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CHE 527 March 16, 2011 HW #3

Problem 1
Construct a Microkinetic model for CO oxidation over a Pd catalyst in
a CSTR using the data provided below. Assume that the reaction is
isothermal (say 450 C) and construct your reactor such that conversion
of the 2:1 CO:O
2
stiochiometric mixture is 50%. At what temperature
can you move into a new reaction regime? What partial pressure of
CO is desirable at 450 C?
Reaction A or So E
act
CO adsorption 0.84 0
CO desorption 1.0 10
13
s
-1
136
O
2
adsorption 0.07 85
O
2
desorption 3.7 10
17
m
2
/mol-s 232
CO oxidation 3.7 10
16
m
2
/mol-s 108
Problem 2
Two mechanisms have been proposed for the water gas shift reaction:
The first mechanism involves complete dissociation of water:
3
2 Pt Pt Pt
OH OH H O O Pt + + +
2
2
2
Pt Pt
H O Pt H OH + +
2 2 2
H O CO H CO + +
1
Pt
CO Pt CO +
a) Derive a rate law assuming reaction 2 is rate limiting and
irreversible.
b) A second mechanism replaces the third and fourth steps with the
following step:
If water dissociation is still rate limiting, derive a rate law for this
mechanism.
c ) How can you distinguish between the two mechanisms (Hint: choose
the case where OH dominates the surface)?
4
2
2
Pt Pt
CO O CO Pt + +
5
2
2
Pt Pt
H H H Pt + +
6
2 Pt Pt Pt
OH CO H Pt CO + + +
CHE 527 March 16, 2011 HW #3
CHE 527 March 16, 2011 HW #3
Problem 3
From the data below, a) deduce a rate law for the hydrogenation of
iso-octene to produce iso-octane in a PFR operated at 200 C.
Run Rate (mol/g-cathr) P
H2
P
C8H16
P
C8h18
1 0.0362 1 1 0
2 0.0239 1 1 1
3 0.0390 3 1 1
4 0.0351 1 3 1
5 0.0114 1 1 3
6 0.0534 10 1 0
7 0.0280 1 10 0
8 0.0033 1 1 10
9 0.0380 2 2 2
10 0.0090 1 1 4
11 0.0127 0.6 0.6 0.6
12 0.0566 5 5 5
b) Suggest a mechanism consistent with the experimental data.
CHE 527 March 5, 2010 HW #3
Problem 1
Construct a Microkinetic model for CO oxidation over a Pd catalyst in
a CSTR using the data provided below. Assume that the reaction is
isothermal (say 450 C) and construct your reactor such that conversion
of the 2:1 CO:O
2
stiochiometric mixture is 50%. Then show how the
conversion fluctuates as a function of the surface coverage.
Reaction A or So E
act
CO adsorption 0.84 0
CO desorption 1.0 10
13
s
-1
136
O
2
adsorption 0.07 85
O
2
desorption 3.7 10
17
m
2
/mol-s 232
CO oxidation 3.7 10
16
m
2
/mol-s 108
The solution is a bit unsatisfying since in the CSTR
everything goes to the final concentration which means
the surface is poisoned with CO. See Matlab Script and
graphs
Problem 2
2
2 2
5 5 H X H
k P C k C

=
2
2
2 H O X
r k P C =
2 2
H H H X
C K P C =
a) Water dissociation is rate limiting: CO + O case
Pt X H OH O CO
C C C C C C = + + + +
2
2
3 OH H O O X
K C P C C =
CO CO CO X
C K P C =
What about C
OH
and C
O
?
CHE 527 March 12, 2010
2
2
4 CO O CO X
K C C P C =
1 1 CO X CO
k P C k C =
HW #3
Problem 2
2 2
2
4 4
CO X CO X
O
CO CO CO
P C P C
C
K C K K P
= =
CHE 527 March 12, 2010
2 2 2
2
2
3 3 4
H O O X H O CO X
OH
CO CO
P C C P P C
C
K K K K P
= =
2
2
2 H O X
r k P C =
2 2 2
2 2
3 4 4
H O CO CO
Pt X H H X X X CO CO X
CO CO CO CO
P P P
C C K P C C C K P C
K K K P K K P
= + + + +
2 2 2
2 2
3 4 4
1
Pt
X
H O CO CO
H H CO CO
CO CO CO CO
C
C
P P P
K P K P
K K K P K K P
=
+ + + +
2
2 2 2
2 2
2
2
3 4 4
1
H O Pt
H O CO CO
H H CO CO
CO CO CO CO
kP C
r
P P P
K P K P
K K K P K K P
=

+ + + +


HW #3
Problem 2
2
2
2 H O X
r k P C =
2 2
H H H X
C K P C =
a) Water dissociation is rate limiting: CO + OH case
Pt X H OH CO
C C C C C = + + +
2
6 OH CO CO H X
K C C P C C =
CO CO CO X
C K P C =
What about C
OH
and C
O
?
CHE 527 March 12, 2010
2 2 2
2
6 6
H H CO X
CO H X
OH
CO CO CO
P K P C
P C C
C
K C K K P
= =
2
2
2 H O X
r k P C =
HW #3
Problem 2
CHE 527 March 12, 2010
2 2 2
2 2
6
H H CO
Pt X H H X X CO CO X
CO CO
K P P
C C K P C C K P C
K K P
= + + +
2 2 2
2 2
4
1
Pt
X
CO H H
H H CO CO
CO CO
C
C
P K P
K P K P
K K P
=
+ + +
2
2 2 2
2 2
2
2
2
6
1
H O Pt
CO H H
H H CO CO
CO CO
k P C
r
P K P
K P K P
K K P
=


+ + +


c) If the OH coverage is important (i.e. high) in both cases,
one can see that the order dependence on the partial
pressure of water goes from zero order to first order in the
second case. Similarly, the order dependence in CO
2
, H
2
and CO all vary slightly. Therefore the best experiment is
to perform is to analyze the effect of concentration of H
2
O
on the reactivity while holding the other species constant.
HW #3
CHE 527 March 5, 2010 HW #3
Problem 3
From the data below, a) deduce a rate law for the hydrogenation of
iso-octene to produce iso-octane in a PFR operated at 200 C.
Run Rate (mol/g-cathr) P
H2
P
C8H16
P
C8h18
1 0.0362 1 1 0
2 0.0239 1 1 1
3 0.0390 3 1 1
4 0.0351 1 3 1
5 0.0114 1 1 3
6 0.0534 10 1 0
7 0.0280 1 10 0
8 0.0033 1 1 10
9 0.0380 2 2 2
10 0.0090 1 1 4
11 0.0127 0.6 0.6 0.6
12 0.0566 5 5 5
b) Suggest a mechanism consistent with the experimental data.
Problem 3
Analyze runs 1, 2, 5, 8, and 10. These runs indicate the
dependence upon C
8
H
18
. This indicates the reaction is
adversely effected by the presence of octane.
Now lets look at H
2
. Examine runs 2, and 3, and 1, and 6;
Here we see a positive effect of the partial pressure of
hydrogen.
What about the dependence on octene concentration? Now
choose runs 1, and 7, and 2 and 4. This indicates a
complicated dependence on C
8
H
16
pressure such that at low
pressure as we increase pressure the rate increases but that
the rate decreases at high octene pressures.
Runs 9, 11, and 12 show a direct dependence on total
pressure. The rate increases with increasing pressure.
Therefore K
C8H18
cannot be much much higher than K
C6H16
( )
2 8 16 8 16
8 16 8 16 8 18 8 18
1
H C H C H
C H C H C H C H
kP K P
r
K P K P
=
+ +
CHE 527 March 5, 2010 HW #3
Problem 3 continued
2
2 2
ads
H X H +
8 16 8 16
ads
C H X C H +
8 17 8 18 ads ads ads
H C H C H X + +
8 16 8 17
ads ads
ads
H C H C H X + +
8 18 8 18 ads
C H C H X +
( )
2 2 8 16 8 16
8 16 8 16 8 18 8 18 2 2 8 16 8 16 2 2
2
1
R H H C H C H
C H C H C H C H H H R C H C H H H
kK K P K P
r
K P K P K P K K P K P
=
+ + + +
Alternatively one could consider a better and more
complete mechanism (although hydrogen and C
8
H
17
would
be small in the denominator) :
8 16 8 16
ads
C H X C H +
2 8 16 8 18
ads ads
H C H C H +
8 18 8 18 ads
C H C H X +
A simple (but probably unrealistic ) mechanism which
explains the data would be:
CHE 527 March 5, 2010 HW #3