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COVERAGE:
Organic Chemistry
Inorganic Chemistry
GOALS:
¾ Organic reaction mechanisms
¾ Stereochemistry
¾ Aromaticity
¾ Spectroscopy
¾ Concepts of coordination chemistry
¾ 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. 3 hrs. 40% Closed book:
Exam. 16% Weightage,
Open book:
24% Weightage.
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NOTICES:
On the Chemistry Group Notice Board only

PASSWORD FOR SLIDES: chem2

TUTORIALS: Total 8
Best 6

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 LECTURE 1

FREE RADICALS

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 FREE RADICALS
Chemical bond in a reaction can cleave in
two ways:
Homolytic/symmetric/radical cleavage:
generates reactive intermediates with
unpaired electrons called radicals.

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 BOND CLEAVAGES
Heterolytic/unsymmetric/ionic cleavage
generates charged intermediates called
anions and cations.

_ +

Note the ‘fish hook’ arrows

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A BRIEF HISTORY OF FREE RADICALS
TRIPHENYLMETHYL RADICAL, PH3C•

(C6H5)3C + I2 (C6H5)3C I

(C6H5)3C + O2 (C6H5)3C O O C(C6H5)3

2 (C6H5)3C X (C6H5)3C C(C6H5)3

Moses Gomberg
(C6H5)3C C6H5
2 (C6H5)3C
H C6H5

Gomberg dimer
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 Free Radicals
¾ Carbon is sp2 hybridized with p orbital
containing odd electron.
¾ Planar
¾ Electron-deficient

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 REACTIONS OF FREE RADICALS
¾ Substitution
¾ Intermolecular Addition (Anti-Markonikov )
¾ Cyclization (Intramolecular addition reactions)
¾ Elimination reactions
¾ Radical recombination reactions

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 A TYPICAL RADICAL REACTION
Overall reaction
hv
H3 C C CH3 CH4 + CO + C2H6 + H2C C O +

O
H 3C C H + H 3C C CH2 CH3 + H3C C C CH3 +
O O O O

H 3C C CH2 C CH3 + H3C C CH2 CH2 C CH3

O O O O

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Homolytic Decomposition
hv
H3C C CH3 H3C + H3C C

O O

Recombination
H3C + H3C C H3 C C CH3

O O
Dimerization
H 3C + H3C C2H6

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Dimerization
H 3C C + H3 C C H3 C C C CH3

O O O O

Abstraction/transfer
H3 C + H 3 C C CH4 + H2C C O

Abstraction/transfer
H 3C + H 3C C CH3 CH4 + H3C C CH2

O O
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Dimerization
H3C C CH2 + H3C C CH2 H3 C C CH2 CH2 C CH3

O O O O

Recombination
H3 C C CH2 + CH3 H3 C C CH2 CH3

O O

Disproportionation
H3 C C + H3 C C H3 C C H + H2C C O

O O O

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Recombination
H 3C C CH3 + H3C C H 3C C CH2 C CH3

O O O O

Abstraction
H3 C C CH2 + H3C C H3 C C CH3 + H2C C O

O O O

Decomposition
H3C C H3C + CO

O
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 FREE 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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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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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 molecules within the
lungs.

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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 RADICAL INHIBITOR
.... EATS RADICALS!
..
Antioxidants: Molecules that scavenge harmful
oxygen-centred radicals (HO., RO.).

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 BOND DISSOCIATION ENERGY (BDE)

Bond breaking requires energy (+BDE).

Bond formation releases energy (-BDE).
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 BOND DISSOCIATION ENERGY
We can use BDE to estimate ΔH0 for a reaction.

ΔH0 = Σ(BDE of bonds broken)-

Σ(BDE of bonds formed)

Comparing bond dissociation energies allows

us to 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 Less Stable Radical
CH3-H → 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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 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 Æ 28
RESONANCE STABILIZATION: ALLYL RADICAL

H H
CH3 C CH3 C
C C H C C H
H H H H
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BENZYL RADICAL

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RELATIVE STABILITIES OF RADICALS

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 Activation Energy
Reaction rates are related to temperature
by the Arrhenius equation:
-Ea/RT
kr = Ae
Frequency Factor (A): fraction of collisions
with proper orientation for reaction to occur.
Activation Energy (Ea): minimum kinetic
energy molecules must possess to overcome
repulsions between their electron clouds
when they collide.
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 Activation Energy
At higher temperatures, more molecules
have the required energy.

=>

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 Rate, Ea, and Temperature

X + CH4 HX + CH3

X Ea Rate @ 300K Rate @ 500K

F 5 kJ 140,000 300,000
Cl 17 kJ 1300 18,000
Br 75 kJ 9 x 10-8 0.015
I 140 kJ 2 x 10 -19 2 x 10 -9

=>
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REACTION-ENERGY DIAGRAMS
For a one-step reaction:
Reactants → Transition state → Products

¾ X-axis - Progress of
the reaction.
¾ Y-axis - Either G or H.
¾ The transition state
state of highest energy
between reactants and
products, unstable, and
cannot be isolated.

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 Multi-step reactions
Reactants → transition state → intermediate
→ transition state →product
¾ Reaction intermediates are stable as long
as they don’t collide with another molecule
or atom, but they are very reactive.
¾ Transition states are at energy maxima.
¾ Intermediates are at energy minima.
¾ The reaction step with highest Ea will be
the slowest, therefore rate-determining for
the entire reaction.
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Rate-Limiting Step

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 reaction
BDE = -58
BDE = -83.5

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The additional energy required comes from the
kinetic energy of the of colliding species. Kinetic
energy is converted into chemical potential energy.

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