UEMK 3153 Chemical Reaction Engineering II

Date: 14 & 21 Jun 2013

Tutor-in-charge: Yap Yeow Hong

Tutorial No.1

Lesson 1: Non-elementary reactions

1. What does it mean by elementary reaction and what are the differences between
elementary and non-elementary reactions?

Chemical reaction in which one or more of the chemical species react directly to
form products in a single reaction step and with a single transition state


2. What do you think is the reason that the rate law derived based on the observation from
experiment is different from the rate law derived based on Law of Mass Action?

Because the rate law derived based on observation from the experiment comprises a
series of elementary steps. That is why Law of Mass Action based on elementary
reaction is not applicable in this case.


3. What are the characteristics of active intermediates and why Pseudo-Steady-State
Hypothesis is used in the search for reaction mechanisms for non-elementary reaction?

Active intermediates results from collision or interaction between molecules and
serve as an intermediate between initial reactants to products. They are extremely
short-lived (because of its high reactivity) and only present in low concentration.

Pseudo-Steady-State Hypothesis states that active intermediates are short-lived and
present in low concentration and overall generation rate can be assumed to be zero.
By assuming PSSH, the concentration of active intermediates derived from
elementary steps can be replaced to obtain a rate law based on concentration that
can be observed and compared against the experimental observation.



4. Based on Fogler Q 7-5: The rate law for formation of phosgene, COCl
2
from chlorine,
Cl
2
, and carbon monoxide, CO, has the rate law




Suggest a mechanism for this reaction that is consistent with this rate law. [Hint: Cl
formed from the dissociation of Cl
2
is one of the two active intermediates]
3/2
Cl CO COCl
2 2
C kC r =
Postulated mechanism:



Net rate of COCl
2
produced (assuming elementary reaction)
------------------------------------------------------------(1)

However, we find that the above rate equation depends on the concentration of active
intermediates (COCl) which we cannot measure. Therefore we need to replace this.


COCl is an active intermediate, so we can derive a concentration of COCl
Net rate of COCl formation:
----------------(2)

Here we obtained the concentration of COCl active intermediate.


Substitute (2) into (1):
----------------------------(3)

Here we find that the equation is dependent on another active intermediate (Cl) and therefore we
need to replace this active intermediate which we cannot measure.


Cl is also an active intermediate, we can derive a concentration of Cl
Net rate of Cl formation:


There are simply too many terms, so we combine the above equation with r
COCl
from (2)
----------------------------------------(4)

Here we obtained the concentration of Cl active intermediate


Substitute (4) into (3) to replace Cl active intermediate:

--------------(5)

Therefore we have postulated a reaction mechanism that is consistent with the
experimental observation.



5. Based on Fogler Q7-7: One of the major reasons for engine oil degradation is the
oxidation of the motor oil. To retard the degradation process, most oils contain an
antioxidant. Without an inhibitor to oxidation process, the suggested mechanism at low
temperatures is













where I
2
is an initiator and RH is the hydrocarbon in the oil
- 2I I
0
2
k
HI R RH I
i
k
+ - + -
- + -
2
k
2
RO O R
p1
- + + - R ROOH RH RO
p2
k
2
inactive 2RO
t
k
2
-

When an antioxidant is added to retard the degradation at low temperatures, the following
additional termination steps occur:







a) Derive a rate law for the degradation of the motor oil in the absence of an antioxidant
at low temperatures
b) Derive a rate law for the degradation of the motor oil in the presence of an antioxidant
for low temperatures.
c) How would you answer to part (a) change if the radicals I were produced at a
constant rate in the engine and then found their way into the oil?

a) Low temperature with absence of anti-oxidant

Pay attention that every step here is not reversible.

Rate law for degradation (consumed) of motor oil, i.e. RH in the red box. We can see
that it is dependent on several active intermediates.

There are three active intermediates here: I, RO
2
, R

Compute for net rate of formation for the active intermediates:


- + + - A ROOH AH RO
A1
k
2
inactive RO A
A2
k
2
- + -



b) Low temperature with presence of anti-oxidant



c) If the radicals are formed at a constant rate, then the differential equation for the
concentration of radicals becomes:





It is at constant rate, and there is no reactant
Lesson 2: Heterogeneous Reactions

6. Based on Fogler 10-8: In 1981 the U.S. government put forth the following plan for
automobile manufacturers to reduce emissions from automobiles over the next few years.


Component Year
1981 1993 2004
Hydrocarbons 0.41 0.25 0.125
CO 3.4 3.4 1.7
NO 1.0 0.4 0.2


All values are in grams per mile. An automobile emitting 3.74 lb of CO and 0.37 lb of
NO on a journey of 1000 miles would meet the current government requirements.

To remove oxides of nitrogen (assumed to be NO) from automobile exhaust, a scheme
has been proposed that uses unburned carbon monoxide (CO) in the exhaust to reduce the
NO over a solid catalyst, according to the reaction:




Experimental data for a particular solid catalyst indicate that the reaction rate can be well
represented over a large range of temperatures by





where P
N
= gas-phase partial pressure of NO
P
C
= gas-phase partial pressure of CO
k, K
1
, K
2
= coefficients dependent only on temperature


a) Based on your experience with such systems, you are asked to propose an adsorption-
surface reaction-desorption mechanism that will explain the experimentally observed
kinetics.
b) A certain engineer thinks that it would be desirable to operate with a very large
stoichiometric excess of CO to minimize catalytic reactor volume. Do you agree or
disagree? Explain.
c) When this reaction is carried out over a supported Rh catalyst, the reaction
mechanism is believed to be




2 2
CO , N NO CO +
( )
2
2 1
1
'
C N
C N
N
P K P K
P kP
r
+ +
=
S CO S CO - +
S NO S NO - +
S O S N S S NO - + - + -






When the ratio of P
CO
/P
NO
is small, the rate law that is consistent with the
experimental data is





What are the conditions for which the rate law and mechanism are consistent?


a) Proposal of mechanism

This is an example of LHHW



- - + OH 2 O O H
2
2S CO S O S CO
2
+ - + -
2S N S N S N
2
+ - + -
( )
2
1
'
CO CO
CO
CO
P K
kP
r
+
=


b)



c) Since P
CO
appears in the denominator, the CO.S surface reaction should be rate
limiting. P
CO
/P
NO
must be small. The mechanism must be a dual site mechanism (which it
is).




7. Based on Fogler Q 10-5: Figure 1 illustrates the experimental data obtained from the
dehydration of n-butyl alcohol (butanol) over an alumina-silica catalyst at 750 F in a
modified differential reactor. The feed consisted of pure butanol.

a) Suggest a mechanism and rate-controlling step that is consistent with the
experimental data
b) Evaluate the rate law parameters
c) At the point where the initial rate is a maximum, what is the fraction of vacant sites ?
What is the fraction of occupied sites by both A and B?
d) What generalization can you make from studying this problem?



Figure 1