Short term programme on updating

applied chemistry

Catalysis

Pradeep Kumar
Department of Chemical engineering
UIET CSJM University Kanpur
1
 Chemistry and Chemical engineering more
integarted to the society
Society:
Cleaner and safer processes
Well accepted and integrated processes
Industry:
Speed-up processes
Energy and cost effective processes
New catalysts and catalytic processes
New technologies
Academia:
New innovations
Deeper knowledge and understanding of phenomena
Control of phenomena
2
Catalysis & Catalysts

Catalysis & Catalysts

Catalysts :Life cycle on the earth
Catalysts (enzyme) participates most part of life cycle
e.g. forming, growing, decaying
Its processes of converting sun energy to various other forms of
energies
e.g. photosynthesis by plant CO2 + H2O=HC + O2
Chemical Industry
ca. $2 bn annual sale of catalysts
ca. $200 bn annual sale of the chemicals that are related products
90% of chemical industry has catalysis-related processes
Catalysts contributes cost @ of 2% of total investment in a chemical
process
3
 Historical background of Industrial catalysis
1900- 1920
Industrial Process Catalyst
1900s: CO + 3H2 CH4 + H2O Ni
Vegetable Oil + H2 butter/margarine Ni
1910s: Coal Liquefaction Ni
N2 + 3H2 2NH3 Fe/K
NH3 NO NO2 HNO3 Pt
1920s: CO + 2H2 CH3OH (HP) (ZnCr)oxide
Fischer-Tropsch synthesis Co,Fe
SO2 SO3 H2SO4 V2O5
4
 Industrial catalysis 1930s and 1940s
1930s:Cat Cracking
C2H4 C2H4O Ag
C6H6 Maleic anhydride V2O5
1940s:Cat Cracking(fluid) amorph. SiAl
alkylation (gasoline) HF/acid- clay
Platforming(gasoline) Pt/Al2O3
C6H6 C6H12 Ni
2000+
Solid catalysts for biodiesel: solid acids, Hydroisom catalysts
Catalysts for carbon nanotubes: Fe (Ni)-Mo-SiO2
5
 What is Catalysis
Catalysis is an action by catalyst which takes part in a chemical
reaction process and can alter the rate of reactions, and yet itself
will return to its original form without being consumed or destroyed
at the end of the reactions
taking part in the reaction
Does not change itself : interaction with reactant/product
altering the rates of reactions
rates of reactions are increased for desirable product and
selectively suppressed for undesired reactions
These can be regenerated reborn
In practice a catalyst has its lifespan - it deactivates gradually
during use
6
 Action of Catalysts
Catalysis action - Reaction kinetics and mechanism
Complexation with reactants/products, controlling the rate . How?
The reaction activation energy is altered

The rates of reactions are altered

Allow reactions occur under a milder conditions, e.g. at lower

temperatures for those heat sensitive materials
uncatalytic

catalytic
energy

reactant

product
reaction process
7
 Action of Catalysts
Use of catalyst DOES NOT vary G & Keq of the reaction
Feasibility of reaction is solely determined by thermodynamics, which
is governed by the values of G & Keq, NOT by the catalysts.
Reaction thermodynamics provide the driving force for a rxn; the
presence of catalysts changes the way how driving force acts on
that process.

e.g CH4(g) + CO2(g) = 2CO(g) + 2H2(g)

G373=151 kJ/mol (100 C)

G973 =-16 kJ/mol (700 C)

8
 Action of Catalysts
At 100C, G373=151 kJ/mol > 0

There is no thermodynamic driving force, the reaction wont

proceed with or without a catalyst
At 700C, G373= -16 kJ/mol < 0
Thermodynamic driving force is there. However, simply putting
CH4 and CO2 together in a reactor does not mean they will
react. Without a proper catalyst heating the mixture in
reactor results no conversion of CH4 and CO2 at all. When
Pt/ZrO2 or Ni/Al2O3 is present in the reactor at the same
temperature, equilibrium conversion can be achieved
(<100%).

9
 Types of Catalysts
based on the its physical state
gas
liquid
Solid
based on the substances from which a catalyst is made
Inorganic (gases, metals, metal oxides, inorganic acids, bases etc.)
Organic (organic acids, enzymes etc.)
based on the ways catalysts work
Homogeneous - both catalyst and all reactants/products are in the same phase (gas or
liq)
Heterogeneous - reaction system involves multi-phase (catalysts + reactants/products)
based on the catalysts action
Acid-base catalysts
Enzymatic
Photocatalysis
Electrocatalysis, etc. 10
 Advantages of Catalyst
Industrial applications
Almost all chemical industries employing catalysts
Petroleum, energy sector, fertiliser, pharmaceutical, fine chemicals
Advantages of catalytic processes
Achieving better process economics and productivity
Increase reaction rates - fast
Simplify the reaction steps - low investment cost
Carry out reaction under mild conditions (e.g. low T, P) - low energy
consumption
Reducing wastes
Improving selectivity toward desired products - less raw materials required, less
unwanted wastes
Replacing harmful/toxic materials with readily available ones
Having better control of process (safety, flexible etc.)

11
 Applications of Catalysis
Environmental applications
Pollution controls in combination with industrial processes
Pre-treatment - reduce the amount waste/change the composition of emissions
Post-treatments - once formed, reduce and convert emissions
Using alternative materials

Pollution reduction
gas - converting harmful gases to non-harmful ones
liquid - de-pollution, de-odder, de-colour etc
solid - landfill, factory wastes

Other applications
Catalysis and catalysts play one of the key roles in new technology development.
12
 Commercial Catalytic Processes
Haber-Bosch process
N2 + 3 H2 2 NH3
Fe/Ru catalysts, high pressure and temperature
Critical for fertilizer and nitric acid production

Fischer-Tropsch
n CO + 2n H2 (CH2)n + n H2O , syn gas to liquid fuels
Fe/Co catalysts

Fluidized catalytic cracking

High MW petroleum low MW fuels, like gasoline
Zeolite catalysts, high temperature combustor

Automotive three-way catalysis

NOx/CO/HC H2O/CO2/H2O
Pt/Rh/Pd supported on ceria/alumina
Makes exhaust 99% cleaner

13
 Research in Catalysis
Reaction kinetics and mechanism
Reaction paths, intermediate formation & action, interpretation of results obtained
under various conditions, generalising reaction types & schemes, predict catalyst
performance
Catalyst development
Material synthesis, structure properties, catalyst stability, compatibility
Analysis techniques
Detection limits in terms of dimension of time & size and under extreme conditions (T,
P) and accuracy of measurements, microscopic techniques, sample preparation
techniques
Reaction modelling
Elementary reactions and rates, quantum mechanics/chemistry, physical chemistry
Reactor modelling
Mathematical interpretation and representation, the numerical method, micro-
kinetics, structure and efficiency of heat and mass transfer in relation to reactor design
Catalytic process
Heat and mass transfers, energy balance and efficiency of process
14
 Catalytic Reaction Processes
Understanding catalytic reaction processes
A catalytic reaction can be operated in a batch manner
Reactants and catalysts are loaded together in reactor for a desired time /
desired conversion
Type of reactor is usually simple, basic requirements
Withstand required temperature & pressure
Some stirring to encourage mass and heat transfers
Provide sufficient heating or cooling
Catalytic reactions are commonly operated in a continuous manner
Reactants, which are usually in gas or liquid phase, are fed to reactor in steady
rate
Usually a target conversion is set for the reaction, based on this target
required quantities of catalyst is added
required heating or cooling is provided
required reactor dimension and characteristics are designed accordingly.
15
 Catalytic Reaction Processes
Reactants in continuous operation are mostly in gas phase or liquid phase
easy transportation
The heat & mass transfer rates in gas phase is much faster than those in
liquid
Catalysts are pre-loaded, when using a solid catalyst, or fed together with
reactants when catalyst & reactants are in the same phase and pre-mixed
It is common to use solid catalyst because of its easiness to separate
catalyst from unreacted reactants and products
With pre-loaded solid catalyst, there is no need to transport catalyst
which is then more economic and less attrition of solid catalyst (Catalysts
do not change before and after a reaction and can be used for number
cycles, months or years),
catalytic reactions are carried out with catalyst in a fixed-bed reactor
(fluidised-bed in case of regeneration being needed)

16
 Catalytic Reaction Processes
General requirements for a good catalyst
Activity - being able to promote the rate of desired reactions
Selective - being to promote only the rate of desired reaction and also
retard the undesired reactions
Note: The selectivity is sometime considered to be more important
than the activity and sometime it is more difficult to achieve
(e.g. selective oxidation of NO to NO2 in the presence of SO2)
Stability - a good catalyst should resist to deactivation, caused by
the presence of impurities in feed (e.g. lead in petrol poison TWC.
thermal deterioration, volatility and hydrolysis of active components
attrition due to mechanical movement or pressure shock
A solid catalyst should have reasonably large surface area needed for
reaction (active sites). This is usually achieved by making the solid
into a porous structure.
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 Example Heterogeneous Catalytic Reaction Process

The long journey for reactant molecules to

j. travel within gas phase
k. cross gas-liquid phase boundary gas phase
reactant molecule
l. travel within liquid phase/stagnant layer
j gas phase
m. cross liquid-solid phase boundary
n. reach outer surface of solid k
o. diffuse within pore l liquid phase /
p. arrive at reaction site mn stagnant layer

q. be adsorbed on the site and activated

r. react with other reactant molecules, either o
being adsorbed on the same/neighbour porous pore
sites or approaching from surface above solid

Product molecules must follow the same track

in the reverse direction to return to gas phase pq r

Heat transfer follows similar track

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 Solid Catalysts
Catalyst composition
Active phase
Where the reaction occurs (mostly metal/metal oxide)
Promoter
Textual promoter (e.g. Al - Fe for NH3 production)
Electric or Structural modifier
Catalyst
Poison resistant promoters
Support
Support / carrier
Increase mechanical strength
Increase surface area (98% surface area is supplied within the porous structure)
may or may not be catalytically active

19
 Solid Catalysts
Some common solid support / carrier materials
Alumina Other supports
Inexpensive Active carbon (S.A. up to 1000 m2/g)
Surface area: 1 ~ 700 m2/g Titania (S.A. 10 ~ 50 m2/g)
Acidic Zirconia (S.A. 10 ~ 100 m2/g)
Silica Magnesia (S.A. 10 m2/g)
Inexpensive Lanthana (S.A. 10 m2/g)
Surface area: 100 ~ 800 m2/g Active site
Acidic

Zeolite
mixture of alumina and silica, porous pore
solid
often exchanged metal ion present
shape selective
acidic

20
 Solid Catalysts Support

Preparation of catalysts
Precipitation
Drying
To form non-soluble precipitate by desired & firing
reactions at certain pH and temperature precursor add acid/base precipitate filter & wash
solution with pH control or deposit the resulting
Adsorption & ion-exchange precipitation precipitate
Support
Cationic: S-OH+ + C+ SOC+ + H+

adsorbed
Amount
Anionic: S-OH- + A- SA- + OH-
Drying
I-exch. S-Na+ + Ni 2+ D S-Ni 2+ + Na+ Concentration
& firing

Support
Impregnation
Fill the pores of support with a metal salt
solution of sufficient concentration to give Drying
the correct loading. & firing
Soln. of metal Pore saturated
Dry mixing precursor pellets
Physically mixed, grind, and fired
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 Solid Catalysts
Preparation of catalysts
Catalysts need to be calcined (fired) in order to decompose the precursor and to
received desired thermal stability. The effects of calcination temperature and time
are shown in the figures on the right. 40

BET S.A. m2/g

100

BET S.A.
Commonly used Pre-treatments 75
50
Reduction 25
if elemental metal is the active phase 0 0
0 10
500 600 700 800 900 Time / hours
Sulphidation Temperature C
if a metal sulphide is the active phase
Activation
Some catalysts require certain activation steps in order to receive the best performance.
Even when the oxide itself is the active phase it may be necessary to pre-treat the
catalyst prior to the reaction ActivityInduction period
Normal use
Typical catalyst life span dead

Can be many years or a few mins.

Time 22
 Adsorption On Solid Surface
Adsorption
Adsorption is a process in which molecules from gas (or liquid) phase land
on, interact with and attach to solid surfaces.
The reverse process of adsorption, i.e. the process n which adsorbed
molecules escape from solid surfaces, is called Desorption.
Molecules can attach to surfaces in two different ways because of the
different forces involved. These are Physisorption (Physical adsorption) &
Chemisorption (Chemical adsorption)

Physisorption Chemisorption
force van de Waal chemcal bond
number of adsorbed layers multi only one layer
adsorption heat low (10-40 kJ/mol) high ( > 40 kJ/mol)
selectivity low high
temperature to occur low high
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 Adsorption On Solid Surface
Adsorption process
Adsorbent and adsorbate
Adsorbent (also called substrate) - The solid that provides surface for adsorption
high surface area with proper pore structure and size distribution is essential
good mechanical strength and thermal stability are necessary

Adsorbate - The gas or liquid substances which are to be adsorbed on solid

Surface coverage, q
The solid surface may be completely or partially covered by adsorbed molecules
number of adsorption sites occupied
define q= q = 0~1
number of adsorption sites available
Adsorption heat
Adsorption is usually exothermic (in special cases dissociated adsorption can be
endothermic)
The heat of chemisorption is in the same order of magnitude of reaction heat;
the heat of physisorption is in the same order of magnitude of condensation heat.
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Catalysis & Catalysts

Adsorption On Solid Surface

Applications of adsorption process
Adsorption is a very important step in solid catalysed reaction processes
Adsorption in itself is a common process used in industry for various purposes
Purification (removing impurities from a gas / liquid stream)
De-pollution, de-colour, de-odour
Solvent recovery, trace compound enrichment
etc

Usually adsorption is only applied for a process dealing with small capacity
The operation is usually batch type and required regeneration of saturated adsorbent
Common adsorbents: molecular sieve, active carbon, silica gel, activated alumina.
Physisorption is an useful technique for determining the surface area, the pore
shape, pore sizes and size distribution of porous solid materials (BET surface area)

25
Catalysis & Catalysts

Adsorption On Solid Surface

Characterisation of adsorption system
Adsorption isotherm - most commonly used, especially to catalytic reaction system, T=const.
The amount of adsorption as a function of pressure at set temperature
Adsorption isobar - (usage related to industrial applications)
The amount of adsorption as a function of temperature at set pressure
Adsorption Isostere - (usage related to industrial applications)
Adsorption pressure as a function of temperature at set volume

V3>V2
P4>P3
V2>V1
P3>P2
T1 V4>V3
Vol. adsorbed
Vol. adsorbed

T2 >T1 V1

Pressure
P2>P1
T3 >T2
P1
T4 >T3

T5 >T4

Pressure Temperature Temperature

Adsorption Isotherm Adsorption Isobar Adsorption Isostere
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Catalysis & Catalysts

Adsorption On Solid Surface

The Langmuir adsorption isotherm
Basic assumptions
surface uniform (DHads does not vary with coverage)
monolayer adsorption, and
no interaction between adsorbed molecules and adsorbed molecules immobile

Case I - single molecule adsorption A

when adsorption is in a dynamic equilibrium
A(g) + M(surface site) D AM
the rate of adsorption rads = kads (1-q) P case I

the rate of desorption rdes = kdes q

at equilibrium rads = rdes kads (1-q) P = kdes q
(kads / kdes ) P
rearrange it for q q
1 (kads / kdes ) B0 P
k ads Cs BP
let B0 q 0 B0 is adsorption coefficient
k des C 1 B0 P
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Catalysis & Catalysts

Adsorption On Solid Surface

The Langmuir adsorption isotherm (contd)
Case II - single molecule adsorbed dissociatively on one site
A-B(g) + M(surface site) D A-M-B
A B
the rate of A-B adsorption rads=kads (1-qA )(1-qB)PAB=kads (1-q )2PAB
A B
q=qA=qB
the rate of A-B desorption rdes=kdesqAqB =kdesq2
case II
at equilibrium rads = rdes kads (1-q )2PAB= kdesq2

rearrange it for q (kads / kdes ) PAB

q
1 (kads / kdes ) PAB

k Cs ( B0 PAB )1/2
Let. B0 ads q
k des C 1 ( B0 PAB )1/2

28
Catalysis & Catalysts

Adsorption On Solid Surface

The Langmuir adsorption isotherm (contd)
Case III - two molecules adsorbed on two sites
A(g) + B(g) + 2M(surface site) D A-M + B-M

the rate of A adsorption rads,A = kads,A (1- qA- qB) PA A B

the rate of B adsorption rads,B = kads,B (1- qA- qB) PB

the rate of A desorption rdes,A = kdes,A qA case III
the rate of B desorption rdes,B = kdes,B qB
at equilibrium rads ,A = rdes ,A and rads ,B = rdes ,B
kads,A(1-qA-qB)PA=kdes,AqA and kads,B(1-qA-qB)PB=kdes,BqB

Cs , A B0 ,A PA Cs ,B B0 ,B PB
rearrange it for q qA qB
C 1 B0 ,A PA B0 ,B PB C 1 B0 ,A PA B0 ,B PB
kads,A k
where B0 ,A and B0 ,B ads,B are adsorption coefficients of A & B.
kdes ,A kdes ,B
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Catalysis & Catalysts

Adsorption On Solid Surface

The Langmuir adsorption isotherm (contd) A B
A A B

case III
case II Cs , A B0 ,A PA
case I qA
C 1 B0 ,A PA B0 ,B PB
C BP Cs ( B0 PAB )1/2
q s 0 q C B0 ,B PB
C 1 B0 P C 1 ( B0 PAB )1/2 q B s ,B
C 1 B0 ,A PA B0 ,B PB
k ads k ads k k
B0 B0 B0 ,A ads,A and B0 ,B ads,B
k des k des kdes ,A kdes ,B

Adsorption Adsorption qA
Cs , A

B0 ,A PA
A, B both strong C B0 ,A PA B0 ,B PB
Strong kads>> kdes kads>> kdes C B0 ,B PB
q B s ,B
B0>>1 q C s 1 B0>>1 q
Cs
1 C B0 ,A PA B0 ,B PB
C C q A Cs ,A / C 1
Weak kads<< kdes kads<< kdes A strong, B weak PB
q B Cs ,B / C ( B0 ,B / B0 ,A )
Cs C PA
B0<<1 q B0 P B0<<1 q s ( B0 P)1/2 q A Cs ,A / C B0 ,A PA
C C A weak, B weak
q B Cs ,B / C B0 ,B PB 30
Catalysis & Catalysts

Adsorption On Solid Surface

Langmuir adsorption isotherm
Strong adsorption kads>> kdes q Cs 1
Cs BP C
case I q 0
C 1 B0 P kads<< kdes C
Weak adsorption q s B0 P
C
Cs ( B0 PAB )1/2
case II q

Amount adsorbed
C 1 ( B0 PAB )1/2
C B0 ,A PA
Case III q A s ,A mono-layer
C 1 B0 ,A PA B0 ,B PB
large B0 (strong adsorp.)
C B0 ,B PB
q B s ,B moderate B0
C 1 B0 ,A PA B0 ,B PB
small B0 (weak adsorp.)

Pressure

Langmuir adsorption isotherm established a logic picture of adsorption process

It fits many adsorption systems but not at all
The assumptions made by Langmuir do not hold in all situation, that causing error
Solid surface is heterogeneous thus the heat of adsorption is not a constant at different q
Physisorption of gas molecules on a solid surface can be more than one layer
31
Catalysis & Catalysts

Adsorption On Solid Surface

Five types of physisorption isotherms are found over all solids
I
Type I is found for porous materials with small pores e.g. charcoal.
It is clearly Langmuir monolayer type, but the other 4 are not
II
Type II for non-porous materials
amount adsorbed

Type III porous materials with cohesive force between adsorbate

III
molecules greater than the adhesive force between adsorbate
molecules and adsorbent
IV Type IV staged adsorption (first monolayer then build up of additional
layers)

Type V porous materials with cohesive force between adsorbate

V
molecules and adsorbent being greater than that between
1.0 adsorbate molecules
relative pres. P/P0
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Catalysis & Catalysts

Adsorption On Solid Surface

Other adsorption isotherms
Many other isotherms are proposed in order to explain the observations
The Temkin (or Slygin-Frumkin) isotherm
Assuming the adsorption enthalpy DH decreases linearly with surface coverage
From ads-des equilibrium, ads. rate des. rate
rads=kads(1-q)P rdes=kdesq

DH of ads
Langmuir
B0 P b1eQs / RT P Temkin
q qs
1 B0 P 1 b1eQs / RT P
q
where Qs is the heat of adsorption. When Qs is a linear function of qi. Qs=Q0-iS (Q0 is a
constant, i is the number and S represents the surface site),
1 1 [b1eQs / RT P RT 1 b1P
the overall coverage q q s dS dS ln
1 b P exp(- i
0 (1 b eQs / RT P i RT
0
1 1

When b1P >>1 and b1Pexp(-i/RT) <<1, we have q =c1ln(c2P), where c1 & c2 are constants

Valid for some adsorption systems.

33
Catalysis & Catalysts

Adsorption On Solid Surface

The Freundlich isotherm
assuming logarithmic change of adsorption enthalpy DH with surface coverage
From ads-des equilibrium, ads. rate des. rate

DH of ads
rads=kads(1-q)P rdes=kdesq Langmuir
Freundlich
B0 P b1eQi / RT P
q qi
1 B0 P 1 b1eQi / RT P q
where Qi is the heat of adsorption which is a function of qi. If there are Ni types of surface
sites, each can be expressed as Ni=aexp(-Q/Q0) (a and Q0 are constants), corresponding to a
fractional coverage qi, i qi Ni 0 [b1eQ / RT P / (1 b1eQ / RT P)] aeQ/Q0 dQ
the overall coverage q
iN
i 0

ae 0 dQ
Q/Q

the solution for this integration expression at small q is:

lnq=(RT/Q0)lnP+constant, or
as is the Freundlich equation normally written, q c1 p1 / C where c1=constant, 1/c2=RT/Q0
2

Freundlich isotherm fits, not all, but many adsorption systems.

34
Catalysis & Catalysts

Adsorption On Solid Surface

BET (Brunauer-Emmett-Teller) isotherm
Many physical adsorption isotherms were found, such as the types II and III, that the
adsorption does not complete the first layer (monolayer) before it continues to stack
on the subsequent layer (thus the S-shape of types II and III isotherms)
Basic assumptions
the same assumptions as that of Langmuir but allow multi-layer adsorption
the heat of ads. of additional layer equals to the latent heat of condensation
based on the rate of adsorption=the rate of desorption for each layer of ads.
the following BET equation was derived
P / P0 1 c -1
( P / P0 )
V ( 1 - P / P0 ) cVm cVm
Where P - equilibrium pressure
P0 - saturate vapour pressure of the adsorbed gas at the temperature
P/P0 is called relative pressure
V - volume of adsorbed gas per kg adsorbent
Vm -volume of monolayer adsorbed gas per kg adsorbent
c - constant associated with adsorption heat and condensation heat
Note: for many adsorption systems c=exp[(H1-HL)/RT], where H1 is adsorption heat of 1st layer &
HL is liquefaction heat, so that the adsorption heat can be determined from constant c.
35
Catalysis & Catalysts

Adsorption On Solid Surface

Comment on the BET isotherm
BET equation fits reasonably well all known adsorption isotherms observed so far
(types I to V) for various types of solid, although there is fundamental defect in the
theory because of the assumptions made (no interaction between adsorbed
molecules, surface homogeneity and liquefaction heat for all subsequent layers
being equal).
BET isotherm, as well as all other isotherms, gives accurate account of adsorption
isotherm only within restricted pressure range. At very low (P/P0<0.05) and high
relative pressure (P/P0>0.35) it becomes less applicable.
The most significant contribution of BET isotherm to the surface science is that the
theory provided the first applicable means of accurate determination of the surface
area of a solid (since in 1945).
Many new development in relation to the theory of adsorption isotherm, most of them
are accurate for a specific system under specific conditions.

36
Catalysis & Catalysts

Adsorption On Solid Surface

Use of BET isotherm to determine the surface area of a solid
At low relative pressure P/P0 = 0.05~0.35 it is found that
P / P0
P / P0 1 c -1 V (1- P / P0 )
( P / P0 ) ( P / P0 )
V ( 1 - P / P0 ) cVm cVm
Y = a +b X P/P0

The principle of surface area determination by BET method:

P / P0
A plot of against P/P0 will yield a straight line with slope of equal to (c-1)/(cVm)
V (1- P / P0 )
and intersect 1/(cVm).
For a given adsorption system, c and Vm are constant values, the surface area of a solid
material can be determined by measuring the amount of a particular gas adsorbed on the
surface with known molecular cross-section area Am,
V Vm - volume of monolayer adsorbed gas molecules calculated from the plot, L
As Am N m Am m 6.022 1023 VT,P - molar volume of the adsorbed gas, L/mol
VT , P
Am - cross-section area of a single gas molecule, m2

* In practice, measurement of BET surface area of a solid is carried out by N2 physisorption

at liquid N2 temperature; for N2, Am = 16.2 x 10-20 m2

37
Catalysis & Catalysts

Adsorption On Solid Surface

Summary of adsorption isotherms

Name Isotherm equation Application Note

Cs BP Chemisorption and Useful in analysis of

Langmuir q 0
C 1 B0 P physisorption reaction mechanism

Temkin q =c1ln(c2P) Chemisorption Chemisorption

Easy to fit adsorption

Freundlich q c1 p1/ C2 Chemisorption and
data
physisorption

P / P0 1 c -1
BET ( P / P0 ) Multilayer physisorption Useful in surface area
V ( 1 - P / P0 ) cVm cVm determination

38
Catalysis & Catalysts

Mechanism of Surface Catalysed Reaction

Langmuir-Hinshelwood mechanism
A B
This mechanism deals with the surface-catalysed reaction in which + " P
that 2 or more reactants adsorb on surface without dissociation

A(g) + B(g) D A(ads) + B(ads) " P (the desorption of P is not r.d.s.)

The rate of reaction ri=k[A][B]=kqAqB B0 ,A PA

q
1 B0 ,A PA B0 ,B PB
A

From Langmuir adsorption isotherm (the case III) we know B0 ,B PB

q B
We then have 1 B0 ,A PA B0 ,B PB
B0 ,A PA B0 ,B PB kB0 ,A B0 ,B PA PB
ri k



1 B0 ,A PA B0 ,B PB 1 B0 ,A PA B0 ,B PB 1 B0 ,A PA B0 ,B PB
When both A & B are weakly adsorbed (B0,APA<<1, B0,BPB<<1),
ri kB0 ,A B0 ,B PA PB k' PA PB 2nd order reaction
When A is strongly adsorbed (B0,APA>>1) & B weakly adsorbed (B0,BPB<<1 <<B0,APA)
kB0 ,A B0 ,B PA PB
ri kB0 ,B PB k' ' PB 1st order w.r.t. B
B0 ,A PA
39
Catalysis & Catalysts

Mechanism of Surface Catalysed Reaction

B
Eley-Rideal mechanism
A
This mechanism deals with the surface-catalysed reaction in which " P
that one reactant, A, adsorb on surface without dissociation and
other reactant, B, approaching from gas to react with A
+ B(g)
A(g) D A(ads) P (the desorption of P is not r.d.s.)

The rate of reaction ri=k[A][B]=kqAPB

B0 ,A PA
From Langmuir adsorption isotherm (the case I) we know qA
1 B0 ,A PA
B P kB P P
We then have ri k 0 ,A A PB 0 ,A A B
1 B0 ,A PA 1 B0 ,A PA

When both A is weakly adsorbed or the partial pressure of A is very low (B0,APA<<1),
ri kB0 ,A PA PB k' PA PB 2nd order reaction
When A is strongly adsorbed or the partial pressure of A is very high (B0,APA>>1)
kB0 ,A PA PB
ri kPB 1st order w.r.t. B
B0 ,A PA
40
Catalysis & Catalysts

Mechanism of Surface Catalysed Reaction

Mechanism of surface-catalysed reaction with dissociative adsorption
The mechanism of the surface-catalysed reaction in which one
reactant, AD, dissociatively adsorbed on one surface site B
+ B(g) A B
AD(g) D A(ads) + D(ads) P " P
(the des. of P is not r.d.s.)

The rate of reaction ri=k[A][B]=kqADPB

q AD
(B0 ,AD PAD
1/ 2

From Langmuir adsorption isotherm (the case I) we know

1 (B0 ,AD PAD
1/ 2

We then have ri k
(B0 ,AD PAD
1/ 2

P
k (B0 ,AD PAD PB
1/ 2

1 (B0 ,AD PAD 1 (B0 ,AD PAD

1/ 2 B 1/ 2

When both AD is weakly adsorbed or the partial pressure of AD is very low (B0,ADPAD<<1),
ri k (B0,AD PAD PB k' PAD
1/ 2 1/ 2
PB The reaction orders, 0.5 w.r.t. AD and 1 w.r.t. B
When A is strongly adsorbed or the partial pressure of A is very high (B0,APA>>1)
k (B0 ,AD PAD PB
1/ 2

ri kPB 1st order w.r.t. B

(B0,AD PAD
1/ 2
41
Catalysis & Catalysts

Mechanism of Surface Catalysed Reaction

Mechanisms of surface-catalysed rxns involving dissociative adsorption
In a similar way one can derive mechanisms of other surface-catalysed reactions,
in which
dissociatively adsorbed one reactant, AD, (on one surface site) reacts with
another associatively adsorbed reactant B on a separate surface site
dissociatively adsorbed one reactant, AD, (on one surface site) reacts with
another dissociatively adsorbed reactant BC on a separate site

The use of these mechanism equations

Determining which mechanism applies by fitting experimental data to each.
Helping in analysing complex reaction network
Providing a guideline for catalyst development (formulation, structure,).
Designing / running experiments under extreme conditions for a better control

42
Catalysis & Catalysts

Solids and Solid Surface

Bulk and surface
The composition & structure of a solid in bulk and on surface
can differ due to
Surface contamination
Bombardment by foreign molecules when exposed to an environment
Surface enrichment
Some elements or compounds tend to be enriched (driving by thermodynamic
properties of the bulk and surface component) on surface than in bulk
Deliberately made different in order for solid to have specific properties
Coating (conductivity, hardness, corrosion-resistant etc)
Doping the surface of solid with specific active components in order perform certain
function such as catalysis

To processes that occur on surfaces, such as corrosion, solid sensors and

catalysts, the composition and structure of (usually number of layers of)
surface are of critical importance
43
Catalysis & Catalysts

Solids and Solid Surface

Morphology of a solid and its surface
A solid, so as its surface, can be well-structured crystalline (e.g. diamond C,
carbon nano-tubes, NaCl, sugar etc) or amorphous (non-crystallised, e.g.
glass)
Mixture of different crystalline of the same substance can co-exist on
surface (e.g. monoclinic, tetragonal, cubic ZrO2)
Well-structured crystalline and amorphous can co-exist on surface
Both well-structured crystalline and amorphous are capable of being used
adsorbent and/or catalyst

44
Catalysis & Catalysts

Solids and Solid Surface

Defects and dislocation on surface crystalline structure
A perfect crystal can be made in a controlled way
Surface defects
Terrace Step
terrace
step
kink
adatom / vacancy
Dislocation
screw dislocation

Defects and dislocation can be desirable for certain catalytic reactions

as these may provide the required surface geometry for molecules to be
adsorbed, beside the fact that these sites are generally highly energised.

45
Catalysis & Catalysts

Pores of Porous Solids

Pore sizes
micro pores dp <20-50 nm
meso-pores 20nm <dp<200nm
macro pores dp >200 nm
Pores can be uniform (e.g. polymers) or non-uniform (most metal oxides)
Pore size distribution
Typical curves to characterise pore size:
Cumulative curve
Frequency curve
wt dw
Uniform size distribution (a) & dd
Dwt a
non-uniform size distribution (b) b a b

Dd d d
Cumulative curve Frequency curve
46
Complex Reactions

Chain Reactions - Process

Many reactions proceed via chain reaction
polymerisation
explosion

Elementary reaction steps in chain reactions

1. Initiation step - creation of chain carriers (radicals, ions, neutrons etc, which are capable of
propagating a chain) by vigorous collisions, photon absorption
E
R R (the dot here signifies the radical carrying unpaired electron)
2. Propagation step - attacking reactant molecules to generate new chain carriers
R + M R + M
3. Termination step - two chain carriers combining resulting in the end of chain growth
R + M R-M
There are also other reactions occur during chain reaction:
Retardation step - chain carriers attacking product molecules breaking them to reactant
R + R-M R + M(leading to net reducing of the product formation rate)
Inhibition step - chain carriers being destroyed by reacting with wall or foreign matter
R + W R-W (leading to net reducing of the number of chain carriers)
47
Complex Reactions

Chain Reactions - Rate Law

Rate law of chain reaction
d [HBr] k[H 2 ][Br2 ]3/2
Example: overall reaction H2(g) + Br2(g) 2HBr(g) observed:
dt [Br2 ] k' [HBr]
elem step rate law
a. Initiation: Br2 2Br ra=ka[Br2]
b. Propagation: Br + H2 HBr + H rb=kb[Br][H2]
H + Br2 HBr + Br rb=kb[H][Br2]
c. Termination: Br + Br Br2 rc=kc[Br][Br]=kc[Br]2
H + H H2 (practically less important therefore neglected)
H + Br HBr (practically less important therefore neglected)
d. Retardn (obsvd.) H + HBr H2 + Br rd=kd[H][HBr]

HBr net rate: rHBr= rb+ rb- rd or d[HBr]/dt=kb[Br][H2]+kb[H][Br2]-kd[H][HBr]

Apply s.s.a. rH= rb- rb- rd or d[H]/dt=kb[Br][H2]- kb[H][Br2]-kd[H][HBr]=0
rBr= 2ra-rb+rb-2rc +rd or d[Br]/dt=2ka[Br2]-kb[Br][H2]+kb[H][Br2]-2 kc[Br]2 +kd[H][HBr]=0

d [HBr] 2kb (k a / kc [H 2 ][Br2 ]3/2

1/2
solve the above eqns we have
dt [Br2 ] (k d / k'b [HBr]
48
Complex Reactions

Chain Reactions - Polymerisation

Monomer - the individual molecule unit in a polymer
Type I polymerisation - Chain polymerisation
An activated monomer attacks another monomer, links to it, then likes another
monomer, so on, leading the chain growth eventually to polymer.
initiator chain-carrier rate law is the yield of Ix to xR
Initiation: Ix xR (usually r.d.s.) ri=ki[I] d [M ]
R + M M1 (fast) x ki [I]
dt
Propagation: M + M1 (MM1) M2 (fast)
M + M2 (MM2) M3 (fast)

M + Mn-1 (MMn-1) Mn rp=kp[M][M] (ri is the r.d.s.)
Termination: Mn + Mm (MnMm) Mm+n rt=kt[M]2
1/ 2
d [M] x ki [I]
Apply s.s.a. to [M] formed x ri - 2rp x ki [I]-2kt [M]2 0 [M]
dt 2 k t
The rate of propagation 1/ 2
d [M] d [M] x ki
or the rate of M consumption -rp -k p [M][M ] i.e. -k p [I]1/2[M]
or the rate of chain growth dt dt 2k t
49
Complex Reactions

Chain Reactions - Polymerisation

Type II polymerisation - Stepwise polymerisation
A specific section of molecule A reacts with a specific section of molecule B forming chain
(a-A-a) + (b-B-b) {a -A-(ab)-B-b}
H2N(CH2)6NH2 + HOOC(CH2)4COOH H2N(CH2)6NHOC(CH2)4COOH + H2O (1)
H-HN(CH2)6NHOC(CH2)4CO-OH
H-[HN(CH2)6NHOC(CH2)4CO]n-OH (n)
Note: If a small molecule is dropped as a result of reaction, like a H2O dropped in rxn (1), this type of
reaction is called condensation reaction. Protein molecules are formed in this way.
The rate law for the overall reaction of this type is the same as its elementary step
involving one H- containing unit & one -OH containing unit, which is the 2nd order

d [A] [A]0
-k[A][-OH] -k[A] 2 or [A]
dt 1 kt[A]0
the conversion of B (-OH containing substance) at time t is
[A]0 - [A] kt[A]0
XB
[A]0 1 kt[A]0
50
Complex Reactions

Chain Reactions - Explosion

Type I Explosion: Chain-branching explosion
Chain-branching - During propagation step of a chain reaction one attack by a
chain carrier can produce more than one new chain carriers
Chain-branching explosion
When chain-branching occurs the number carriers increases exponentially
the rate of reaction may cascade into explosion
Example: 2H2(g) + O2(g) 2H2O(g)

Initiation: H2 + O2 O2H + H

Propagation: H2 + O2H OH + H2O (non-branching)

H2 + OH H + H2O (non-branching)

O2 + H O + OH (branching) Lead to explosion

O + H2 OH + H (branching)

51
Complex Reactions

Explosion Reactions
Type II Explosion: Thermal explosion
A rapid increase of the rate of exothermic reaction with temperature
Strictly speaking thermal explosion is not caused by multiple production of chain carriers
Must be exothermic reaction
Must be in a confined space and within short time
DH T r DH T r DH
A combination of chain-branching reaction with heat accumulation can occur
simultaneously

52
Complex Reactions

Photochemical Reactions
Photochemical reaction
The reaction that is initiated by the absorption of light (photons)
Characterisation of photon absorption - quantum yield
A reactant molecule after absorbing a photon becomes excited. The excitation may lead
to product formation or may be lost (e.g. in form of heat emission)
The number of specific primary products (e.g. a radical, photon-excited molecule, or an ion)
formed by absorption of each photon, is called primary quantum yield,
The number of reactant molecules that react as a result of each photon absorbed is call
overall quantum yield, F
E.g. HI + hv H + I primary quantum yield =2 (one H and one I)
H + HI H2 + I
2I I2 overall quantum yield F =2 (two HI molecules reacted)

Note: Many chain reactions are initiated by photochemical reaction. Because of chain reaction
overall quantum yield can be very large, e.g. F = 104

The quantum yield of a photochemical reaction depends on the wavelength of light used
53
Complex Reactions

Photochemical Reactions
Wave-length selectivity of photochemical reaction
A light with a specific wave length may only excite a specific type of molecule
Quantum yield of a photochemical rxn may vary with light (wave-length) used
Isotope separation (photochemical reaction Application)
Different isotope species - different mass - different frequencies required to match
their vibration-rotational energys
508 nm light
e.g. I36Cl + I37Cl I36Cl + I37Cl* (only 37Cl molecules are excited)
C6H5Br + I37Cl* C6H537Cl + IBr
Photosensitisation (photochemical reaction Application)
Reactant molecule A may not be activated in a photochemical reaction because it
does not absorb light, but A may be activated by the presence of another molecule
B which can be excited by absorbing light, then transfer some of its energy to A.
254 nm light
e.g. Hg + H2 Hg* + H2 (Hg is, but H2 is not excited by 254nm light)
Hg* + H2 Hg + 2H* & Hg* + H2 HgH + H*
CO H2
H* HCO HCHO + H*
2HCO HCHO + CO
54