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COVERAGE:
Organic Chemistry
Inorganic Chemistry

GOALS:

Organic reaction mechanisms

Stereochemistry

Aromaticity

Spectroscopy

Concepts of coordination chemistry

Chemistry of representative elements
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TEXT BOOKS:
1. Organic Chemistry, L. G. Wade, Jr. and
Maya Shankar Singh 6th Edition,
Pearson Education, Inc. 2006.

2. Concise Inorganic Chemistry, J. D. Lee,

5th ed. (Blackwell Science, Oxford,1999)
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Evaluation Components
Component

Duration Weightage

Remarks

Test I

50 min.

20%

Closed Book

Test II

50 min.

20%

Closed Book

Tutorials*

----

20%

Closed Book

Compre.
Exam.

3 hrs.

40%

Closed book:
16% Weightage,
Open book:
24% Weightage.
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Tutorial Hour Tests:

Two types

A set of objective type questions

(different types) which the student will have
to answer and submit during the tutorial
class

A set of problems will be assigned

periodically, of which one to be solved in
the tutorial hour of the following week
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LECTURE 1

FREE RADICALS

FREE RADICALS
Radicals are species with a single,
unpaired electron.
Chemical bond in a reaction can cleave
in two ways:
Homolytic cleavage:
generates reactive intermediates with
unpaired electrons called radicals.
+

BOND CLEAVAGES
Heterolytic cleavage
generates charged intermediates called
anions and cations.
_

+
+

Note the fishhook arrows

Radicals
Pairs of electrically neutral "free"
radicals are formed via homolytic bond
breakage.
This can be achieved by heating in nonpolar solvents or the vapour phase.

Radicals
DNA Ckl

DNA Cleavage
O
Base
O

O
O

OH
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Polystyrene

11

PVC

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A RADICAL INHIBITOR

..
Antioxidants: Molecules that scavenge
harmful oxygen-centred radicals (HO., RO.).
HO

Vitamin E

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Generation of radicals

Energy in form of heat or light.

Start from compounds containing a
weak bond,
bond, e.g. peroxides.

Start from compounds that readily loose
a stable compound such as nitrogen
gas.

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Generation of radicals
Homolysis of weak sigma bonds

Chlorine

Cl

Cl

2 Cl

Peroxide
O

15

RADICALS
Radicals are all around us because
molecular oxygen is itself a diradical.
Radical reactions are ubiquitous
(everywhere) in living things, because
radicals are produced in the normal
course of metabolism.
Nitric oxide plays a remarkable number of
important roles in living systems.
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RADICALS
In the body, it is known that enzymes can
convert oxygen to the extremely reactive
hydroxyl radical (HO.).
This radical can react with most of the
chemicals within the body (e.g. proteins,
fats, DNA) causing damage, which
interferes with the proper functioning of
cells.
The formation of hydroxyl radicals has
been linked to many important diseases
as well as the ageing process.
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RADICALS
Excessive exposure to environmental
pollution (e.g. exhaust fumes), UV light or
cigarette smoke, can cause the body to
produce harmful radicals.
It has been estimated for example, that
1015 radicals are present in ONE PUFF of
cigarette smoke.
These radicals include nitrogen monoxide
(.NO) and nitrogen dioxide (.NO2), which are
known to react with many biological
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molecules within the lungs.

RADICALS
Radical reactions are important in many
industrial processes.
Polymerization: polyethylene (PE),
Teflon (polytetrafluoroethylene, PTFE),
polystyrene (PS), etc.
Radical reactions are central to the
cracking process by which gasoline
and other fuels are made from
petroleum.
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A BRIEF HISTORY OF FREE RADICALS

Triphenylmethyl radical, Ph3C
Triphenylmethyl chloride
reacts with metallic silver to
form the triphenylmethyl
radical, Ph3C
Moses Gomberg

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A BRIEF HISTORY OF FREE RADICALS

TRIPHENYLMETHYL RADICAL, Ph3C
(C6H5)3C
(C6H5)3C

+ I2

(C6H5)3C O O C(C6H5)3

+ O2

2 (C6H5)3C

2 (C6H5)3C

(C6H5)3C I

(C6H5)3C

C(C6H5)3

(C6H5)3C

C6H5

C6H5

Gomberg dimer

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REACTIONS OF FREE RADICALS

Substitution

Intermolecular Addition (Anti-Markonikov )

Cyclization (Intramolecular addition reactions)

Elimination reactions

Radical recombination reactions

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Radical cation and anion

Radicals can be charged: when a neutral,
species gains a single electron it becomes
both radical and an anion, a radical anion.
Likewise, when a neutral, species loses an
electron it becomes a radical cation.
Radical anions and radical cations are
dual classified as both radicals and Lewis
acid/base species.

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Detection of radicals
Low temperature isolation

High speed spectroscopic probes

Electron Paramagnetic Resonance (EPR)
(ESR signal for methyl radical generated at
-200 degree celsius from methyl iodide is a
quartet)

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Free Radicals

Carbon is sp2 hybridized with p orbital
containing odd electron.

Planar, Electron-deficient

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BOND DISSOCIATION ENERGY (BDE)

Bond breaking requires energy (+BDE).

Bond formation releases energy (-BDE).
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BONDBOND-DISSOCIATION ENERGY
We can use BDE to estimate
H0 for a reaction.
H0 = (BDE of bonds broken)(BDE of bonds formed)
Comparing bond dissociation energies
allows us to compare relative bond
strengths.
The stronger the bond, the higher its
bond dissociation energy.
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BOND DISSOCIATION ENERGY

BDE

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RELATIVE STABILITIES OF RADICALS

BDE values provide us a convenient way
to estimate relative stabilities of
radicals.
C-H Bond Stronger
CH3-H

Less Stable Radical

CH3 + H

(435 kJmol-1)

CH3CH2CH2-H

CH3CH2CH2 + H (423 kJmol-1)

(CH3)2CH-H

(CH3)2CH + H (413 kJmol-1)

(CH3)3C-H

(CH3)3C + H

(400 kJmol-1)

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30

STABILITY OF RADICALS
Hyperconjugation: The overlap between
the sigma bonding orbitals and the
orbital containing the unpaired electron

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No Hyperconjugation

Increasing Hyperconjugation 

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RESONANCE STABILIZATION: ALLYL RADICAL

H
CH3

C
H

C H
H

CH3

C
H

C H
H
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BENZYL RADICAL

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RELATIVE STABILITIES OF RADICALS

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HALOGENATION OF ALKANES

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halogenation of Alkanes
Experimental observations
1. There is no reaction in the dark at room
temperature.
2. Reaction will occur at high temperature in
the dark.
3. Reaction occurs at low temperature in the
presence of UV light.

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5. One photon can initiate a reaction which

yields a large number of product molecules.
6. The presence of oxygen will slow down the
reaction for some time.
7. Fluorine reacts explosively.
8. Chlorine reacts at a moderate rate.
9. Bromine must be heated to react.
10. Iodine does not react (detectably).
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Chlorination of Methane

The most effective wavelength is blue, which

is absorbed by chlorine gas.

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The relative amounts of the various

products depend on the proportion
of the two reactants used.

Excess of the hydrocarbon
CH3Cl

Excess of chlorine
CHCl3 and CCl4
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Free-Radical Chain Reaction

(1) Initiation: generates a reactive intermediate.
(2) Propagation: the intermediate reacts with a
stable molecule to produce another reactive
intermediate (and a product molecule).
(3) Termination: side reactions that destroy
the reactive intermediate.
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Initiation Step
A chlorine molecule splits homolytically
into chlorine radicals

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Propagation Step (1)

The chlorine radical collides with a methane
molecule and abstracts a H, forming another
free radical and one of the products (HCl).

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Propagation Step (2)

The methyl free radical collides with another
chlorine molecule, producing the other product
(CH3Cl) and regenerating the chlorine radical.

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Termination Steps

Collision of any two free radicals.

Combination of free radical with
contaminant or collision with wall.

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Reaction with other halogens

The order of reactivity of methane
substitution with halogens,
fluorine > chlorine > bromine > iodine
Assuming the mechanism for reaction of
methane with fluorine, bromine and iodine
to be the same as that for chlorine, we can
explain the variation in reactivity by
examining Ho and Eact for each step.
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Reaction with other halogens

Chain initiating step:
Fluorination
Chlorination
F2 2F
Cl2 2Cl
+159 +159
+243
+243
H0
Eact
H0
Eact
Chain propagating step (1):
Fluorination
Chlorination
F + CH4 HF + CH3
Cl + CH4 HCl +CH3
-130
+5
+8
+16
H0
Eact
H0
Eact
(All energies are in kJmol-1)

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Reaction with other halogens

Fluorination
Overall H0
Eact of I step

-432
+5

Chlorination
-101
+16

The chain initiating step is highly endothermic

in both the cases.
Eact therefore is high.
Chain initiating step occurs only infrequently
relative to the chain propagating steps.
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Reaction with other halogens

Since, one initiating step is able to
produce thousands of product molecules,
high Eact of initiation is therefore, not an
impediment to any of the halogenation
reactions.
Can by contrast, chain propagating steps
have high Eact ?
No.
If they do then they are slow and highly
reactive intermediates are consumed by
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chain terminating steps.

Reaction with other halogens

Chain propagating steps have small Eact
thereby allowing large number of
energetic collisions even at room
temperature.
Low Eact and large overall H0 account
for the high reactivity of F2 .
Higher Eact in chlorination compared to
fluorination partly explains the lower
reactivity of Cl2.
The greater energy required to break ClCl bond too, has some effect.
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Reaction with other halogens

Chain initiating step:
Fluorination
Bromination
F2 2F
Br2 2Br
+159
+159
+193 +193
H0
Eact
H0
Eact
Chain propagating step (1):
Fluorination
Bromination
F + CH4
Br + CH4
HF + CH3
HBr + CH3
-130
+5
+74
+78
H0
Eact
H0
Eact

Iodination
I2 2 I
+151 +151
H0
Eact
Iodination
I + CH4
HI + CH3
+142 +140
H0
E
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Reaction with other halogens

Chain propagating step (2):
Fluorination
Bromination
CH3 + F2
CH3 + Br2
CH3F + F
CH3Br + Br
-302
small
-100
small
H0
Eact
H0
Eact

Iodination
CH3 + I2
CH3I +I
-89 small
H0
Eact

Fluorination Bromination Iodination

Overall H0
-422
-26
+53
Eact of I step
+5
+78
+140
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Reaction with other halogens

In the case of bromination Eact is very high
in the first chain propagating step.
Only small fraction of all the collisions
between Br and methane molecules will
therefore be energetically effective even at
3000 C even though overall H0 is
negative.
Therefore the reactions is very slow.
In the case of iodination the first chain
propagating step has large Eact.

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54

Chlorination of Propane

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Product Distribution
mixture
Product

Typical product mix: 40% 1-chloropropane

and 60% 2-chloropropane.

Therefore, all Hs are not equally reactive.

To compare hydrogen reactivity,
find amount of product formed per hydrogen.

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Product Distribution

40% 1-chloropropane from 6 hydrogens
and 60% 2-chloropropane from 2 hydrogens.

40% 6 = 6.67% per primary H and
60% 2 = 30% per secondary H

Secondary Hs are 30% 6.67% = 4.5
times more reactive toward chlorination
than primary Hs.
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Bromination of Propane
1 C
Br

Br
CH3

CH2

CH3

+ Br2

heat

CH2

CH2

CH3 + CH3

CH CH3

2 C

Typical product mix: 3% 1-bromopropane and

97% 2-bromopropane !!!

Bromination is more selective than chlorination.

3% 6 = 0.5% per primary H and
97% 2 = 48.5% per secondary H

Secondary Hs are 48.5% 0.5% = 97 times
more reactive than primary Hs.
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Bromination vs. Chlorination

Chlorination is faster than bromination.

Chlorination is unselective, yielding a

mixture of products, but bromination is

often selective, yielding one major
product.

This difference in chlorination and
bromination can be explained by
considering the energetics of each type
of reaction.
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Abstraction of a 10 or 20 hydrogen by Br is
endothermic, but it takes less energy to form
the more stable 20 radical.

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