10.

2 ALKANES
1. Introduction
Saturated
Acyclic: CnH2n+2; Cyclic: CnH2n
-

Cyclopropane & cyclobutane

are unstable due to ring strain
and unfavourable bond angles

Nomenclature: -ane; label from C

nearer to the first branch point
Isomerism: only alkanes with 4C
exhibit structural

(i) Combustion

( 4y ) O x C O + 2y H O

C x H y + x+
-

Incomplete pdts: CO/ C + H2O

Complete pdts: CO2 + H2O

Used as fuels as they burn readily in

(g). (s) and (l) state alkanes must be
vaporised before they will burn.
Higher alkanes are less volatile and
burn less readily due to strong TDID
(sooty flames)
(ii) Free radical substitution

2. Physical Properties
C & H have similar electro-ve, hence
non-polar. TDID
-

MP & BP: with Mr (TDID

.) but with branching
(smaller surface area of
contact)
Density: with Mr (stronger
TDID = brings molecules
closer, smaller volume) but
with branching
Solubility: soluble in non-polar
solvents (eg CCl4, benzene)
but insoluble in polar solvent
(water)
Viscosity (liquid alkanes):
measure of internal resistance
to flow of a fluid, arises due to
friction between molecules.
with Mr (TDID)

3. Chemical Properties
Generally unreactive due to nonpolarity & equal sharing of electrons
in bonds -> no significant charge to
act as electrophiles/ nucleophiles to
attract reactive species (unreactive
towards ionic, polar reagents)

Mechanism
Initiation

- homolytic cleavage of bond to

prduce free radicals
- light/heat only needed at start of
rxtn
Propagation
Cl + CH4 CH3 + HCl
CH3 + Cl2 Cl + CH3Cl
- for each radical consumed, one
radical produced
- chain reaction with pdtion of Cl
Termination
Cl + Cl Cl2
CH3 + CH3 CH3Cl
CH3 + Cl CH3Cl
- 2 reactive free radicals combining
to form stable product
- when relatively few reactant
molecules available to collide with

free radical
- any 2 equations, but one must
generate product of reaction
Why does Cl-Cl bond break
preferentially over C-H bond?
Bond energy lower
Does H radical form during prop?
No. CH4 + Cl gives either CH3 +
HCl OR CH3Cl + H. Energetically
more feasible for alkyl radical than
hydrogen rad to be formed (BE)

Highest activation energy step

Initiation, only step involving bondbreaking and requires input of
energy. The others are bond-forming
involving highly reactive radicals

Rate of substitution at different

carbons
Substitution of radical leads to 1o/ 2o
etc alkyl radicals, which leads to
different pdts

Multi-substitution
Monosub pdts undergo further
substitution. FRS does not give a
single organic product (mixture)
Cl + CH3Cl CH2Cl + HCl
CH2Cl + Cl2 Cl + CH2Cl2
Cl + CH2Cl2 CHCl2 + HCl
CHCl2 + Cl2 Cl + CHCl3
- Monosub as major pdt: excess of
alkane/ limited halogen used so
higher probability of radical to collide
with alkane instead of monosub pdt

Expected yield: count number of H

atoms which can be substituted
(60%:40%)
Experimental yield: 30%:70%
Discrepancy

- Higher sub as major pdt: excess of

halogen used

Reactivities of halogens
F2: explosively
Cl2, then Br2: at high temp/ UV light
I2: least reactive
Size of halogen = weaker cov bond
(..) = energy released in formation of
C-halogen and H-halogen bonds in
propagation = decreasing ease of
substitution
-

Weaker bond = BE lower =

lesser energy released =
reaction more endothermic

More stable alkyl radicals

formed preferentially, leading
to higher rate of substitution
of H at __ C. Higher __ radical
formed which reacts to form __
as major pdt.

More alkyl groups = more

stable alkyl radicals
o Electron donating/
releasing, shifts electron
density towards e-

deficient C radical,
hence in e- deficiency
4. Petroleum & environment

ability
-

Pollutions
-

Smog: incomplete combustion,

unburnt hydrocarbons escape
into atm under sunglight
causes lung damage
CO: incomplete combustion,
binds strongly to haemoglobin
in RBC, reduces oxy-carrying

Nitrogen oxides: combustion of

fuels in car engines raises
temp so high it can break
triple N bonds in N2 gas, which
form NO, NO2 = smog & ozone
& PAN

Catalytic converter
-

Redox
Converts harmful C, CO, NO,
NO2 into less harmful CO2, H2O,
N2, O2
Eg 2CO + 2NO 2CO2 + N2