Alkanes

Alkanes: Saturated Hydrocarbons

• Hydrocarbons are molecules composed of carbon &
hydrogen
– Each carbon atom forms 4 chemical bonds
– A saturated hydrocarbon is one where all C - C bonds are
―single‖ bonds & the molecule contains the maximum number
of H-atoms
– Saturated hydrocarbons are called ALKANES
 Normal vs Branched Alkanes
• NORMAL alkanes consist of
CH2 CH2 continuous chains of carbon
CH3 CH2 CH3 atoms
• Alkanes that are NOT
continuous chains of carbon
atoms contain branches
CH2 CH3 • The longest continuous chain
CH3 CH of carbons is called the parent
chain
CH3
 The First 10 “Normal” Alkanes

Name Formula M.P. B.P. # Structural Isomers

• Methane CH4 -183 -162 1
• Ethane C2H6 -172 -89 1 C1 - C4 are Gases
at Room Temperature
• Propane C3H8 -187 -42 1
• Butane C4H10 -138 0 2
• Pentane C5H12 -130 36 3C5 - C16 are Liquids
• Hexane C6H14 -95 68 at
5Room Temperature
• Heptane C7H16 -91 98 9
• Octane C8H18 -57 126 18
• Nonane C9H20 -54 151 35
• Decane C H -30 174 75
 Alkane Nomenclature
• Alkanes represent the simplest of the functional groups.

• An alkane contains only carbon and hydrogen (a hydrocarbon) and

contains only single bonds (termed a saturated hydrocarbon).

• Alkanes have the general formula CnH2n+2, thus, an alkane with 10 carbons
(n = 10) will have 2(10) + 2 = 22 hydrogens, or the molecular formula
C10H22.

• The root, or parent name for an unbranched alkane is taken directly from
the number of carbons in the chain according to a scheme of nomenclature
established by the International Union of Pure and Applied Chemistry
(IUPAC), as shown below:

No of 1 2 3 4 5 6 7 8 9 10 11 12
Carbon
Name Meth Eth Prop But Pent Hex Hept Oct Non Dec Undec Dodec
 IUPAC naming for alkanes:
1. Parent chain = longest continuous carbon chain  ―alkane‖.

2. Branches on the parent chain are named as ―alkyl‖ groups.

3. Number the parent chain starting from the end that gives you the
lower number for the first branch (principle of lower number).

4. Assign ―locants‖ to the alkyl branches.

5. If an alkyl group appears more than once use prefixes: di, tri, tetra,
penta…; each alkyl group must have a location!

6. The name is written as one word with the parent name last.
The names and locants for the alkyl branches are put in
alphabetic order (ignore all prefixes except iso), separating
numbers from numbers with commas and letters from
numbers with hyphens.
 IUPAC nomenclature

International Union of Pure and Applied Chemistry

No of 1 2 3 4 5 6 7 8 9 10 11 12
Carbon
Name Meth Eth Prop But Pent Hex Hept Oct Non Dec Undec Dodec
IUPAC nomenclature (Geneva, 1920)

names of radicals (alkyl groups):

CH3- ―methyl‖ CH3Cl methyl chloride
CH3OH methyl alcohol, etc.
CH3CH2- ―ethyl‖
CH3CH2CH2- ―-propyl‖
CH3CHCH3 ―isopropyl‖ (1-methylethyl)
|
CH3CH2CH2CH2- ―-butyl‖

CH3
CH3CH2CHCH3 or CH3CH2CH- ―sec-butyl‖
| (1-methylpropyl)

CH3
CH3CHCH2- ―isobutyl‖
(2-methylpropyl)

CH3
CH3CCH3 ―tert-butyl‖
|
(1,1-dimethylethyl)
IUPAC NAMES OF ALKYL GROUPS

-isohexyl
 Example 1: 2,2-dimethylpentane

• The parent chain is indicated by 2 4

the ROOT of the name - 1 CH2 3 CH2 5
―pentane‖. This means there are CH3 CH2 CH3
5 carbons in the parent chain.
• ―dimethyl‖ tells us that there are
CH3 TWO methyl branches on the
4
parent chain. A methyl branch is
C CH2 made of a single carbon atom.
CH3 CH2 CH3
• ―2,2-‖ tell us that BOTH methyl
1
3 5

CH3
branches are on the second carbon
atom in the parent chain.
 Example 2: 3-ethyl-2,4-dimethylheptane

2 4
• The parent chain is indicated CH2 3 CH2 5
1
by the ROOT of the name - CH CH2 CH2
―heptane‖. This means there 3

are 7 carbons in the parent

H2C 6 7
chain.
CH3 CH3 CH3
• ―2,4-dimethyl‖ tells us there are
CH CH TWO methyl branches on the
CH3 CH CH2 parent chain, at carbons #2 and
#4.
CH2 CH2 • ―3-ethyl-‖ tell us there is an
CH3 CH3 ethyl branch (2-carbon branch)
on carbon #3 of the parent
 Example 3: 2,3,3-trimethyl-4-propyloctane
• The parent chain is indicated 3 5
by the ROOT of the name - 4 6
2
―octane‖. This means there
are 8 carbons in the parent 1
7

chain. 8
CH3
3 5 • ―2,3,3-trimethyl‖ tells us there
2 4
6
CH3are THREE
C methylCHbranches
2 -
CHon carbon
one CH#2 and two CHon2
1
7 CH3
8 carbon #3.
CH3 CH2 CH2
• ―4-propyl-‖ tell us
CH there is a CH3
2
propyl branch (3-carbon
CH#4
branch) on carbon 3 of the
 Example 4: Name the molecules shown!
CH3
• parent chain has 5 carbons -
―pentane‖
CH2 CH
• two methyl branches - start CH3 CH CH3
counting from the right - #2
and #3
CH3
• 2,3-dimethylpentane
• parent chain has 8 carbons -
―octane‖
• two methyl branches - start
4 counting from the left - #3 and #4
3 5
• one ethyl branch - #5
• name branches alphabetically
5-ethyl-3,4-dimethyloctane
 Cycloalkanes
• Cycloalkanes have one or more rings of carbon atoms.
• The simplest examples of this class consist of a single,
unsubstituted carbon ring, and these form a homologous series
similar to the unbranched alkanes.
• The last (yellow shaded) column gives the general formula for
a cycloalkane of any size.
• If a simple unbranched alkane is converted to a cycloalkane
two hydrogen atoms, one from each end of the chain, must be
lost.
• Hence the general formula for a cycloalkane composed of n
carbons is CnH2n.
Examples of Simple Cycloalkanes

Name Cyclopropane Cyclobutane Cyclopentane Cyclohexane Cycloheptane Cycloalkane

Molecular
Formula
C 3H 6 C 4H 8 C5H10 C6H12 C7H14 CnH2n

Structural
Formula (CH2)n

Line
Formula
IUPAC Rules for Cycloalkane Nomenclature

1. For a monosubstituted cycloalkane the ring supplies the root name

(table above) and the substituent group is named as usual. A
location number is unnecessary.

2. If the alkyl substituent is large and/or complex, the ring may be

named as a substituent group on an alkane.

3. If two different substituents are present on the ring, they are listed
in alphabetical order, and the first cited substituent is assigned to
carbon #1. The numbering of ring carbons then continues in a
direction (clockwise or counter-clockwise) that affords the second
substituent the lower possible location number.
IUPAC Rules for Cycloalkane Nomenclature

….cont.

4. If several substituents are present on the ring, they are listed in

alphabetical order. Location numbers are assigned to the
substituents so that one of them is at carbon #1 and the other
locations have the lowest possible numbers, counting in either a
clockwise or counter-clockwise direction.

5. The name is assembled, listing groups in alphabetical order and

giving each group (if there are two or more) a location number.
The prefixes di, tri, tetra etc., used to designate several groups of
the same kind, are not considered when alphabetizing.
 Alkanes Review - Cycloalkanes
• A cycloalkane is made of a hydrocarbon chain that
has been joined to make a ―ring‖.
109.5° bond angle H2
60° bond angle
CH2 C unstable!!

CH3 CH3
H2C CH2
n-propane cyclopropane
C3H8 C3H6
•Note that two hydrogen atoms were lost in forming the
ring!
•What is the general formula for a cycloalkane?
Cycloalkanes are named by using similar rules, but the prefix cyclo-
immediately precedes the name of the parent.

1. Find the parent cycloalkane.

2. Name and number the substituents. No number is needed to
indicate the location of a single substituent.

For rings with more than one substituent, begin numbering at one
substituent and proceed around the ring to give the second
substituent the lowest number.
With two different substituents, number the ring to assign the lower
number to the substituents alphabetically.

Note the special case of an alkane composed of both a ring and a long
chain. If the number of carbons in the ring is greater than or equal to
the number of carbons in the longest chain, the compound is named
as a cycloalkane.
Two contrasting examples—
Naming compounds containing both a ring
and a long chain
of carbon atoms
Figure 4.3
Examples of cycloalkane
nomenclature
 IUPAC name for hexanes C6H14

CH3
CH3CH2CH2CH2CH2CH3 CH3CHCH2CH2CH3
(n-hexane) (isohexane)
n-hexane 2-methylpentane
or hexane
CH3 CH3
CH3CH2CHCH2CH3 CH3CCH2CH3
CH3
3-methylpentane (neohexane)
2,2-dimethylbutane
CH3
CH3CHCHCH3
CH3
2,3-dimethylbutane
CH3CH2
CH2CHCH2CHCH3 2,4-dimethylheptane
CH3 CH3

CH3 CH3
CH
CH3CH2CH2CHCH2 CH3
CH2CH2CCH3
CH3

6-isopropyl-2,2-dimethylnonane
 Naming Priority

• Acids • Alkenes
• Esters • Alkynes
• Amide • Benzene
• Aldehydes • Alkanes
• Ketones • Halides
• Alcohols
• Amines
 Physical Properties
• Boiling Point-the temperature at which a
liquid boils and turns to vapour.

• Melting Point- temperature at which a solid

becomes a liquid at normal atmospheric
pressure.

• Solubility-maximum amount of solute that

dissolves in a given quantity of solvent at a
specific temperature.
 Basic Principles
• 1.The relative strength of the four
intermolecular forces is: Ionic > Hydrogen
bonding > dipole dipole > Van der Waals
dispersion forces.The influence of each of
these attractive forces will depend on the
functional groups present.
• 2. Boiling points increase as the number of
carbons is increased.
• 3. Branching decreases boiling point.
• Polarity of Organic Compounds
• Principles of Polarity:
• The greater the electronegativity difference between atoms in a
bond, the more polar the bond. Partial negative charges are
found on the most electronegative atoms, the others are
partially positive. In general, the presence of an oxygen is
more polar than a nitrogen because oxygen is more
electronegative than nitrogen.

• The combination of carbons and hydrogens as in hydrocarbons

or in the hydrocarbon portion of a molecule with a functional
group is always NON-POLAR.
Polarity Ranking of the Functional
Groups:

Amide > Acid > Alcohol > 1°

Amine > 2° Amine > Ketone >
Aldehyde > 3°Amine > Ester
> Ether > Alkane
Principle: The greater the forces of attraction the higher the boiling
point or the greater the polarity the higher the boiling point.
 Physical Properties of Alkanes
1. Combustion - Alkanes are inflammable, i.e. they burn.

CH 4 + 2 O2 CO2 + 2 H2O

2. Boiling and melting points

a. Both bp and mp increase with increasing carbon number for straight-

chain alkanes with formula CnH2n+2

Carbon Number Physical State

C1- C4 gases
C5 – C16 liquids
C17 – C30 oils and greases
C30 – C50 paraffin waxes
>C50 plastics (polyethylene)

b. Branching tends to raise the melting point.

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 b. Branching tends to lower the boiling point

BP 60oC 58oC 50oC

Explanation:

BP Branching reduces surface area (more compact structure), and therefore London
dispersion forces which control boiling point for these molecules.

3. Solubility – alkanes are nonpolar molecules and therefore insoluble in water, which
is polar. Alkanes are hydrophobic.

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Physical Properties of Alkanes
 Chemical reactions of Alkanes

Low reactivity

1- Combustion:
• Alkanes react with oxygen.
• CO2, H2O, and energy are produced.
• Alkane + O2 CO2 + H2O + heat
CH4 + 2O2 CO2 + 2H2O + energy
• Alkanes undergo combustion—that is, they burn in the presence of oxygen to
form carbon dioxide and water.
• This is an example of oxidation. Every C—H and C—C bond in the starting
material is converted to a C—O bond in the product.
 Chemical reactions of Alkanes

2- Halogenation:
Alkanes react with Halogens.

Chloromethane
CH4 + Cl2 light CH3Cl + HCl

CH3Cl+ Cl2 CH2Cl2 + HCl Dichloromethane

light

CH2Cl2+ Cl2 CHCl3 + HCl Trichloromethane

light

CHCl3+ Cl2 CCl4 + HCl Tetrachloromethane

light
Mechanism: FREE RADICAL SUBSTITUTION

Alkanes react with chlorine in the presence of

sunlight.
• The reaction is slow.
• ex: When methane reacts with chlorine, the
hydrogen atoms are substituted with chlorine until
CCl4 is obtained.
CH4 + Cl2 CH3Cl + HCl
CH3Cl + Cl2 CH2Cl2 + HCl
CH2Cl2 + Cl2 CHCl3 + HCl
CHCl3 + Cl2 CCl4 + HCl
• Free radical substitution is a reaction that substitutes a
chlorine or a bromine for a hydrogen on an alkane.
This reaction is a photochemical one. That is, it
occurs only when performed in the presence of uv
light.

• Typically, free radical reactions are described in three

steps: initiation steps, propagation steps, and
termination steps.
Reaction of Alkane with Cl2 or Br2
Radicals are formed by homolytic cleavage.
When a bond breaks leaving the bonding electrons equally divided between the
atoms, the process is called homolytic cleavage or homolysis:

Species containing more than one atom and an unpaired electron are called
radicals.
Free atoms and radicals exist as intermediates in small concentrations during the
course of many reactions but cannot usually be isolated.

Ch03 41
Some Examples of Radicals

Ch03 42
Consider the relative stabilities of alkyl radicals,

The stable alkyl radical is formed faster, therefore

2-chlorobutane is formed faster
 Radical Halogenation: Predict the Product
Cl
? Cl + HCl OR
+ Cl2 →
? ?
1-chloropropane 2-chloropropane

OR Cl

3-chloropropane?

Remember that any H on the alkane can be replaced by a halogen

+ Br2 → Br OR
Br
1-bromo-2-methylbutane 2-bromo-2-methylbutane
Radical Halogenation: Predict the Product

+ Br2 → Br OR
Br
1-bromo-2-methylbutane 2-bromo-2-methylbutane

Br
Br
OR OR
Br

2-bromo-3- 1-bromo-3- 1-bromo-2-

methylbutane methylbutane methylbutane
3. Cracking

a. Catalytic hydrocracking – produces small alkanes from large alkanes by

adding hydrogen.
H2, heat
Si-Al catalyst

b. Catalytic cracking – produces small alkenes and alkanes by cracking in the absence
of hydrogen.
heat

Si-Al catalyst

c. Catalytic Reforming – the alkanes and cycloalkanes are upgraded to higher octane
number by conversion into aromatic compounds.

-H2 -3H2

catalyst, heat catalyst, heat

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