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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 Test II Tutorials* Compre. Exam.

50 min. 50 min. ---3 hrs.

20% 20% 20% 40%

Closed Book Closed Book Closed Book Closed book: 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
(C6H5)3C

+ I2
+ O2

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

2 (C6H5)3C

X

(C6H5)3C

C(C6H5)3

Moses Gomberg
(C6H5)3C
H

2 (C6H5)3C

C6H5 C6H5
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Gomberg dimer

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

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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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A TYPICAL RADICAL REACTION
Overall reaction
H3 C C O
H 3C C O H + H 3C C O CH2

CH3

hv

CH4 + CO + C2H6 + H2C C O +

CH3 + H3C

C O

C O

CH3 +

H 3C

C O

CH2

C O

CH3 + H3C

C O

CH2

CH2

C CH3 O
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Homolytic Decomposition
H3C C O CH3 hv H3C + H3C C O

Recombination
H3C + H3C C O H3 C C O CH3

Dimerization
H 3C + H3C C2H6
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Dimerization
H 3C C O + H3 C C O H3 C C O C O CH3

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

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

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

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

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

C

O

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

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

Decomposition
H3C C O
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H3C + CO

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 CH3-H CH3CH2CH2-H (CH3)2CH-H (CH3)3C-H Less Stable Radical → CH3• + H• (435 kJmol-1) → CH3CH2CH2• + H• (423 kJmol-1) → (CH3)2CH• + H• (413 kJmol-1) → (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

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RESONANCE STABILIZATION: ALLYL RADICAL

H CH3 C H C C H H CH3 C H

H C C 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:

kr = Ae

-Ea/RT

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
X F Cl Br I

+ CH4

HX
Rate @ 300K 140,000 1300 -8 9 x 10 2 x 10 -19

+

CH3
Rate @ 500K 300,000 18,000 0.015 2 x 10 -9
=>
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Ea 5 kJ 17 kJ 75 kJ 140 kJ

REACTION-ENERGY DIAGRAMS
For a one-step reaction: Reactants → Transition state → Products X-axis - Progress of the reaction. Y-axis - Either G or H. 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 Reaction intermediates are stable as long as they don’t collide with another molecule or atom, but they are very reactive. Transition states are at energy maxima. Intermediates are at energy minima. 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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BDE = -83.5

reaction BDE = -58

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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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