I

NORMAN

L.

CARRl

The Pure Oil Co., Research Center, Crystal Lake, Ill.

Kinetics of Catalytic Isomerization of n-Pentane

Mathematical models developed from statistical analysis are useful in
studying

b
b

Reaction kinetics
Reactor design

C A T A L Y T I C ISOMERIZATION of n-pentane
was studied to obtain information about
kinetics of the reaction, and to use mathematical models, derived from rate data,
to design isomerization reactors.
T h e use of statistical tools in the
experimental part of this work is a new
and important contribution to the study
of the rates of catalytic reactions. T h e
efficient design of experiments is emphasized so that the mathematical models
derived therefrom apply to the whole
area of interest. This type of design
and analysis is based on previous work
(7-4, 8). The central composite rotatable design in three dimensions was
especially useful in developing secondorder mathematical models.
One mathematical model, developed
for the differential reaction rate, was
applied to integral reactor design. Basic
equations, used to simulate operation,
produced the effect of any desired change
caused by variation of feed composition,
total pressure, reactor size, and hydrogen-to-hydrocarbon mole ratio. Thus,
the need for extensive experimentation
was eliminated and optimum regions for
further study were pointed out.
The data could not be represented by
simple first-order kinetics, although the
pseudo-first-order kinetics model was
approximately valid when the conversion interval was small for operation at
constant pressure, hydrogen-to-hydrocarbon ratio, and feed composition.
T h e kinetic equations developed were
rather complicated when wide ranges of
variables were included.
That the data can be represented
mathematically by the idealized adsorption surface-reaction model implies
that this physical model may reflect
1 Present address, Gulf Research and Development Co.. Pittsburgh, Pa.

b
b

Nature

of the reaction

Optimum operating conditions

the true catalytic picture: T h e ratecontrolling step is a reaction on the surface; the reaction appears to occur
through an interaction involving two
adjacent sites on the surface; and
numerical values of partial pressure
coefficients show that the adsorption
constants for isopentane and hydrogen
are 17 and 6.4 times, respectively, those
for n-pentane. This latter point explains why the reation rate of n-pentane decreases more than can be explained by a decrease in the driving
force as equilibrium is approached.
Experimental Design

The first problem is to determine the

rate of reaction of n-pentane to isopentane in a reactor containing a solid
catalyst operated at a fixed temperature.
Hydrogen is employed as an inert in
the flow reactor system. In a practical
sense, the only net reaction occurring
is the isomerization of n-pentane to
isopentane (2-methylbutane). This is
a first-order, reversible reaction for
which the equilibrium constant is known.
The three variables which affect the
rate of reaction for this system are the
partial pressures of the three components:
n-pentane, isopentane, and hydrogen.
These variables of partial pressure are
defined in each case as the product of the
total pressure and the mole fraction of
that component in the reactor. The
instantaneous partial pressures within a
reactor are considered as the independent
or controlled variables. The basic response variable is the differential rate of
reaction expressed as grams of isopentane
produced per gram of catalyst per hour.
The Hougen and Watson (7) approach
to the Langmuir-Hinshelwood (5) concepts of reactions on solid catalysts

has served in interpreting kinetic data

where applicable and where the data
have been properly taken. Two mechanisms which are most likely to be valid
in this work are, first, the single site
model by which the reaction proceeds
through an adsorbed reactant molecule acquiring sufficient energy to cause
it to form a product molecule. Only
a single active center is required in this
case. T h e second mechanism is the
dual site model for which the adsorbed
molecule on one site acquires sufficient
energy to form a complex or intermediate
with an adjacent active center. In further arrangement, the complex forms an
adsorbed product molecule.
If it is assumed that the surface reaction rate is the controlling rate and
that adsorption processes for each component are at equilibrium, the differential reaction-rate expressions for a reB is
action such as A

Single site mechanism

The reaction rate is ra, the K,s are adsorption equilibrium constants, the
xis are partial pressures, K is equilibrium
constant, y is a constant dependent on
the catalyst and temperature, and subscripts 1, 2, and 3 refer to hydrogen, npentane, and isopentane, respectively.

Dual site mechanism

The essential difference between these
two models is the power to which the
denominator is raised. The expression
for ra in Equation 1 cannot have a
maximum with respect to any of the
VOL. 52, NO. 5

M A Y 1960

391

for setting the values of the variablesfive levels each in this case. The fitted
equation has equal precision at a given
radial distance from the center and
precision is highest at the center. hleans
for measuring the residual, experimenral
error, and lack of fit sum of squares is
built into the plan to test statistical adequacy of the fitted model.
Experimental Procedure

Figure 1. Geometric location of points

for a central composite rotatable design with center point
partial pressures, xvhereas in Equation
2, ra can have a maximum with respect
to xz and/or x 3 , but not for xl.
Equivalent forms of Equations 1 and 2
are employed as a theorerical basis for
fitting mathematical models to experimental data. By definition, t\vo neiv
response variables are

Also for convenience in planning and

numerical calculations, the partial pressure terms are coded. Considerable
judgment is needed to establish the
satisfactory range for coded and natural
variables. T h e new coded variables are
Xi'

i - 300
z - 150
= X___
, X ? ' = x___
, and

Equations 1 and 2 are rewritten in

terms of the new var'ables :

+
= ha +

= Qa

.Yl

YZ

UlX;

f UsX;

61~;

b2X;

+
+ b&

(3)

(4)

The quantities in 3.1 and 3 . 2 are either

observed, measured, or known. Equations 3 and 4 are in proper form for
applying the method of least squares ;
the former is a first order model in three
dimensions and the latter is a special
second order model for y 1 and a first
order model for y ~ . The right side of
Equation 3 can be pictured as a "resistance" term and the quantities in the
definition of y l represent a "driving
force" term, (x, - x 3 / K ) , and a "rate"
term, ra.
The basic experimental design chosen
is called a central composite rotatable
design (Figure 1 and Table I). T h e
statistical advantages of such a design
are enumerated elsewhere (2, 4, 8).
This design with replication a t the cenrer point has important merits: U p
to second order models (quadratic expressions involving 10 terms) can be
fitted, if needed. This provides the
experimenter with an efficient method

392

Rate equations are best established

from differential rate measurements in a
reactor containing a bed of catalyst sized
so that relatively small changes in composition are produced with concomitant
precise measurement. Particle size of
the catalysr and reacror diameter should
be carefully chosen to achieve essentially
a flat velocity profile. I t is important
to maintain a mass velocity of the flowing
stream so that interparticle transport
resistance is negligible. Because of the
strong influence of temperature on the
reaction rate, the bed should be at a
uniform temperature which requires a
small diameter reactor and good heat
Transfer provisions around the walls of the
vessel. I n this investigation all these
conditions were met satisfactorily either
by experimentation or by calculation.
The reaction system was a bench-scale
catalytic reactor unit capable of being
operated over a wide range of temperatures, pressures, liquid and gas flow rates,
and reactor bed depths. This system
was composed of a liquid feed pump, a
hydrogen-metering system, an isothermal-type reactor, liquid and gas
recovery sections, and measuring devices for all materials entering and
leaving- the unit. Most equipment was
equivalent to that in common use.
The reactor-furnace portion was of
special design. The 1-inch stainlesssteel pipe reactor, about 3 feet long, was
surrounded by an aluminum-bronze
block, 5 inches in outside diameter,
around which electrical heaters were
placed. The reactor was equipped with
spacers so that various bed depths could
be obtained, although only a ll/,-inch
depth was employed. Axial temperatures were measured by a thermocouplepotentiometer system. Automatic temperature control was also provided.
The catalyst was composed of a metal
deposited on a refractory support. The
particle size was nominally l / 1 6 inch and
the shape was that from a '/s-inch diameter pellet which was divided in half.
Full pellets were used in the experiments
on the effect of particle size. hTominally 10 grams of catalyst were charged
for each run. Eight separate batches of
fresh catalyst were charged.
The nominal operating conditions
were as follows: temperature, 750' F.;
liquid-weight-hourly space velocity, 60;
feed liquid, a mixture of n-pentane and
isopentane defined by design in Table

INDUSTRIAL AND ENGINEERING CHEMISTRY

Table I. Design of Experiments Locating Levels of the Three Independent

Variables
Run No.
, Coded Variahles
Code
d
4
Central Coiiiuosite Rotatable DcsiRii
1
2
3
4

5
6

7
8
9
10
11
12
13
14
15
16
17
18

-1
1
-1
1
-1
1
-1
1
-1.68
1.68
0
0

-1
-1
1
1
-1
-1
1
1
0

0
-1.68
1.68

0
0

0
0
0
0
0

0
0
0

-1
-1
-1
-1
1
1
1
1
0
0
0
0
-1.68
1.68
0
0
0
0

-1uxilial.y Points
19
20
21
22
23
24

0
-1.93
1.17
-0.49
-0.50
-1.55

-1.31
1.75
-1.29
3.56
0.18
3.68

-0.38
-1.57
-1.07
-1.53
-1.61
-1.52

I ; hydrogen-to-hydrocarbon raiio, defined by design; pressure, defined by

design; and time, a prerun period and a
steady-state period of 15 minutes each.
Temperature deviations occurring
around the planned level were adjusted
to a common temperature of 750' F.
Reaction rates were corrected by using
an established estimate for energy of
activation (AE*) as 29 kcal. per grammole and the relationship

in which R,] is the gas constant, and 7'

is the absolute temperature.
The effect of processing time over the
range of times employed had a negligible
effect upon rhe results at operating conditions most conducive to aging.
The analytical methods used for the
liquid feeds and products, and for the
off-gases were chromatographic and
mass spectrometric, respectively. The
parent feed stocks for the blends were
prepared in pure "pentane" form by
superfractionation. The hydrogen fed
to the unit was a high purity (electrolytic) hydrogen obtained from the National Cylinder Gas Co.
The experimental data are sh0Lt-n in
Table I1 which forms the basis for the
analyses. The partial pressures of the
components in the reactor inlet and
outlet streams were averaged arithmetically to produce the component values
associated with the observed reaction
rate for the differential reactor analysis.
Both Table I1 and Table VI are available from the American Documentation
Institute, Washington, D. C .

CATALYTIC ISOMERIZATIONS
The equilibrium constant at 750' F.
was taken as 1.632, which is equivalent
to 62% isopentane and 3870 n-pentane.
Experimental Results and
Mathematical Analysis

The next problem concerns the determination of a mathematical expression which adequately fits the data and
the condition that the rate must equal
zero a t equilibrium. T h e chemical
and catalytic concepts previously discussed are especially helpful in defining
proper response functions. These response functions, y l and yz, were fitted
by the method of least squares with firstand second-order models in three dimensions-i.e.,
with the three partial
pressures. This produced four models
for representing the differential rate data.
Table I11 shows the experimentally
based values of the average reactor
partial pressures ( X I , X ? , X Q ) and the corresponding observed responses, y l and
y z . This part of the table is the basis
for the numerical fitting of response y l
by two models and likewise, yz for two
models. These four models are listed in
Table I V and the numerical regression
parameters are given. T h e Model I1
results given in Table I11 show the correspondence between the observed values
and the computed values from this
regression equation for the response yz
and for the reaction rate.
Recorded in Table I V are the five
models tested for this work. The first
four regression equations were obtained
with the aid of an IBM 650 computer.
Model V is a second order model in
three dimensions containing the theoretically based integral-form response
function. In this case only the central
composite design values were used in the
analysis and here the coded coordinates
were utilized directly. Since this is an
integral model applicable to finite reactors of any size, it is unnecessary to
average the partial pressures as was done
for the differential method. T h e integral reactor equation could also be
applied to reactor design by making a
number of finite steps and summing the
results. This integral-form expression
( k ) is normally called the pseudo-firstorder reaction rate constant; it is obtained by integrating the equation
derived from a material balance around
a differential reactor section wherein the
reaction rate is represented by first
order kinetics. Equation 12 is derived
by a similar, but more general, treatment and it also contains this function.
The principles involved in the decision as to whether a mathematical
model adequately represents the data
are those defined by statistical methods.
After a model is proposed and fitted by

Table 111. Experimental Data in the Form for Regression Analysis. Predicted
Rates from Model II Equation Are Compared with Observed Values
Experimental Values
Model I1 Results
Partial Pressures.
Reaction Rate T ,
Run
P.S.I.A.
Responses
G./G. Cat./Hr.
No.
Calculate:d
Code
Calcd.
Exptl.
21
22
23
Res., YZ
Y1
Y2
1
2
3
4
5

205.8
404.8
209.7
401.6
224.9

90.9
92.9
174.9
187.2
92.7

37.1
36.3
49.4
44.9
116.3

19.249
29.475
21.604
33.816
36.120

4.3873
5.4290
4.6480
5.8151
6.0100

4.4152
5.5532
4.7019
5.7515
5.7399

3.4965
2.2911
6.5417
4.8271
0.6502

3.541
2.397
6.694
4.722
0.593

6
7
8
9
10

402.6
212.7
406.2
133.3
470.9

102.2
186.9
192.6
140.8
144.2

128.9
134.4
134.9
87.6
86.9

86.556
37.370
44.846
27.255
44.997

9.3035
6.1131
6.6967
5.2207
6.7079

6.9671
6.0316
7.1611
4.8152
6.7558

0.4779
2.8731
2.1435
3.7570
1.9925

0.268
2.797
2.451
3.196
2.021

11
12
13
14
15

300.0
301.6
297.3
314.0
305.7

68.3
214.6
142.2
146.7
142.0

81.7
101.7
10.5
157.1
86.0

20.334
29.950
23.876
42.257
33.720

4.5094
5.4727
4.8864
6.5005
5.8068

5.6214
6.0689
4.5822
6.9275
5.7867

0.5768
4.1341
6.4659
1.0505
2.6666

0.896
5.084
5.686
1.193
2.648

16
17
18
19
20

300.1
305.4
305.2
300.1
106.6

143.7
141.1
141.5
83.0
209.6

90.2
87.4
87.0
66.4
33.0

26.768
28.661
26.704
33.283
16.258

5.1738
5.3536
5.1676
5.7691
4.0321

5.8202
5.8056
5.7986
5.4010
3.8871

2.6101
2.5971
2.6224
1.4502
12.533

3.303
3.054
3.302
1.271
11.648

21
22
23
24

417.2
251.0
250.3
145.1

83.9
294.4
148.0
291.0

32.9
41.5
14.7
50.2

31.835
28.006
17.925
22.453

5.6423
5.2915
4.2343
4.7384

5.5646
4.9271
4.3806
4.4461

2.0584
11.079
7.2431
13.164

2.002
9.604
7.754
11.590

least squares, it is desirable to set up a

regression analysis table which shows
the breakdown of the total sum of squares
of the observations 2yz into component
parts : ZjP, where the individual terms 9
are predicted values derived from the
fitted model, and a residual sum of
squares, ~ ( Y - Y ) ~ . The residual sum of
squares can be broken into two parts : an
error sum of squares which measures
the failure of individual observations to
be equal, although taken under identical
experimental conditions, and a lack of
fit sum of squares which equals the re-

Table IV.

sidual sum of squares minus the error

sum of squares. An F-test is then applied
to the lack of fit variance and error
variance to determine whether the lack
of fit variance is statistically different
from the experimental error variance.
A fitted model is termed adequate to
represent the data when the lack of
fit variance is not significantly different
from the error variance. This procedure was used in this work and the
details are shown in Table V. The
results of this analysis show that three
of the five models proposed are adequate

Regression Equations for Five Fitted Models Showing the Form and
Numerical Coefficients for First and Second Order Models

Differential rate data analysis

Model I. Single site mechanism and first order model for response
6.7635 X 10-a,,
5.273 X 1 0 - 3 ~ 2 1.85179 X lO-'za

~ J I= -2.6116 +
+
Model 11. Dual site mechanism and first order model for response y ~ :uz = 2.57746 +
5.7708 X 10-3x1 + 9.023 X l O - ' ~ z + 1.53128 X 10-2x8
Model 111. Second order model for response yl:
= - 11.6003 - 1.327 X 10-2
+
2.3172 X 10-1 zz+ 2.2658 X lO-'xa + 1.8898 X 10-4 X? - 3.625 X 10-6 z
g f 1.4015
z: - 3.047 X
z1z2+ 3.787 X lo-'
- 2.4266 X 10-3
X
Model IV. Second order model for response Y Z :
= 5.0799 - 9.001 X 10-4x1 + 1.3262
X 10-2 xz + 2.5190 X 10-2za + 1.6257 X 10-622 + 2.366 X 10-8 xi + 1.0119 X 10-4 X:

VI:

y1

XI

zlZ3

22x3

y2

1.3946 X

2122 -

1.713 X IO-'

2153

1.663 X

z228

Integral reactor treatment of data

Model V. Pseudo-first order rate constant (k) a s response function represented by second
order model: k = 5.2771
0.7960 z; 1.3230 x; - 0.1420 xi - 0.2758
- 3.497 z X
- 0.1963 xL2 5.479 X lowz~iz: 0.1188 $;a; 0.1165 xLzi
10-2s;'

(1 - N B ~ / N A ~ K )

where k = (LWHSV)loglo

(1

- N B O / N A , K) (K
:

NAON

B~))

and the (z;)'sare the coded values corresponding to the initial partial pressure.

VOL. 52, NO. 5

MAY 1960

393

T h e numerical computations and the

integrations of the design equations
were carried out on an IBM 705 computer. A sample of the results is shown
in Table V I and Figure 4 for the case
wherein the reactor outlet stream contains a distribution of pentanes equivalent to 95% of the equilibrium value.
There is an optimum operating pressure
for each hydrogen-to-hydrocarbon ratio
and smaller reactors are indicated as
this ratio decreases. These results are
consistent with other integral reactor
information, although a comparison is
not made here.
Figure 5 shows the reactor design
relationships between three fundamental
variables with the equilibrium approach
as the response surface. This provides
a physical picture of the type of results
which were obtained from applying
numerical methods to kinetic data.

Figure 2. These contour surfaces which represent the resistance term show differences in nature of the models
Left, first order model

and two are not. It is interesting to

note that the integral model (V) has the
best numerical F-test. Since model I1
is the simplest acceptable model, it was
chosen as the differential rate model for
further attention.
T h e success of model I1 and the failure
of model I can be qualitatively attributed to the nature of the resistance
term in the basic rate equation. This
resistance term is the quantity which is
sought. Figure 2 depicts the geometric
differences in the shapes of the contour surfaces (constant resistance surfaces) for the linear model and the
quadratic model; one is a planar surface and one is curved. For example,
if the true response surface is curved,
this shows why the linear (first order)
model might fail to represent the data.
Representation of reaction rate contours graphically is impossible, because
the models developed are really four
dimensional ones ; the dimensions for
the reaction rate response are the driving
force ( X Z - x ~ / K ) and
,
the partial pressures, X I , XZ, and x 3 .
Initial reaction rates can be computed
from these models by letting the isopentane partial pressure equal zero.
This was done for model I1 and three
rate contour lines are plotted in Figure
3. The dotted lines are constant hydrogen-to-hydrocarbon mole ratio lines
and the light, diagonal lines are constant
pressure lines. I t is easy to see that there
is an optimum pressure for each ratio.

Right, second order model

gration of the proper design equation

in which the differential rate equation
is a part. An example case was selected to show the utility and the nature
of the results. I n the design of the
reactor, it is assumed that this reactor
is operated isothermally and with the
catalyst used in this study. The liquid
feed contains 90% n-pentane and 10%
isopentane. Two conversion levels expressed as the percentage approach to the
equilibrium ratio of isopentane-to-npentane in the reactor outlet stream
were considered. The 85 and 95%
levels of equilibrium approach were
chosen. T h e total pressure and the
hydrogen-to-hydrocarbon
ratio
are
varied and required space velocity is
computed. This space velocity is proportional to the reciprocal of reactor size.

Useful process aspects of reactor design can be obtained from model I1 by

taking one more step involving the inte-

394

In the work up to this point the role of

intraparticle diffusion has been neglected
because of the complexitj- of the development of mathematical solutions for the
simultaneous consideration of complex
kinetics and diffusion. However, if
simplified kinetics can be justified, then
other factors can be properly treated
and concepts from theoretical approaches
can be formulated. Simple kinetics of
the pseudo-first-order type are applicable
to certain situations. For example, this
simple model is reasonably valid in
most isomerization reactors wherein
the temperature, pressure, and hydrogento-hydrocarbon ratio are fixed and
wherein the reactor efflcent distribution
is not too near the equilibrium value.
In this case, a model can be derived to
consider other physical factors such as
particle size, diffusivities, mass transfer
coefficients, and catalyst void volume.
This type of approach has received
considerable attention. Amundson and
others, especially Smith and Arnundson
(TO), have worked out problems taking
into consideration the intraparticle dif-

I
ZOO

300

400

500

600

700

800

PRESSURE, PSIA
'0

I00

200

X I , HYDROGEN

Reactor Design

Consideration of
Intraparticle Diffusion

330

PARTIAL

400

500

600

PRESSURE, P S I A

Figure 3.
Contour lines for initial
reaction rate, computed from model II,
show relationship of partial pressures
which give the same rate

INDUSTRIAL AND ENGINEERING CHEMISTRY

Figure 4. When model II i s applied to

integral reactors, these curves represent space velocity requirements for
obtaining 95% equilibrium at the outlet reactor

CATALYTIC ISOMERIZATIONS
fusion of reactant& and products and
reaction rates within catalyst pores
for first-order reversible reactions and
for different types of reactors.
T h e following development will be
made for the primary purpose of obtaining a relationship which will predict the effect of particle size of the catalyst on the over-all rate of reaction and
the relative magnitude of the measured
rate and the true surface reaction rate.
I t is assumed that first-order reversible
reaction A
B is described kinetically
within the catalyst pores by the equation
r , = k,Ca -

kbCb

5 as the rate of reaction results in the

following two equations for the steady
state :

The two additional equations needed are

the inlet bulk concentrations of A and B
at x = 0:

c,

p$$+ 7 z ] +
2

dcb

kaCa - kaCb = 0

(7)

These two relationships define the simultaneous

diffusion-reaction
problem

e,,

The complete mathematical description for this problem is given by Equations G through 11.
The rigorous analytical solution for
this problem can be written as

(5)

where ca and c b are intraparticle concentrations of A and B, respectively,

and k , and kb are velocity constants for
the forward and reverse reactions, respectively. These velocity constants are
characterized by the catalyst and the
fundamental operating conditions.
I t is assumed that no volume changes
occur, that diffusivities (D)of the reactant and product are equal and constant [this is consistent with Knudsen
diffusion in small pores (77)], that the
catalyst is small spheres of constant size,
and that the resistance to mass transfer
in the bulk stream is negligible.
Consideration of a single porous sphere
with radial dimension r and a spherical
shell using Knudsen's diffusion as a
means of transport of mass and Equation

within a single particle.

I n order to set up the complete reactor
problem the spheres must be put into
packed bed of length dimension x and
another mass balance made over an
elemental reactor section. T h e C'S
are bulk stream concentrations, q is the
flow rate per unit area, p and p . are
densities of the particle and the bulk
spheres, respectively, R is sphere radius,
and y is fractional voids within the particle. T h e two new equations are

where K is the equilibrium constant,

S, = ( q p / p g x ) and is proportional to
total weight-hourly space velocity, and

( R w ) is a dimensionless group containing

the particle radius, the equilibrium
constant, and the ratio of the forward
rate constant and the diffusivity. T h e
left side of Equation 12 is also in dimensionless form, so that the concentration
terms can have any consistent set of
units which are porportional to concentration, such as moles, or mole fraction.
Therefore, it is directly related to the
previously defined k in Table IV.
Two special cases of Equation 12
can be stated: First, its limit as D
approaches infinity is

9'0 OF EQUILIBRIUM AT
REACTOR OUTLET
This is identical to the expression obtained by Hougen and Watson for the
equivalent case where intraparticle diffusion is neglected. Second, its limit
as R approaches zero is

Figure 5. Response surface shows the relationship between

three variables which produce the same conversion

This represents the case where the

true surface kinetics is identical to the
observed kinetics. This is useful in
computing the limiting values which
are shown in Figure 6.
Equation 12 can be applied to experimental kinetics to predict the effect
of particle size of the catalyst. Relative changes in the pseudo-first-order
rate constant (k) can be obtained when
only w is known. This parameter can
be determined from proper reactor
measurements using a minimum of two
reactors with two catalyst sizes.
The experimental determination of the
parameter u11 was carried out using two
particle sizes; one size was nominally
l/s-inch pellets and the other l/le-inch.
VOL. 52, NO. 5

M A Y 1960

395

-VAo,

Table V.

Regression Analysis Table for All Fitted Equations Indicates Acceptability

of Three Models
Model
I
I1
I11
v
IV

Residual
Sum of squares
Degrees of freedom
Experimental error
Sum of squares
Degrees of freedom
Mean square (variance)
Lack of fit
Sum of squares
Degrees of freedom
Mean square (variance)
Variance ratio (F-test)
5Y0 F statistic
Model adequate?

1993.56
20
22.63
3
7.55

VARIABLE W A L E

i I UNIT G

22.63
3
7.55

8.952
17
0.527
5.58
8.7

1170.57
11
106.4
14.1
8.8

No

Yes

No

SIZE

0.283
3
0.0943

1193.20
14

1970.93
17
115.9
15.4
8.7

PARTICLE

9.235
20

?%I

Figure 6. Effect of particle size on

fast recctions i s appreciable. O b served rates for large particles can
b e much lower than those for small ones

Three sets of data were obtained in the

high reaction rate region (ks about 25
to 35). T h e average ratio of the observed rate constants of the l j 1 6 to the
l / 8 inch was 1.32.
T h e larger size was
chosen as a basis in the following computations. T h e numerical value of
w1 is obtained as the root of an equation resulting from the combination of the
two basic formulas for the two particle sizes as a ratio of the two equations.

396

0.283
3
0.0943
5.712
11
0.519
5.50
8.8
Yes

4.272
8
1.143
3
0.381
3,129
5
0.626
1.64
9.01
Yes

version data and/or differential reactor

data may be used directly.
I n conclusion to intraparticle diffusion considerations in solid catalytic
reactions, a simple general model has
been developed and applied to isomerization kinetics. Within the high reaction
rate region studied, the true surface
rate constant was about 15y0 higher than
that observed, and in most of the experimental region this difference was
less than about 5%. This latter magnitude was within the experimental precision. This situation, however, does
not alter the validity of the results
represented by any of the acceptable
mathematical models.
Acknowledgment
T h e author wishes to thank Vincent
Brozowski for his able contributions in
the experimental work and calculations,
and E. D. Blum for his programming of
the integration work.
Nomenclature
constants related to adsorption constants
bo, b l , 62, b s = constants related to adsorption constants
C,, C,
= concn. of reactant and product, respectively, inside
rhe particle
C,, Ca = concn. of reactant and product, respectively, in the
bulk phase
C,, Cbb0 = initial or feed concn. of
reactant and product, respectively, in reactor
D
= diffusivity of reactant or
product
k
= pseudo-first-order rate constant; value based on
natural logarithms except for model V
k,, kb
= forward and reverse velocity constant, respectively, of reaction inside
particle
K
= reaction equilibrium constant
K1,K P ,K3 = adsorption constants
aa, a ] , a%,a3 =

T h e root is
= 3.17.
This knowledge can be applied to
other particle sizes and the true forward reaction rate constant (k,) can
be predicted (Figure 6). This information gives the experimenter a knowledge as to the importance of diffusion
and particle size on kinetic measurements. Also, effect of faster or slower reaction rates can be determined with this
model-e.g., in Figure 6, if w2 = ( w 1 ) / 2 ,
the effect of particle size diminishes as
the rate constant decreases.
This method of including intraparticle
transport is similar to that originally
developed by Thiele (72) where a single
sphere and a first-order irreversible reaction were considered. His work is now
extended to reversible reactions and to
integral reactors for which integral con-

5.995
14

INDUSTRIAL AND ENGINEERING CHEMISTRY

iVBo = mole fraction of reactant

and product, respectively,

in reactor feed
.VB
= mole fraction of product at
reactor outlet
Q
= total reactor volumetric flow
rate per unit reactor area
r
= radius variable inside particle
= forward reaction rate
= particle radius
st
= ( q p / p , x ) or total space velocity
tu
= parameter defined by Equation 13
X
= distance variable measured
along reactor
XI,xz, x 3 = partial pressures of hydrogen, n-pentane, and isopentane, respectively
XI, XZ, x3 = coded dimensionless variables corresponding to
hydrogen, n-pentane,
and isopentane, respectively
L 1
= response variably defined
as (x2 - x z / K ) , / r a
,Y3
= ( ~ 1 ) ~ / *a, response variable
= consrant in Equation
1,
Y
and fractional void volume in catalyst particle
= constant in Equation 2
*I,
P
= particle density
= bed or bulk catalyst density
Ps

Literature Cited
(1) Box, G. E. P.: Biometrics 10, 16 (1954).
(2) Box, G. E. P., Hunter, J. S.:4nn. Math.
Stat. 28, No. 1: 195 (1957).
(3) Box, G. E. P., Youlc, P. V., Blomebics
11,287 (1955).
(4) Davies, 0. A , , Design and Analysis of
Experiments, Hafner Publishing CO.,
New York, 1954.
(5) Hinshelwood, C. N., Kinetics of
Chemical Change, Clarendon Press,
Oxford, 1942.
(6) Hougen, 0. A , , Reaction Kinetics in
Chemical Engineering, C. E. P. Monograph Ser. 47, No. 1, A.I.Ch.E., New
York, 1951.
(7) Hougen, 0. A,, Watson, K hl.,
Chemical Process Principles, Pt. 111,
Wiley, h-ew York, 1947.
(8) Hunter, J. S.? Trans. Amer. SOC.Qual.
Control 1958, 531 JMay).
( 9 ) Smith, J. M., Chemical Engineering
Kinetics, h,IcGraw-Hill, Piew York,
1956.
0 ) Smith, N. L., Amundson, N. R.,
IND.EKG.CHEM.43, 2156 (1951).
1) Wheeler, A.. Advances in Catalysis
vol. 111, Academic Press, New York.
1951.
(12) Thiele, E. lv., IND.ENG. CHEM. 31,
916 (1939).
RECEIVED
for review June 10, 1959
ACCEPTED February 17, 1960
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