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Organic Chemistry, 5th Edition

L. G. Wade, Jr.

Chapter 4
The Study of
Chemical Reactions

Jo Blackburn
Richland College, Dallas, TX
Dallas County Community College District
2003, Prentice Hall
Tools for Study
• To determine a reaction’s
mechanism, look at:
Equilibrium constant
Free energy change
Enthalpy
Entropy
Bond dissociation energy
Kinetics
Activation energy =>

Chapter 4 2
Chlorination of Methane
H H
heat or light
H C H + Cl2 H C Cl + HCl
H H

• Requires heat or light for initiation.


• The most effective wavelength is blue, which
is absorbed by chlorine gas.
• Lots of product formed from absorption of
only one photon of light (chain reaction).
=>

Chapter 4 3
Free-Radical Chain Reaction
• Initiation generates a reactive intermediate.
• Propagation: the intermediate reacts with a
stable molecule to produce another reactive
intermediate (and a product molecule).
• Termination: side reactions that destroy the
reactive intermediate.
=>

Chapter 4 4
Initiation Step
A chlorine molecule splits homolytically
into chlorine atoms (free radicals)

Cl Cl + photon ( h) Cl + Cl

=>

Chapter 4 5
Propagation Step (1)
The chlorine atom collides with a methane
molecule and abstracts (removes) a H,
forming another free radical and one of
the products (HCl).
H H
H C H + Cl H C + H Cl
H H

=>

Chapter 4 6
Propagation Step (2)
The methyl free radical collides with
another chlorine molecule, producing
the other product (methyl chloride) and
regenerating the chlorine radical.
H H
H C + Cl Cl H C Cl + Cl
H H
=>

Chapter 4 7
Overall Reaction
Cl Cl + photon ( h) Cl + Cl
H H
H C H + Cl H C + H Cl
H H
H H
H C + Cl Cl H C Cl + Cl
H H
H H
H C H + Cl Cl H C Cl + H Cl =>
H H
Chapter 4 8
Termination Steps
• Collision of any two free radicals
• Combination of free radical with
contaminant or collision with wall.
H H
H C + Cl H C Cl
H H

Can you suggest others?


=>
Chapter 4 9
Equilibrium constant
• Keq = [products]
[reactants]
• For chlorination Keq = 1.1 x 1019
• Large value indicates reaction “goes to
completion.”

=>

Chapter 4 10
Free Energy Change
• DG = free energy of (products - reactants),
amount of energy available to do work.
• Negative values indicate spontaneity.
• DGo = -RT(lnKeq)
where R = 1.987 cal/K-mol
and T = temperature in kelvins
• Since chlorination has a large Keq, the free
energy change is large and negative.
=>
Chapter 4 11
Problem
• Given that -X is -OH, the energy difference for
the following reaction is -1.0 kcal/mol.
• What percentage of cyclohexanol molecules
will be in the equatorial conformer at
equilibrium at 25°C?

=>

Chapter 4 12
Factors Determining DG
• Free energy change depends on
enthalpy
entropy
• DH = (enthalpy of products) - (enthalpy
of reactants)
• DS = (entropy of products) - (entropy of
reactants)
• DG = DH - TDS =>
Chapter 4 13
Enthalpy
• DHo = heat released or absorbed during
a chemical reaction at standard
conditions.
• Exothermic, (-DH), heat is released.
• Endothermic, (+DH), heat is absorbed.
• Reactions favor products with lowest
enthalpy (strongest bonds).
=>
Chapter 4 14
Entropy
• DSo = change in randomness, disorder,
freedom of movement.
• Increasing heat, volume, or number of
particles increases entropy.
• Spontaneous reactions maximize
disorder and minimize enthalpy.
• In the equation DGo = DHo - TDSo the
entropy value is often small.
Chapter 4
=>15
Bond Dissociation Energy
• Bond breaking requires energy (+BDE)
• Bond formation releases energy (-BDE)
• Table 4.2 gives BDE for homolytic cleavage
of bonds in a gaseous molecule.
A B A + B

We can use BDE to estimate DH for a reaction.


=>
Chapter 4 16
Which is more likely?
Estimate DH for each step using BDE.
CH4 + Cl CH3 + HCl
104 103
CH3 + Cl2 CH3Cl + Cl
58 84
or
CH4 + Cl CH3Cl + H
104 84
H + Cl2 HCl + Cl
103 =>
58
Chapter 4 17
Kinetics
• Answers question, “How fast?”
• Rate is proportional to the concentration
of reactants raised to a power.
• Rate law is experimentally determined.

=>

Chapter 4 18
Reaction Order
• For A + B  C + D, rate = k[A]a[B]b
 a is the order with respect to A
 a + b is the overall order
• Order is the number of molecules of that
reactant which is present in the rate-
determining step of the mechanism.
• The value of k depends on temperature as
given by Arrhenius: ln k = -Ea + lnA
RT
=>
Chapter 4 19
Activation Energy
• Minimum energy required to reach
H
the transition state.
H C H Cl
H
• At higher temperatures, more molecules
have the required energy.

=>

Chapter 4 20
Reaction-Energy Diagrams
• For a one-step reaction:
reactants  transition state  products
• A catalyst lowers the energy of the
transition state.

=>

Chapter 4 21
Energy Diagram for a
Two-Step Reaction
• Reactants  transition state  intermediate
• Intermediate  transition state  product

=>
Chapter 4 22
Rate-Determining Step
• 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 maximums.
• Intermediates are at energy minimums.
• The reaction step with highest Ea will be the
slowest, therefore rate-determining for the
entire reaction. =>
Chapter 4 23
Rate, Ea, and Temperature
X + CH4 HX + CH3

X Ea Rate @ 300K Rate @ 500K


F 1.2 kcal 140,000 300,000
Cl 4 kcal 1300 18,000
Br 18 kcal 9 x 10-8 0.015
-19 -9
I 34 kcal 2 x 10 2 x 10

=>

Chapter 4 24
Conclusions
• With increasing Ea, rate decreases.
• With increasing temperature, rate
increases.
• Fluorine reacts explosively.
• Chlorine reacts at a moderate rate.
• Bromine must be heated to react.
• Iodine does not react (detectably).
=>
Chapter 4 25
1 C
Chlorination of Propane
Cl Cl
CH3 CH2 CH3 + Cl2 h CH2 CH2 CH3 + CH3 CH CH3
2 C
• There are six 1 H’s and two 2 H’s. We
expect 3:1 product mix, or 75% 1-
chloropropane and 25% 2-chloropropane.
• Typical product mix: 40% 1-chloropropane
and 60% 2-chloropropane.
• Therefore, not all H’s are equally reactive.
=>
Chapter 4 26
Reactivity of Hydrogens
• To compare hydrogen reactivity, find
amount of product formed per hydrogen:
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 H’s are 30%  6.67% = 4.5
times more reactive toward chlorination
than primary H’s. =>

Chapter 4 27
Predict the Product Mix
Given that secondary H’s are 4.5 times as
reactive as primary H’s, predict the
percentage of each monochlorinated
product of n-butane + chlorine.

=>

Chapter 4 28
Free Radical Stabilities
• Energy required to break a C-H bond
decreases as substitution on the carbon
increases.
• Stability: 3 > 2 > 1 > methyl
DH(kcal) 91, 95, 98, 104

=>

Chapter 4 29
Chlorination Energy Diagram
Lower Ea, faster rate, so more stable
intermediate is formed faster.

=>
Chapter 4 30
1 C
Bromination of Propane
Br Br
heat
CH3 CH2 CH3 + Br2 CH2 CH2 CH3 + CH3 CH CH3
2 C

• There are six 1 H’s and two 2 H’s. We


expect 3:1 product mix, or 75% 1-
bromopropane and 25% 2-bromopropane.
• Typical product mix: 3% 1-bromopropane
and 97% 2-bromopropane !!!
• Bromination is more selective than
chlorination. Chapter 4
=>
31
Reactivity of Hydrogens
• To compare hydrogen reactivity, find
amount of product formed per hydrogen:
3% 1-bromopropane from 6 hydrogens and
97% 2-bromopropane from 2 hydrogens.
• 3%  6 = 0.5% per primary H and
97%  2 = 48.5% per secondary H
• Secondary H’s are 48.5%  0.5% = 97
times more reactive toward bromination
than primary H’s.
Chapter 4 =>
32
Bromination Energy Diagram
• Note larger difference in Ea
• Why endothermic?

=>

Chapter 4 33
Bromination vs. Chlorination

Chapter 4
=>
34
Endothermic and
Exothermic Diagrams

Chapter 4 35
=>
Hammond Postulate
• Related species that are similar in energy are
also similar in structure. The structure of a
transition state resembles the structure of the
closest stable species.
• Transition state structure for endothermic
reactions resemble the product.
• Transition state structure for exothermic
reactions resemble the reactants.
=>

Chapter 4 36
Radical Inhibitors
• Often added to food to retard spoilage.
• Without an inhibitor, each initiation step
will cause a chain reaction so that many
molecules will react.
• An inhibitor combines with the free
radical to form a stable molecule.
• Vitamin E and vitamin C are thought to
protect living cells from free radicals.
=>
Chapter 4 37
Reactive Intermediates
• Carbocations (or carbonium ions)
• Free radicals
• Carbanions
• Carbene

=>

Chapter 4 38
Carbocation Structure

• Carbon has 6 electrons,


positive charge.
• Carbon is sp2 hybridized
with vacant p orbital.
=>

Chapter 4 39
Carbocation Stability
• Stabilized by alkyl
substituents 2 ways:
• (1) Inductive effect:
donation of electron
density along the
sigma bonds.
• (2) Hyperconjugation:
overlap of sigma
bonding orbitals with
empty p orbital.
=>

Chapter 4 40
Free Radicals
• Also electron-
deficient
• Stabilized by alkyl
substituents
• Order of stability:
3 > 2 > 1 >
methyl

=>
Chapter 4 41
Carbanions
• Eight electrons on C:
6 bonding + lone pair
• Carbon has a negative
charge.
• Destabilized by alkyl
substituents.
• Methyl >1 > 2  > 3 

=>
Chapter 4 42
Carbenes
• Carbon is neutral.
• Vacant p orbital, so
can be electrophilic.
• Lone pair of
electrons, so can be
nucleophilic.

=>

Chapter 4 43
End of Chapter 4

Chapter 4 44