Chapter 3 Reactions of Alkanes

I. Bond Dissociation
A. Bond Strength = Bond Dissociation Energy = DH0 = energy input to break bond
1) Homolytic Cleavage
H H 2H DHo = 104 kcal/mol

2) Heterolytic Cleavage

H H H+ +
H-
Bond Dissociation Energies of Various A—B Bonds
 3) H OH H + OH DHo = 119 kcal/mol

H OH H+ + OH- DE much smaller

Polar solvents stabilize ions

4) DHo depends on how well orbitals overlap: HF > HCl > HBr > HI

B. Stability of Radicals
1) Alkyl Radicals: 3o > 2o > 1o > Methyl

CH3-H 105
CH3CH2-H 101 DHo
Stability
(CH3)2CH-H 98.5
(CH3)3C-H 96.5

2) Hyperconjugation Explains Radical Stability

a) Hyperconjugation = delocalization of s-bond electron pair into a
partly empty p-orbital
Delocalization = spreading e- over multiple atoms
 b) Alkyl Radicals are planar (sp2) with single e- in p-orbital
c) Must have s-bond in proper geometry to help
d) Hyperconjugation is similar to p-bonding, but has odd # of e-

Methyl
Radical
 C. Pyrolysis
1) Pyrolysis = breaking of CH, C-C bonds with heat

CH3 +
D Radical
+
Combinations
+

2) Cracking = breaking into smaller fragments

a) Control with catalysts
b) Petroleum into gasoline

II. Radical Chain Mechanisms

A. Chlorination of Methane
Dhn
CH4 + Cl2 CH3Cl + HCl DE = -25 kcal/mol

1) D = heat, hn = light
2) Ea is high, so energy is required to start the reaction
B. Mechanism
A. Initiation Dhn 2 Cl
Cl Cl

B. Propagation
1) Cl + H-CH3 HCl + CH3

2) CH3 + Cl2 CH3Cl + Cl

C. Termination 2 Cl Cl2

Cl + CH3 CH3Cl

2 CH3 CH3CH3

1) Termination is rare because radicals are few, small odds of meeting

2) Radical chains use up “fuel” before termination
C. Reactivities of other Halogens
1) F2 > Cl2 > Br2 > I2

2) Propagation 1
a) F2 DH = -31 kcal/mol
b) Cl2 DH = +2 kcal/mol
c) Br2 DH = +18 kcal/mol
d) I2 DH = +34 kcal/mol

3) Hammond Postulate
a) Early TS = little bond breaking = exothermic reaction
b) Late TS = much bond breaking = endothermic reaction
c) At TS, Bond Breaking Energy = Bond Forming Energy

4) Propagation 2
a) Exothermic for all halides
b) Total DE for Prop. 1 and Prop. 2
F(-) > Cl(-) > Br(-) > I(+)
Iodine won’t react with methane to give MeI