. We feel that three of

the ingredients, the competition for CO, the dominance of
one of the two reactions, and a much higher activation
energy for the dominant reaction, are sufficient to reproduce
an apparent negative activation
energy for the nondominant reaction, in the regime of pore diffusion control.
The negative activation energy of cqn (7) is actually surnrisingly large. We suspect that it might have something to
do with the strong adsorption term in the denominator of
eon (8). This strone CO inhibition may add to the three
ingreddlentsmentioned above to result inthe large, negative,
apparent activation energy for the C&NO
reaction in the
presence of oxygen.
The additional ingredient may be visualized as follows.
The C&NO
reaction obviously depends critically on the
CO concentration which, in turn, is controlled by the
dominant CO-O,
reaction. At the lower temperatures, a
moderate decrease in CO concentration
due to pore
diffusion limitations can provide an enhancing effect on the
CO-NO
reaction, via the CO-inhibition
term in (8). At
higher temperatures this term becomes smaller, thus lessening the enhancing effect and contributing to the apparent
negative activation energy (eqn 7) of the C&NO
reactio-.
in the presence of oxygen. This analysis assumes that eqn
(8), though falsified by pore diffusion effects, qualitatively
rcflccts the intrinsic kinetics of the CGNO
reaction, since
it applies to data for which the competing, and complicating, C-r
reaction is absent.
Engineering and Research Staff
Ford Moior Comoanv
r

MAX BEITMAN
NORMAN
C. O-l-l-0

NOTATION
concentration

of

concentration
mole fractions

WOI
Fig. 2. Space velocity: 930,000 hr- . Inlet concentrations:
2440 ppm NO,
0.18% CO,
with
10% H,O,
12% CO,,
20 ppm SO,, balance N,. Curve modeled with eqn (8).

drdr

(7). Both are falsified by pore diffusion effects, but (8)

predicts conversions which monotonically increase with temperature, as indeed is shown by the measured conversions.

of

indicated

species,

in

d[NOl

surface. reaction fluxes, in kg-mole/sec/ms

of geometrical surface area
D, effective pore diffusion constant
E,>Ez activation energies
k,>k, first order rate constants
=n,=c reaction rates
R gas constant, J/g-mole/deg. K
RP pellet radius
T temperature, deg. K
effectiveness factor
tl

DlSCUSSlON

If the intrinsic kinetics for both CC&NO and CO-O,

reactions were first order in CO and zero order in the other
components, our example would correspond exactly to eqns
(1x4)
of the introduction. It would also correspond to
approximation (5), since we know that the CM,
reaction
predominates in our regime of inlet concentrations. Clearly,

REFERENCES

[l]

Rajadhyaksha R. A. and Doraiswamy L. K., Catal. Rev.

Sci. EPWZP 1976 13 209 (see D. 236).
[2] E.g., G&tldhi H. S., Piken A.=G., Shelef M. and DeLosh
R. G., SAE Trans., Section 2, 85, paper 760201 1976.
131 Hamilton W. C., Acra Crysr. 1965 18 502.