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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
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
=>
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
=>
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
=>
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
=>
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
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