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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)
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)
KA
r K A pAcl
kA
K
R r K R pR cl
kR
From (4): c Al
(8)
From (6): c Rl
(9)
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
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)
p p
r k 1 p A R S c l
Kp B
(8)
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
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
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
KA
A l Al
Al l Rl Sl
Rl R l
Sl S l
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
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
kR
KR
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:
dt
K m (S) (k 4 /k 1 )(P)
dt
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)
(2)
from which:
(ES)
k 1 (S) k 4 (P)
(E)
k2 k3
(3)
d(S)
k (S) k 4 (P)
k1 (S) k 2 1
(E)
dt
k 2 k3
(4)
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
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
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)
rsr k sr
s
C C
C AlCl Rl Sl
Ct
K sr
(5)
rdR k R Rl p R Cl
KR
(6)
Total sites
C t Cl C Al C Rl CSl
(7)
rsr k sr
s
C KpC
K A p A Cl2 Rl S S l
Ct
K sr
(8)
C t C Rl
1 K A p A K S pS
(9)
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)
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
(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)
kR
k C
C Rl R Rl
KR
K R Ct
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
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
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
kR
KR
k sr K A p A
2K A p A
1 k sr
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
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
(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
(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
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
rA D
c t MrA K A c A c t c A MrA
kA
k sr
rA 2
D
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
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 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 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
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)
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
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)
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)
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)
(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)
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
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
(8)
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
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)
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
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)
(2)
c
, it follows Bl K 2 , or the ratio is constant.
c Al
(1)
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
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
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