CHAPTER 2

2.1 Derive the basic equation (2.3.1-7) for a single reversible catalytic reaction.
Solution
For the single reversible reaction A B , the following elementary steps can be written:
1) A l Al

c
K 1 K A Al
pA cl

2) Al Rl

c
K 2 K sr Rl
c Al eq

3) Rl R l

K3

p c
1
R l
K R c Rl

eq

eq

(1)
(2)
(3)

Reaction rates of elementary reactions:

- rate of adsorption:
- rate of surface reaction:
- rate of desorption:

c
ra k A p A c l Al
KA

c
rsr k sr c Al Rl
K sr

rd k R Rl p R c l
KR

(4)
(5)
(6)

When adsorption, surface reaction and desorption are simultaneously rate determining, all
rates are identical:

ra rsr rd r

(7)

The problem is to express c l , c Al and c Rl as function of measurable quantities.

KA
r K A pAcl
kA
K
R r K R pR cl
kR

From (4): c Al

(8)

From (6): c Rl

(9)

These concentrations are substituted in the overall balance on all sites:

c t c l c Al c Rl
from which c l is determined:

(10)

KA
K
r R r
kA
kR
cl
1 K ApA K R pR
ct

(11)

Substitution of (8), (9) and (11) in the rate equation for the surface reaction and solving for r
yields:
p

k sr K A c t p A R
K

r
k sr K A k sr K R
p K
K

1
1 K A p A K R p R k sr K A p A R A R

kA
k R K sr
K k A k R

Rearranging the denominator in a constant term, a term in p A and a term in p R leads to:

k sr K A c t p A R
K

r
k K
k K
k K
k K
k K
k K
1 sr A sr R K A 1 sr R sr R p A K R 1 sr A sr A
kA
k R K sr
kR
kA
K sr k A
k R K sr

Or equivalently, since K

p R

K A K sr
KR

ct pA R
K

r
1
1
1 K sr
1 K sr
1
1
1
p A K R

K A

k sr K A k A k R K
kRK
k sr K A
k sr K A k A K sr

p R

2.2 Consider the catalytic reaction:

a) Derive the Langmuir-Hinshelwood-Hougen-Watson kinetic rate expression,

assuming that adsorption is rate controlling.
b) Compare the result of part (a) with that found from Yang and Hougen Table
2.3.1-1.
Solution
For the reversible reaction A B R S , the following elementary reactions can be written:
1) A l Al

K1 K A

c Al
pA cl

(1)

2) B l Bl

K2 KB

3) Al Bl Rl Sl

K3

4) Rl R l
5) Sl S l

c Bl
pB cl

(2)

c Rl c Sl
c Al c Bl
p c
1
K4
R l
KR
c Rl
p c
1
K5
S l
KS
c Sl

(3)
(4)
(5)

When the adsorption of A is rate controlling e.g., the reaction rate is given by:

c
r k 1 p A c l Al
K1

(6)

Reactions 2-5 are assumed to reach chemical equilibrium, so that use can be made of the
corresponding equilibrium relations to determine the unmeasurable concentration of adsorbed
A:
c c p c p c
c
K 2 K 3 K 4 K 5 Bl Rl Sl R l S l
p B c l c Al c Bl c Rl
c Sl

c Al

Hence,

p p
K p p
1
R S cl A R S cl
K 2K 3K 4K 5 p B
K pB

since

(7)

K 1 K 2 K 3 K 4 K 5 K (overall equilibrium constant).

The reaction rate equation (6) becomes:

p p
r k 1 p A R S c l
Kp B

(8)

The unmeasurable concentration of unoccupied active sites, c l , is determined from an overall

balance on all sites:

c t c l c Al c Bl c Rl c Sl

(9)

The unknown concentrations of adsorbed B, R, and S are solved from the equilibrium
relations (2), (4) and (5) respectively:
From (2):

c Bl K B p B c l

(10)

From (4):

c Rl K R p R c l

(11)

From (5):

c Sl K S p S c l

(12)

Substitution of (7) and (10) - (12) into (9), followed by solving (9) for c l yields:

cl

ct

(13)

K p p
1 A R S K B p B K R p R K SpS
K pB

Substituting this expression into (8) yields:

p p
k 1c t p A R S
Kp B

rA
K p p
1 A R S K B p B K R p R K SpS
K pB
which is exactly the result found by Yang and Hougen and shown in Table 2.3.1-1.
2.3 In a study of the dehydrogenation over a brass catalyst of sec-butyl alcohol to
methyl ethyl ketone,

H
2

H
2
C
O
C
3
H
C

H
C2
H
O
H
C
3
H
C

L. H . Thaller and G. Thodos [AIChE J., 6, 369 (1960)] obtained data that
appeared to show two different steps controlling, depending on the temperature
level. At low temperatures, surface reaction was controlling, while at high
temperatures desorption of (perhaps) hydrogen seemed rate controlling. A
selection of their initial rate data is given in the table below.
a)
Using the data at T = 371C, determine the parameters of the appropriate
initial rate expression.
b)
Using the data at T = 288C and 302C, again determine the parameters.
T (C)
371
371
371
371
371
315.5
315.5
315.5
315.5
315.5
315.5
315.5
315.5
315.5
315.5
302
302
302
302
302
288
288
288

Pt (bar.)
1.0
2.0
4.0
9.0
12.0
1.0
7.0
4.0
10.0
14.6
5.5
8.5
3.0
0.22
1.0
1.0
3.0
5.0
7.0
9.6
1.0
3.0
2.0

rA0 (kmol/kg cat. h)

0.195
0.189
0.188
0.198
0.190
0.0392
0.0416
0.0416
0.0326
0.0247
0.0415
0.0376
0.0420
0.0295
0.0410
0.0227
0.0277
0.0255
0.0217
0.0183
0.0115
0.0161
0.0146

Note that the intermediate temperature level results should presumably depend
upon both surface reaction and desorption steps, since at some point both steps will
have equal rates (see Problem 2.5)
Solution
A R S

Surface reaction controlling

C Al
Cl p A
C C
K sr Rl Sl
C AlCl
C
K R Rl
Cl p R
C
K S Sl
C l pS

KA

A l Al
Al l Rl Sl
Rl R l
Sl S l

Total active sites:

C t Cl C Al C Rl CSl
Cl (1 K A p A K R p R K SpS )
Then,

rA rsr k sr

s
C C
C AlCl Rl Sl
Ct
K sr

s 2
K p Kp
Cl K A p A R R S S
Ct
K sr

(p A p R pS /K)
k sr C t s K A
1 K A p A K R p R K SpS 2

k sr

Initial rate

rA0 k sr K A

pA

1 K A p A 2

Desorption of R controlling same as above, except

K sr

C RlCSl
C
and K R Rl
C AlCl
Cl p R

Then
C t Cl K A p A Cl

and

K sr K A p A Cl
K S p SC l
K S pS

rA rR k R Rl Cl p R
KR

K K p

k R Cl sr A A p R
K R K Sp A

pA

K
p R
pS

k R C t

p
1 K A p A K R K A K SpS
pS

For the initial rate, multiply through by p S , and let p R , p S 0 :

rA0

kR

KR

a) At high temperatures, if desorption controls, a plot of rA0 vs. p should give a

horizontal line, from which ( k R /K R ) can be determined:

rA0 (k R /K R )
From the data at 371C, the plot on Fig. 2.3-1 shows random scatter about a
horizontal line, to give

(k R /K R ) 0.19

kmol
kg cat - h

Figure 2.3-1

b) At lower temperatures, with surface reaction control, a straight line should result
from plotting

KA
p
1

p
rA0
k sr
k sr K A
Then,

k sr slopeintercept

K A (slope) / (intercept)
Figure 2.3-2 shows these plots for the two lower temperatures, with the results:
T = 302C
k sr 0.113 kmol / kg cat h

K A 0.403 atm -1
T = 288C
k sr 0.064 kmol / kg cat h

K A 0.299 atm -1

Figure 2.3-2

Note that K A increases with temperature, the reverse of the usual behavior of adsorption
equilibrium constants.
Finally, Fig. 2.3-3 shows the good agreement with the data of the surface reaction controlling
rate equations using the above values for the parameters.

Figure 2.3-3

2.4 The Michaelis-Menten mechanism in enzyme kinetics is based upon the following
reaction scheme between the reactant (substrate S), and the catalyst (enzyme E) to
give the product, P:
1

S E ES P E
a) Use the steady state hypothesis for the enzyme-substrate complex, ES, to derive
the Michaelis-Menten kinetic expression:

d(S) (k 3 (EO ))((S) (P)/K) d(P)

dt
K m (S) (k 4 /k 1 )(P)
dt

Where ( EO ) = (E) + (ES) represents the measurable total enzyme concentration

K m (k 2 k 3 )/k 1 is the Michaelis constant

K k 1k 3 /k 2k 4
b) Show that the maximum initial rate is given by:

d(S)
k 3 (E 0 )
dt max

Solution
k1

k3

k2

k4

S E ES P E

a) Disappearance rate of S.

d(S)
k1 (S)(E) k 2 (ES)
dt

(1)

Formation rate of ES.

d(ES)
k1 (S)(E) k 4 (P)(E) (k 2 k 3 )(ES)
dt

(2)

Steady state for ES:

d(ES)
0 (k1 (S) k 4 (P))(E) (k 2 k 3 )(ES) 0
dt

from which:

(ES)

k 1 (S) k 4 (P)
(E)
k2 k3

(3)

Substitution of (3) in (1):

d(S)
k (S) k 4 (P)
k1 (S) k 2 1
(E)
dt
k 2 k3

(4)

From the total balance:

k (S) k 4 (P)
(E)
(E O ) (E) (ES) 1 1
k

k
2
3

from which:
(E)

(E O )
k1 (S) k 4 (P)
1
k 2 k3

Substitution of (5) in (4):

d(S)
k (S) k 4 (P)
(E O )
k1 (S) k 2 1

dt
k 2 k 3 1 k1 (S) k 4 (P)

k 2 k3
k 2 k 3 (S) k 2 /k1k1 (S) k 4 (P)(E O )

k 2 k3
k
(S) 4
k1
k1 (P)

(5)


kk
k 3 (E O ) (S) (P)/ 1 3
k 2 k 4 k 3 (E O )(S) (P)/K

k 2 k3
k4
k
(S) (P)
K m (S) 4 (P)
k1
k1
k1
b) Initial rate is obtained when (P) = 0:

d(S) k 3 (E O )(S) k 3 (E O )

Km
dt
K m (S)
1
(S)

This is maximum when the denominator is minimum or when (S) is maximum. In the
limit: (S) = . Hence

2.5

d(S)
k 3 (E O )
dt max

(a) For the reaction in Problem 2.3, show that the initial rate expression,
assuming that both surface reaction and desorption of R are rate controlling, is

rA0

2
2 2

k 2R 1 K A p A
k 2R 1 K A p A
2
k r

k
R

R
2k sr
K A p A
2k sr
K Ap A

1/2

See Bischoff and Froment [1965].

(b) Show that the result reduces to the proper Yang and Hougen Table 2.3.1-1
results for each of the special cases (k R /k sr ) and (k sr /k R ) .
(c) Using the combined results of Problem 2.3 and the above results, compare the
model with the data at the intermediate temperature level, T = 315.5C. (See also
Shah and Davidson [1965] and R.W. Bradshaw and B. Davidson, Chem. Eng. Sci.,
24, 1519 [1969].)
Solution
Al R S
A l Al
Al l Rl Sl
Rl R l

C Al
p A Cl
C C
K sr Rl Sl
C AlCl
C
K R Rl
p R Cl
KA

(1)
(2)
(3)

Sl S l

KS

CSl
p SC l

(4)

a) Rate of surface reaction

rsr k sr

s
C C
C AlCl Rl Sl
Ct
K sr

(5)

Rate of desorption reaction

rdR k R Rl p R Cl
KR

(6)

Total sites

C t Cl C Al C Rl CSl

(7)

Substitute (1) and (4) into (5):

rsr k sr

s
C KpC
K A p A Cl2 Rl S S l
Ct
K sr

(8)

Substitute (1) and (4) into (7) and rearrange:

Cl

C t C Rl
1 K A p A K S pS

(9)

Now substitute (9) into (6) and (8)

2

C Rl K SpS
C t CRl
s
C t C Rl

rsr k sr K A p A

Ct
1 K A p A K S pS
K sr
1 K A p A K S pS

k
C t C Rl

rdR R C Rl K R p R
KR
1 K A p A K S pS

(10)

(11)

At steady state, rsr rdR

2

C Rl K SpS
C t CRl
s
C t C Rl

k sr K A p A

Ct
K sr
1 K A p A K S pS
1 K A p A K S pS

k
C t C Rl

R C Rl K R p R
KR
1 K A p A K S pS

For initial rates, p R 0, pS 0 :

(12)


C C Rl k R
s

k sr K A p A t
C Rl
Ct
1 K A p A K R

(13)

For initial rates, from (11)

r0 rdR,0

kR
k C
C Rl R Rl
KR
K R Ct

where k R C t k R k R has been used.

Substituting this into (13) gives

1 r0 K R /k R
k sr K A p A

1 K ApA

r0

or

k
r R
KR
2
0

k R K R
2
k sr

1 K A p A 2
kR

r0
KR
k sr K A p A

Solving,
r0

kR
KR

k K
R
R
1
k sr

kR KR
1 K A p A 2

1
2K A p A
k sr

(Note that the result in the book has further grouped

1 K A p A 2

1
2K A p A

kR
k R ).
KR

b) Show that the result reduces to the proper Yang and Hougen Table 2.3.1-1 results for each
of the special cases.
(i)

kR KR
0.
k sr
Then the initial rate becomes:
For desorption control,

r0

kR
1 0
KR

1 02 1

Kk

R
R

which is the correct limiting form (e.g., Problem 2.3).

(ii)

k sr
0 , and the initial rate expression must
kR KR
be rearranged by squaring within the radical:
For surface reaction control,

r0

2
2
k R k R K R 1 K A p A k R K R 1 K A p A
k sr
2K A p A

1 2
1

K R
k sr
2K A p A
k sr
2K A p A
k R K R 1 K A p A 2

Then expanding the radical to three terms gives:

r0

kR
KR

k sr K A p A
2K A p A
1 k sr

(0) (both term, cancel)

2
2 k R K R 1 K A p A 1 K A p A 2

which is the correct limiting form (e.g., Problem 2.3).

c) Using the combined results of Problem 2.3 and the above results, compare the model with
the data at the intermediate temperature level, T = 315.5C (also see Shah and Davidson
[1965] and R.W. Bradshaw and B. Davidson, Chem. Eng. Sci., 24, 1519 [1969].)
An Arrhenius plot of the rate coefficients found in Problems 2.3 is shown in Fig. 2.5-1. Only
k sr and K A are known at two temperatures, and the activation energy for k R K R cannot be
found. Thus, an assumption must be introduced for k R K R at 315.5C. One possibility is to
assume E R 0 (merely for lack of information), which makes it equal to k sr at 315.5C; in
this situation, both steps would surely be rate limiting. Another possibility is to assume the
activation energy for k R K R is similar to k sr K A , which leads to a smaller value at
315.5, and which is the same as that estimated by Shah and Davidson; however, their
activation energy was much smaller (and wouldnt be at all correct at 317C). Note that the
former value (0.192 = const.) is similar in value to k sr at 302C, and only at 288C is there an
order of magnitude difference. Therefore, probably both steps are still rate controlling at
302C. The fact that a good surface reaction control only plot was obtained in Problem 2.3 is
possibly similar to the illustration of Bischoff and Froment [1965].
In any event, Fig. 2.5-2 shows the results of using the extrapolated rate parameter values in
the combined initial rate formula of part a), and it is seen that agreement is not obtained. The
even smaller value of k R K R would give worse agreement. However if the value of k sr =
0.35 is used, reasonable agreement with experiments is obtained. This extrapolated value at
315.5C could have been obtained if the value at 302C was 35% larger, as shown on the
Arrhenius plot. Since surface reaction was probably not truly rate controlling at 302C, this
could be a reasonable value, as shown in the illustration of Bischoff and Froment [1965].
This problem illustrates the difficulties in using rate expressions with more than one rate
controlling step, even though meaningful kinetic parameters can only be found in this way.
When this situation occurs, precise data covering a large temperature range is essential in
elucidating the details and parameter values.

Figure 2.5-1

Figure 2.5-2

2.6 Consider the reaction A R S , occurring on dual sites. Determine the rate
equation in the case that all four elementary steps are simultaneously rate determining.
Solution
A R S

The following steps occur:

A l Al
Al l Rl Sl
Rl R l
Sl S l

Rate equations:

c
(1) ra k A c A cl Al
KA

c c
(2) rsr k sr c Alcl Rl Sl
K sr

(3) rd1 k R Rl c R cl
KR

(4) rd2 k S Sl cScl

KS

In steady state conditions (1) = (2) = (3) = (4)

rA (1) (2) (3) (4)

c t cl c Al c Rl cSl

(5)

A possible procedure is as follows: cl , c Al , c Rl , cSl are calculated from (1), (3), (4) and (5) and
then substituted into (2).
(1) c Al K A c A cl rA k A

(3) c Rl K R A c R cl
kR

(4) cSl K S A cScl

kS

(5) cl c t c Al c Rl cSl

K
K
K
c t rA A R S
k A k R k S c t MrA
cl
1 K A c A K R c R K ScS
D

K A K R KS

kA kR
kS
D 1 K A c A K R c R K ScS

where M

Substitution of cl into (1), (3) and (4) leads to:

KA
r D
c A c t c A MrA A
D
kA
K
r D
c Rl R c R c t c R MrA A
D
kR
c Al

cSl

KS
r D
cSc t cS MrA A
D
kS

Equation (2) becomes:

rA D

c t MrA K A c A c t c A MrA

kA
k sr

rA 2
D

K SK R c R c t c R MrA rA D cSc t cS MrA rA D

k R
k S
K sr
or

K MD K SK R 2
K K
c

K A M 2c A A

M c R cS S R MD R

kA
k sr
K sr
kR
D rA

rA2
cS K S K R 2 1
k sr
K SK R

K MD k K D k k

sr
S
sr
R S

K A Dc t K SK R

c R cSc t M
K A Mc A c t K A c A Mc t k
K sr
A

rA
K SK R
K S K R cSc t
K SK R c R c t
D
c R cSc t M
D
K
kS
K sr
K sr k R
sr

K A c A c 2t

K SK R
cSc R c 2t
K sr

This is a quadratic equation in rA : ArA2 BrA C 0

 rA

B B2 4AC
2A

K K
KK
K
whereby: A D 2 R S MD S R k ScS k R c R A
kA
K sr k R k S
K sr k R k S
1
KK
K
c c
c t D S R k ScS k R c R A 2c t K A M c A R S
B c t D 2
kA
K

k sr
K sr k R k S
c c

C c 2t K A c A R S
K

K is the overall equilibrium constant,

K A K sr
.
K R KS

2.7 The following data were obtained by Sinfelt and co-workers [Sinfelt, J.H. et al., J.
Phys. Chem., 64, 1559 (1960)] for the dehydrogenation of methylcyclohexane to toluene.
In addition, they found that the product toluene had essentially no effect on the rate.
T (C)
315
315
315
315
315
344
344
344
344
344
372
372
372
372

pM (bar)
0.36
0.36
0.07
0.24
0.72
0.36
0.36
0.08
0.24
0.68
0.36
0.36
1.1
2.2

pH2 (bar)
1.1
3.0
1.4
1.4
1.4
1.1
3.1
1.4
1.4
1.4
1.1
4.1
4.1
4.1

rD (kmol/kg cat. h)
0.012
0.012
0.0086
0.011
0.013
0.030
0.032
0.020
0.034
0.034
0.076
0.080
0.124
0.131

(a) Discuss which of the stepsadsorption, surface reaction, or desorptionmight

be rate controlling in view of the data in the table above.
(b) Show that a rate expression based on the mechanism

A l Al
Al Rl
Rl Q S l
fit the data; also estimate the activation energies.
(c) Discuss the results of (b) in view of (a).
The reaction

Solution
(a) The rates at T 315C show:
1. Rate is independent of H2 pressure.
2. Rate increases with pM, but approaches saturation; no maximum.
The rates at T 344C show:
1. Rate is nearly independent of H2 pressure.
2. Rate increases with pM, possibly approaching saturation.
The rates at T = 372C show:
1. Rate is nearly independent of H2 pressure.
2. Rate increases with pM.
The conclusion is:
Since toluene and H2 have no effect on the rate, the final step is irreversible, and the
other steps possibly in quasi-equilibrium-thus try desorption control.
(b) The suggested kinetic steps are:
A l Al
Al Rl
Rl Q S l

K1
K2
K3

Then

C Al K1p A Cl
C Rl K 2C Al K1K 2 p A Cl
and

C t Cl C Al C Rl

Cl 1 K1 1 K 2 p A

The rate is:

r k 3 C Rl K 3 k 3K1K 2 p A Cl K 3
k C K K K p
kp A
3 t 1 2 3 A
1 K1 1 K 2 p A
1 Kp A

(1)

Note that (1) has the features observed in part (a).

The parameters could be estimated from a plot of

1 K 1 1

r k k pA
The plot shows that the slopes at all three temperatures have essentially the same
value, and so the combined activation energy E 3 Q1 Q 2 Q3 is zero. The rate
coefficient has a value k = 0.4 kmol/kgcat h atm. From the intercepts, the following
are found:
TC
315
344
372

K/k
80
26
7

K, atm-1
32
10
2.8

A semilog plot gives a slope of 15.6, and so the activation energy of K1 1 K 2 is

31 kcal/gmol.
(c) Since the postulated kinetic scheme of irreversible desorption control reasonably fits
both the qualitative observations of the data, plus yields quantitative consistent
parameter estimate plots and activation energies, it will be accepted. The original
reference then uses this for further postulates about the catalyst behavior.
2.8 The isomerization of n-pentane was considered in the text, where several rate
expressions were stated. Derive the final result for desorption of i-pentene
controlling:

kK 5 K D K 6 p a p B K
p H 2 K 5 K D 1 K 6 p A

Solution
The global isomerization A B can be decomposed in the elementary reactions shown in
Chapter 2.
When desorption of i-pentene is rate controlling, i.e., the 7-th reaction, the overall reaction
rate is given by:

p c
r k 7 c N N
K7

From the equilibrium relations with respect to the fifth and sixth reactions:

c N K 5 K 6 p M c

(1)

c M K 5 p M c

(2)

Total balance on acid active sites:

c t c c M c N 1 K 5 1 K 6 p M c

(3)

Hence:

p
k 7 c t K 5 K 6 p M N
KI

r
1 k 5 1 K 6 p M

(4)

where K I is the equilibrium constant for M N on acid sites. The unmeasurable gas phase
partial pressures of the pentenes, pM and pN, are expressed as a function of the gas phase
partial pressures of the pentanes by making use of the assumption that the hydrogenation and
dehydrogenation stages are in equilibrium:
K1K 2 K 3K 4 K D

pH 2 pM

K 8 K 9 K 10 K 11 K H

pA

pM K D

pA
pH 2

pB
1 pB
pN
p H2 p N
K H p H2

(5)

(6)

Substitution of (5) and (6) into (4) yields:

r

kK D K 5 K 6 p A p B K
p H 2 K 5 K D 1 K 6 p A

where

K KDKIKH
k k 7 ct
2.9 For the isomerization of n-pentane, derive the rate expression if the surface
reaction step of the dehydrogenation reaction were rate controlling. Contrast this
with the correct rate of Problem 2.8, especially regarding variations with total
pressure.
Solution
When step 2 is rate determining:

c c

r k 2 c Al cl Ml H 2 l
K2

(1)

From the equilibrium relations with respect to reaction(s):

(1): c Al K1p A cl
1
(3): c H 2 l
p H cl
K3 2
1 pB
(4) - (11): c Ml 11
cl
pH 2
Ki

(2)
(3)
(4)

i4

By having considered reactions (4) - (11), c Ml is expressed directly in terms of the observable
partial pressures p B and p H 2 .
A total balance on all Pt sites:
c t cl c Ml c Nl c Al c Bl c H 2 l

(5)

requires still c Nl and c Bl to be determined.

From the equilibrium relations with respect to reaction(s):
(11): c Bl

1
p Bc l
K11

(9) - (11): c Nl

1
pB
cl
K 9 K10 K11 p H 2

(6)
(7)

Hence:

1 pB
1
pB
1
1

c t 11

K1p A
pB
p H 2 c l

pH
K 9 K10 K11 p H 2
K11
K3
Ki 2

i4

Substitution of (2) (4) and (8) into (1) yields:

p

k 2 K1 p A B
K

r
2

1
1
1 pB K p 1 p 1 p
1 A
B
H
K K K 11
pH
K11
K3 2
9 10 11
2
K

i
i4

where K is the overall equilibrium constant of the overall reaction A B .

(8)

Obviously, this rate equation is not independent of total pressure.

2.10 For the isomerization of n-pentane, the following experimental data were collected
by Hosten and Froment [1965]:
x
0.4025
0.35
0.2784
0.2001
0.3529
0.2728
0.2028
0.3248
0.2571
0.2011
0.3017
0.2413
0.1734

4.853
5.253
5.29
5.199
6.833
7.33
7.344
7.638
8.514
8.135
10.598
11.957
10.227

W/FA0 (kg cat. h/kmol)

5.92
3.84
2.84
1.75
5.74
3.84
2.66
5.28
3.9
2.65
5.73
4.37
2.65

is the molar ratio H2/n-pentane. The pentane feed consisted of 92.65 mole % n-C5 and
6.37 mole % i-C5. The overall equilibrium constant is 2.07, while the selectivity for
isomerization is nearly constant and equal to 0.91. Estimate the parameters in the
adsorption model by means of the integral method of kinetic analysis. Both W/FA0 and x
can be used as dependent variable. Comment on this choice. Compare the results and
the computational effort for both cases.
Solution
The reaction network for the isomerization of n-pentane (A) into i-pentane (B), accompanied
by the cracking of the n-C5 into C1C4 (C) to a small extent can be written:

B
A
C
When the adsorption of n-pentene is rate determining for the isomerization, the reaction rate
equation for isomerization is given by:

rB
p H2

kK D p A p B K
k p A p B K

p H2 K B p B

1 1

1p B
K7KH K6

(1)

(It is assumed that the cracked products are not adsorbed on the acid sites). The integral
method of kinetic analysis makes use of the continuity equation for species B. For an ideal
tubular reactor with plug flow:

FA0 dx B rB dW

(2)

(1) has to be substituted in (2), which is then integrated. This requires the expression of the
partial pressures as a function of xB. The feed contains P mol % n-pentane, Q mol % of ipentane and R mol % of an inert I, cyclopentane. The following balances can then be written:
Number of moles Conversion of A: XA
Component
Feed
Conversion into B: XB
A
P
P (1 - XA)
B
Q
Q + P XB
I
R
R
H2
P
P [ - (XA - XB)]
C
O
2P (XA - XB)

100 P

100 P

It is hereby assumed that 1 cracked mole of A gives rise to two moles of cracked products C.
It is seen that cracking does not give rise to expansion or contraction.
Since the selectivity for isomerization, x B x A , is constant, the partial pressures read:

pA

P(1 x B /
B Px B
P - 1 - 1x B
pt ; pB
pt ; pH 2
pt
100 P
100 P
100 P

(3)

Integration of (1) can now be carried out analytically:

K
W
K 1

a B c
FA0
P(K ) k
k

(4)

in which:

1
PK Q 1
1 ln u P1 x B
a P
K

PK Q
c Q
ln u Px B
K

PK
u 1
xB
PK Q
Parameters can now be estimated, using the given data pairs x | W/FA0, .
If W/FA0 is used as dependent variable, the criterion reads:
2

W W
Min

F
F
i 1
A0 i A0 i
n

(5)

Notice that (4) is linear in the groups 1/k and K B /k, so that linear regression will surface to
estimate these groups. Values of k and K B are unambiguously determined afterwards. If x B is
used as the dependent variable, the appropriate least squares criterion,

Bi

x Bi

Min

(6)

requires non-linear regression. Moreover (4) is implicit in the conversion x B so that this
implicit equation has to be solved for x Bi for each experiment. Since W and FA0 will
generally be precisely known, W/FA0 is likely to be considered as a discrete rather than a
random variable, so that criterion (5) seems to be inappropriate. The conversion on the other
hand seems to be the true observed variable, subject to experimental error and hence,
estimation should be based on criterion (6) indeed.
Results
k

KB

Dependent variable
W/FA0
XB
0.89
0.89
6.57
8.5

Both criteria yield estimates which agree very well. Clearly, required computational effort is
much higher when x B is the dependent variable.
2.11 A catalytic reaction A B is carried out in a fixed bed reactor. Comment on the
concentration profiles of adsorbed species as a function of bed depth for various
rate determining steps.
Solution
A l Al
Al Bl
Bl B l

c Al
p A cl
c
K 2 Bl
c Al
p c
K3 B l
c Bl
K1

Adsorption rate determining:

K 2 K3

c Bl p Bcl

c Al c Bl

or
1
p Bc l
K 2K 3
1
c Bl
p Bc l
K3

c Al

c t cl c Al c Bl

(1)
(2)

1
1
ct
1
pB
p B cl cl
K3
1
1
K 2K 3
1
1
pB
K2
K3

(3)

and
c Al

1
pB
K 2K 3

ct
1
1
1
1
pB
K2
K3

ct
K 2K 3
1 K2
pB

(4)

Since p B is continuously increasing as a function of bed depth, it follows from

(3): cl decreases;
(4): c Al increases.
From

(2)
c
, it follows Bl K 2 , or the ratio is constant.
c Al
(1)

Desorption rate determining:

From an identical reasoning, the reverse is obtained for cl and c Al when the desorption is rate
determining.
c
The ratio Bl remains constant.
c Al
Surface reaction rate determining:

c Al =K1p A cl
1
c Bl
p Bcl
K3
ct
cl =
1
1+K1p A +
pB
K3
K1 p A c t
c Al =
1
1+K1p A +
pB
K3
p Bc t
1
c Bl =
K 3 1+K p + 1 p
1 A
B
K3
All kinds of profiles are possible. In the case that the denominator is nearly constant or, at
least, varies slower than p A , or p B , c Al is decreasing, c Bl increasing, and cl nearly constant
1
as a function of bed depth. Also with, strong product inhibition, this means that
>>K1 ,cl
K3

will be decreasing. So will c Al at an even greater rate since not only the denominator
increases, but also the numerator decreases.
2.12 The dehydrogenation of ethanol was carried out in an integral reactor at 275C
with the following results:
x
0.2
0.4
0.6
0.88
1.53
1.6
2.66
4.22
4.54

pt (atm) W/FA0 (kg cat. h/kmol)

1
0.118
1
0.196
1
0.262
1
0.339
1
0.446
1
0.454
1
0.524
1
0.59
1
0.60

x
0.14
0.2
0.25
0.286
0.352
0.14
0.196
0.235
0.271

pt
3
3
3
3
3
4
4
4
4

W/FA0
0.2
0.4
0.6
0.88
1.6
0.2
0.4
0.6
0.88

x
0.32
0.112
0.163
0.194
0.214
0.254
0.1
0.148
0.175
0.188
0.229

pt
4
7
7
7
7
7
10
10
10
10
10

W/FA0
1.6
0.2
0.4
0.6
0.88
1.6
0.2
0.4
0.6
0.88
1.6

The overall equilibrium constant is 0.589. The feed consisted of the azeotropic mixture
ethanol-water, containing 13.5 mole % water. Water is not adsorbed on the catalyst.
Estimate the parameters of the adsorption, surface reaction, and desorption models,
using conversion as the regression variable. Comment on the feasibility for the
estimation of the parameters. Which model is the best? On what basis?
Solution
As shown in Chapter 2, the continuity equation (a) has to be integrated after substituting the
appropriate rate equation and expressing the partial pressures of the reaction partners as a
function of conversion and independent variables. The result is an expression of the form:
W 1
= D1 +D 2 +D3
F C

(1)

for all three rate equations with D1 ,D 2 ,D3 given in Chapter 2. The functional dependence for
C and A1 ,B1 ,C1 ,A 2 ,B2 ,C2 are different for each model, however. They are shown in Chapter 2
for the surface reaction controlling rate model. They are given below for the two other
models:
Adsorption controlling:
C=k
A1 = 1.334

B1 = 2.31 + K R +K S p t

C1 1 K A p 2t /K (K R K S )p t

A 2 = 1.155 p t
B2 0.155p t
C 2 p t (1 p t /K )

Desorption controlling:
C = kK
A1 = 1.155 K R

A 2 = 1.155

B1 = 1.155 + K A p t - 0.155 KK R
C1 = 1 + K A p t - KK R + K S p t

B2 = - 0.155

C2 = - 1+ p t K

The parameters are estimated in all three models by means of the least squares criterion based
on the conversion:
n

x -x
i

Min

(2)

i=1

This again necessitates the solution of the implicit equation (1) for x i for each experiment
and all models. The objective function (2) is minimized e.g., by means of the Marquardt
technique.
Results
The next table presents the point estimates for the parameters and their 95% confidence limits,
as well as the residual sum of squares.
Adsorption Surface reaction
k ts (k)
0.551 0.14
4.36 0.58
A
A
K ts (K )
12.46 2.4
0.43 0.052
KR ts (K R)
KS ts (K S)
KR + K S ts (K R + K S)
-5.694 1.75
2.895 0.6
Residual sum of squares
0.0086
0.0021

Desorption
0.205 0.2
-0.0337 0.19
0.321 0.36
1.329 2.32
0.0036

Note that the parameters K R and K S can be estimated separately in the desorption model,
even when pure feed, i.e., containing no reaction products, is used. This is not possible in the
adsorption and surface reaction rate models: only their sum is estimable. Compared to the
differential method of kinetic analysis, discussed in Chapter 2 the estimation technique
discussed above is undoubtedly much more laborious.
From this analysis, it is clear that the surface reaction model is the best:
1) It is the best fitting model and has a residual sum of squares which is only of that of
the adsorption model.
2) All parameter estimates are positive and significantly different from zero.
3) The adsorption model fits much worse to the data and contains a significantly negative
parameter estimate; this is in conflict with thermodynamic requirements for adsorption
constants; hence the adsorption model must be discarded.
4) The desorption model fits relatively well to the data, but none of the parameter
estimates is significantly different from zero from the statistical point of view.
2.13

Boolean Relation Matrix and Label representation of molecules and ions.

a) Write the Boolean relation matrix and the label representation of
(i) 3-Me-pentane -2+ carbenium ion
(ii) Naphthalene
(iii) Cumene (i-Propylbenzene)

b) What are the Me-shift isomerizations and the -scissions that the 3-Mepentane -2+ ion can undergo ? What are the products ? Hint: For the scissions first construct the matrix M2-1 in order to determine the 3 -carbon
atoms.
Solution

2
1 2 3 2 1 1
8 8 8 8 8 8

0
3 2 2 2 2 3 2 2 2 2
1 4 4 4 4 1 4 4 4 4

0
3 2 2 2 2 2 3 1 1
4 4 4 4 4 4 8 8 8