Chapter 6

Complex Reaction Mechanism

Topic Outcomes
Week

Topic

12-14 Complex reaction

mechanisms
Catalysis

Topic Outcomes
It is expected that students are able
to:
Discuss the radical chain reaction

Homogeneous
and Describe
the
catalyst
reaction
heterogeneous catalysis
including enzyme catalysis and
homogeneous and heterogeneous
Adsorption and desorption
catalytic process
kinetic isotherm
Analyze the adsorption and desorption
Radical chain reaction
kinetic isotherm.

Scope of Lecture
Catalysis
Homogeneous & heterogeneous catalysis

Catalysis

Introduction
Increasing T usually increases the rate of reaction,
k.
Another way to speeding up a reaction is by the use
of a catalyst.

A catalyst - a substance that speeds up the rate of the

reaction without being consumed in the overall
reaction.

Rate
Consider the following 2 reactions
A+BC
Rate constant k

A+BC
Rate constant kcat
Rate with catalyst > Rate without catalyst

Effectiveness of Catalyst
Consider the reaction
H2O2

H2O

Catalase

1
H2O
2

Catalyst

Velocity (d[H2O2]/dt)
(M/sec)

Ea (kJ/mole)

None

108

71

HBr

104

50

Fe2+/Fe3+

103

42

Catalase (enzyme)

107

Reaction velocity accelerates by a factor of 1015

Effectiveness of Catalyst
NH2 C O H2O

CO 2 NH2

Urease

Catalyst

d[Urea]/dt

Ea (kJ/mole)

None

No reaction

H3O+

108

100

Urease

107

Again, an acceleration of of 1015

Concept
Catalysts work by changing the activation energy for a
reaction, i.e., the minimum energy needed for the reaction to
occur

Transition state

Energy

Uncatalyzed
reaction
2H2O +
+
2Br + 2H

Ea

Reactants

H2O2 + 2H2O + Br2

Catalyst
reaction
2O +
E 2H
+

Products
Reaction pathway

O2+ 2H

Activation Energy
The energy required to overcome the reaction barrier (Ea or G).
The Ea determines how fast a reaction occurs.
Higher Activation barrier, the slower the reaction rate.
Lower the Activation barrier, the faster the reaction.

Activation Energy
Catalyst lowers the activation energy for both forward and
reverse reactions.

Activation Energy

This means, the catalyst changes the reaction path by lowering

its activation energy and consequently the catalyst increases
the rate of reaction.

Example: Function of a Catalyst

In the case above Ea is lowered from 71 to 8 kJ/mole, However, for the
reaction,
k2

A C k2 B C
The equilibrium constant is

K eq

k2
B C B

k2 A C A

Thus, the position of the equilibrium is not altered by the presence of C.

Homogeneous & Heterogeneous

Catalysis

Types of Catalyst
The type of catalyst depends on the phase of the
catalyst and the reacting species.

Homogeneous

Heterogeneous

Enzyme

Homogeneous Catalysis
The catalyst and the reactants are in the same phase
E.g. Oxidation of SO2 (g) to SO3 (g)
2 SO2(g) + O2(g) 2 SO3 (g)

SLOW

Presence of catalyst NO(g) with the same phase as the

reactants,
NO (g) + O2 (g) NO2 (g)
NO2 (g) + SO2 (g) SO3 (g) + NO (g)

FAST

Example: Homogenous
SO3 (g) is a potent acid rain gas
H2O (l) + SO3 (g) H2SO4 (aq)
Note: the rate of NO2(g) oxidizing SO2(g) to SO3(g)
is faster than the direct oxidation.
NOx(g) are produced from burning fossil fuels such as
gasoline, coal, oil.

Heterogeneous Catalysis
Involves more than 1 phase (catalyst & the reactants are in
different phases
Usually catalyst is a solid & the reactants & products are
in liquid / gaseous form.

Pt on
Al2 O3 x H2 O

+ 3H2

Advantageous: Simple and complete separation of fluid

product mixture from the solid catalyst; reusable.

Example: Heterogeneous
The hydrogenation of ethene (C2H4(g)) to ethane
C2H4(g) + H2(g) C2H6(g)
Reaction is energetically favourable
rxnH = 136.98 kJ/mole of ethane

With a finely divided metal such as Ni (s), Pt (s), or Pd (s), the

reaction goes very quickly .

Example: Heterogeneous
3H2 CO

CH4 H2O

Ni Al2O3

G (500 K) = -94.4 kJ/mole, Keq~ 1.2 x 1010 but in the absence of a

catalyst, the rate is very slow.

Mechanism of
3H2 + CO on Ni

Thus, heterogeneous or surface catalysis involves ADSORPTION

of reactants on active sites.

Catalyst Properties
Catalytic reaction occurs at the fluid-solid interface.

Large interfacial area can be helpful or even essential in

attaining a significant reaction rate.

This area is provided by a porous structure.

The solid contains many fine pores, and the surface of
these pores supplies the area needed for the high rate
of reaction.

Catalyst Types
Molecular sieves

Porous

Pores with large area

Small pores that admit only small

molecules but prevent large ones
form entering

Nickel, platinum-on-alumina, iron

Clays, zeolite

Catalyst Types
Supported

Monolithic

Porous or non-porous
Resist to pressure drop
& heat removal

Consists
active
material dispersed
over a less active
substance.

Platinum-on-alumina,
vanadium pentoxide
on silica.

Unsupported

Platinum

Pure
material
(active ingredients)

Platinum, palladium

Deactivation
Catalysts do not maintain their activities at the same levels for indefinite
periods.
The activity of catalyst can decreases by factor of

Poisoning: fouling of
the catalyst

Coking: deposit of carbonaceous material

Aging: surface change,

deposit on structure

Classification of Catalysts
Several classes of reactions and the catalysts used in each class

Alkylation &
dealkylation

Hydrogenation &
dehydrogenation

Isomerization

Oxidation

Hydration &
dehydration

Halogenation &
dehalogenation

Representative Reactions &

Catalysts
Reaction

Catalyst

1. Halogenation-dehalogenation

CuCl2, AgCl, Pd

2. Hydration-dehydration

Al2O3, MgO

3. Alkylation-dealkylation

AlCl3, Pd

4. Hydrogenation-dehydrogenation Co, Pt, Cr2O3, Ni

5. Oxidation

Cu, Ag, Ni, V2O5

6. Isomerization

AICl3, Pt/ Al2O3, Zeolites

Catalytic Reaction by Solid Surface

Adsorption takes place when reactant and attached to
catalyst surface concentrate on gas phase reaction
Physical adsorption
Similar to condensation
Exothermic
T arises lower van der Waals forces between gas
molecule and surface

Chemisorption
Gas molecule absorbed to the surface by valence
forces of same type in bonded atom in molecule.

Adsorption on Active Sites

Adsorption: the binding of molecules on a surface.
Adsorption on the surface occurs on active sites
Places where reacting molecules are adsorbed & physically
bond to the solids/metal surface

4 Main Steps in the Process

Molecules approach the surface

H2(g) & C2H4(g) adsorb on the surface

Hydrogen
Carbon
Active site

H2 dissociates to form H(g) on the Product desorbs from the surface &
diffuses back to the gas phase
surface.
Adsorbed H atoms migrate to the
adsorbed C2H4 & react to form the
product (C2H6) on the surface.

Enzyme Catalysis
Enzymes - proteins (MW > 10000 g/mol)
High degree of specificity (i.e., they will react with
one substance primarily)
Living cell > 3000 different enzymes
Typically, they are ~ 10-100 nm diameter and are
sometimes immobilized in membranes.

The Lock and Key Hypothesis

Enzymes are large, usually floppy molecules.

Being proteins,
configuration

they

are

folded

into

fixed

According to Fischer, active site is rigid, the

substrates molecular structure exactly fits the
lock (hence, the key).

Lock and Key

Reaction Rate
E = enzyme; S = substrate; P = product
E + S ES
ES E + P
Rate = k [ES]
The reaction rate depends
concentration of the substrate.

directly

on

the

Reaction Step

Michaelis-Menten Mechanism
Enzyme kinetics
k1

E S k1 ES k2 E P

The formation of the product depends directly on the enzymesubstrate [ES]

The net rate of formation of [ES],

The intermediate

dES
k1E S o k1ES k2 ES
dt

Michaelis-Menten Mechanism
Steady state approximation, d[ES]/dt = 0

dES
0
dt

k1E S o k1ES k2 ES

ES k1E S o
k1 k2

Let
[E]o = [E] + [ES]

[E] = [E]o [ES]

Initial enzyme conc. Free enzyme conc. Complex conc.

Michaelis-Menten Mechanism
ES

k1E o S o
k1 k2 k1 S o

Substituting into the rate law R0=vp.

vp k2 ES

k1E o S o
k E S
2 o o
So K M
k1 k2 k1 S o

vp k2

Michaelis-Menten Mechanism
The Michaelis constant is defined as

k2 k1
KM
k1
KM is also known as composite constant
The rate constant for product formation, k2, is the turnover
number for the catalyst.

Ratio of k2 / KM indication of catalytic efficiency.

The Maximum Velocity

lim vp k2 E o vmax
S o

vmax
vmax/2
Rate

As [S]o gets very large.

KM

[S]

Note: Vmax is the maximum rate for the reaction. The limiting value
of the reaction rate high initial substrate concentrations.

Lineweaver-Burk Equation
Plot the inverse of the reaction rate vs. the inverse of the initial
substrate concentration.

Km 1
1
1

R 0 R max R max S 0

1/R0

Slope = KM/Rmax
1/Rmax
1/[S]0

Example 1
Determine the Michaelis-Mentan parameters Vmax and Km for the reaction
k1

Urea urease k2 urea urease * k3 2NH3 CO 2 urease

H2O

The rate of reaction is given as a function of urea concentrations in the

following table:
Curea(kmol/m3)

0.2

0.02

0.01

0.005

0002

rurea (kmol/m3.s)

1.08

0.55

0.38

0.2

0.09

Scope of Lecture

Adsorption & desorption kinetic isotherm

Radical chain reaction

Adsorption & Desorption Kinetic

Isotherm

Adsorption
Adsorption: interaction between gas & solid at the interface
Adsorbent: solid on whose surface adsorption occurs
E.g., silica gel, activated carbon, metals, metal oxides.
Adsorbate: the adsorbed gas. E.g., He, N2, H2, CO2, CH4, NH3,
SO2.
Physisorption:
(physical)
adsorption
intermolecular van der Waals forces.

due

to

weak

Chemisorption: (chemical) adsorption due to strong chemical

bonds.

Physisorption
Important step in reactions adsorption of 1 or more
reactants to the solid surface.
Particles adsorb to the surface without changing their internal
bonding.
Dynamic equilibrium exist btw the free and surface-adsorbed
species(adsorbate)
Information regarding the kinetic of surface adsorption &
desorption
Studying the equilibrium as a function of reactants P over
the surface catalyst.

Fractional Coverage,
A critical parameter in evaluating surface adsorption Fractional
coverage,
Gas phase

Numberof adsorptionsites occupied

Total numberof adsorption
sites
Volume of adsorbate
at specific P

Vadsorbed
Vm
Volume of adsorbate in the high-P
limit corresponding to monolayer
coverage

Adsorbed to 1
of these sites

Adsorption Isotherm
Variation of with P at fixed T is called adsorption isotherm.
Can be described using Langmuir model.
Reagent

Unoccupied
adsorption site

Rate const. adsorption

Occupied
adsorption site

ka

R g M surface kd RM surface
Rate const. desorption

Assumptions: monolayer
uncooperative process.

coverage,

uniform

surface,

Change in Fractional Coverage

The change in with time is equal to zero at equilibrium, thus yields
the Langmuir isotherm
d

dt

abs

dt

des

Number of vacant sites

d
0 kaPN1 kdP
dt
Total no. of adsorption sites

Fraction of sites that are open

kaPN kdN kaPN

Equilibrium
const. = ka/kd

kaP
kaPN kdN

KP
KP 1

Langmuir isotherms equation

Langmuir Isotherms
Rate
constant
for
desorption
increases relative to adsorption

Higher P must be employed to reach

= 1 for kd > ka

If ka > kd (kd is very small)

becomes independent of P.

Chemisorption
Adsorption is commonly accompanied
by
dissociation
of
adsorbatechemisorption

ka

R 2 g 2M surface kd 2RM surface

Kinetic analysis of the mechanism
12

KP

KP 1 2 1

Weaker P dependence compared to

physisorption (Nondissociative)

Le Chteliers Principle

Adsorption is an exothermic
process
Increase in T, the amount
adsorbed at given P decreases

Example 2
The following data were obtained for the adsorption of Kr on charcoal at
193.5 K. Using the Langmuir model, construct the adsorption isotherm,
and determine Vm and the equilibrium constant for adsorption/desorption.
Vads (cm3g1)

P (Torr)

5.98

2.45

7.76

3.5

10.1

5.2

12.35

7.2

16.45

11.2

18.05

12.8

19.72

14.6

21.1

16.1

Example 3
The adsorption of ethyl chloride on a sample of charcoal at 0C
measured at several different pressures is as follows:
PC2H5Cl(Torr)

Vads (mL)

20

3.0

50

3.8

100

4.3

200

4.7

300

4.8

Using the Langmuir isotherm, determine the fractional coverage,

at each pressure and Vm.

Radical Chain Reaction

Radical Chain Reactions

Radicals are extremely reactive chemical species
with an unpaired electron.

E.g. Mechanisms of thermal decomposition of

ethane to ethylene,
C 2H6 g C 2H4 g H2

Thermal Decomposition of Ethane

Initiation step: creation of 2 methyl radicals

Initiation: C 2H6 k1 2CH3

Indicate that the

species
is
radical

Propagation steps: radical reacts with another species to produce

radical & non-radical products

Propagation : CH3 C 2H6 k2 2CH4 C 2H5

C 2H5 k2 C 2H4 H
H C 2H6 k4 C 2H5 H2
Termination step: radicals from propagation steps recombine to
produce non-radical product

Termination : H C 2H5 k5 C 2H6

Rate Expression of Ethane Decomposition

To derive rate law, begin with the differential rate expression for
disappearance of ethane

d C 2H6
k1 C 2H6 k2 C 2H6 CH3 k4 C 2H6 H k5 C 2H5 H
dt

CH3 is a reactive intermediate apply steady state approx.

d CH3
0 2k1 C 2H6 k2 C 2H6 CH3
dt

CH3 2k1
k2

Steady State Approximation

Apply steady state approx. to the differential rate expression for the
C2H5 & H

d C 2H5
0 k2 CH3 C 2H6 k3 C 2H5 k4 C 2H6 H k5 C 2H5 H
dt
dH
0 k3 C 2H5 k4 C 2H6 H k5 C 2H5 H
dt
Add

0 2k1 C 2H6 2k5 C 2H5 H

k1 C 2H6
k5 C 2H5

Expression for [C2H5]

H

k1 C 2H6
k5 C 2H5

dH
0 k3 C 2H5 k4 C 2H6 H k5 C 2H5 H
dt

Substitute

k1 C 2H6
k C H
k5 C 2H5 1 2 6
k5 C 2H5
k5 C 2H5

0 k3 C 2H5 k4 C 2H6

k k C H
0 k3 C 2H5 4 1 2 6 k1 C 2H6
k5 C 2H5
2

k k C H
k
0 C 2H5 4 1 2 6 1 C 2H6 C 2H5
k5k3
k3
2

C 2H5 k1k4
k3k5

12

C 2H6

Order of Reaction
Solving quadratic expression

H k1 C 2H6 k1 k3k5
k5 C 2H5 k5 k1k4

12

kk
1 3
k4k5

12

The differential expression for the disappearance of ethane becomes

kk k
d C 2H6

k2 CH3 1 3 4

dt
k5

12

C H
2 6

CH3 2k1
k2

d C 2H6 k1k3k4

dt
k5

12

C 2H6

Equation predicts that the decay of ethane should be 1st order with
respect to ethane.

Example 4
Consider the following reaction of methane with molecular chlorine:
CH4(g) + Cl2(g) (g) CH3Cl(g) + HCl (g)
Experimental studies have shown that the rate law for this reaction is onehalf order with respect to Cl2. Is the following mechanism consistent
with this behavior?

Cl2 k1 2Cl
Cl CH4 k2 HCl CH3
CH3 Cl2 k3 CH3Cl Cl
Cl Cl k4 Cl2