Structural formula

Name

CH4
CH3CH3
CH3CH2CH3
CH3(CH2)2CH3
CH3(CH2)3CH3
CH3(CH2)4CH3
CH3(CH2)5CH3
CH3(CH2)6CH3
CH3(CH2)7CH3
CH3(CH2)8CH3
CH3(CH2)9CH3
CH3(CH2)10CH3
CH3(CH2)14CH3

methane
ethane
propane
butane
pentane
hexane
heptane
octane
nonane
decane
undecane
dodecane
hexadecane

Number of Isomers

BP (C)

1
1
1
2
3
5
9
18
35
75
159
355
10, 359

-164
-89
-42
0
36
69
98
126
151
174
196
216

Rules:
1. Find the longest, continuous carbon chain and
designate this as the parent chain. If there are
two or more chains of equal length, choose the
chain with a greater number of branch points.

CH 3
CH 3 CH

CH 3
CH

CH 2 CH 2

CH 2CH 3

CH 3

NOT

CH 3 CH

CH

CH 2 CH 2

CH 2CH 3

CH 3

2. Number the carbon atoms in the parent chain so that

the carbons bearing the alkyl substituents or other
groups are given the lowest possible number.
Start from the end nearest to the first branch point.
If there is branching at an equal distance from both
ends of the chain, begin numbering from the end
nearer to the second branch point.

3. Name the substituents. Alkyl groups (derived from small

alkanes by removal of 1H) are named by replacing the ending
-ane of the corresponding alkane with -yl. Alkyl groups
with prefixes iso-, neo- and cyclo- can be used in the
IUPAC system.
4. If the same alkyl group occurs more than once as a
substituent, indicate this by the prefix di-, tri-, tetra-,
etc. and assign a number for each substituent to indicate its
position. There must be as many number designations as
there are substituents.

5. Write the name of the compound by first arranging all

substituents (preceded by the position numbers) in
alphabetical order and then adding the name of the parent
chain. Prefixes such as iso-, neo- and cyclo- are included
in alphabetization. However, the numerical and hyphenated
prefixes, e.g. tert-, sec-, n-, di-, tri- are ignored.
compound 1: 3-ethyl-2-methylhexane
compound 2: 3-ethyl-4,7-dimethylnonane

PHYSICAL PROPERTIES:
structural basis:
C-C
C-H

non-polar; 1.54 A; 85 kcal/mol

very slightly polar; 1.09 A; 95 kcal/mol

tetrahedral geometry dipoles cancel out; non-polar or

very weakly polar intermolecular
forces: van der Waals type

1. Physical state
C1 C4
C5 C17
C18 and higher
examples:

gases
liquids
solids

C3H8 BP 42.1 C
C6H14 BP 68.9 C
C20H42 BP 220C/30 mm

2. Boiling point (BP)

a) The larger the molecule, the greater the surface area
the stronger the imf; the higher the BP
Note: BP rises 20 30 C for each added carbon (true for all
homologous series of cpds)
n-pentane
BP 36.1 C
n-hexane
BP 68.9 C
n-heptane
BP 98.4 C

b.

BP decreases with increasing degree of branching (for all

homologous series)
n-butane
isobutane

0 C
-12 C

n-pentane
36 C
isopentane 28 C
neopentane 9.5 C

c.

Cycloalkanes have a higher BP than the open-chain

compounds with the same number of carbons.

n-propane
-42.1 C
cyclopropane -32.7 C
n-butane
-0.5 C
cyclobutane 12 C

n-hexane
68.9 C
cyclohexane 80.7 C

3. Solubility behavior
Recall: LIKE DISSOLVES LIKE

a. soluble in non-polar solvents, e.g. benzene, ether,

chloroform
b. insoluble in water and highly polar organic solvents
**Low molecular weight alkanes are good solvents for nonpolar or weakly polar compounds.
4. Density - less than that of water; floats in water due to weak
intermolecular attractive forces that result in "loose packing"
of molecules; density= 0.8

Reactions:
1. Combustion

- a free radical reaction with a complex reaction

mechanism
- initially, energy is required to obtain the
reactive species but once started, chain-carrying steps
proceed readily and exothermically

a. open-chain alkanes
CnH2n+2

e.g.

+ excess O2

C5H12

flame or
heat

8 O2

n CO2 + (n+1) H2O + heat

flame or
heat

5 CO2 + 6 H2O + 845 kcal/mol

b. cycloalkanes
CnH2n

e.g.

+ excess O2

C6H12

9 O2

flame or
heat

flame or
heat

n CO2 + (n) H2O + heat

6 CO2 + 6 H2O + heat

2. Free Radical Substitution

Net equation:
RCH3
alkane

X2, CCl4 or gas phase

light, 25 C

RCH2
X
alkyl halide

HX

where X = Cl or Br
F may react but only under inert atmosphere at low temperature
I does not react at all

Experimental observations:
requires heat or light to initiate the reaction; no
reaction in the dark at room temperature
occurs in the gas phase or non-polar solvent; recall
the bromine test in the laboratory

Br2
red

HBr
colorless

oxygen inhibits the reaction

in the light-induced reaction, several thousands of
molecules are obtained per photon of light absorbed

Reaction mechanism:
Consider the reaction of methane with chlorine
shown below as the model reaction:
H

H
light

Cl2

Cl

+ HCl

steps in the mechanism:

I . Chain initiation step starts the chain reaction;
reactive species are produced

Cl

light
Cl

2 Cl

II. Chain propagation steps result in the formation of

the reaction products as well as the reactive
intermediates that propagate the chain; up to 5,000
cycles per halogen atom
H

H
(2)

Cl

HCl

H
H

C
H

H
methyl free radical

(3)

H
+

Cl

Cl

Cl

Cl

H
then (2), (3), (2), (3), (2), (3), ....... until the reactants are used up

III. Chain termination step occurs after all the

reactants have been used up; involves all the possible
combinations of free radical species produced in the
course of the reaction
(a)

Cl

Cl2

Cl
H

(b)

Cl

Cl

H
H

(c)

C
H

H
H

C
H

Examples:

Conclusions:
1. Reaction rates reflect the ease of hydrogen abstraction
2. Reaction rates parallel the stabilities of the alkyl free
radicals formed in the chain propagation steps.
3. Reaction rates are also affected by the type of halogen.
Cl more reactive; less selective
Br less reactive; more selective

***Remember***
The more stable the free radical, the more easily it is formed!

Relative proportion of products =

reactivity factor (r) x probability factor (p)
Where the reactivity factors are as follows:

Free radical stabilties:

Reactivity factors:
X = Cl
5.0
X = Br
1600

3 > 2 > 1 > methyl

3.8
82

1.0
1.0

3. Ring Opening Reactions of Small Cycloalkanes

*small rings (i.e., cyclopropane and cyclobutane) may
be prone to ring opening reactions due to angle strain.
Examples of such reactions are: