Ch. 3 Alkane Structure vs.

Reactivity
I. Alkane Structure and Radical Halogenation
A. R-H reacts with halogens just like methane
Dh DE = -27 kcal/mol
CH3CH3 + Cl2 CH3CH2Cl + HCl
1) DHo for Et-H = 98 kcal/mol
DHo for Me-H = 105 kcal/mol (DE = -25 kcal/mol)

2) Only one possible product

B. Halogenation of Propane: 2o and 1o hydrogens

1) 6 primary H CH3CH2CH3
2) 2 secondary H Cl
3) Statistical product distribution = 3:1 CH3CH2CH2Cl / CH3CHCH3
4) But what are bond strengths?
a) 2o C-H = 94.5 kcal/mol
b) 1o C-H = 98 kcal/mol
5) Secondary H abstraction
is easier than Primary
H abstraction
a) Secondary radical
is more stable
b) Primary radical
is less stable

43% Cl 57%
6) Experimental ratio of products: CH3CH2CH2Cl / CH3CHCH3

2 (57% / 2H ) 4
a) Relative Reactivity = 
 
1 (43% / 6H ) 1

b) Secondary H about 4 time more reactive than Primary H

c) Chlorine has a 4:1 Selectivity for Secondary:Primary
d) Selectivity depends on X2, temp, etc…; not always 4:1
C. Tertiary H abstraction: Halogenation of (CH3)3CH
CH3 Cl2 CH3 CH3
CH3 C H ClCH2 C H + CH3 C Cl
CH3 64% CH3 36% CH3
1) DHo Tertiary = 93 kcal/mol DHo Primary = 98 kcal/mol
2) Statistical Product Distribution = 9:1
3 (36% / 1H ) 5
3) Experimental = 64:36 Selectivity =   
1 (64% / 9H ) 1

4) 3o:2o:1o = 5:4:1 for Chlorination

D. Selectivity or F2 and Br2 Halogenations

1) Reactivity: F > Cl > Br > I
2) F2
a) Unselective, products =
statistical product distribution

b) Early TS = reactants = alkanes

= very similar reactivities
 3) Br2
a) Very Selective
b) 3o:2o:1o = 1700:80:1
c) Late TS = products = radicals
= very different stabilities

E. Synthesis Using Radical Halogenation

1) Consider: selectivity, cost, convenience
2) I2 doesn’t work; F2 is expensive, corrosive, unselective
3) Cl2 is cheap (NaCl), but not very selective; Industrial Use
a) Lab Use only when you can get only one product
Cl2
Cl

b) Use safer Cl. generators:

SO2Cl2 Cl
Sulfuryl Chloride O

N-chlorosuccinimide N Cl Cl

(NCS)
O
 4) Br2 = cheap, selective, liquid
a) Reagent of choice in the lab, even though it’s not as reactive as Cl2
b) NBS = N-bromosuccinimide solid alternative Br radical source

II. Ozone Depletion

A. Ozone, O3, blocks harmful 200-300 nm UV light
h O2 UV
O2 2O O3 O2 + O
B. CFC’s (chlorofluorocarbons) Destroy atmospheric ozone
1) Refrigerants, propellants: CCl3F, CCl2F2, CCl2FCClF2
2) Radical Chain Mechanism with ozone
h
F3C Cl F3C + Cl

Cl + O3 ClO + O2

ClO + O O2 + Cl

3) Worldwide O3 down 6% since 1978

4) Replacements: HCFC’s, HFC’s (best)
React faster than CFC’s; Destroyed before reaching ozone layer
III. Combustion
A. Oxidation of alkanes
2 CnH2n+2 + (3n+1) O2 2n CO2 + (2n+2) H2O + Heat
DE = heat of combustion = -DHocomb = relative energy content of the alkane

B. Trends
1) More C’s = larger -DHocomb

2) Isomers do not have the same -DHocomb