Catalysis

A catalyst,
speeds up a reaction
lowers E
a
by providing an
alternative path for a
thermodynamically viable reaction
only small amounts are required
regenerated during the reaction
often reaction specific
widely employed in industrial &
laboratory syntheses
>$900B USD in 2009 alone
Two Types
Heterogeneous (different
phase)
Homogeneous (same phase)
Number of Collisions
E
a
(uncatalyzed )
Effective
collisions
(uncatalyzed)
Effective
collisions
(catalyzed)
E
a
(catalyzed )
(a)
(b)
N
u
m
b
e
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f

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g
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e
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e
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N
u
m
b
e
r

o
f

c
o
l
l
i
s
i
o
n
s
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Energy Energy
Hydrogenation of Ethene
CH
2
=CH
2
+ H
2
CH
3
CH
3
catalysed by Ni surface
Catalyst is in a different phase
to the reactants
generally solid
eg. Pt
Steps involved
Adsorption & activation of
the reactants
Migration of the adsorbed
reactants on the surface
Reaction of the adsorbed
substances
Escape, or desorption, of
the products
Heterogeneous Catalysis
Adsorption
Two possibilities
Physisorption
van der Waals force holds adsorbate to surface
~20 kJ mol
-1
adsorbate retains its identity
Chemisorption
adsorbate is chemically bonded to the surface
~200 kJ mol
-1
adsorbate may be torn apart
exothermic (G = H - TS)
A
2
Adsorption Energies
Not activated Activated
Langmuir Adsorption Isotherm
Limit to the amount of gas that can adsorb
assumed to be at monolayer coverage
adsorption unaffected by neighbour occupancy
all sites equivalent
At equilibrium, evaporation rate = adsorption
rate
k
d
N = k
a
N(1-)p
where is the fraction of surface covered, p is the gas
pressure and N is the number of sites
the Langmuir Adsorption Isotherm follows,
where K = k
a
/k
d
Kp
Kp
p k k
p k
a d
a
+
=
+
=
1

Rate of Adsorption
Large number of collisions with
surface per time,
10
23
collisions cm
-2
s
-1
at STP
Small number of atoms on an
atomically flat surface,
10
15
atoms cm
-2
Therefore each surface atom is hit
10
8
times per second
Adsorption depends on success of
sticking, S
S = rate of adsorption
rate of collision
Activated process (adsorbate
in potential well)
First order process,
Arrhenius form:
where E
a
is the activation energy
of desorption
Rate of Desorption
RT E
a
Ae k
/
=
Catalytic Adsorption
(1) Very little adsorption,
<< 1
so,
(1-) 1
therefore,
k
d
= k
a
p or = Kp
ie. amount adsorbed gas
pressure
Thus rate gas pressure
(first order)
v = k = kKp
(2) High adsorption,
1
therefore,
k
d
= k
a
(1-)p
or,
ie. fraction of free sites
1/pressure
v = k = k (zero order)
(1 ) =
1
Kp
eg. Hydrogenation of ethene
on Ni catalyst
H
2
weakly adsorbed
Ethene strongly adsorbed
Rate determining step is
the adsorption of H
2
Mechanism
Adsorbed molecule often
held by 2 adjacent sites,
can distort (activate)
towards reaction
Different catalysts host
adsorbates in different
ways,
activation of different
bonds
reaction may be
specific to a certain
catalyst
) (
) (
4 2
2
H C p
H p
rate
H
2
O
2
decomposition in H
2
O
catalysed by MnO
2
Catalytic Converters
Engine CO
(g)
k
1
CO
(g)
+ O
2(g)
CO
2(g)
k
2
, slow, E
a
~80 kJ/mol
Pt/Pd/Rd deposited as thin film onto a high surface area ceramic substrate
Sulfuric Acid Contact Process
Making the sulfur dioxide
Either by burning sulfur in an excess of air
S
(s)
+ O
2(g)
SO
2(g)
or by heating sulfide ores like pyrite in an excess of air
4FeS
(s)
+ 7O
2(g)
2Fe
2
O
3(s)
+ 4SO
2(g)
In either case, an excess of air is used so that the SO
2
produced is already mixed with
oxygen for the next stage
Converting the sulfur dioxide into sulfur trioxide
This is a reversible reaction, and the formation of the SO
3
is exothermic
2SO
2(g)
+ O
2(g)
2SO
3(g)
H = -196 kJ/mol
Converting the sulfur trioxide into sulfuric acid
Can't be done by simply adding water to the SO
3
the reaction is so uncontrollable that it creates a fog of sulfuric acid.
Instead, the SO
3
is first dissolved in concentrated sulfuric acid
H
2
SO
4(l)
+ SO
3(g)
H
2
S
2
O
7(l)
The product is known as fuming sulfuric acid or oleum
This can then be reacted safely with water to produce concentrated sulfuric acid - twice
as much as you originally used to make the fuming sulfuric acid
H
2
S
2
O
7(l)
+ H
2
O
(l)
2H
2
SO
4(l)
2SO
2(g)
+ O
2(g)
2SO
3(g)
The gases actually react with the surface of the catalyst,
temporarily changing it
It is a good example of the ability of transition metals & their
compounds to act as catalysts because of their ability to change
their oxidation state
Sulfur dioxide is oxidised to sulfur trioxide by the
vanadium(V) oxide. In the process, the vanadium(V) oxide is
reduced to vanadium(IV) oxide
SO
2(g)
+ V
2
O
5(s)
SO
3(g)
+ V
2
O
4(s)
Vanadium(IV) oxide is then re-oxidised by the oxygen
2V
2
O
4(s)
+ O
2(g)
2V
2
O
5(s)
This is a good example of the way that a catalyst can be
changed during the course of a reaction. At the end of the
reaction, though, it will be chemically the same as it started
Catalysed by V
2
O
5
Gas Phase Reactions
Example: NO
2
catalysis of SO
2
oxidation prior to
sulfuric acid production
SO
2
+ NO
2
SO
3
+ NO
0.5O
2
+ NO NO
2
overall,
SO
2
+ 0.5O
2
SO
3
Solution Phase Reactions
Example 1. Os(VIII) catalysis of Ce(IV)/As(III)
In acidic solution with excess Ce(IV),
v = k[Os(VIII)][As(III)]
Proposed mechanism,
Os(VIII) + As(III) Os(VI) + As(V) r.d.s.
2Ce(IV) + Os(VI) Os(VIII) + 2Ce(III)
Overall,
2Ce(IV) + As(III) 2Ce(III) + As(V)
Example 2. Fe
2+
catalysis of S
2
O
8
2-
+ 2I
-
2SO
4
2-
+ I
2
In aqueous solution this requires the collision of two anions,
S
2
O
8
2-
+ I
-
SO
4
-
+ SO
4
2-
+ I slow (r.d.s)
SO
4
-
+ I
-
SO
4
2-
+ I fast
2I I
2
fast
has the following rate law,
Small amounts of Fe
2+
or Cu
2+
catalyse the otherwise electrostatically
opposed reaction,
S
2
O
8
2-
+ Fe
2+
SO
4
-
+ SO
4
2-
+ Fe
3+
SO
4
-
+ Fe
2+
SO
4
2-
+ Fe
3+
2Fe
3+
+ 2I
-
2Fe
2+
+ I
2
] ].[ [
] [
2
] [
2
8 2
2

= = I O S
dt
I d
dt
I d

Acid-Base Catalysis
Common
Catalyst is either a Brnsted acid or base
Both an acid & a base must be present
Water often plays a key role (acid or base)
H
3
O
+
abbreviated to H
+
Each acid-base species contributes to k:
k = k
0
+ k
H+
[H
+
] + k
OH-
[OH
-
] + k
HA
[HA] + k
A-
[A
-
]
for a weak acid catalyst, HA
Specific Acid Catalysis
Rate [H
+
] only
k
H+
>> other k
i
s so,
k = k
H+
[H
+
]
or log k = log k
H+
- pH
log k vs pH linear (slope = -1)
Similarly specific base catalysis:
k = k
OH-
[OH
-
]
or log k = log k
OH-
+ log k
w
+ pH
log k vs pH linear (slope = 1)
pH
l
o
g

k
Examples
inversion of sucrose
(B3)
depolymerisation of
diacetone alcohol
hydrolysis of esters
halogenation of
acetone
General Acid-Base Catalysis
Reaction between substrate, S & acid, HA:
HA + S SH
+
+ A
-
k
f
& k
b
SH
+
+ H
2
O products k
2
Rate,
Steady state approximation,
d[SH
+
]
dt
= k
f
[HA][S] k
b
[SH
+
][A

] k
2
[SH
+
] = 0
d[P]
dt
= k
2
[SH
+
]
Rearranging,
Two limiting cases:
(a) k
2
>> k
b
[A
-
]
ie. general acid catalysis
[SH
+
] =
k
f
[HA][S]
k
b
[A

] + k
2
[SH
+
] =
k
f
[HA][S]
k
2
d[P]
dt
[HA]
(b) k
2
<< k
b
[A
-
]:
ie. specific acid catalysis:
[SH
+
] =
k
f
[HA][S]
k
b
[A

]
then,
K =
[H
+
][A

]
[HA]
so,
[SH
+
] =
k
f
[H
+
][S]
k
b
K
d[P]
dt
[H
+
]
Enzyme Catalysis
Enzyme Characteristics
Proteins with mw 10
4
-10
6
Several orders of magnitude more effective than other catalysts,
effective at low [enzyme] under mild conditions:
[enzyme] ~ 10
-8
-10
-10
mol/L compared with [substrate] ~ 10
-6
mol/L
Can be extracted & used under laboratory or industrial conditions
Denature at high T & extreme pH
Enzyme Kinetics
Rate often [enzyme]
at low [substrate], rate [substrate]
Michaelis-Menten mechanism:
E + S ES k
f
& k
b
ES E + products k
2
steady state:
d[ES]
dt
= k
f
[E][S] k
b
[ES] k
2
[ES] = 0
Kinetic Pathway
E
n
e
r
g
y
Progress of reaction
Activation
energy
Activation
energy
S E + S
ES
E + P
P
Progress of reaction
E
n
e
r
g
y
A B
Total enzyme concentration,
[E]
0
= [ES] + [E]
substituting in,
Now reaction rate,
Michaelis constant:
[ES] =
k
f
[E]
0
[S]
k
b
+ k
2
+ k
f
[S]
v = k
2
[ES] =
k
2
k
f
[E]
0
[S]
k
b
+ k
2
+ k
f
[S]
=
k
2
[E]
0
[S]
K
m
+[S]
K
m
=
k
b
+ k
2
k
f
Two limiting cases:
[S] << K
m
more commonly, [S] >> K
m
v
max
= k
2
[E]
0
the limiting maximum rate
so,
v =
k
2
[E]
0
[S]
K
m
v =
v
max
[S]
K
m
+[S]
Rearranging,
linear plot 1/v vs. 1/[S]
Turnover number
k
2
= v
max
/[E]
0
The number of substrate
molecules converted per
active site per unit time.
1
v
=
1
v
max
+
K
m
v
max
[S]
E + I EI
Necessary adjustments,
[E]
0
= [ES] + [E] + [EI]
k
2
<< k
b
, so K
m
= [E][S]/[ES]
thus,
K
I
=
[E][I]
[EI]
[EI] =
[E][I]
K
I
=
K
m
[ES][I]
K
I
[S]
Competitive Inhibition
therefore,
which rearranges to,
or,
[E]
0
=[ES] +
K
m
[ES]
[S]
+
K
m
[ES][I]
K
I
[S]
[ES] =
[S][E]
0
[S] + K
m
1 +
[I]
K
I






then,
v = k
2
[ES] =
k
2
[S][E]
0
[S] + K
m
1+
[I]
K
I






1
v
=
1
v
max
+
1+
[I]
K
I






K
m
v
max
[S]
Noncompetitive Inhibition
ES + I IES
Necessary adjustments,
[E]
0
= [ES] + [E] + [IE] + [IES]
with only ES giving rise to products
K
I
& K
m
as before
Assume K
I
= K
I
*
because the binding sites are
distant
K
I
*
=
[ES][I]
[IES]
so,
or,
[E]
0
=[ES] +
K
m
[ES]
[S]
+
K
m
[ES][I]
K
I
[S]
+
[ES][I]
K
I
=
[ES]
[S]
[S] + K
m
+
K
m
[I]
K
I
+
[S][I]
K
I






=
[ES]
[S]
1 +
[I]
K
I





[S] + K
m
( )
thus,
v = k
2
[ES] =
k
2
[S][E]
0
1+
[I]
K
I






[S] + K
m
( )
1
v
=
1+
[I]
K
I






v
max
+
1+
[I]
K
I






K
m
v
max
[S]
Inhibition?? Plot 1/v vs 1/[S]
1/v
1/v
max
Slope = K
m
/v
max
Noncompetitive
inhibition
Competitive
inhibition
Slope = (K
m
/v
max
).(1+[I]/K
I
)
Application: Biofuel Production
Barnard, Casanueva, Tuffin, & Cowan, 'Extremophiles in biofuel synthesis', Environmental Technology, 31:8, 871 888 (2010)
From 2006 to 2008, total biofuel consumption in the EU increased from 5625
Mtoe (million tons of oil equivalent) to 10064 Mtoe
>90%
Example: Bioethanol Production
http://biofuelsandclimate.wordpress.com/background-info/
Example: Biodiesel Production
Biodiesel is a mixture of methyl esters of long-chain fatty acids
Biodiesel is a better lubricant than petrodiesel, but is currently disadvantaged by higher viscosity,
lower energy content, higher NO
x
emissions, lower engine compatibility, speed & power, $
Full life-cycle analysis must be considered for production to be viable
Production Chemistry
Oil or fat reacts in a transesterification reactions with (m)ethanol in the presence of a strong base catalyst
(KOH, NaOH) to yield biodiesel: (m)ethyl esters and glycerol
The triglyceride may be an edible oil or an inedible oil such as Jatropha oil in which e.g. the Indian government is
investing in huge plantations in wasteland regions
Disadvantage is treatment of alkaline wastewater & removel of glycerol
Alternatively lipase can catalyse the biodiesel production although currently not commercially competitive
Milder conditions (pH, T)
Slower rate
Lower yield
Lipase is currently too expensive
Demirbas, Progress and recent trends in biodiesel fuels', Energy Conversion & Management, 50, 14-34 (2009).
Kumari, Mahapatra, Garlapati & Banerjee, Enzymatic transesterification of Jatropha oil, Biotechnology for Biofuels, 2:1 (2009).