Octane Rating
Steps in Catalytical Reaction
Rate Limiting Step
Regulation for Automotive Exhaust Emissions
Chemical Vapor Deposition
Types of Catalyst Deactivation
Temperature-Time Trajectories
Moving Bed Reactors & Straight Through Transport Reactors
1. Octane Rating
top
English-
Espanol-
Molecular Adsorption
At equilibrium:
Langmuir Isotherms
Dissociative Adsorption
Svenska-
At equilibrium:
Adsorption on Surface
Surface Reaction
Single Site
Dual Site
Adsorption on Surface
Surface Reaction
Dual Site
Eley-Rideal
top
Rationale:
Surface Reaction
Desorption
top
Assume surface
reaction is rate limiting
Site balance:
Substituting for CN-S, CI-S, and CV into CT = CV (1 + K N P N + K I P I) :
Single site
A)
Dual Site
B)
C)
Eley-Rideal
D)
Principle Reactions:
top
Multiplying by CV:
(A)
(B)
top
We see that a number of the key steps in the microelectronic fabrication involve CVD, we shall consider the
CVD of silicon.
I Mechanism
(1)
(2)
(3)
then
where:
Types of Decay
1.) Sintering
2.) Coking
3.) Poisoning
Temperature-Time Trajectories
Moving Bed
top
STTR
7. Temperature-Time Trajectories
top
The catalyst decay rate is a function of temperature, so you can vary the temperature with time to keep the
rate of decay as constant as possible.
Then:
or solving for
top
Batch Reactor
Mole Balance:
Rate Law:
Straight Through
Transport Reactor
Decay Law:
Stoichiometry:
, T = T0, and P = P 0
Combine:
rate is 1 kg/s to a reactor containg 10 kg of catalyst. The rate of decay is second order in activity and first
order in concentration for the product, B, which poisons the catalyst. Plot the conversion and activity as a
function of catalyst weight down the reactor.
Additional information:
Solution:
Polymath
Mole Balance:
Rate Law:
Decay Law:
Stoichiometry:
Combine:
When there is a change in the velocity due to a change in the number of moles up through the STTR, one
cannot directly substitute t = z/U in the coking activity equation:
(1)
Instead, one must add another equation to the Polymath program. We know that at any location, the gas
velocity up the column is:
(2)
Then:
(3)
where t = 0 at z = 0.
You can use either Polymath or MatLab to solve this equation and substitute it for t in the activity
equation:
Along with:
etc.
(same as the program in Table E10-7.1)
* All chapter references are for the 4th Edition of the text Elements of Chemical Reaction Engineering .
top
Fogler & Gurmen
2008 University of Michigan
The following data were obtained for the oxidation of CO over a catalyst. All rates are initial rates
.020
0.01
.035
0.01
.049
.01
.060
.01
.196
.1
.384
.2
.902
.5
1.653
4.44
5.00
10
4.44
20
2.77
50
versus CO2.
Hint 2 Sketch
Hint 3 Sketch
Hint 1
Use only the data points for which the concentration of CO is the same.
Back to Hints
Back to Problem
Back to Hints
Back to Problem
High concentration
Hint 1
From the denominator of the rate law, we see that CO is adsorbed and that O2 is either weakly adsorbed
(K O2P O21/2 << 1) or not adsorbed at all.
The 1/2 order with respect to oxygen suggests dissociative adsorption.
Because the initial rate is independent of CO2, it is either not adsorbed on the surface or weakly
adsorbed.
Back to Hints
Back to Problem
Hint 2
The following mechanism is consistent with the rate law
Molecular Adsorption
Dissociative Adsorption
Surface Reaction
Back to Hints
Back to Problem
Molecular Adsorption
Dissociative Adsorption
Surface Reaction
Assume surface reaction limits
1)
2)
3)
4)
5)
) such that
Back to Chapter 10
Fogler & Gurmen
2008 University of Michigan
Solution
Solution
Answer:(d)
Recall
-r'A=-r'B=r'C=r'D
Figure (a) suggests
Back to Problem
Back to Chapter 10
Fogler & Gurmen
2008 University of Michigan
Return to Chapter 10
Fogler & Gurmen
2008 University of Michigan
If K CO =1 atm-1 amd K NO =5 atm-1, what is the ratio of sites containing CO to those containing NO when
the conversion is 20%? 99%? What fraction of sites are occupied by NO? by CO? The feed is equal molar
in CO and NO with P O =2 atm.
Solution
Fraction of CO sites.
For X=.2
at 20% conversion 15% of the sites are occupied by CO and 9.4% are vacant.
For X=.99
at 99% conversion 1.8% of the sites are occupied by CO and 89% are vacant.
Back to Chapter 10
Fogler & Gurmen
2008 University of Michigan
CHAPTER 10 EXAMPLE
Dimethyl Ether
Self Test 1
1) Why doesn't water initially exit the reactor the same as DME? Which of
the following best describes the data?
Solution
Self Test 2 - Dimethyl Either
Solution
Self Test 3
Dimethyl Either
If the
rate law
is
Which set of figures describes the rate the functionality of the partial pressure of this rate law.
Solution
Solution #1
No ME exits the reactor so it is either being consumed to form
DME or being adsorbed on the surface or both.
One mole of DME and one mole of water are formed for every two
moles of ME consumed. DME exits the reactor while water does
not, consequently it must be adsorbed on the surface.
We note when we reach steady state after a period of time, the
exit concentration of DME and water are the same. Steady state
has indeed been reached because the concentrations of W and
DME are equal and the concentrations are no longer changed with
time.
Ans: E
Back to Problem 1
Back to Chapter 10
Solution
F
For every DME formed one water is formed. DME initially comes
out the end of the reactor, while water does not. If DME were on
the surface it would take up sites and would not exit for a while.
The concentration of DME reaches a maximum because it initially
has so many sites on which to react. After a while the water
occupies a number of the sites so that there are fewer for ME to
adsorb upon and react.
Back to Problem 2
Back to Chapter 10
Solution 3
W:
DME:
ME :
Combining
Answer D
Back to Problem 3
Back to Chapter 10
Fogler & Gurmen
2008 University of Michigan
CHAPTER 10 EXAMPLE
Example Exam Questions
Question 1
Go To Solution #1
Question 2
Go To Solution #2
Question 3
Go To Solution #3
Question 4
(a)
(b)
(d)
(e)
(c)
Go To Solution #4
Question 5
(b)
1.
The reaction is
irreversible.
2.
Species B is on the
surface.
3.
Species C is on the
surface.
A.
B.
C.
D.
E.
(c)
Go To Solution #5
Question 6
For the reaction
Go To Solution #6
Solution #1
If the reaction is reversible the increase in P C will
decrease the rate. If C is on the surface it will be in the
denomination of the rate law and thus increasing P C will
decrease the rate.
Ans: C
Back to Problem #1
Problem #2
Back to Chapter 10
Solution #2
Figure 1
Figure 2
Figure 3
Combining
Possible
Mechanism
From the rate law we know species B and C are adsorbed on the
surface. From the data you cant tell whether or not C is
adsorbed on the surface.
Ans: E
Back to Problem #2
Problem #3
Back to Chapter 10
Solution #3
Recall
Figure (a)
suggests
Figure (b)
suggests
Combining
Figure (c)
suggests
Combining
all the above
Therefore (b)
is consistent
Back to Problem #3
Problem 4
Back to Chapter 10
Solution #4
1. The reaction is irreversible because when P B = 1 atm,
increasing the product C does not change the rate. (TRUE)
2. Species B is on the surface because in 1 we showed that
the reaction is irreversible, therefore the only way the rate
could decrease were if were in the denominator of the rate law.
If a species is in the denominator of the rate law its on the
surface. (TRUE)
3. Species C is not on the surface because increasing P C
does not affect the rate.(FALSE)
Ans: A
Back to Problem #4
Problem #5
Back to Chapter 10
Solution #5
Low P T
High P T
Combining
Ans: (c)
Back to Problem #5
Problem #6
Back to Chapter 10
Solution #6
Ans: (e)
Back to Problem #6
Back to Chapter 10
Fogler & Gurmen
2008 University of Michigan