Reaction Mechanisms

A reaction mechanism is a full description of

how a reaction occurs.
It describes what takes place at each stage of a chemical
transformation
Reactions occur in defined steps that lead from reactant to
product
A reaction mechanism describes these steps
the types of bonds that are broken and formed,
the order and relative rates in which they are broken and
formed,

Indicating Steps in Mechanisms

Curved arrows indicate breaking and forming of bonds

Arrowheads with a half head

(fish-hook) indicate homolytic
and homogenic steps (called
radical processes)

Arrowheads with a complete head

indicate heterolytic and

heterogenic steps (called polar
processes)

Identify Cleavage of covalent

bond in following compound-

BREAKING COVALENT
There are 3 ways to split the shared electron pair in an unsymmetrical covalent bond.
BONDS
UNEQUAL SPLITTING
produces IONS
known as HETEROLYSIS or
HETEROLYTIC FISSION

EQUAL SPLITTING
produces RADICALS
known as HOMOLYSIS or
HOMOLYTIC FISSION

If several bonds are present the weakest bond is usually broken first
Energy to break bonds can come from a variety of energy sources - heat / light
In the reaction between methane and chlorine either can be used, however...
In the laboratory a source of UV light (or sunlight) is favoured.

Homolysis and Heterolysis of

Covalent Bonds

Homolysis

A B

homolytic
bond
cleavage

Forms free
radicals
Ch. 3 - 5

A +B
radicals

Homolytic Breaking of a Covalent Bond

It is a symmetrical cleavage
Each product gets one electron from the bond

Not common in organic chemistry

What constituent product do you obtain

from Hetrolytic cleavage of C3H7Br?

 Heterolysis

A B

A B
Ch. 3 - 8

heterolytic
bond
cleavage

A + B
ions

A +B

What is the difference between

Radical and Ion?

Heterolytic Breaking of a Covalent Bond

It is an unsymmetrical cleavage
Both electrons from the bond that is broken
become associated with one resulting fragment

A common pattern in reaction mechanisms

terolysis of Bonds to Carbon:

Carbocations and Carbanions

heterolysis

carbocation

heterolysis

carboanion
Ch. 3 - 11

Carbocations are electron deficient. They

have only six electrons in their valence
shell, and because of this, carbocations
are Lewis acids.

carbocation
(a Lewis acid)
Ch. 3 - 12

anion
(a Lewis base)

carbocation
(a Lewis acid)

H
water
(a Lewis base)

O
H

All Lewis acids are electrophiles. By

accepting an electron pair from a Lewis
base, a carbocation fills its valence
shell.

anion
carbocation
(a Lewis base)
(a Lewis acid
and electrophile)
Ch. 3 - 13

Which Carbonium ion is less

stable in below mentioned?

H3C

C+

+
C

Methyl radical

Ethyl radical
(primary)

Which is more stable

compound?

H3C

CH3

H3C

CH3

Isopropyl radical
(secondary)

tert-Butyl radical
(tertiary)

CH3

Carbon atoms that are electron poor

because of bond polarity, but are not
carbocations, can also be electrophiles.

Lewis base

Ch. 3 - 16

C O

Lewis acid
electrophile

Practice Problem: Which of the following species

is likely to be
an electrophile, and which
a nucleophile?

a. HCl
b. CH3NH2
c. CH3SH
d. CH3CHO

Electrophiles and
Nucleophiles

An electrophile

is electron-loving
is an electron-poor species
can form a bond by accepting a pair of electrons
may be either neutral or positively charged
is a Lewis acid

A nucleophile
is nucleus-loving
is an electron-rich species
can form a bond by donating a pair of electrons
may be either neutral or negatively charged
is a Lewis base
Ch. 3 - 18

Carbanions are Lewis bases.

A nucleophile is a Lewis base that seeks a
positive center such as a positively charged
carbon atom.

Nu

nucleophile

C
electrophile

Ch. 3 - 19

C O

Nu

electrophile

Nu
nucleophile

Nu

 Examples
HO

N
H

NOT

O
C

HO

NOT
N
H

O
H3Ch.C3 - 20

O
O

H + OH

H3C

O +H

O
CH3

O
O

+ H2O

acetic acid

CH3CH2

ethanol
Ch. 3 - 22

H + H2O

CH3

+ H3O

acetate

CH3CH2

O + H3O

ethoxide

Kinds of Organic Reactions

A. Addition reactions
B.

Elimination reactions

C.

Substitution reactions

D.

Rearrangement reactions

A.

Addition reactions

Addition reactions occur when two reactants

combine to form a single new product with no
atoms left over.
Two molecules combine

B.

Elimination reactions

Elimination reactions occur when a single

reactant splits into two products.
One molecule splits into two

C.

Substitution reactions

Substitution reactions occur when two reactants

exchange parts to give two new products.
Parts from two molecules exchange

D.

Rearrangement reactions

Rearrangement reactions occur when a single

reactant undergoes a reorganization of bonds and
atoms to yield an isomeric product.
A molecule undergoes changes in the way its atoms are connected

Practice Problem: Classify each of the following reactions as an

addition, elimination, substitution, or
rearrangement:

a. CH3Br + KOH CH3OH + KBr

b. CH3CH2OH H2C=CH2 + H2O

c. H2C=CH2 + H2 CH3CH3

CHLORINATION OF METHANE
Reagents

chlorine and methane

Conditions

UV light or sunlight - heat is an alternative energy source

Equation(s)

CH4(g) + Cl2(g)

> HCl(g)

CH3Cl(g) + Cl2(g) > HCl(g)

CH2Cl2(l) + Cl2(g)

> HCl(g)

Cl2(g) > HCl(g)

Mixtures

+ CCl4(l)

+ CH3Cl(g)

+ CH2Cl2(l)

+ CHCl3(l)

chloromethane

dichloromethane

trichloromethane

CHCl3(l) +

tetrachloromethane

free radicals are very reactive - they are trying to pair their electron
with sufficient chlorine, every hydrogen will eventually be replaced.

Mechanism Mechanisms portray what chemists think is going on in the reaction,

whereas an equation tells you the ratio of products and reactants.
Chlorination of methane proceeds via FREE RADICAL SUBSTITUTION
because the methane is attacked by free radicals resulting in
hydrogen atoms being substituted by chlorine atoms.
The process is a chain reaction.
In the propagation step, one radical is produced for each one used

CHLORINATION OF
METHANE
Cl > 2Cl
RADICALS CREATED

Initiation

The single dots represent UNPAIRED ELECTRONS

During initiation, the WEAKEST BOND IS BROKEN as it requires less energy.

There are three possible bonds in a mixture of alkanes and chlorine.

412

348

242

Average bond enthalpy kJ mol-1

The Cl-Cl bond is broken in preference to the others as it is the weakest and
requires requires less energy to separate the atoms.

CHLORINATION OF
METHANE

Cl + CH4 > CH3 + HCl

RADICALS USED and
Cl2 + CH3 > CH3Cl + Cl
then RE-GENERATED

Propagation

Free radicals are very reactive because they want to pair up their single electron.
They do this by abstracting a hydrogen atom from methane; a methyl radical is formed
The methyl radical is also very reactive and attacks a chlorine molecule
A chlorine radical is produced and the whole process can start over again

Termination

CHLORINATION OF
METHANE

l + Cl > Cl2 RADICALS REMOVED

Cl + CH3 > CH3Cl
CH3 + CH3 > C2H6
Removing the
reactive free
radicals brings an
end to the reaction.
This is not very
likely at the start of
the reaction
because of their low
concentration.

CHLORINATION OF METHANE
OVERVIEW
Initiation

Cl2

Propagation
Cl2
Termination

> 2Cl

radicals created

Cl + CH4
> CH3 + HCl
radicals used and
+ CH3 > CH3Cl + Cl then re-generated

Cl + Cl > Cl2
Cl + CH3 > CH3Cl
CH3 + CH3 > C2H6

radicals removed

Summary
Due to lack of reactivity, alkanes need a very reactive species to persuade them to react
Free radicals need to be formed by homolytic fission of covalent bonds
This is done by shining UV light on the mixture (heat could be used)
Chlorine radicals are produced because the Cl-Cl bond is the weakest
You only need one chlorine radical to start things off
With excess chlorine you get further substitution and a mixture of chlorinated products

Initiation

CHLORINATION OF
METHANE

RADICALS
PRODUCED

Propagation
RADICALS USED
AND REGENERATED

Termination

RADICALS
REMOVED

CHLORINATION OF
METHANE
If excess chlorine is present, further substitution takes place

Further
propagation
The equations show the propagation steps for the formation of...
dichloromethane
Cl + CH3Cl > CH2Cl + HCl
Cl2 + CH2Cl > CH2Cl2 + Cl

trichloromethane
Cl + CH2Cl2 > CHCl2 + HCl
Cl2 + CHCl2 > CHCl3 + Cl

tetrachloromethane
Cl2 + CCl3

Cl + CHCl3
>

>

CCl4 + Cl

CCl3 + HCl

Write the complete reaction of

Propene with Hydrochloric acid-