Suggested Problems:

10.1-10.18, 10.21, 10.24, 10.28

(in text)

Bond Dissociation Energies.

heterolytic bond breaking is not bond dissociation
H O

H 2O

H O +

H O +

Ka = 10-16

H O

H = 498 kJ/mol

homolytic bond breaking is bond dissociation

Bond Dissociation Energies.

H
H

H
H

H = 435 kJ/mol

H H = 410 kJ/mol

H O
H

H O +

H = 498 kJ/mol

Bond Dissociation Energies.

H
H

H
H

H
C

H
H

C
C
H

H = 435 kJ/mol

H H = 410 kJ/mol

H
H

C
H

C
C
H

+
H

H = 395 kJ/mol

H
H

C
H
H

15

C
H

Energy (H)

410 kJ/mol
395 kJ/mol

H
H

C
H
H

C
C
H

H
H

Reaction

H +

C
H
H

H
H

C
C
H

+
H

H
H

29
H

Energy (H)

381 kJ/mol

H
H
H

C
H
H

H
C
C
C
H

H
H
H

Reaction

H
H

H +

410 kJ/mol

C
H
H

H
C
C
C
H

+
H

A 2 radical is more stable than a 1 radical but less

stable than a 3 radical.
radical stability:
R
R C
R

>

R
R C
H

>

H
R C
H

>

H
H C
H

Groups that delocalize electrons are important in the

stabilization of double bonds, cations and radical.
These groups include alkyl and conjugated
substituents.
R
R C
R

>

R
R C
H

>

H
R C
H

>

H
H C
H

Alkyl group stabilization of radicals.

electron delocalization
resonance

H
H C
H

H
H

H
H C
H

H
H

Alkyl group stabilization of radicals.

electron delocalization
orbitals

H C
H

H C
H

H
C

H
H

Give an explanation for the difference in the

following bond dissociation energies.

CH3 CH2

CH3

CH3 CH2

CH2

H = 395 kJ/mol

H
CH2

CH

CH2

CH2

CH

CH2

H = 356 kJ/mol

H
CH2

CH

CH2

H C
H

H
H

C H bonds are reactive towards free radicals.

Table of Bond Dissociation Energies page 434
H
H C H + Cl
H
435

Cl

H
H C Cl + H Cl H = -102 kJ/mol
H

or h

243

bonds broken (678)

349

431

= bond dissociation
energies in kJ/mol

bonds made (780) = -102 kJ/mol

G = H - TS
G ~ H

when T = 298 K G = -103 kJ/mol

In most organic reactions the TS term is small.

The reaction mechanism for the chlorination of methane.

How are the bonds made and broken?

H C H

+ Cl

H C

435

H C

+ Cl Cl

H
H
H C H + Cl
H

H C Cl

H = +4 kJ/mol

431

+ Cl

H = -106 kJ/mol

243

Cl

+ H Cl

349

or h

H
H C Cl + H Cl H = -102 kJ/mol
H

The reaction mechanism for the chlorination of

methane.
H

H C H

+ Cl

H C

H
+16

Energy (H)

+ H Cl

activation energy
H (Ea)

+4
-106

-102

H
H C

Reaction

+ Cl Cl

H C Cl
H

+ Cl

An alternative mechanism can be postulated for the

chlorination of methane.
H
Cl + H C H
H 435
H + Cl

Cl

+ Cl

H 435
H
H

H C Cl + H

H = +86 kJ/mol

H349
H Cl + Cl
H

H C H

H C

+ Cl Cl

H C

+ H Cl

H
H
H C Cl
H

431

+ Cl

H = +4 kJ/mol

H C Cl + H

Cl + H C H
H

Energy (H)

86

+4

H
H C H

+ Cl

H C

Reaction

+ H Cl

The reaction mechanism for the chlorination of methane.

Cl

Cl

or h

2 Cl

H C H

+ Cl

H
H
H C

H C
H

H C

+ H Cl

H
H

+ Cl Cl

H
H

initiation

H C Cl

Only one Cl is
required to produce
many CH3Cl molecules.
This is a radical chain
Cl
mechanism.

H H

+ C H

H C C H

H H

The reaction mechanism for the chlorination of methane.

Cl

Cl

or h

2 Cl

H C H

+ Cl

H
H
H C

+ Cl Cl

+ H Cl

H C Cl

H
H

H C
H
H

H C

initiation

+ Cl

H C Cl
H

Only one Cl is
required to produce
propagation
many
CH3Cl molecules.
This is a radical chain
Cl
mechanism.

termination

The reaction mechanism for the chlorination of methane.

Cl

Cl

or h

H
H C H
H
H
H C
H

2 Cl

+ Cl

+ Cl Cl

H
H C
H

H
H C
H
H

+ H Cl

H C Cl
H

+ Cl

+ Cl

H C Cl
H

Cl

Cl

H Cl

H C H

H C Cl

H = -102 kJ/mol

Stereochemistry of chlorination.

Cl
Cl

Cl

+
H

Cl

+
Cl

Cl

Stereochemistry of chlorination.
Cl
H

.
Cl

Cl

Cl

+
H

+
H

Cl
Cl

+
Cl

Stereochemistry of chlorination.

Cl H
HH
Cl

Cl H

H
Cl
H CH
3

Cl

Cl

Cl H

H Cl

Cl H

The reaction of the other halogens with alkanes.

H

H C H

+ Cl

H C

H435

H C

+ Cl Cl

243

431

H C Cl

+ Cl

H = -106 kJ/mol

349

+ F

H C

435

H = +4 kJ/mol

H C H

H C

+ H Cl

+ F F
159

+H F

H C F
H452

H = - 134 kJ/mol

569

+ F

H = - 293 kJ/mol

transition state

H
H C H

+ I

-138 H C H + Br

Energy (H)

+69
+4

H C

H C

H C H

+ Cl

H C

+H I

+ H Br

+ H Cl

-134
H C H
H

Reaction

+ F

H C
H

+H F

Not all C-H bonds have the same reactivity.

Secondary C-H bonds are more reactive than
primary C-H bonds.

expected yield
based on available hydrogens: 40%
H H

Cl2

H H

60%
Cl
+

Cl

actual yield: 71%

29%

Not all C-H bonds have the same reactivity.

Secondary C-H bonds are more reactive than
primary C-H bonds.
Cl

Cl
H

2
Cl2
h

Cl
Cl

+
Cl
71%

29%
Cl

Cl

Cl

Not all C-H bonds have the same reactivity.

Secondary C-H bonds are more reactive than
primary C-H bonds.

expected yield
based on available hydrogens: 40%
H H

Cl2

H H

60%
Cl
+

Cl

actual yield: 71%

29%

Conclusion: 2 hydrogens are more reactive

than 1hydrogens.

Not all C-H bonds have the same reactivity.

Secondary C-H bonds are more reactive than
primary C-H bonds.

expected yield
based on available hydrogens: 40%
H H

Cl2

H H

60%
Cl
+

Cl

actual yield: 71%

29%

2 reactivity
2 71 x 60
=
= 3.7 =
ratio ?
40
1
1 29

Relative reactivities of C-H bonds in

chlorination.

Cl2

5.0

3.7

Bromination is more selective than

chlorination.
Cl

Cl2
h

+
Cl
71%

Br

Br2
h

29%

+
Br
98%

2%

Relative reactivities of C-H bonds in

Bromination.
3
2
1
Br2

1600

82

Relative reactivities of C-H bonds in

chlorination.
3
2
1
Cl2

5.0

3.8

Radical addition of H-Br to alkenes.

RO

OR

RO

+ H

Br

RO

Br

OR

initiation

ROH +

Br

Br
C

+ H

Br

Br

Br

propagation

Br

Br

Br

Br

termination

Radical addition of H-Br to alkenes.

Regiochemistry.
RO OR

major
product

RO

H Br

H Br
Br

Br

Br
Br

Br

H Br
H

Free Radical Polymerization of Alkenes.

O
R

R
O

initiation
R +

Free Radical Polymerization of Alkenes.

O
R

R
O

R +

propagation

Free Radical Polymerization of Alkenes.

O
R

R
O

initiation
R +

propagation

Free Radical Polymerization of Alkenes.

O
R

R
O

initiation
R +

propagation

Free Radical Polymerization of Alkenes.

R

O
R

R
O

initiation
R +

termination

ethylene

polyethylene

Free Radical Polymerization of Alkenes.

O
R

R
O

H
R +

Free Radical Polymerization of Alkenes.

O
R

R
O

H
R +

Free Radical Polymerization of Alkenes.

O
R

R
O

R +

Free Radical Polymerization of Alkenes.

O
R

R
O

R +
n

ethylene

polyethylene

Free Radical Polymerization of Alkenes.

O
R

R
O

+
n

styrene polystyrene

Free Radical Polymerization of Alkenes.

O
R

R
O

F
R

F
F

tetrafluoroethylene

F
n

polytetrafluoroethylene
teflon

Free radicals can damage cells.

Free radicals

DNA

DNA
damage

H = 498

OH

H = 435

CH3

CH2OH

H = 387

H + OH

H + CH3

H + CH2OH

DNA and RNA are

polyesters.

Free radicals can damage cells.

NH2

NH2
N
N
O

H
H

O P
O

O
NH2
N

H
N

H
H

H O
HO

RH

O P
O

DNA

H
N

H O

H
H

N
NH2

HO

H
H

single
DNA
strand
scission

Free Radical Traps

H O +

H O

H = 498 kJ/mol

H = 336kJ/mol

Many chemicals can destroy free radicals.

vitamin E.
O

BHT

OH

OH

Vitamin C
OH
HO

OH
O

OH

There are necessary biological processes that

proceed by free radical reaction mechaniams
O

blood
clotting

O2

fatty
acids

pain

HOO
O
O
O

inflammation

Arachadonic
acid

Prostaglandin H2

There are necessary biological processes that

proceed by free radical reaction mechaniams
O

O
H
O

O
O

O
O

O
O
H

There are necessary biological processes that

proceed by free radical reaction mechaniams

HOO

O
O
H

Prostaglandin H2

O
O
H

O
H

O
H

There are necessary biological processes that

proceed by free radical reaction mechaniams
O

O2

HOO

O
O

H
H

Arachadonic
acid

Prostaglandin H2

Summary:
Free radicals are among the few species that will react with C-H bonds.
Free radical stability can be estimated from bond energies.
H
H

H
H

H O +

H O

H = 435 kJ/mol

H = 498 kJ/mol

Free radical reactions usually occur by a chain reaction mechanism.

C

+ X

X +

X +

The reaction of chlorine with butane gives two

monochlorinated derivatives.
Cl2

two monochloro derivatives

(a) Give the structures of these two products.

(b) Postulate reaction mechanisms for their formation.
(c) Predict the major product of the reaction.

The reaction of chlorine with butane gives two

monochlorinated derivatives.
Cl
Cl2

Cl

(a) Give the structures of these two products.

(b) Postulate reaction mechanisms for their formation.
(c) Predict the major product of the reaction.

The reaction of chlorine with butane gives two

monochlorinated derivatives.
+

Cl

Cl

Cl2

Cl

Cl

Cl

+ H Cl

(a) Give the structures of these two products.

(b) Postulate reaction mechanisms for their formation.
(c) Predict the major product of the reaction.

The reaction of chlorine with butane gives two

monochlorinated derivatives.
+

Cl

Cl

Cl2

Cl

Cl

Cl

Cl
Cl

Cl

+ H Cl

+ H Cl

(a) Give the structures of these two products.

(b) Postulate reaction mechanisms for their formation.
(c) Predict the major product of the reaction.

The chlorination of (R)-2-butane gives a mixture of

isomers.
Cl H

Cl2

a mixture of chlorinated compounds

(a) Draw all of the isomers with the formula

C4H8Cl2.
(b) Circle those that are chiral.

The chlorination of (R)-2-butane gives a mixture of

isomers.
Cl H

Cl2

Cl H

Cl Cl

Cl

Cl H

+
Cl H

Cl H

Cl H

+
Cl
H Cl

(a) Draw all of the isomers with the formula

C4H8Cl2.
(b) Circle those that are chiral.