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Radical Reactions
Ch. 10 - 1
1. Introduction: How Radicals Form
and How They React
Heterolysis
heterolytic
A B bond
A + B
cleavage ions
Homolysis
homolytic
A B bond
A + B
cleavage radicals
Ch. 10 - 2
1A. Production of Radicals
Homolysis of covalent bonds
● Need heat or light (hν)
(alkoxyl radical)
heat
R O O R 2R O
(chlorine radical)
hν
Cl Cl 2 Cl
Ch. 10 - 3
1B. Reactions of Radicals
Almost all small radicals are short-lived,
highly reactive species
Cl + H CH3 Cl H + CH3
R
R + C C C C
Ch. 10 - 4
2. Homolytic Bond Dissociation
Energies (DH°)
H + H H H
∆Ho = −436 kJ/mol Bond formation is
an exothermic
Cl + Cl Cl Cl process.
∆Ho = −243 kJ/mol
H H H + H
Reactions in which
∆Ho = +436 kJ/mol
only bond breaking
Cl Cl Cl + Cl occurs are always
endothermic.
∆Ho = +243 kJ/mol
Ch. 10 - 5
The energies required to break
covalent bonds homolytically are called
homolytic bond dissociation
energies, and they are usually
abbreviated by the symbol DH °
Ch. 10 - 6
Single-Bond Homolytic Dissociation
Energies (DH°) at 25°C
H–H 436
F–F 159
Cl–Cl 243
Br–Br 193
I–I 151
Ch. 10 - 7
Single-Bond Homolytic Dissociation
Energies (DH°) at 25°C
H–F 570
H–Cl 432
H–Br 366
H–I 298
Ch. 10 - 8
Single-Bond Homolytic Dissociation
Energies (DH°) at 25°C
Bond Broken kJ/mol Bond Broken kJ/mol
H3C–H 440
H3C–F 461
H3C–Cl 352
Cl 354 Br 294
Cl 355 Br 298
Cl 349 Br 292
Ch. 10 - 10
Single-Bond Homolytic Dissociation
Energies (DH°) at 25°C
Bond Broken kJ/mol Bond Broken kJ/mol
H H
423 369
H 413 H 465
H 400 Ph H 474
Ph H 375 HC C H 547
Ch. 10 - 11
2A. Use Homolytic Bond Dissociation
Energies to Calculate Heats of Reaction
o o
(DH = 436 kJ/mol) (DH = 432 kJ/mol) ☓ 2
o
(DH = 243 kJ/mol)
H H + Cl Cl 2H Cl
+679 kJ is required -864 kJ is evolved
to cleave 1 mol of in formation of
H2 bonds and bonds in
1 mol of Cl2 bonds 2 mol of HCl
Ch. 10 - 12
o
∆H = −2 (432 kJ/mol) + (436 kJ/mol + 243 kJ/mol)
= −864 kJ/mol + 679 kJ/mol
= −185 kJ/mol
Ch. 10 - 13
2B. Use Homolytic Bond Dissociation
Energies to Determine the Relative
Stabilities of Radicals
∆Ho = +423 kJ/mol
H + H
Propyl radical
(a 1o radical)
+ H
Isobutyl radical
∆Ho = +422 kJ/mol
(a 1o radical)
Ch. 10 - 15
Relative Stability
● Carbon radicals are considered to
be electron deficient (similar to
carbocations), thus electron
donating groups stabilize radicals
o o o
3 >2 >1
CH3 H H H
CH3 C CH3 > CH3 C CH3 > CH3 C H>H C H
Ch. 10 - 17
Alkanes react with molecular halogens
to produce alkyl halides by a
substitution reaction called radical
halogenation
heat
R H + X2 R X + H X
or
light (hν)
Ch. 10 - 18
3A. Multiple Halogen Substitution
H H Cl
heat
H C H + Cl2 H C Cl + H C Cl
or
H light H H
Cl Cl
+ Cl C Cl + Cl C Cl
H Cl
+H Cl
Ch. 10 - 19
3B. Lack of Chlorine Selectivity
Chlorination of most higher alkanes
gives a mixture of isomeric monochloro
products as well as more highly
halogenated compounds
● Chlorine is relatively unselective;
it does not discriminate greatly
among the different types of
hydrogen atoms (primary,
secondary, and tertiary) in an
alkane
Ch. 10 - 20
Cl2 Polichlorinated
Cl + + products + HCl
light
Cl (23%)
Isobutane Isobutyl tert-Butyl
chloride chloride
(48%) (29%)
Ch. 10 - 22
heat Cl
+ Cl2 + H Cl
or
Neopentane light Neopentyl
(excess) chloride
Ch. 10 - 23
4. Chlorination of Methane:
Mechanism of Reaction
Most radical reactions include 3 stages
(steps)
(1) chain initiation
(2) chain propagation
(3) chain termination
Ch. 10 - 24
Mechanism of Free Radical Chlorination
of CH4
(1) Chain initiation
hν
Cl Cl 2 Cl
(homolytic
cleavage)
Ch. 10 - 25
(2) Chain propagation
H
(i) Cl + H C H H Cl + CH3
H
Ch. 10 - 27
(2) Chain propagation
Cl
(ib) Cl + H C Cl H Cl + CHCl2
H
Cl
(ic) Cl + H C Cl H Cl + CCl3
Cl
Cl + CH3 Cl CH3
Cl + CH2Cl CH2Cl2
Ch. 10 - 29
(3) Chain termination
● Free radical reactions cannot be
completed without chain
termination
● All radicals are quenched in this
step
● Radical reactions usually provide
mixture of many different products
● Synthesis of CH3Cl or CCl4 is
possible using different amounts of
reactants (CH4 and Cl2)
Ch. 10 - 30
e.g.:
CH4 (large excess) + Cl2
hν
CH3Cl (mainly)
hν
CCl4 (mainly)
Ch. 10 - 31
5. Chlorination of Methane:
Energy Changes
Chain initiation
Step 1 Cl Cl 2 Cl
(DHo = 243)
∆Ho = +243 kJ/mol
Ch. 10 - 32
Chain propagation
Step 2 H3C H + Cl CH3 + H Cl
(DHo = 440) (DHo = 432)
∆Ho = +8 kJ/mol
Ch. 10 - 33
Chain termination
Ch. 10 - 34
The addition of the chain-propagation
steps yields the overall equation for the
chlorination of methane
H3C H + Cl CH3 + H Cl
∆Ho = +8 kJ/mol
CH3 + Cl Cl H3C Cl + Cl
∆Ho = −109 kJ/mol
H3C H + Cl Cl H3C Cl + H Cl
∆Ho = −101 kJ/mol
Ch. 10 - 35
5A. The Overall Free-Energy Change
o o o
∆G = ∆H – T ∆S
Ch. 10 - 36
CH4 + Cl2 → CH3Cl + HCl
2 mol of the products are formed from the
same number of moles of the reactants
● Thus the number of translational
degrees of freedom available to
products and reactants is the same
CH3Cl is a tetrahedral molecule like CH4, and
HCl is a diatomic molecule like Cl2
● This means that vibrational and
rotational degrees of freedom available
to products and reactants should also be
approximately the same
Ch. 10 - 37
CH4 + Cl2 → CH3Cl + HCl
o
∆S = +2.8 J K-1 mol-1
o
At room temperature (298 K) the T∆S
term is 0.8 kJ mol-1
o
∆H = −101 kJ mol-1
o
∆G = −102 kJ mol-1
Ch. 10 - 38
5B. Activation Energies
A low energy of activation means a reaction
will take place rapidly; a high energy of
activation means that a reaction will take
place slowly
Chain initiation
Step 1 Cl2 → 2 Cl •
Eact = +243 kJ/mol
Chain propagation
Step 2 Cl • + CH4 → HCl + CH3 •
Eact = +16 kJ/mol
Step 3 Cl • + Cl2 → CH3Cl + Cl •
Eact = ~8 kJ/mol Ch. 10 - 39
Estimates of energies of activation
(1) Any reaction in which bonds are
broken will have an energy of activation
greater than zero. This will be true even
if a stronger bond is formed and the
reaction is exothermic. The reason:
Bond formation and bond breaking do
not occur simultaneously in the
transition state. Bond formation lags
behind, and its energy is not all
available for bond breaking
Ch. 10 - 40
Estimates of energies of activation
(2) Activation energies of endothermic
reactions that involve both bond
formation and bond rupture will be
o
greater than the heat of reaction, ∆H
H3C H + Cl CH3 + H Cl
o o
(DH = 440) ∆H = +8 kJ/mol (DHo = 432)
Eact = +16 kJ/mol
H3C H + Br CH3 + H Br
o o
(DH = 440) ∆H = +74 kJ/mol (DHo = 366)
Eact = +78 kJ/mol
Ch. 10 - 41
Ch. 10 - 42
Estimates of energies of activation
(3) The energy of activation of a gas-
phase reaction where bonds are broken
homolytically but no bonds are formed
o
is equal to ∆H
Cl Cl 2 Cl o
∆H = +243 kJ/mol
(DHo = 243) Eact = +243 kJ/mol
Ch. 10 - 43
Estimates of energies of activation
(4) The energy of activation for a gas-
phase reaction in which small radicals
combine to form molecules is usually
zero
2 CH3 H3C CH3 o
∆H = −378 kJ/mol
(DHo = 378) Eact = 0
Ch. 10 - 44
5C. Reaction of Methane with Other
Halogens
FLUORINATION
o
∆H Eact
(kJ/mol) (kJ/mol)
Chain initiation
F2 → 2 F • +159 +159
Chain propagation
F • + CH4 → HF + • CH3 −130 +5.0
• CH3 + F2 → CH3F + F • −302 small
o
Overall ∆H = −432
Ch. 10 - 45
CHLORINATION
o
∆H Eact
(kJ/mol) (kJ/mol)
Chain initiation
Cl2 → 2 Cl • +243 +243
Chain propagation
Cl • + CH4 → HCl + • CH3 +8 +16
• CH3 + Cl2 → CH3Cl + Cl • −109 small
o
Overall ∆H = −101
Ch. 10 - 46
BROMINATION
o
∆H Eact
(kJ/mol) (kJ/mol)
Chain initiation
Br2 → 2 Br • +193 +193
Chain propagation
Br • + CH4 → HBr + • CH3 +74 +78
• CH3 + Br2 → CH3Br + Br • −100 small
o
Overall ∆H = −26
Ch. 10 - 47
IODINATION
o
∆H Eact
(kJ/mol) (kJ/mol)
Chain initiation
I2 → 2 I • +151 +151
Chain propagation
I • + CH4 → HI + • CH3 +142 +140
• CH3 + I2 → CH3I + I • −89 small
o
Overall ∆H = +53
Ch. 10 - 48
6. Halogenation of Higher Alkanes
Mechanism for radical halogenation of
ethane
Chain initiation
light
Step 1 Cl2 2 Cl
or heat
Chain propagation
CH3CH2 + Cl CH3CH2 Cl
Cl + Cl Cl Cl
Ch. 10 - 50
Cl
Cl2
Cl +
light
25oC
Cl2
Cl +
light Cl
25oC
Cl2
Cl +
300oC Cl
+ +
Cl
Cl Ch. 10 - 51
6A. Selectivity of Bromine
Bromination is slower than chlorination
because the 1st propagation step is
more endothermic (overall still
exothermic). As a result, bromination
is more selective than chlorination
hν H
H + Br2 Br
+
Br
Ch. 10 - 52
Mechanism
hν
Br Br 2 Br
H
Br + H Br
H
H
Br + H Br
H
(minor; 1o radical less stable)
Ch. 10 - 53
Mechanism
Br
Br (major)
H H
Br (minor)
Br
Ch. 10 - 54
Br2
Br +
hν Br
127oC (trace) (> 99%)
Cl2 Cl +
hν Cl
25oC (63%) (37%)
Ch. 10 - 55
7. The Geometry of Alkyl Radicals
p-orbital
R
R C
R
sp2 hybridized
Ch. 10 - 56
8. Reactions That Generate
Tetrahedral Chirality Centers
Cl
Cl2 Cl
+ *
achiral
Pentane 1-Chloropentane ( )-2-Chloropentane
(achiral) (achiral) (a racemic form)
Cl
3-Chloropentane
(achiral)
Ch. 10 - 57
The Stereochemistry of chlorination at
C2 of pentane C2
CH3CH2CH2CH2CH3
Cl
+ Cl + Cl
CH3
CH3 Cl2 Cl2 H3C
Cl C Cl
H (a) (b) H
CH2CH2CH3 H3CH2CH2C
H CH2CH2CH3
(S)-2-Chloropentane trigonal planar (R)-2-Chloropentane
(50%) radical (achiral) (50%)
enantiomers Ch. 10 - 58
8A. Generation of a Second Chirality
Center in a Radical Halogenation
diastereomers
Cl Cl Cl
Cl2
2 3 2 3 + 2 3
hν
H H Cl Cl
(S)-2- (2S,3S)- (2S,3R)-
Chloropentane Dichloropentane Dichloropentane
(chiral) (chiral) (chiral)
Ch. 10 - 60
9. Radical Addition to Alkenes: The
Anti-Markovnikov Addition of
Hydrogen Bromide
Anti-Markovnikov addition of HBr to
alkenes – peroxide effect
● Addition of HBr to alkenes usually
follows Markovnikov’s rule
Br H not H Br
HBr
Ch. 10 - 61
● In the presence of peroxides (RO–
OR), anti-Markovnikov addition is
observed
H Br not Br H
HBr
RO OR
heat
Ch. 10 - 62
Mechanism
● Via a radical mechanism
heat
RO OR 2 RO
(homolytic cleavage)
(chain initiation)
RO + H Br ROH + Br
Ch. 10 - 63
Br +
Br
o
(3 radical, more stable)
Br
not Br +
o
(1 radical, less stable)
H
+ H Br + Br
Br Br Ch. 10 - 64
Synthetic application
Br
HBr
HBr Br
RO-OR
heat (via more stable
2o radical)
Ch. 10 - 65
Hydrogen bromide is the only hydrogen
halide that gives anti-Markovnikov
addition when peroxides are present
Ch. 10 - 66
10. Radical Polymerization of
Alkenes: Chain-Growth Polymers
peroxide
n CH2 CH2 CH2CH2
heat n
(monomer) (polymer)
Ch. 10 - 67
Via radical mechanism
∆
(i) RO OR 2 RO
RO CH2CH2CH2CH2
RO CH2CH2 CH2CH2
2 Ch. 10 - 68
(v) RO CH2CH2 CH2CH2 + OR
2
RO CH2CH2 CH2CH2OR
n
+ RO CH2CH2 CH2CH2
n
RO CH2CH2 OR
Ch. x
10 - 69
Other common polymers
ROOR
n CH2 CHCH3 CH2CH
∆
Polypropylene CH3 n
ROOR
n CH2 CHCl CH2CH
∆
PVC (plumbing polymer) Cl n
ROOR
n CF2 CF2 CF2CF2
∆ n
Polytetrafluroethene (Teflon)
Ch. 10 - 70
Other common polymers
CH3 CH3
ROOR
n CH2 C CH2C
∆
COOMe COOMe
n
Polymethyl methacrylate
(windshield, contact lenses)
ROOR
n CH2 CHPh CH2CH
∆
Ph
Polysterene (styrofoam, n
coffee cup, etc.)
Ch. 10 - 71
END OF CHAPTER 10
Ch. 10 - 72