10.

CATALYSIS AND CATALYTIC REACTIONS*

Topics
1.
2.
3.
4.
5.
6.
7.
8.

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

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A Typical Engine Piston

1. a uniform burning front

2. spontaneous combustion producing
detonation waves and knock

Determine the compression ratio, CR,

to achieve the standard knock intensity.
The more compact molecules are (for a given
number of carbon atoms), the greater the
octane number they will have.

to further explanation on octane rating

English-

Espanol-

Molecular Adsorption

At equilibrium:

Langmuir Isotherms

Dissociative Adsorption

Svenska-

At equilibrium:

2. Steps in a Catalytic Reaction

Adsorption on Surface

Surface Reaction

Single Site

Dual Site

Desorption from Surface

Adsorption on Surface

Surface Reaction

Dual Site

Eley-Rideal

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Desorption from Surface

Example: Catalytic Reaction to Improve the Octane Number of Gasoline

Rationale:

n-pentane: Octane No. = 62

i-pentane: Octane No. = 90

The difference in octane ratings provides

an economic incentive for carrying out this
reaction.

Steps in this reaction:

Focusing on the second reaction:

3. Rate Limiting Steps

Adsorption

Surface Reaction

Desorption

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Assume surface
reaction is rate limiting

If the surface reaction

is limiting then:

see also stirctly speaking link

see also strictly speaking link

Site balance:
Substituting for CN-S, CI-S, and CV into CT = CV (1 + K N P N + K I P I) :

where K P is the thermodynamic equilibrium constant for the reactor.

Linearizing the Initial Rate:

on setting rad/k a=0

Single site

A)

Dual Site
B)

C)

Eley-Rideal

D)

10.1 Finding the rate law and mechanism for

10.2 Finding the rate law and mechanism for A+B<=>C+D

4. Regulations for Automotive Exhaust Emissions

Principle Reactions:

Surface reaction limiting:

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10.3 CO + NO; -r' CO = f(P CO , P NO , P N2 , P CO2)

Example
Let's see what fraction of sites are covered by CO at the optimum:

Multiplying by CV:

(A)
(B)

10.4 Calculating Fractional Coverage

10.1 Dimethyl Ether Examples
10.2 Example Exam Questions

5. Chemical Vapor Deposition, CVD (Chapter 10)

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Manufacturing of a Silicon Layer

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)

II Rate Limiting Step (Reaction 3)

rdep=rs =k s f SiH2
III Expressing f SiH2 in Terms of Partial Pressures

IV Site / Surface Area Balance:

For the homogeneous reaction:

then

where:

6. Types of Catalyst Deactivation

Separable Kinetics:

Types of Decay

1.) Sintering

2.) Coking

3.) Poisoning

4.) Slow Decay

Temperature-Time Trajectories

5.) Moderate Decay

Moving Bed

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6.) Rapid Decay

STTR

7. Temperature-Time Trajectories

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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

10.5 Decaying Catalyst in a Batch Reactor

8. Moving Bed Reactors & Straight Through Transport Reactors

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Catalyst Decay Example

The gas-phase, irreversible reaction

is elementary with first order decay. The reaction is carried out

at constant temperature and pressure.

Batch Reactor

Mole Balance:

Rate Law:

Moving Bed Reactor

Straight Through
Transport Reactor

Decay Law:

Stoichiometry:

gas phase, but

, T = T0, and P = P 0

Combine:

Another Catalyst Decay Example

The second-order, irreversible reaction

is carried out in a moving bed reactor. The catalyst loading

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:

Conversion vs. Catalyst Weight

Catalyst Activity vs. Catalyst Weight

10.6 Moving Bed Reactor

Example 10-7: Strictly Speaking

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)

10.3 Catalyst Decay in a Packed Bed

Object Assessment of Chapter 10

* All chapter references are for the 4th Edition of the text Elements of Chemical Reaction Engineering .

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Fogler & Gurmen
2008 University of Michigan

CHAPTER 10 SELF TEST

Finding the Mechanism

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

The initial rate was found to be independent of CO2.

a) Suggest a rate law consistent with the data
Hint 1 Sketch

versus CO2.

Hint 2 Sketch

versus CCO at low concentration.

Hint 3 Sketch

versus CCO at high concentration.

Full Solution What is the rate law?

b) Suggest mechanisms consistent with the rate law

Hint 1 What do the trends suggest?
Hint 2 What is the mechanism?
Full Solution

Hint 1
Use only the data points for which the concentration of CO is the same.

Back to Hints
Back to Problem

Hint 2: Low concentration

For constant CO2

We see at low concentration the rate is linear in CO and

Back to Hints
Back to Problem

Hint 3: High concentration

At high concentrations the rate decreases with increasing concentration

Back to Hints
Back to Problem

Full Solution: Part A

Combining

For fixed concentration of O2 and low concentration of CO and

High concentration

Consequently the rate law

Satisfies the data

Back to Part b

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

Full Solution: Part B

The following mechanism is consistent with the rate law

Molecular Adsorption

Dissociative Adsorption
Surface Reaction
Assume surface reaction limits

1)

2)

3)
4)

5)

We see that oxygen is weakly adsorbed (very small

) such that

Back to Chapter 10
Fogler & Gurmen
2008 University of Michigan

CHAPTER 10 SELF TEST

Finding the rate law and mechanism for A+B<=>C+D
The following data were reported for the reaction A + B goes to C + D

Which of the following mechanisms is consistent with the above data?

Solution

Solution
Answer:(d)
Recall
-r'A=-r'B=r'C=r'D
Figure (a) suggests

Figure (b) suggests

Figure (c) suggests

-rA is not a function of P D, therefore the reaction is irreversible and D is not on the surface.Figure (d)
suggests

Combining all the above

Therefore, (d)is consistent

Back to Problem
Back to Chapter 10
Fogler & Gurmen
2008 University of Michigan

SURFACE REACTION LIMITING

Return to Chapter 10
Fogler & Gurmen
2008 University of Michigan

CHAPTER 10 SELF TEST

Calculating Fractional Coverage
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

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?

A. There is more DME than water.

B. Steady state has been reached.
C. Water reacts with ME.
D. Water is adsorbed on the surface.
E. Two of the above are true.

Solution
Self Test 2 - Dimethyl Either

2) Which of the following are true?

The concentration of DME reaches a maximum because
A. it just does.
B. the rate of reaction is very rapid initially.
C. all the sites are vacant initially so that (Methanol) ME is rapidly
adsorbed.
D. there is very little water initially adsorbed on the surface.
E. DME is probably not on the surface.
F. All of the above.

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

All of the above.

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

Figure 1: Data from a differential reactor.

Which of the following best describe the data in the

above figure?
A. Species C could be adsorbed on the surface.
B. The reaction could be reversible.
C. Both the above statements could be true.
D. Neither A or B are on the surface.
E. None of the above could be true.

Go To Solution #1

Question 2

Assume the reaction is irreversible

What can you tell from the above figures?

1. Species A could be adsorbed on the surface but only very weakly adsorbed.
2. Species A is not adsorbed on the surface.
3. Species B is on the surface.
4. Species A is adsorbed on the surface.
5. Species C is adsorbed on the surface.

A. 1 and 2 are true.

B. 1 and 3 are true.
C. 1 and 4 are false.
D. 4 and 5 are true.
E. 2 and 5 are true.

Go To Solution #2

Question 3

The following data were reported for the reaction

Which of the following mechanism is consistent with the above data

Go To Solution #3

Question 4

(a)

(b)

(d)

(e)

(c)

The initial rate of reaction is shown below

(a)

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.

1 and 2 are true.

B.

1 and 2 are false.

C.

1 and 3 are false.

D.

2 and 3 are false.

E.

2 and 3 are true.

(c)

The initial rate of reaction is shown below

1. The rate law is

Go To Solution #5

Question 6
For the reaction

from Self Tests 12 and 13 we found

which mechanism is consistent with the rate law

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

A is not on the surface or if it is K AP A << 1. B is on the

surface and we see as we increase P B, the rate reaches a
plateau. The curves from A, B, and C partial pressure suggest a
rate law of the for

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

therefore reaction is irreversible and D is not on

surface
Figure (d)
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