Section 2.

19

CYCLOALKANE
NOMENCLATURE

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 Cycloalkanes: Cyclic Alkanes
Cycloalkanes are cyclic alkanes with the general
formula CnH2n, where n > 2
Found in a wide variety of organic compounds

Parent cycloalkanes are named using the prefix cyclo–

Substituents are named in the usual way

Where do we start numbering?

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 Numbering Cycloalkanes
As for alkanes, we number cycloalkanes so that
the substituent at the first point of difference gets
the lowest number

Typically, this means that the most substituted

carbon is C1
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 Cycloalkanes as Substituents
Simple cycloalkanes bonded to longer alkyl chains
are treated as cycloalkyl substituents

Note that the cyclobutane ring is smaller than

the attached pentane chain.

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 Section 2.20

INTRODUCTION TO
FUNCTIONAL GROUPS

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 Introduction to Functional Groups
Functional groups are structural units containing
heteroatoms or multiple bonds
We can imagine (and name) many organic compounds as
alkyl derivatives of functional groups
Alkyl halides contain an alkyl group bound to a halogen atom

Alcohols contain an alkyl group bound to a hydroxyl group

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 Section 2.21

SOURCES OF ALKANES AND

CYCLOALKANES

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 Alkanes from Petroleum
Petroleum deposits are a very common source of
alkanes and other hydrocarbons
Crude oil can be distilled over a range of
temperatures to separate it into pure compounds

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 Biological Sources
Organic compounds, including alkanes, are commonly
found in biological organisms
• The linear pentacosane, CH3(CH2)23CH3, is present in the waxy
covering of many insects
• Hentriacontane, CH3(CH2)29CH3, is found in beeswax and other
natural waxes
Biological compounds based on cycloalkanes are rare, but
do appear in some contexts

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 Section 2.22

PHYSICAL PROPERTIES OF
ALKANES AND CYCLOALKANES

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 Intermolecular Forces in Alkanes
Alkanes consist of nonpolar C–C bonds and very weakly
polarized C–H bonds. Hence, they are nonpolar overall
However, alkane molecules usually exhibit instantaneous
dipoles due to asymmetric distributions of electrons at any
point in time
Instantaneous dipoles can induce a dipole in a nearby
molecule, resulting in attractive forces
The instantaneous dipole–induced dipole force is called a
van der Waals interaction or London dispersion force

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 van der Waals Forces
There are three types of van der Waals forces:
1. dipole–dipole (including hydrogen bonding)
2. dipole/induced-dipole
3. induced-dipole/induced-dipole
These forces are electrical in nature, and in order to
vaporize a substance, enough energy must be added to
overcome them.
Most alkanes have no measurable dipole moment, and
therefore the only van der Waals force to be considered is
the induced-dipole/induced-dipole attractive force.

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 Boiling Points
Boiling points of alkanes increase with molecular weight
Branched alkanes have lower boiling points than linear
alkanes

Branched alkanes have

smaller surface area than
isomeric linear alkanes.
van der Waals forces are
weaker in branched alkanes
as a result.

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 Melting Points
Solid alkanes are typically soft and waxy substances
with relatively low melting points
Molecules in the solid pack together closely
Melting points points of alkanes also increase with
molecular weight
Branched alkanes have lower melting points than linear
alkanes

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 Solubility in Water
Alkanes are nonpolar substances characterized by
very weak van der Waals interactions
van der Waals interactions of alkanes with water
cannot overcome the strength of hydrogen bonds
in water
Hence, alkanes are not generally soluble in water
The Hydrophobic Effect: alkane molecules
cluster together and exclude water molecules

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 Section 2.23

CHEMICAL PROPERTIES:
COMBUSTION OF ALKANES

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 Alkanes React with Oxygen
Alkanes are highly reduced forms of organic
compounds, which contain only C–C and C–H bonds
They react vigorously and exothermically with O2
gas in combustion reactions to form CO2 and H2O

  
H  H products H reactants

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 Heats of Combustion
TABLE 2.3 Heats of Combustion (−∆H°) of Representative Alkanes
−∆H° −∆H°
Compound Formula kJ/mol kcal/mol
Unbranched alkanes
Hexane CH3(CH2)4CH3 4,163 995.0
Heptane CH3(CH2)5CH3 4,817 1,151.3
Octane CH3(CH2)6CH3 5,471 1,307.5
Nonane CH3(CH2)7CH3 6,125 1,463.9
Decane CH3(CH2)8CH3 6,778 1,620.1
Undecane CH3(CH2)9CH3 7,431 1,776.1
Dodecane CH3(CH2)10CH3 8,086 1,932.7
Hexadecane CH3(CH2)14CH3 10,701 2,557.6
2-Methyl-branched alkanes
2-methylpentane (CH3)2CHCH2CH2CH3 4,157 993.6
2-methylpentane (CH3)2CH(CH2)3CH3 4,812 1,150.0
2-methylpentane (CH3)2CH(CH2)4CH3 5,466 1,306.3

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 Branching and Stability
Intramolecular forces affect heats of combustion of isomeric
alkanes
Branched isomers generally have less exothermic heats of
combustion, indicating greater stability

Attractive
intramolecular forces in
the branched isomer
stabilize it relative to
n-octane.

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 Section 2.24

OXIDATION AND REDUCTION IN

ORGANIC CHEMISTRY

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 Calculating Oxidation Number
The oxidation number of carbon is calculated by assuming:
1. The overall oxidation number of a neutral compound is zero
2. Electronegative heteratoms have oxidation number –n, where n is
the number of bonds to carbon
3. Electropositive heteroatoms have oxidation number +n
4. Hydrogens have oxidation number +1
In essence, subtract 1 for each bond to a nonmetal and
add 1 for each bond to hydrogen or a metal

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 Oxidation and Reduction at Carbon
An oxidation reaction increases the oxidation number of
carbon by replacing a C–H bond with a C–X bond

A reduction reaction decreases the oxidation number of

carbon by replacing a C–X bond with a C–H bond

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 Oxidation and Reduction at Carbon-1
An oxidation reaction increases the oxidation number of
carbon by replacing a C–H bond with a C–X bond

A reduction reaction decreases the oxidation number of

carbon by replacing a C–X bond with a C–H bond

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