CHAP 10: Catalysis and Catalytic Reactions

Objectives

After completing Chapter 10 of the text the student will be able to:
• Define a catalyst, a catalytic mechanism and a rate limiting step.
• Describe the steps in a catalytic mechanism and how one goes
about deriving a rate law and a mechanism and rate limiting step
consistent with the experimental data.
• Use Regression to discriminate between reaction rate laws and
mechanisms.
• Size catalytic reactors
• Discuss the different types of catalyst deactivation and the reactor
types and describe schemes that can help offset the deactivation.
 History
Catalysis was practiced long before it was defined.

•Digestion
•Fermentation

•Faraday Adsorption Theory (M. Faraday, Phil. Trans.

Roy. Soc., 1834, pt. 1, 55-71)

He study reaction of hydrogen and oxygen on platinum

surface “…at all times, and was always effective when
the surface was perfectly clean.”

Faraday discovered poisoning effect, e.g., H2S for Pt.

He stressed that H2 and O2, even when compressed, do

not react unless a surface of Pt, etc. is present.
 History
1834 Mitscherlich defined contact action using many
of the same examples that Berzelius used to define
catalysis two years later.

1836 Berzelius defined and named catalysis, catalytic

action and catalytic force as well as indicating
their effects.

1885 H. E. Armstrong defines catalyst

 History
1894 Ostwald Era, As Co-Editor of Zeit. Phys. Chem., “

He wrote “ Catalysis is the acceleration of a

chemical reaction, which proceeds slowly, by the
presence of a foreign substance …This acceleration
occurs without alteration of the general energy
relations, since after the end of the reaction the foreign
body can be separated from the field of the reaction, so
that the energy used by the addition can once more be
obtained by the separation, or the reverse.”
“…these processes, like all natural ones, must always
occur in such a direction that the free energy of the
entire system is decreased… .”

• Nobel Prize 1909

 History
1912 Paul Sabatier

“Having arrived at the end of my career as a chemist, I

have thought that it might be of interest, and at the
same time of some utility, to relate how I was led to
develop the direct hydrogenation method by finely
divided metals, it is the faith in the theory of temporary
compounds furnished by the catalyst [chemisorption;
activated complex] which has constantly guided me in
these various labors; it is to these inductions that I owe
all my new results .”

• Nobel Prize 1912

• Research continue on catalyst….

1990's: Fischer-Tropsch as a source of alpha-olefins.

1990's: Combinatorial approaches to catalyst screening and new catalyst
discovery (e.g., K. D. Shimizu et al., Chem. Eur. J., 4, 1885 (1998)).
1992: Commercial use of non-iron catalyst for ammonia synthesis.
1992: Synthesis of MCM-41, the first uniformly structured mesoporous
aluminosilicate, announced by Mobil Oil (J. S. Beck, et al., JACS, 114, 10834
(1992).
1995: Introduction of oxone catalytic converter for airplane air purification.
1999: UOP Cyclar Process for the production of aromatics for LPG.

2005 : New nanocatalyst and bio catalyst

2015 : New material like graphene, silicone etc..
 2000 AD - 2005 AD
The Future
Zeolites in fine chemicals production · Biocatalytic removal of S, N and
metals · Extensive use of metallocene-based polymers · Alkene-to-alkane
feedstock transition · Catalytic combustion (VOC's, NOx) · Solid acids
replace strong liquid acids.

2005 AD - 2015 AD
Nanotechnology in catalyst manufacturing · Chemical-biochemical
bifunctional catalysts · Engineered enzymes in chemicals/fuels production ·
Chiral polymeric materials. Ionic liquid etc.

2010 AD - 2020 AD
Fuel cell powered vehicles · High-temperature inorganic-organic polymers ·
Membrane and other multifunctional reactors · Broader use of
electrocatalysis · Biopolymers, e.g., biosilk, biodegradables

2020 AD - 2040 AD
Photocatalytic water splitting: hydrogen economy · Catalytic antibodies,
biomimetics, synthetic enzymes in chemicals production · Engineering of
microbes for chemicals · Production of chemicals, materials in living plants
• Definitions:-

• Catalyst – substance that effects the rate of reaction but

emerges unchange

• Catalyst changes reaction rate by promoting different

molecular path - mechanism

• Catalysis – the occurrence, study and use of catalysts and

catalytic process

• Catalyst affects yield and selectivity

• Catalyst only changes the rate of reaction; it does not

effect the equilibrium

• Catalyst can accelerate or slow(inhibitor) the formation of

product
• Homogeneous catalysis – catalyst is in
solution with at least one of the reactant.
Eg : biodiesel production from triglycerides
Homogeneous catalyst : KOH and NAOH

• Heterogeneous catalysis – involve more

than one phase, usually catalyst is solid,
reactants and products in liquid or
gaseous
Eg : Reforming of methanol to produce H2
catalysts : Cu supported on alumina
Reaction gas-liquid mass transfer limited
 Catalyst Properties
• Heterogeneous catalyst - Reaction occurs at fluid-solid
interface, need large interfacial area.

• Eg: using porous catalyst : surface area = 300m2/g

• Molecular sieve : porous material that admit small molecule,

prevent large one. Eg : zeolites -> selectivity

Reaction : formation of xylene from toluene and methane

· Monolithic catalyst : either porous or nonporous

Eg: honeycomb(porous) or wiregauze(nonporous)

Reaction : Production of nitric acid from ammonia over
platinum gauze/honeycomb catalyst

Platinum – primary material in catalyst

 Catalyst Component
• Support catalyst : small particle of active material dispersed over
less active material. Eg : platinum on alumina. Active material
usually pure metal or metal alloy. Less active material usually less
expensive material such as alumina, activated carbon etc

• Promoters : small amount of active ingredients added to support

catalyst. Eg : vanadium impregnate to Pt/Al2O3 catalyst

• Deactivation : decline in catalyst activity as time progresses due to

aging(gradual change in surface crystal structure), or
poisoning(irrevesible deposition of substance on active site) or
fouling/coking(deposit of carbon or other material on the entire
surface)

Consider gas-phase reaction catalysed by solid catalyst

 Catalytic Processes
• Adsorption – physical or chemisorption. At least one
reactant attached to catalyst surface. Exothermic.
Chemisorption normally affects rate of reaction.

• Active sites : points on the catalyst surface that can form

strong chemical bonds with and adsorbed molecule

• Turnover frequency, f, (TOF), number of molecules

reacting per active site per second

• Dispersion, D, fraction of metal atoms deposited on the

surface

• Octane Rating – conversion of normal hydrocarbon

chains to branched chains gives higher octane number
 Catalyst requirement
• Active - to be economic, it must be highly active. Catalysts has
'active sites' in their structures. Adsorption or transient bonding at
the active site allows the reacting molecules to undergo a
particular chemical transformation at much lower energy. A
reasonable rate of reaction is needed

• The number of active sites and ease of access controls the rate of
turnover of reacting molecules.

• Example - Enzyme catalase, destroys hydrogen peroxide

generated in our bodies at a rate of a million molecules per second
at each active site

• Iron catalyst - turns over only one molecule per active site per
second - therefore need to contain large number of active sites per
unit surface area.
 Catalyst requirement
• Long lifetime - for instance, the iron catalyst of the ammonia
process lasts 15 years!

• cracking catalyst Catalytic crude oil reforming need to be change

every few minutes!

• It is costly to replace the catalyst frequently

• Ammonia synthesis. Performed over a promoted iron catalyst

N2 + 3H2 -> 2NH3

• Promoted means additives has been used to enhance the catalyst

» Mechanism of action is often not clear!

» Reaction performed at high T for kinetic reasons even though
thermodynamically this is a bad thing (reduces the equilibrium
constant). NN bond is difficult to breaks
 Catalyst requirement
• Selectivity – Byproducts and waste should be minimized .
Catalysts direct the course of the reaction as well as speed it up.
For example, a copper-based catalyst converts 'syn gas' (a
mixture of carbon monoxide and hydrogen produced by the
controlled burning of natural gas) into methanol. However, other
metal catalysts yield mixtures of hydrocarbons suitable for various
fuels.

• Enzymes are incredibly selective. They are able to recognise a

reacting molecule by its shape and transform it in a geometrically
specific way.

• Cost – The acceptable cost depends upon the catalyst

lifetime and product value
 Biocatalyst
• In recent years, chemists work on enzymes, the biocatalysts used
by nature, to transform simple molecules into more complex fine
chemicals for the pharmaceutical and agrochemical industries.

• Enzymes
- environmentally friendly, and they work at room
temperature and in water.

- They are also very selective.

- derive from microorganisms.

- The enzyme may be used in its natural state, as a whole cell

system, or isolated as the pure compound.

- Example : Hydrogen can be produce by catalytic chemical

reaction using methanol, but recently, it is proposed to use
microbes to produce hydrogen
 Heterogeneous catalysis
• Many heterogeneous catalysts are multiphase
– dispersed metals on a support » automobile
catalytic converters

• Some are uniform catalysts – the acid catalysts

ZSM5 is porous and active throughout the bulk
of the solid material

• In all cases, good activity requires a very high

accessible surface area as the reaction take
place on the surface
 Automobile catalytic converters
• Automobile catalytic converters need to catalyze several reactions

CHx + O2 -> CO2 + H2O

CO + O2 -> CO2
NOx +CHx -> N2 + H2O + CO2

• This is achieved by the use of a supported precious metal catalyst

» mixture of metals is used, platinum, palladium etc

• Note catalyst does not work at low temps (when engine first starts)

• Catalyst needs O2 to operate, so there can be problems when the

engine is running fuel rich
• » CeO2 and other oxygen buffers are being examined
• Acts as a temporary regenerable source of O2.

CeO2 -> Ce2O3 + 1/2O2

 Catalyst surface area

• Heterogeneous catalysts have their active sites on the

surface
– high surface area materials produce better catalysts

• This implies the use of very small catalyst particles or

solids that are porous on a molecular lengths scale
– Typically, very high surface area supports (silica gel,
gamma alumina etc.) are used to support very small
particles of active material

• zeolites are porous and have a lot of accessible internal

surface
 Zeolites
• Zeolites are crystalline microporous solids.
• The walls of the pore system can be
functionalized and used for catalysis.
 Acid and base sites

• A lot of industrial processes that are carried out

with heterogeneous catalysts make use of acid or
base sites – Alkylation, alkene isomerization etc.

• Dehydration of γ alumina and various zeolites

produces materials with acidic and in some cases
basic sites
– low temperatures produce acid OH on γ alumina
– high T produces Lewis acid sites as well
 Characterizing surface acid sites
• It is difficult to directly examine the nature of
surface acid sites

• Typically, probe molecules are used to evaluate the

nature of surface sites

– The IR spectrum of pyridine (a base) shows frequency

shifts depending on whether it is interacting with a
Bronsted site or Lewis acid site

» This can be used to distinguish and quantify the sites

that are present on a catalyst surface
Steps in Catalytic Reaction

Consider gas-phase reaction catalysed by solid catalyst

 Steps in Catalytic Reaction
1. Mass trasfer (diffusion) of reactants from bulk fluid to external
surface of catalyst
2. Diffusion of reactant from the pore mouth through catalyst pores to
immediate vicinity of internal surface
3. Adsorption of reactant onto catalyst surface
4. Reaction on catalyst surface
5. Desorption of the products from the surface
6. Diffusion of products from interior to the pore mouth
7. Mass transfer of products from external surface to bulk fluid

Reaction takes place on the surface, but species involved must

get to and from the surface.
Overall rate of reaction = the slowest step in the meachanism
Consider : 3, 4, 5 slow
Rate laws in heterogeneous catalyst
1. Seldom follow power law, more difficult to
formulate from data
2. Postulate catalytic mechanisms, then derive rate
laws
3. View the trends in the data, deduce rate laws
4. Estimate rate laws parameters
5. Use rate law to design catalytic reactors
 Adsorption isotherms
1. S – active site, alone denote vacant site with no
atom, molecule, or complex adsorbed on it
2. Combination of S with other letter eg. A·S
means one unit of species A adsorbed on site S
3. Ct = total molar concentration of active sites per
unit mass of catalyst
4. Cv = molar concentration of vacant sites
5. Isotherm – amount of gas adsorbed on a solid
at different pressure but at one temperature
rate of attachment

rate of detachment
 Molecular Adsorption

At equilibrium:

Langmuir isotherm – concentrations of H2 adsorbed

on the surface as a function of partial pressure of H2
 Langmuir Isotherms

Dissociative Adsorption

At equilibrium:
 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

Example reaction of propylene (g) and benzene

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:

 Rate Limiting Steps

Adsorption

Surface Reaction

Desorption
Assume surface reaction is rate limiting

If the surface reaction is limiting then:

 Site balance:

Substituting for CN-S, CI-S, and CV into CT = CV (1 + KN PN + KI PI) :

 Linearizing the Initial Rate:

on setting rad/ka=0
 Irreversible, Surface-reaction limited rate laws

Single site
Dual Site
Dual Site
Eley-Rideal
 Hydrogen Adsorption
A typical adsorption isotherm, shown in Figure 10.1,
adsorption of hydrogen on powdered copper at 25°C (Table 10.1)

Figure 10.1 Adsorption of hydrogen on copper

 A. Molecular Adsorption

The collision rate is proportional to the hydrogen partial pressure, .

Hydrogen molecules can adsorb only on vacant sites and not on sites already
occupied by other hydrogen molecules, the rate of attachment
is also directly proportional to the concentration of vacant sites, Cv .
rate of attachment

rate of detachment
K A = k A / k - A is the adsorption equilibrium constant
On this particular catalyst the data show that hydrogen does not
adsorb as molecules (H 2 )
B. Dissociative Adsorption
The dissociative adsorption of H2 model fits the
experimental data for this catalyst
.
Note :-

• Mechanism and rate-limiting step may fit the rate

data, but that does not imply the mechanism is
absolutely correct.
• Spectroscopic measurements needed to confirm
mechanism
• Development of various mechanism and rate-
limiting steps can provide insight into the best
way to correlate the data and develop a rate law
Next Steps: -

1) Developing an algebraic rate law consistent

with experimental observations
2) Analyzing the rate law to get rate law
parameters from experimental data
3) Finding mechanism and rate-limiting step
consistent with experimental data
4) Designing a catalytic reactor to achieve
specified conversion
Example : Finding the rate law and mechanism for

The following data were obtained for the oxidation of

CO over a catalyst. All rates are initial rates

.020 0.01 1
.035 0.01 3
.049 .01 6
.060 .01 9
.196 .1 1
.384 .2 1
.902 .5 1
1.653 1 1
4.44 5 1
5.00 10 1
4.44 20 1
2.77 50 1

The initial rate was found to be independent of CO2.

 a) Suggest a rate law consistent with the data
Sketch versus CO2.

Use only the data points for which the concentration of CO is the same.
 Sketch versus CCO at low concentration.

Low concentration For constant CO2

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

 Sketch versus CCO at high concentration.

High concentration

At high concentrations the rate decreases with increasing concentration

 What is the rate law? Combining

For fixed concentration of O2 and low concentration of CO and

High concentration

Consequently the rate law

Satisfies the data

b) Suggest mechanisms consistent with the rate law

From the denominator of the rate law, we see that

CO is adsorbed and that O2 is either weakly
adsorbed (KO2PO21/2 << 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.
 The following mechanism is consistent with the rate law

Molecular
Adsorption

Dissociative
Adsorption

Surface
Reaction
Assume surface
reaction limits
We see that oxygen is weakly adsorbed (very small )

such that
Example : Finding the rate law and mechanism for A+B<=>C+D
The following profile were reported for the reaction A + B goes to C + D
Which of the following mechanisms is consistent with the above data?
Solution:-

r'A = -r'B = r'C = r'D

Figure (a) suggests

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

Figure (d) suggests

Combining all the above

Therefore, (d)is consistent
 Types of Catalyst Deactivation

Separable Kinetics :

1.) Sintering

2.) Coking

3.) Poisoning
 4.) Slow Decay : Temperature-Time Trajectories

The catalyst decay rate is a function of temperature,

vary the temperature with time to keep the rate of
decay as constant as possible.

Then
or solving for
 Catalyst Decay in a Batch Reactor

The elementary irreversible gas phase catalytic reaction

is carried out isothermically in a batch reactor. The catalyst deactivation

follows a first order decay law and is independent of the concentrations
of both A and B.
Additional information:

CA0 = 1 mol/dm3
V0 = 1 dm3
W = 1 kg
kd = 0.1 min-1 at 300 K Ed/R = 2,000 K
k1 =0.2 dm3/(kg cat · min) at 300 K Ea/R = 500 K
Batch–

First-order decay law

 Sketch a(t)

a(t) never equals zero for a first-order decay law

 Determine X(t)

Separate and Integrate

Calculate conversion after 10 minutes