Chemistry 232

Kinetics of Complex
Reactions

The Pre-Equilibrium
Approximation
Examine

the following process

k1

A B
k1

v1 k1 A
v1 k1 B

k2

B C

v2 k2 B
d C
k2 B
dt

Pre-Equilibrium (II)
B

is obviously an intermediate in the

above mechanism.

Could use SSA.

What

if the initial equilibrium is fast?

Step 2 is the rds!

k1
B A A K
k1

Pre-Equilibrium (III)
We

now have a simple expression for the

[B]; hence
d C

k1
k2 B k2 A k ' A
dt
k1

Lindemann-Hinshelwood
Mechanism

An early attempt to explain the kinetics

of complex reactions.
Mechanism
k1

A A A A

k 1

A A 2A

k2

A P

Rate Laws

v1 k1 A

v 1 k 1 A A

v 2 k2 A

The Activated Intermediate

Formation of the product depends

directly on the [A*].
Apply the SSA to the net rate of
formation of the intermediate [A*]

k A

d A
dt

k 1 A A k2 A 0

Is That Your Final Answer?

Substituting and rearranging

d P
k2 k1 A

dt
k2 k 1 A
2

The Apparent Rate Constant

Depends on Pressure

The rate laws for the LindemannHinshelwood Mechanism are pressure

dependent.
High Pressure Case

d P k2 k1 A

dt
k 1
k A
/

Low Pressure Case

d P
2
k1 A
dt
k A
/

The Pressure
Dependence of k

In the Lindemann-Hinshelwoood
Mechanism, the rate constant is
pressure dependent.

1
1
k 1

/
k1 A k1k2
k

Catalysts
So

far, we have considered one way of

speeding up a reaction (i.e. increasing T
usually increases k). Another way is by
the use of a catalyst.

catalyst - a substance that speeds up

the rate of the reaction without being
consumed in the overall reaction.

look at the following two reactions

A+B C

rate constant k

A+B C rate constant with catalyst is kcat

NOTE: RATE WITH CATALYST > RATE

WITHOUT CATALYST

Types of Catalyst
We

will briefly discuss three types of

catalysts. 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 NO (g), the following occurs.

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

FAST

 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
The

catalyst and the reactants are in

different phases

adsorption the binding of molecules on a

surface.

Adsorption

on the surface occurs on

active sites

Places where reacting molecules are adsorbed

and physically bond to the metal surface.

 The

hydrogenation of ethene (C2H4 (g))

to ethane
C2H4 (g) + H2(g) C2H6 (g)

Reaction

rxn

With

is energetically favourable

H = -136.98 kJ/mole of ethane.

a finely divided metal such as Ni

(s), Pt (s), or Pd(s), the reaction goes
very quickly .

There are four main steps in the process

the molecules approach the surface;

H (g) and C H (g) adsorb on the surface;
H dissociates to form H(g) on the surface; the
2

adsorbed H atoms migrate to the adsorbed

C2H4 and react to form the product (C 2H6) on
the surface
the product desorbs from the surface and
diffuses back to the gas phase

Simplified Model for Enzyme

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

Enzyme Catalysis
Enzymes

- proteins (M > 10000 g/mol)

High degree of specificity (i.e., they will
react with one substance and one
substance primarily
Living cell > 3000 different enzymes

The Lock and Key Hypothesis

Enzymes

are large, usually floppy

molecules. Being proteins, they are
folded into fixed configuration.
According to Fischer, active site is rigid,
the substrates molecular structure
exactly fits the lock (hence, the key).

The Lock and Key (II)

The Michaelis-Menten
Mechanism

Enzyme kinetics use the SSA to examine

the kinetics of this mechanism.
k1

k2

E S ES P E
k1

ES the enzyme-substrate complex.

Applying the SSA to the

Mechanism
Note

that the formation of the product

depends directly on the [ES]
What is the net rate of formation of [ES]?

d ES
k1 E S o k 1 ES k2 ES
dt

ES The Intermediate
Apply

the SSA to the equation for

d[ES]/dt = 0

d ES
0
dt
k1 E S o k 1 ES k2 ES
k1 E S o
ES
k 1 k2

Working Out the Details

Let

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

Initial enzyme
concentration

Free enzyme

concentratio
Note that [E] = [E]on[ES]
k

Complex
concentrati
on

E o S o
ES
k 1 k2 k1 S o
1

The Final Equation

Substituting

into the rate law vp.

v p k2 ES
k1 E o S o
v p k2
k 1 k2 k1 S o
k 2 E o S o

S o K M

The Michaelis Constant and the

Turnover Number

The Michaelis Constant is defined as

KM

k2 k 1

k1

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

As [S]o gets very large.

lim v p

S o

k2 E o v max

Note Vmax is the maximum velocity

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.

1
1
KM 1

v o v max v max S o

Chain Reactions
Classifying

steps in a chain reaction.

Initiation
CH

CH

(g) 2 CH3

Propagation Steps
2

+ CH3 C2H5 + CH4

Branching Steps

H O + O 2 OH
2

Chain Reactions (Contd)

Retardation

HBr + H

Step

H2 + Br

Terminations

2 CH CH
3

Inhibition

Steps

CH3CH2CH2CH3

Steps

R + CH
3

RCH3

The H2 + Br2 Reaction

The overall rate for the reaction was

established in 1906 by Bodenstein and Lind

d HBr
k H 2 Br2 2

/
Br2 k HBr
dt
3

The Mechanism
The

mechanism was proposed independently by

Christiansen and Herzfeld and by Michael
Polyani.
Mechanis
Br m2Br

Rate Laws

v 1 k1 Br2
Br H 2 HBr H v 2 k 2 Br H 2
H Br2 HBr Br v 2 k 2 Br2 H

H HBr H 2 Br v 3 k 3 H HBr
2
v 4 k 4 Br
Br Br Br2
2

Using the SSA

Using

the SSA on the rates of formation

of Br and H

3
k

2k 2 1 H 2 Br2 2
k4
d HBr

k
dt
Br2 3 k / HBr
2

Hydrogenation of Ethane
The

Rice-Herzfeld Mechanism
C2

Mechanis
H m2CH
6

C2H 6 CH 3 CH 3CH 2 CH 4

CH 3CH 2 CH 2CH 2 H
CH 3CH 3 H CH 3CH 2 H 2
CH 3CH 2 H C2H 6

Rate Laws for the RiceHerzfeld Mechanism

The

rate laws for the elementary

reactions are as follows.
v 1 k1C2H 6

v 2 k 2 C2H 6 CH 3

v 2 k 2 CH 3CH 2
v 2 / k 2 / H CH 3CH 3

v 3 k 3 H CH 3CH 2

Explosions
Thermal

explosions

Rapid increase in the reactions rate with

temperature.

Chain

branching explosions

chain branching steps in the mechanism lead

to a rapid (exponential) increase in the
number of chain carriers in the system.

Photochemical Reactions
Many reactions are initiated by the
absorption of light.
Stark-Einstein Law one photon is absorbed
by each molecule responsible for the primary
photochemical process.

vI I
I = Intensity of the absorbed radiation

Primary Quantum Yield

Define

the primary quantum yield,

# of primary products

# of photons absorbed
Define the overall quantum yield,

# of reactant molecules that react

# of photons absorbed

Photosensitization
Transfer

of excitation energy from one

molecule (the photosensitizer) to another
nonabsorbing species during a collision..
254 nm

Hg Hg
Hg H 2 Hg 2H
Hg H 2 HgH H

Polymerization Kinetics
Chain

polymerization

Activated monomer attacks another

monomer, chemically bonds to the monomer,

and then the whole unit proceeds to attack
another monomer.

Stepwise

polymerization

A reaction in which a small molecule (e.g.,

H2O) is eliminated in each step.

Chain Polymerization
The overall polymerization rate is first order
in monomer and order in initiator.
The kinetic chain length, kcl

Measure of the efficiency of the chain

propagation reaction.

kcl

vp

# of monomer units consumed

vi
# of active centres produced

Mechanism

Initiation
I 2 R
Or
M + R M1

Rate Laws

v i k i I

Propagation
M + M 1 M 2
M + M 2 M 3
M + M 3 M 4
Etc.

v p k p M M n 1

Mechanism (Contd)
Termination

M + M3 M4

v t k t M

Note Not all the initiator molecules produce chains

Define = fraction of initiator molecules that produce chains

d M

2k i I
dt

Return to Kinetic Chain Length

We

can express the kinetic chain length

in terms of kt and kp

kcl

k p M M

2
2kt M
1
2

k p M I

1
2 ki kt 2

Stepwise Polymerization
A

classic example of a stepwise

polymerization nylon production.
NH2-(CH2)6-NH2 + HOOC-(CH2)4COOH
NH2-(CH2)6-NHOC-(CH2)4COOH + H2O

After many steps

H-(NH-(CH2)6-NHOC-(CH2)4CO)n-OH

The Reaction Rate Law

Consider

the condensation of a generic

hydroxyacid
OH-M-COOH

Expect

the following rate law

v poly k poly OH COOH

The Reaction Rate Law (Contd)

Let

[A] = [-COOH]
A can be taken as any generic end
group for the polymer undergoing
condensation.
Note 1 OH for each COOH

v poly k poly OH A
k poly A

The Reaction Rate Law (Contd)

If

the rate constant is independent of the

molar mass of the polymer

COOH o
COOH t
1 k poly t COOH o

A o

1 k poly t A o

The Fraction of
Polymerization
Denote

p = the fraction of end groups

that have polymerized

A o A t
p
A o
p

k poly t A o

1 k poly t A o

Statistics of Polymerization
Define

Pn = total probability that a

polymer is composed of n-monomers

Pn p

n 1

1 p

The Degree of
Polymerization
Define

<n> as the average number of

monomers in the chain

1
A o

n
A t
1 p

Degree of Polymerization
(contd)
The

average polymer length in a

stepwise polymerization increases as
time increases.

k poly t A o
1
1
n
1 k poly t A o
1 p
1 k poly t A o

Molar Masses of Polymers

The

average molar mass of the polymer

also increases with time.
Two types of molar mass distributions.

<M>

= the number averaged molar mass of

the polymer.
<M>w = the mass averaged molar mass of the
polymer.
n

Definitions of <M>n
Two

definitions!

Mo
1 p

nJ M J

J
n
Mo = molar mass of monomer
n = number of polymers of mass Mn
MJ = molar mass of polymer of length nJ

Definitions of <M>w
<M>w

is defined as follows

1 p M o j x n p
2

nJ M J

J n J M J
Note - xn the number of monomer
units in a polymer molecule

x n 1

The Dispersity of a Polymer

Mixture
Polymers

consists of many molecules of

varying sizes.
Define the dispersity index () of the
mass distribution.

M
M

w
n

Note monodisperse sample

ideally has <M>w=<M>n

The Dispersity Index in a Stepwise

Polymerization
The

dispersity index varies as follows in

a condensation polymerization

M
M

w
n

Note as the polymerization

proceeds, the ratio of <M>w/<M>n
approaches 2!!!

Mass Distributions in
Polymer Samples
For

a random polymer sample

Monodisperse Sample
Polydisperse Sample

Pn

09

11

13

15

17

19

21

23

25

27

29

31

33

35

37

Molar mass / (10000 g/mole)

39

41