2 main mechanisms

Langmuir-Hinshelwood
Reaction between antara adsorbates
Eley-Rideal
Reaction between adsorbate and incoming
molecule
LH model for unimolecular reaction
A (g) A (ads) B
Dekomposisi terjadi secara merata di seluruh permukaan.
Produk yang dihasilkan mempunyai ikatan yang lemah
dan mudah terdesorpsi.
Tahap menentukan kecepatan tergantung pada tahap
dekomposisi permukaan.
Rate = k pA
A B
A
fast RDS
For Langmuir adsorption khet
fast

kKp
Rate
1 Kp
 LH model for unimolecular reaction
Two kasus
Tekanan rendah/
Ikatan lemah
Kp<<1
Rate kKp High pressures/

Rate linearly Strong binding

dependent on gas Kp>>1
pressure
Rate k
First order reaction
Rate independent
of gas pressure
Cakupan Zero order reaction
permukaan sgt
rendah Cakupan
luas,hampir seluruh
permukaan
tertutupi
 LH model for bimolecular reaction
Langmuir-Hinshelwood reaction with surface reaction as rds
yang kecepatannya ditentukan oleh reaksi permukaan.

A (g) A (ads)
B (g) B (ads)
A (ads) B (ads) AB (ads) AB (g)
rds fast

pA B
pB AB
Rate = k A B A
fast RDS fast

khet

Langmuir adsorption of mixed
components
ka
Ag S surface A S surface
kd
ka
Bg S surface B S surface
kd
d A
adsorption rate of A k a p A (1 A B )
dt
d A
desorption rate k d A
dt
d B
adsorption rate of B k a pB (1 A B )
dt
d B
desorption rate k d B
dt
 Langmuir adsorption of mixed
components
At equilibrium
k a A p A S k d A A
ka A S 1 A B
A K A p A S , K A S A B 1
kd A
k a B pB S k d B B
ka B
B K B pB S , K B
kd B
Langmuir adsorption of mixed
components
S K A p A S K B pB S 1
S 1 K A p A K B p B 1
1
S
1 K A p A K B p B
K A pA
A
1 K A p A K B p B
K B pB
B
1 K A p A K B p B
LH model for bimolecular reaction
Rate = k A B

kK A p A K B pB
Rate
1 K A p A K B p B 2
 LH model for bimolecular reaction

Kecepatan terbatas oleh For constant PB

luas permukaan A
Rate limited by
surface concentration of
rate

Rate limited by
surface concentration of B

pA

 Eley-Rideal
bimolecular surface reactions

pA
A
pB AB
B
RDS
An adsorbed molecule may khet
fast
react directly with an
impinging gas molecule by a
collisional mechanism
Molekul yang teradsorb
dapat bereaksi secara
langsung dengan menimpa
molekul gas dari mekanisme
tumburan.
 Eley-Rideal
bimolecular surface reactions
rate = k pB k KApA pB / (1+KApA)

= 1

Note: For constant pA, the

rate is always first order
rate

wrt pB
For constant PB

Low pressure
High pressure
Weak binding pA Strong binding
KApA << 1
KApA >> 1
rate = khet KA pA pB .. first order in A
rate = k pB .. zero order in A

kexp
kexp
 Diagnosis of mechanism
Jika kita mengukur kecepatan reaksi sebagai fungsi dari
cakupan A, kecepatan akan diawali dengan kenaikan
mekanisme keduanya.
Eley-rideal: kecepatan naik sampai permukaan tertutupi
oleh A
LH: fasa kecepatan maksimum dan berakhir pada nol,
ketika permukaan tertutupi oleh A.

B + S B-S
tidak bisa terjadi ketika A memblok seluruh sisi.
 Transition State Model of Catalyst Activity

transition state
#hom Langmuir-Hinshelwood Kinetics
Adsorption of reactants and desorption of products
are very fast. Eads and Edes very small.

Surface Reaction is RDS: Ehet

Ehom #het
potential energy

Eads
reactants Ehet

products
adsorbed reactants Edes

adsorbed products
reaction co-ordinate
 Principle of Sabatier
When different metals are used to catalyse the same reaction, it is generally
observed that the reaction rate can be correlated with the position of the metal in the
periodic table:

A volcano
curve
 Catalyst Preparation
For a catalyst the desired properties are
high and stable activity
high and stable selectivity
controlled surface area and porosity
good resistance to poisons
good resistance to high temperatures and temperature fluctuations.
high mechanical strength
no uncontrollable hazards

Once a catalyst system has been identified, the parameters in the

manufacture of the catalyst are
If the catalyst should be supported or unsupported.
The shape of the catalyst pellets. The shape (cylinders, rings, spheres,
monoliths) influence the void fraction, the flow and diffusion phenomena and
the mechanical strength.
The size of the catalyst pellets. For a given shape the size influences only
the flow and diffusion phenomena, but small pellets are often much easier to
prepare.
Catalyst based on oxides are usually activated by reduction in H 2 in the
reactor.
 Case studies
Ammonia synthesis (Haber-Bosch)
Hydrogenation of CO (Fischer-Tropsch)

http://www.uyseg.org/greener_industry/index.htm
Ammonia synthesis

A: Steam reforming
B: High temperature water-gas shift
C: Low temperature water-gas shift
D: CO2 absorption
E: Methanation
F: Ammonia synthesis
G: NH3 separation.
 Ammonia reactants
Steam reforming
CH4(g) + H2O(g) CO(g) + 3 H2(g)
15-40% NiO/low SiO2/Al2O3 catalyst (760-816C)
products often called synthesis gas or syngas

Water gas shift

CO(g) + H2O(g) CO2(g) + H2(g)
Cr2O3 and Fe2O3 as catalyst
carbon dioxide removed by passing through sodium hydroxide.
CO2(g) + 2 OH-(aq) CO32-(aq) + H2O(l)
Ammonia Synthesis

Fe/K catalyst

exothermic
 Mechanism

1 N2(g) + * N2*
2 N2* + * 2N*
3 N* + H* NH* + *
4 NH* + H* NH2* + *
5 NH2* + H* NH3* + *
6 NH3* NH3(g) + *
7 H2(g) + 2* 2H*
Step 2 is generally rate-limiting. Volcano curve is
therefore apparent with d-block metals as catalysts.
Ru and Os are more active catalysts, but iron is used.
 Hydrogenation of CO
Hydrogenation of CO is thermodynamically favourable; the first example,
methanation catalysed by nickel was reported by Sabatier and Senderens in
1902

CO+3H2CH4+H2O ( G298, -140 kJ/mol)

In their classic 1926 papers Fischer and Tropsch showed that linear alkenes
and alkanes (as well as some oxygenates) are formed at 200300C and
atmospheric pressure over Co or Fe catalysts

nCO+(2n+1)H2CnH2n+2+nH2O

2nCO+(n+1)H2=CnH2n+2+nCO2

Since syngas (CO + H2) is readily available from a variety of fossil fuels,
including coal, the FischerTropsch process became industrially important
for economies which had good supplies of cheap coal but which lacked oil
 Fischer-Tropsch
Iron catalysts give mainly linear alkenes and
oxygenates, while cobalt gives mostly linear
alkanes. Ruthenium, one of the most active
catalysts but one which, owing to its expense is
little used industrially, can give high molecular
weight hydrocarbons; rhodium catalysts make
significant amounts of oxygenates in addition to
hydrocarbons, while nickel gives mainly
methane. Catalyst can be immobilised on
Kieselguhr (diatomaceous silicate earth),
alumina, active carbon, clays and zeolites.
 FT mechanism

adsorption and cleavage of CO and the stepwise hydrogenation of surface

carbide giving methylene and other species

Maitlis, P. M.; Quyoum, R.; Long, H. C.; Turner, M. L. Appl. Catal. A: Ge

neral 1999, 186, 363-374. Towards a Chemical Understanding of the Fischer
-Tropsch Reaction: Alkene Formation
 Other mechanisms?
Boudouard reaction. Important in methanation
(over Nickel).
2CO C + CO2
Some evidence that hydrogenation of adsorbed
carbon leads to formation of hydrocarbons.
Also an important side (undesired) reaction in
some hydrocarbon conversion reactions (coking)